HANDBOOK OF

COMPOSITES

SECOND EDITION

Edited by

S.T.Peters
Process Research, Mountain View, Calfornia, USA

CHAPMAN & HALL

- - - -
London Weinheim . New York Tokyo Melbourne Madras
Published by Chapman & Hall, an imprint of Thomson Science, 2-6 Boundary
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CONTRIBUTORS

SURESH G. ADVANI KENNETH R. BERG

Department of Mechanical Engineering, Riggs Corporation,
University of Delaware, 837 Agate Street,
Spencer Laboratory, Medford, OR 97501,
Newark, DE 19716, USA
USA
LARS A. BERGLUND
MAURICE E AMATEAU LuleH University of Technology,
Applied Research Laboratory, SE-97187 LuleH,
Pennsylvania State University, Sweden
PO Box 30,
State College, PA 16804, D. BROWN
USA Boeing Commercial Airplane Group,
Douglas Products Division,
EVER J. BARBER0 Mail Stop D001-0018,
315 Engineering Science Building, Long Beach, CA 90846,
West Virginia University, USA
Morgantown, WV 26506-6106,
USA JOHN D. BUCKLEY
23 East Governor Drive,
A.I. BEIL' Newport News, VA 23602,
Institute of Polymer Mechanics, USA
Latvian Academy of Sciences,
23 Aizkraukles Street, JERRY L. CADDEN
Riga LV-1006, C & S Technologies,
Latvia 42759 Mountain Shadow,
Murrieta, CA 92562,
JEROME S. BERG USA
True Temper Sports,
5421 Avenida Encinas, ZHONG CAI(deceased)
Suite G, 4180 Berkeley Creek Drive,
Carlsbad, CA 92008, Duluth, GA 30136,
USA USA
x Handbook of composites

FRANK A. CASSIS MIRIA M. FINCKENOR

FAC Associates, EH12 Bldg 4711,
1150 N. Mountain, Suite 1028, Marshall Space Flight Center,
Upland, CA 91786, AL 35812,
USA USA

LINDA L. CLEMENTS LIHWA FONG

C & C Technologies,
PO Box 1089,
Dayton, NV 89403,
USA
DOUGLAS L. DENTON
Chrysler Corporation,
CIMS 482-00-13,
800 Chrysler Drive,
Auburn Hills, MI 48326-2757,
USA
EDDY A. DERBY
Composite Optics,
9617 Distribution Ave,
San Diego, CA 92121,
USA
GEORGE W. DU
Principal Engineer,
16331 Bay Vista Drive
Cleanvater, FL 34620,
USA
HARRY W. DURSCH
Boeing Defense and Space Group,
PO Box 3999, Mail Stop 73-09,
Seattle, WA 98124-2846,
USA
DON 0. EVANS
Cincinnati Milacron,
4701 Marburg Avenue,
Cincinnati, Ohio 45209,
USA
BLK G 5,
Nanyang Avenue,
Singapore 63616
HUGH H. GIBBS
Polycomp Consulting, Inc.,
25 Crestfield Road,
Wilmington, DE 19810,
USA
TIMOTHY GUTOWSKI
Department of Mechanical Engineering,
Massachusetts Institute of Technology,
Bldg 35-234,
Cambridge, MA 02139,
USA
RICHARD N. HADCOCK
6 Sue Circle,
Huntington, NY 11743,
USA
ENAMUL HAQUE
Azdel, Inc.,
Technology Center,
658 Washburn Switch Road,
Shelby, NC 28151-2284,
USA
L.J. HART-SMITH
Boeing Commercial Airplane Group,
Douglas Products Division,
Mail Stop D800-0019,
4000 Lakewood Boulevard,
Long Beach, CA 90846,
USA
 Confributors xi

JENNIFER HETH VALERY I. KOSTIKOV

Cytec Fiberite, Niigrafit Institute,
501 W. Third Street, 2 Electrodonaya Street,
Winona, MN 55987-2854, Moscow, 111524,
USA Russia

THOMAS S. JONES GARY C. KRUMWEIDE

Industrial Quality, Inc., Composite Optics,
640 E. Diamond Ave., Suite C, 9617 Distribution Avenue,
Gaithersburg, MD 20877, San Diego, CA 92121,
USA USA

THOMAS JUSKA V.L. KULAKOV

Naval Surface Warfare Center, Institute of Polymer Mechanics,
Carderock Division, Latvian Academy of Sciences,
Structures and Composites Department, 23 Aizkraukles Street,
Bethesda, MD 20084-5000, Riga LV-1006,
USA Latvia

JOHN T. KANNE KHALID LAFDI

2201 Johnson Road, Center for Advanced Friction Studies,
Memphis, TN 38139, Southern Illinois University at Carbondale,
USA Carbondale, IL 62901-4343,
USA
HARRY S. KATZ
Utility Development Corporation, CHRISTY KIRCHNER LAPP
112 Naylon Avenue, 1412 Bellingham Way,
Livingston, NJ 07039, Sunnyvale, CA 94087,
USA USA

V.S. KILIN ROBERT A. LATOUR

Niigrafit Institute, Clemson University,
2 Electrodonaya Street, Clemson, SC 29634,
Moscow, 111524, USA
Russia
BURR L. LEACH
FRANK K. KO Cambridge Industries,
Drexel University, 1700 Factory Avenue,
Fibrous Materials Research Laboratory 27-439, Marion, IN 46952,
Philadelphia, PA 19104, USA
USA
STEWART N. LOUD
KENT E. KOHKONEN Composites Worldwide Inc.,
Brigham Young University, 991 Lomas Santa Fe Drive, C469,
435 CTB Technology Department, Solana Beach, CA 92075-2125,
Provo, UT 84602, USA
USA
xii Handbook of composites

VICKI P. MCCONNELL NITIN POTDAR

Ray Publishing, Brigham Young University,
Independence Street, 435 CTB Technology Department,
Suite 270, Wheat Ridge, Provo, UT 84602,
CO 80033, USA
USA
KENNETH REIFSNIDER
ANDREW C. MARSHALL Virginia Polytechnic Institute and State
Marshall Consulting, University,
720 Appaloosa Drive, Patton Hall 120,
Walnut Creek, CA 94596, Blacksburg, VA 24061-0219,
USA USA

ANTHONY MARZULLO THEODORE J. REINHART

39 Harold Street, 345 Forrer Boulevard,
COSCob, CT 06807-2132, Dayton, OH 45419-3238,
USA USA

DONALD W. OPLINGER PAUL E SADESKY

Federal Aviation Administration, C & S Technologies,
Wm. J. Hughes Technical Center AAR-431, 23547 Mountain Court,
Atlantic City, International Airport, Murrieta, CA 92562,
NJ 08405, USA
USA
FRANK J. SCHWAN
HARRY E. PEBLY 36671 Montecito Drive,
198 Center Grove Road, Fremont, CA 94536,
Randolph, NJ 07869, USA
USA
ANTON L. SEIDL
LYNN S. PENN 18941 Mellon Drive,
Department of Chemical and Materials Saratoga, CA 95070,
Engineering, USA
177 Anderson Hall,
University of Kentucky, JOCELYN M. SENG
Lexington, KY 40506-0046, Owens Corning Science and Technology
USA Center,
2790 Columbus Road,
S.T. PETERS Granville, OH 43023-1200,
Process Research, USA
925 Sladky Avenue,
Mountain View, CA 94040-3625, SHALABY W. SHALABY
USA Clemson University,
301 Rhodes Res.,
Clemson, SC 29634,
USA
 Contributors xiii

DAVID A. SHIMP WAYNE C. TUCKER

PO Box 974, Naval Undersea Warfare Center,
Prospect, KY 40059, PO Box 86,
USA Exeter, RI 02822,
USA
DONALD R. SIDWELL
44609 Grove Lane, V. V. VASILIEV
Lancaster, CA 93534-2833, Moscow State University,
USA 14-1-110 Podolskih Kursantov Street,
Moscow 113545,
BRIAN E. SPENCER Russia
Spencer Composite Corporation,
3220 Superior Street, PO Box 4377, DENNIS J. VAUGHAN
Lincoln, NE 68504-0377, 146 Longview Drive,
USA Anderson, SC 29621,
USA
ROBERT C. TALBOT
7199 Lorine Court, H. WANG
Columbus, OH 43235-5125, Department of Chemical and Materials
USA Engineering,
177 Anderson Hall,
YU.M. TARNOPOL'SKII University of Kentucky,
Institute of Polymer Mechanics, Lexington, KY 40506-0046,
Latvian Academy of Sciences, USA
23 Aizkraukles Street,
Riga LV-1006, ANN E WHITAKER
Latvia EHOl Bldg 4612,
Marshall Space Flight Center,
R.C. TENNYSON AL35812,
University of Toronto, USA
Institute for Aerospace Studies,
4925 Dufferin Street, BRIAN A. WILSON
Downsview, Ontario, Wilson Composite Group,
Canada M3H 5T6 6611 Folsom-Auburn Road, Suite C,
Folsom, CA 95630,
JAMES L. THRONE USA
Shenvood Technologies, Inc.,
158 Brookside Boulevard, S. WONG
Hinckley, OH 44233-9676, Boeing Commercial Airplane Group,
USA Douglas Products Division,
Mail Stop D001-0018,
FRANK TRACESKI Long Beach, CA 90846,
Department of Defense, USA
5203 Leesburg Pike Suite 1403,
Falls Church, VA 22041,
USA
xiv Handbook of composites

MAURICE A. WRIGHT PHILIP R. YOUNG

Center for Advanced Friction Studies, Emory & Henry College,
Southern Illinois University at Carbondale, Department of Chemistry,
Carbondale, IL 62901-4343, Emory, VA 24327,
USA USA
ABOUT THE EDITOR
S.T. Peters was previously a fellow engineer
with Westinghouse Electric Corporation,
Marine Division prior to devoting full time to
composite and materials and processing con-
sulting for his own company, Process
Research, in Mountain View, CA. He has writ-
ten many articles on composites and filament
winding, a book on filament winding, edited
one previous book and holds several patents
on winding techniques and composite joints.
He is a private consultant with worldwide
clients and has presented tutorials on compos-
ites to many audiences, including the US
Navy and NASA, several technical societies
and two universities. He is a licensed profes-
sional engineer in the state of California, a
member of ASM, and the composites division
of SME and has been elected a fellow of
SAMPE.
ACKNOWLEDGEMENTS
As with any large undertaking there is a sup-
porting group of people without whose help
the objective would not be met. I wish to
acknowledge my wife, Lynn, for her help in
deciphering and rewriting some of the articles
and for enduing my sometimes uncivil
approach to resolving problems. Thanks also
go to Mr Frank Heil and Dr Alvin Nakagawa
of Westinghouse Electric, Marine Division
(now Norton Grumman) for their editorial
and review help. I also wish to thank Dr Linda
Clements for her advice and support.
PREFACE

Today, fiber reinforced composites are in use 0 properties of different component (fiber,
in a variety of structures, ranging from space- matrix, filler) materials;
craft and aircraft to buildings and bridges. 0 manufacturing techniques;
This wide use of composites has been facili- 0 analysis and design;
tated by the introduction of new materials, 0 testing;
improvements in manufacturing processes 0 mechanically fastened and bonded joints;
and developments of new analytical and test- 0 repair;
ing methods. Unfortunately, information on 0 damage tolerance;
these topics is scattered in journal articles, in 0 environmental effects;
conference and symposium proceedings, in 0 health, safety, reuse, and disposal;
workshop notes, and in government and com- 0 applications in:
pany reports. This proliferation of the source aircraft and spacecraft;
material, coupled with the fact that some of land transportation;
the relevant publications are hard to find or marine environments;
are restricted, makes it difficult to identify and biotechnology;
obtain the up-to-date knowledge needed to construction and infrastructure;
utilize composites to their full advantage. sporting goods.
This book intends to overcome these diffi-
Each chapter, written by a recognized expert,
culties by presenting, in a single volume,
is self-contained, and contains many of the
many of the recent advances in the field of
'state-of-the-art' techniques required for prac-
composite materials. The main focus of this
tical applications of composites. Thus, this
book is on polymeric matrix, metal matrix,
book should serve as a useful source of infor-
and ceramic matrix composites. The book
mation for practicing engineers and
treats a wide range of subjects. The topics, pre-
specialists, as well as for workers new to this
sented in 49 chapters and two appendices
field.
include:
George S. Springer
0 overview of composite material systems
and products;
CONTENTS

Contributors ix

Preface xv

About the editor xvi

Foreword xvii

Acknowledgements xviii

Introduction, composite basics and road map 1

S.T. Peters
1 Overview of composite materials 21
Theodore J. Reinhart

PART ONE: BASIC MATERIALS

Polymeric matrix systems
2 Polyester and vinyl ester resin 34
Frank A. Cassis and Robert C. Talbot
3 Epoxyresins 48
L.S. Penn and H . Wang
4 High temperature resins 75
Hugh H . Gibbs
5 Speciality matrix resins 99
David A . Shimp
6 Thermoplastic resins 115
Lars A. Berglund

Reinforcements and composites

7 Fiberglass reinforcement 131
Dennis J. Vaughan
vi Handbook of composites

8 Boron, high silica, quartz and ceramic fibers 156

Anthony Marzullo
9 Carbon fibers 169
Khalid Lafdi and Maurice A. Wright
10 Organic fibers 202
Linda L. Clements
11 Particulate fillers 242
Harry S. Katz
12 Sandwich construction 254
Andrew C. Marshall
13 Metal matrix composites 29 1
V l . Kostikov and V S . Kilin
14 Ceramic composites 307
M.E Amateau
15 Carbon-carbon composites 333
John D. Buckley

PART TWO: PROCESSING METHODS

General composites and reinforced plastics
16 Hand lay-up and bag molding 352
D.R. Sidwell
17 Matched metal compression molding of polymer composites 378
Enamul Haque and Burr (Bud) L. Leach
18 Textile preforming 397
Frank K. KO and George W. Du
19 Table rolling of composite tubes 425
John T. Kanne and Jerome S. Berg
20 Resin transfer molding 433
Lihwa Fong and S.G. Advani
21 Filament winding 456
Yu.M. Tarnopol’skii, S.T. Peters, A.I. Beil’
22 Fiber placement 476
Don 0. Evans
23 Pultrusion 488
Brian A. Wilson
24 Processing thermoplastic composites 525
James L. Throne
 Contents vii

Advanced composites
25 Tooling for composites 556
Jerry L. Cadden and Paul F. Sadesky
26 Consolidation techniques and cure control 576
Zhong Cui and Timothy Gutowski
27 Composite machining 596
Kent E. Kohkonen and Nitin Potdar
28 Mechanical fastening and adhesive bonding 610
D. W. Oplinger
29 Surface preparations for ensuring that the glue will stick in bonded
composite structures 667
L.J. Hart-Smith, D. Brown and S. Wong

PART THREE: DESIGN AND ANALYSIS

30 Laminate design 686
Jocelyn M . Seng
31 Design of structure with composites 709
F.J. Schwan
32 Analysis methods 736
V.V. Vasiliev
33 Design allowables substantiation 758
Christy Kirchner Lapp
34 Mechanical tests 778
Yu.M. Tarnopol'skii and V.L. Kulakov

PART FOUR. ENVIRONMENTAL EFFECTS

35 Durability and damage tolerance of fibrous composite systems 794
Ken Reifsnider
36 Environmental effects on composites 810
A n n F. Whitaker, Miria M . Finckenor, Harry W. Dursch, R.C. Tennyson
and Philip R. Young
37 Safety and health issues 822
Jennifer A. Heth
38 Nondestructive evaluation methods for composites 838
Thomas S. Jones
39 Repair aspects of composite and adhesively bonded aircraft structures 857
Anton L. Seidl
40 Reuse and disposal 883
Harry E , Pebly
viii Handbook of composites

PART FIVE APPLICATIONS

41 Land transportation applications 905
Douglas L. Denton
42 Marine applications 916
Wayne C. Tucker and Thomas Juska
43 Commercial and industrial applications of composites 931
Stewart N. Loud
44 Composite biomaterials 957
Shalaby W. Shalaby and Robert A. Latour
45 Scientificapplications of composites 967
Vicki I? McConnell
46 Construction 982
Ever J. Barber0
47 Aerospace equipment and instrument structure 1004
G a y C. Krumweide and Eddy A. Derby
48 Aircraft applications 1022
Richard N. Hadcock
49 Composites in the sporting goods industry 1044
Brian E. Spencer

APPENDICES
Appendix A
Typical properties for advanced composites 1053
Kenneth R. Berg
Appendix B
Specifications and standards for polymer composites 1059
Frank T. Traceski
Index 1069
INTRODUCTION, COMPOSITE BASICS AND
ROAD MAP*
S.T. Peters
This is an introduction to composites and will
encourage the reader to obtain more informa-
tion. Only the basic concepts will be covered
here; reference will be made to the chapters in
the book that expand or follow up and elabo-
rate on these basics. The reader will see that
the subjects of this book cover the spectrum of
composites and range from the basic and sim-
ple to the complex. Thus, there are
complicated equations because they are the
tools that are used every day to describe real
structures; and there will also be the more gen-
eral, less complicated approaches that are
limited in analysis power. These chapters have
been developed by the most knowledgeable
composite professionals in the world; a blend
of academicians and the engineers who fabri-
cate real composite structures.
Modern structural composites, frequently
referred to as ’Advanced Composites’, are a
blend of two or more components, one of
which is made up of stiff, long fibers, and the
other, a binder or ’matrix’ which holds the
fibers in place. The fibers are strong and stiff
relative to the matrix and are generally
orthotropic (having different properties in two
different directions). The fiber, for advanced
structural composites, is long, with length to
diameter ratios of over 100. The fiber’s
strength and stiffness are usually much
greater, perhaps several times more, than the
matrix material. The matrix material can by
polymeric (e.g. polyester resins, epoxies),
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
metallic, ceramic or carbon. When the fiber
and the matrix are joined to form a composite
they retain their individual identities and both
directly influence the composite’s final proper-
ties. The resulting composite will generally be
composed of layers (laminae) of the fibers and
matrix stacked to achieve the desired proper-
ties in one or more directions.
The high strength or stiffness to weight
ratios of advanced composites are well known,
but there are other advantages also (Table 1.1).
These advantages translate not only into air-
craft, but into everyday activities, such as
longer drives with a graphite-shafted golf club
(because more of the mass is concentrated at
the clubhead) or less fatigue and pain because
a graphite composite tennis racquet has mher-
ent damping. Generally, the advantages accrue
for any fiber/composite combination and dis-
advantages are more obvious with some. These
advantages have now resulted in many more
reasons for composite use as shown in Table
1.2. Proper design and material selection can
circumvent many of the disadvantages.
1.1 MATERIAL SYSTEMS
An advanced composite laminate can be tai-
lored so that the directional dependence of
strength and stiffness matches that of the load-
ing environment. To do that, layers of
unidirectional material called laminae are ori-
* This chapter has been adapted from S.T. Peters, in
Handbook of Plastics Elastomers and Composites, 3rd edn, (ed.
C.A. Harper). McGraw-Hill, New York, 1996, and is used
with permission of the McGraw-Hill companies.
2 Introduction, composite basics and road map

Table 1.1 Advantages/disadvantages of advanced composites

Advantages Disadvantages
___-
Weight reduction Cost of raw materials and fabrication
High strength or stiffness to weight ratio
Tailorable properties Transverse properties may be weak
Can tailor strength or stiffness to be in the
load direction
Redundant load paths (fiber to fiber) Matrix is weak, low toughness
Longer life (no corrosion) Reuse and disposal may be difficult
Lower manufacturing costs because of Difficult to attach
less part count
Inherent damping Analysis is difficult
Increased (or decreased) thermal or Matrix subject to environmentaldegradation
electrical conductivity

ented to satisfy the loading requirements. These Carbon/graphite fibers (Chapter 9) have
laminae contain fibers and a matrix. Because of demonstrated the widest variety of strengths
the use of directional laminae, the tensile, flex- and modulii and have the greatest number of
ural and torsional shear properties of a suppliers. The fibers begin as an organic fiber,
structure can be disassociated from one another rayon, polyacrylonitrile or pitch which is
to some extent and a golf shaft, for example, can called the precursor. The precursor is then
be changed in torsional stiffness without chang- stretched, oxidized, carbonized and graphi-
ing the flexural or tensile stiffness. tized. There are many ways to produce these
Fibers can be of the same material within a fibers, but the relative amount of exposure at
lamina or several fibers mixed (hybrid). The temperatures from 2500-3000°C results in
common commercially available fibers are as greater or less graphitization of the fiber.
follows: Higher degrees of graphitization usually
result in a stiffer fiber (higher modulus) with
0 fiberglass;
greater electrical and thermal conductivities
0 graphite;
and usually higher cost.
0 aramid;
The organic fiber Kevlar 49, (Chapter 10)
0 polyethylene;
also called aramid, essentially revolutionized
0 boron;
pressure vessel technology because of its great
0 silicon carbide;
tensile strength and consistency coupled with
0 silicon nitride, silica, alumina, alumina silica.
low density, resulting in much more weight
The advantages of fiberglass (Chapter 7) are its effective designs for rocket motors. Aramid
high tensile strength and strain to failure, but composites are still widely used for pressure
heat and fire resistance, chemical resistance, vessels but have been largely supplanted by
moisture resistance and thermal and electrical the very high strength graphite fibers. Aramid
properties are also cited as reasons for its use. composites have relatively poor shear and
It is by far the most widely used fiber, primar- compression properties; careful design is
ily because of its low cost; but its mechanical requires for their use in structural applications
properties are not comparable with other that involve bending or compression.
structural fibers.
 Material systems 3
Table 1.2 The reasons for using composites

Reason for use Material selected Appl ica t ion/driver

Lighter, stiffer stronger
Controlled or zero
thermal expansion
Environmental resistance
Lower inertia, faster startups,
less deflection
Lightweight, damage tolerance
More reproducible complex
surfaces
Less pain and fatigue
Reduces logging in
‘old growth’ forests
Reduces need for intermediate
support and resists constant
100% humidity atmosphere
Tailorability of bending and
twisting response
Transparency to radiation
Crashworthiness
Higher natural frequency, lighter Carbon/ graphite-epoxy
Water resistance
Ease of field application
___
Boron, all carbodgraphites,
some aramid
Very high modulus
carbon/graphite
Fiberglass, vinyl esters,
bisphenol A fumarates,
chlorendic resins
High strength
carbon/graphite, epoxy
High strength carbon/graphite, CNG tanks for ’green’cars, trucks
fiberglass, (hybrids), epoxy
High strength or high
modulus carbon graphite/
epoxy
Carbon/graphite/epoxy
Aramid, carbon/graphite
High strength
carbon/graphite-epoxy
Carbon/graphite-epoxy
Carbon/ graphite-epoxy
Carbon/ graphite-epoxy
Fiberglass (woven fabric),
polyester or isopolyester
Carbon/graphite, fiberglass
- epoxy, tape and fabric
Military aircraft, better
performance
Commercial aircraft, operating costs
Spacecraft with high positional
accuracy requirements for optical
sensors
Tanks and piping, corrosion
resistance to industrial chemicals,
crude oil, gasoline at elevated
temperatures
Industrial rolls, for paper, films
and busses to reduce environmental
pollution
High-speed aircraft. Metal skins
cannot be formed accurately
Tennis, squash and racquetball
racquets. Metallic racquets are no
longer available
Laminated ‘new’ growth wooden
support beams with high modulus
fibers incorporated
Cooling tower driveshafts
Golf shafts, fishing rods
X-ray tables
Racing cars
Automotive and industrial
driveshafts
Commercial boats
Freeway support structure repair
after earthquake

The polyethylene fibers have the same their use to composites that cure or operate
property drawbacks as aramids, but also suf- below 149°C (300°F) and a susceptibility to
fer from low melting temperature which limits degradation by ultraviolet light exposure.
4 lntvodmction, composite basics and road map

Both of these types of fibers have wide usage
in personal protective armor. In spite of the
drawbacks, production of both of these fibers
is enjoying strong worldwide growth.
Boron fibers (Chapter 8), the first advanced
composite fibers to be used on production
aircraft, are produced as individual mono-
filaments upon a tungsten or carbon substrate
by pyrolytic reduction of boron trichloride
(BC1,) in a sealed glass chamber. The relatively
large cross section fiber is used today primar-
ily in metal matrix composites which are
processed at temperatures which would attack
carbon/graphite fibers.
1.2 MATRIX SYSTEMS
If parallel and continuous fibers are combined
with a suitable matrix and cured properly, uni-
directional composite properties such as those
shown on Table 1.3 are the result.
The functions and requirements of the
matrix are to:
0 keep the fibers in place in the structure;
0 help to distribute or transfer loads;
0 protect the filaments, both in the structure
and before and during fabrication;
0 control the electrical and chemical proper-
ties of the composite;
0 carry interlaminar shear.

Table 1.3 Properties of typical unidirectional graphite/epoxy composites (Fiber volume fraction, V , = 0.62)

High strength High modulus

Elastic constants GPa (psi x I O 6 ) GPa (psi x IO6)
~~

Longitudinal modulus, E, 145 (21) 220 (32)

Transverse modulus, E , 9.6 (1.4) 6.9 (1.0)
Shear modulus, G , 5.8 (0.85) 4.8 (0.7)
Poisson’s ratio (dimensionless)u ~ , 0.30 0.30
~~~ ~~ .~ ~ ~~ ~~ ~~

Strength properties MPa ( Z 0 3 psi) MPa (lo3psi)

~ ~~~ ~~~~ ~ ~

Longitudinal tension, Ft”, 2139 (310) 760 (110)

Transverse tension, FtUT 54 (7.8) 28 (4)
Longitudinal compression, FCUL 1724 (250) 690 (100)
Transverse compression, FCUT 76 (11) 170 (25)
Inplane shear, PLT 87 (12.6) 70 (10)
Interlaminar shear, F’,”” 128 (18.5) 70 (10)

Ultimate strains %
- -~
Longitudinal tension, 1.4 0.3
Transverse tension, 0.67 0.4
Longitudinal compression, ECUL 0.9 0.3
Transverse compression, EC1lT 3.6 2.8
Inplane shear 2.0 -

Physical properties
Density, kg/m3 (Ib/in3) 1600 (0.056) 1700 (0.058)
Longitudinal CTE,
ye/K (pe/OF) -0.079 (-0.044) -0.54 (-0.3)
Transverse CTE
~ E / (pe/OF)
K 21.6 (12) 58 (32)
From References 1, 2 and 3; CTE = coefficient of thermal expansion

The needs, or desired properties of the
matrix, that depend on the purpose of the struc-
ture are:
0 minimize moisture absorption;
0 have low shrinkage;
0 Must wet and bond to fiber;
0 low coefficient of thermal expansion;
0 must flow to penetrate the fiber bundles
completely and eliminate voids during the
compacting/curing process;
have reasonable strength, modulus and
elongation (elongation should be greater
than fiber);
0 must be elastic to transfer load to fibers;
0 have strength at elevated temperature
(depending on application);
0 have low temperature capability (depend-
ing on application);
0 have excellent chemical resistance (depend-
ing on application);
0 be easily processable into the final compos-
ite shape;
0 have dimensional stability (maintain its
shape).
There are many matrix choices available; each
type has impact o n the processing technique,
physical and mechanical properties and envi-
ronmental resistance of the finished
Table 1.4 Selection criteria for epoxy resin systems
Advantages
Adhesion to fibers and to resin
No by-products formed during cure
Low shrinkage during cure
High or low strength and flexibility
Solvent and chemical resistance
Resistance to creep and fatigue
Solid or liquid resins in uncured state
Wide range of curative options
Adjustable curing rate
Good electrical properties
Matrix systems 5
composite. The common thermoset matrices
for composites include the following:
0 polyester and vinylesters (Chapter 2);
0 epoxy (Chapter 3);
0 bismaleimide (BMI) (Chapter 4);
0 polyimide (Chapter 4);
cyanate ester and phenolic triazine
(Chapter 5).
Each of the resin systems has some drawbacks,
which must be accounted for in design and
manufacturing plans.
Polyester matrices have been in use for the
longest period, and are used in the widest
range and greatest number of structures. The
usable polymers may contain up to 50% by
weight of unsaturated monomers and solvents
such as styrene. Polyesters cure via a catalyst
(usually a peroxide) resulting in an exothermic
reaction, which can be initiated at room tem-
perature.
The most widely used matrices for
advanced composites have been the epoxy
resins. These resins cost more than polyesters
and do not have the high temperature capabil-
ity of the bismaleimides or polyimides, but
because of the advantages shown in Table 1.4
they are widely used.
Disadvantages
Resins and curatives somewhat toxic in uncured form
Absorb moisture
Heat distortion point lowered by moisture absorption
Change in dimensions and physical properties
due to moisture absorption
Limited to about 200°C upper temperature use (dry)
Difficult to combine toughness and high
temperature resistance
High thermal coefficient of expansion
High degree of smoke liberation in a fire
May be sensitive to ultraviolet light degradation
Slow curing
6 Introduction, composite basics and road map
There are two resin systems in common use
for higher temperatures, bismaleimides and
polyimides. New designs for aircraft demand
a 177°C (350°F) operating temperature not met
by the other common structural resin systems.
The primary bismaleimide in use is based on
the reaction product from methylene dianiline
(MDA) and maleic anhydride: bis (4-maleimi-
dophenyl) methane (MDA BMI).
Two newer resin systems have been devel-
oped and have found applications in widely
diverse areas. The cyanate ester resins, mar-
keted by Ciba-Geigy, have shown superior
dielectric properties and much lower moisture
absorption than any other structural resin for
composites. The dielectric properties have
enabled their use as adhesives in multilayer
microwave printed circuit boards, and the low
moisture absorbance have caused them to be
the resin of universal choice for structurally-
stable spacecraft components.
The phenolic triazine (PT) resins also have
superior elevated temperature properties,
along with excellent properties at cryogenic
temperatures. Their resistance to proton
ROVING WEAUE?
N?
COLLIMRTE
UNI TRPE
Fig. 1.1 Manufacturing steps in composite structure.
radiation under cryogenic conditions was a
prime cause for their choice for use in the
superconducting supercollider, subsequently
canceled by the US Congress.
Polyimides are the highest temperature
polymer in general advanced composite use
with a long term upper temperature limit of
232°C (450°F) or 316°C (600°F). Two general
types are: condensation polyimides, that
release water during the curing reaction, and
addition type polyimides with somewhat eas-
ier process requirements.
1.3 FIBER MATRIX SYSTEMS
The end user sees a composite structure.
Someone else, probably a prepregger, com-
bined the fiber and the resin system and
someone else caused the cure and compaction
to result in a laminated structure. A schematic
of the steps to arrive at a finished composite
from the initial fiber is shown in Fig. 1.1.
In many cases, the end user of the structure
has fabricated the composite from prepreg,
which is a low-temperature-stable combination
 Fiber matrix systems 7

of the resin, its curing agents and the fiber. The
three types of continuous fibers, roving, tape
and woven fabric available as prepregs give
the end user many options in terms of design
and manufacture of a composite structure.
Although the use of dry fibers and impregna-
tion at the work (i.e. filament winding,
pultrusion or hand lay-up) is very advanta-
geous in terms of costs; there are many
advantages to the use of prepregs as shown in
Table 1.5, particularly for the manufacture of
modem composites.
Table 1.5 Advantages of prepregs over wet impregnation
The prepreg process for thermoset matrices
can be accomplished by feeding the fiber con-
tinuous tape, woven fabric or roving through a
resin-rich solvent solution and then removing
the solvent by hot tower drying. The excess
resin is removed via a doctor blade or meter-
ing rolls and then the product is staged to the
cold-stable prepreg form, (B stage) (Fig. 1.2).
The newer hot melt procedure for prepregs
is gradually replacing the solvent method
because of environmental concerns. A film of
resin that has been cast hot onto release paper

Prepregs reduce the handling damage to dry fibers

Improve laminate properties by better dispersion of short fibers
Prepregs allow the use of hard-to-mix or proprietary resin systems
Allow more consistency because there is a chance for inspection before use
Heat curing provides more time for the proper laydown of fibers and for the resin to move and degas
before cure
Increased curing pressure reduces voids and improves fiber wetting
Most prepregs have been optimized as individual systems to improve processing

Release
Poly
Unwind

Prepreg
Wind

Pump and Unwind

Reservoir

Fig. 1.2 Schematic of typical solvent prepregging process. (Adapted from Reference 2.)
8 Introduction, composite basics and road map
0 0
Doctor
Plate 1
Impregnation
Zone
Creel Paper
Plate 2
Fig. 1.3 Schematic of typical film impregnating process. (Adapted from Reference 2.)
is fed, along with the reinforcement, through a
series of heaters and rollers to force the resin
into the reinforcement. Two layers of resin are
commonly used so that a resin film is on both
sides of the reinforcement; one of the release
papers is removed and the prepreg is then
trimmed, rolled and frozen (Fig. I.3)2.The sol-
vent technique has been largely replaced for
advanced fibers because of environmental pol-
lution concerns and a need to exert better
control over the amount of resin on the fiber.
1.3.1 UNIDIRECTIONAL PLY PROPERTIES
The manufacturer of the prepreg reports an
areal weight for the prepreg and a resin per-
centage, by weight. Each of the different fibers
has a different density, resulting in a composite
of different density at the same fiber volume
percentage. Since fiber volume is used to relate
the properties of the manufactured composites,
the following equations can be used to convert
between weight fraction and fiber volume.
where:
Pauer
Paper
T
Take-up
Prepreg
Windup
Chill
Plate
Wf = weight fraction of fiber
wf = weight of fiber
wc= weight of composite
pf = density of fiber
p, = density of composite
uf = volume of fiber
u, = volume of composite
Vf = volume fraction of fiber
V, = volume fraction of matrix
p, = density of matrix.
A percentage fiber that is easily achievable
and repeatable in a composite and convenient
for reporting mechanical and physical proper-
ties for several fibers is 60%. The properties of
unidirectional fiber laminates are shown in
Table 1.3 for carbon/graphite/epoxy. Values
for the other fibers can be seen in their respec-
tive chapters. These values are for individual
lamina or for a unidirectional composite, and
they represent the theoretical maximum (for
that fiber volume) for longitudinal in plane
properties. Transverse, shear and compression
properties will show maxima at different fiber
volumes and for different fibers, depending on
how the matrix and fiber interact. These val-
ues can be used to calculate the properties of a
laminate which has fibers oriented in several
directions. To do that, the methods of descrip-
tion for ply orientation must be introduced.

1.4 PLY ORIENTATIONS, SYMMETRY AND
BALANCE
1.4.1 PLY ORIENTATIONS
One of the advantages of using a modern com-
posite is the potential to orient the fibers to
respond the load requirements. This means
that the composite designer must show the
material, the fiber orientations in each ply, and
how the plies are arranged (ply stackup).
A 'shorthand' code for ply fiber orientations
has been adapted for use in layouts and studies.
Each ply (lamina)is shown by a number rep-
resenting the direction of the fibers in degrees,
with respect to a reference ( x ) axis. 0" fibers of
both tape and fabric are normally aligned with
the largest axial load (axis) (Fig. 1.4(a)).
Individual adjacent plies are separated by a
slash in the code if their angles are different
(Fig. 1.4@)).
The plies are listed in sequence, from one
laminate face to the other, starting with the ply
first on the tool and indicated by the code
arrow with brackets indicating the beginning
and end of the code.
Adjacent plies of the same angle of orienta-
tion are shown by a numerical subscript (Fig.
1.4(c)).
When tape plies are oriented at angles equal
in magnitude but opposite in sign, (+) and (-)
are used. Each (+) or (-) sign represents one
ply. A numerical subscript is used only when
there are repeating angles of the same sign.
Positive and negative angles should be consis-
tent with the coordinate system chosen. An
orientation shown as positive in one right
handed coordinate system may be negative in
another. If the y and z axis directions are
reversed, the f 45 plies are reversed (Fig. 1.4(d)).
Symmetric laminates with an even number
of plies are listed in sequence, stating at one
face and stopping at the midpoint. A subscript
'S' following the bracket indicates only one
half of the code is shown (Fig. 1.4(e)).
Symmetric laminates with an odd number
of plies are coded as a symmetric laminate
except that the center ply, listed last, is over-
Quasi-isotropic laminate 9
lined to indicate that half of it lies on either
side of the plane of symmetry (Fig. 1.4(f)).
1.4.2 SYMMETRY
The geometric midplane is the reference sur-
face for determining if a laminate is
symmetrical. In general, to reduce out-of-
plane strains, coupled bending and stretching
of the laminate and complexity of analysis,
symmetric laminates should be used.
However, some composite structures (e.g. fila-
ment wound pressure vessels) can achieve
geometric symmetry so that symmetry
through a single laminate wall is not neces-
sary, if it constrains manufacture. To construct
a midplane symmetric laminate, for each layer
above the midplane there must exist an identi-
cal layer (same thickness, material properties,
and angular orientation) below the midplane
(Fig. 1.4(e)).
1.4.3 BALANCE
All laminates should be balanced to achieve in-
plane orthotropic behavior. To achieve balance,
for every layer centered at some positive angle
+e there must exist an identical layer oriented
at -8 with the same thickness and material
properties. If the laminate contains only 0"
and/or 90" layers it satisfies the requirements
for balance. Laminates may be midplane s p -
metic but not balanced and vice versa. Figure
1.4(e) is symmetric and balanced whereas Fig.
1.4(g)is balanced but unsymmetric .
1.5 QUASI-ISOTROPICLAMINATE
The goal of composite design is to achieve the
lightest, most efficient structure by aligning
most of the fibers in the direction of the load.
Many times there is a need, however, to pro-
duce a composite which has some isotropic
properties, similar to metal, because of multi-
ple or undefined load paths. A 'quasi-isotropic'
laminate lay-up accomplishes this for the x and
y planes only; the z or through-the-laminate-
 -
10 Introduction, composite basics and road map

90"

Reference Axis

lz;
90"

Tool side
Tape Laminate ,/
.-,

[0/9O]s
0" 45' 90' -45' 0"

Typical Callout
I I P 1
I \ \

0" -450 w +450 0" L

[0/903/0]

T
[0/90/*45]s
P I
Typical Callout
90"
+45"
-45"
-45"
+45"
Line of Symmetry
90"
V I

Tape and Fabric Laminate

[ 0/f45/To1 s.
Typical Callout

0
Line of Symmetry

Fig. 1.4 Ply orientations, symmetry and balance. (Continued on next page)
 Methods of analysis 11

Tape Laminate

p,
+45"
-45"
[0/90/f45/i452/9 0/ 01
Typical Callout
-45"

+45"

Fabric Laminate [(0,90)/(~45)/(0,90)]

I 0".90" I Typical Callout

j 0",90" I h)

Fig. 1.4 Ply orientations, symmetry and balance. (Continued)

thickness plane is quite different and lower. 1. arrive at quick values to determine if a com-
Most laminates produced for aircraft applica- posite is feasible;
tions have been, with few exceptions, 2. arrive at values for insertion into computer
'quasi-isotropic'. As designers become more programs for laminate analysis or finite ele-
confident and have access to a greater database ment analysis;
with fiber-based structures, more applications 3. check on the results of computer analysis.
will evolve. For a quasi-isotropic laminate, the
The rule of mixtures holds for composites. The
following are requirements:
micromechanics formula to arrive at the
0 It must have three layers or more. Young's modulus for a given composite is:
0 Individual layers must have identical stiff-
Ec = V,E, + Vm Em
ness matrices and thicknesses.
0 The layers must be oriented at equal angles. and v,+ vm= 1
For example, if the total number of layers is
= V ,E , + Em (1- V,) (1.3)
M , the angle between two adjacent layers
should be 360"ln. If a laminate is con- where
structed from identical sets of three or more
Ec = composite or ply Young's modulus in
layers each, the condition on orientation
tension for fibers oriented in direction of
must be satisfied by the layers in each set,
applied load
for example: ( O o / + 60"), or ( O o / + 45"/90)s.
V = volume fraction of fiber ( f ) or matrix (m)
E = Young's modulus of fiber ( f ) or matrix
1.6 METHODS OF ANALYSIS (m).
There are a number of methods in common But, since the fiber has much higher
use for the analysis of composite laminates. Young's modulus than the matrix, the second
The use of micromechanics, i.e. the application part of the equation can be ignored.
of the properties of the constituents to arrive at
E, >> Em
the properties of the composite ply can be
used to: Ec = E,V, (1.4)
12 Introduction, composite basics and road map

This is the basic rule of mixture and repre- appropriate for a particular application.
sents the highest Young’s modulus composite, Figure 1.5 shows the progression of physical
where all fibers are aligned in the direction of properties for Young’s modulus in tension, E,
load. The minimum Young’s modulus for a (fiber), E, (lamina) and Ex,, (laminate), longi-
reasonable design (other than a preponder- tudinal tensile strength, and coefficient of
ance of fibers being orientated transverse to thermal expansion a where the subscripts L
the load direction) is the quasi-isotropic com- and X stand for in-plane in the principal fiber
posite and can be approximated by: direction and t and Y stand for the transverse
direction for a theoretical high strength (from
Ec = (3/8) E,V, (1.5) Table 1.3) carbon/graphite fiber composite
The quasi-isotropic modulus, E, of a composite from the fiber to the laminate. The values
laminate is (3/8)E,+(5/8)EZ where E,, is the decrease or are ’translated’in a logical fashion
modulus of the lamina in the fiber direction and and reflect the law of mixtures. The analysis is
E, is the transverse modulus of the lamina3. relatively simple for modulus dominated
The transverse modulus for polymeric-based properties but strength-dominated values
composites is a small fraction of the longitudinal must be treated in light of one of several fail-
modulus (see E, in Table 1.3)and can be ignored, ure theories and changes in the thermal
for preliminary estimates, resulting in a slightly coefficient of expansion are not predictable
lower-than-theoretical value for Ec for a quasi- from laws of mixtures. Other factors which
isotropic laminate. This approximate value for enter into the translation efficiency are: com-
the quasi-isotropic modulus represents the patibility of the resin system with the fiber and
lower limit of composite modulus. It is useful in the fiber finish, strain-to-failure of the resin
comparing of composite properties to those of system and the damage the fiber undergoes
metals and in establishing if a composite is during impregnation, laydown and cure.

.6 GPa, FT‘“ =54 MPa

E x = 76 GPa
a x = 4.98peK

r a2 >ay

Fig. 1.5 The anatomy of a composite laminate.

E y = 76 GPa
a y = 4.98~ E K
 Composite fabrication techniques 13

Table 1.6 High-strength carbon/graphite laminate competitor, so vendor values in a generic

properties class may differ widely.
4. Most tables of values are presented as 'typi-
Laminate Longitudinal Bending Shear cal values'. Those values and the values that
modulus modulus, modulus, are part of the menu of many computer
E,, (GPa) E , (GPa) G,, (GPa) analysis programs should be used with care.
(0/90,/0) 76.5 126.8 5.24 Each user must find their own set of values
(90/0,/90) 76.5 26.3 5.24 for design, develop useful design allow-
(02/902/OJ 98.5 137.8 5.24 ables, and apply appropriate 'knock down'
(0,/~45,/0,) 81.3 127.5 21.0 factors, based on the operating environ-
(0/+45/90)> 55.0 89.6 21.0
ments expected in service. (Chapter 33 and
Aluminum 41.34 41.34 27.56
Appendix A give guidelines.)

Table 1.6 shows mechanical values for sev-
eral composite laminates with the fiber of
Table 1.3 and a typical resin system. The first
and second entries are for simple 0/90 lami-
nates and show the effect of changing the
position of the plies. The effect of increasing
the number of 0 plies is shown next and the
1.7 COMPOSITE FABRICATION TECHNIQUES
The goals of the composite manufacturing
process are to:
0 achieve a consistent product by controlling
- fiber thickness;
- fiber volume;

final two laminates demonstrate the effect of - fiber directions;

+45 plies on mechanical properties, particu- 0 minimize voids;

larly the shear modulus. The last entry is a
quasi-isotropic laminate. These laminates are
then compared to a typical aluminum alloy.
When employing the data extracted from
tables, some caution should be observed by
the reader. The values seen in many tables of
data may not always be consistent for the
same materials or the same group of materials
from several sources for the following reasons:
1. Manufacturers have been refining their pro-
duction processes so that newer fibers may
have greater strength or stiffness. These
new data may not be reflected in the com-
piled data.
2. The manufacturer may not be able to
change the value quoted for the fiber
because of government or commercial
restrictions imposed by the specification
process of his customers.
3. There are many different high-strength
fibers commercially available. Each manu-
facturer has optimized their process to
maximize their mechanical properties and
each process may differ from that of the
0 reduce internal residual stresses;
0 process in the least costly manner.
The procedures to reach these goals involve
iterative processes to select the three key com-
ponents:
0 composite material and its configuration;
0 tooling;
0 process.
Once material selection has been completed,
the first step leading to the acceptable com-
posite structure is the selection of tooling,
which is intimately tied to process and mater-
ial. For all curing techniques the tool must be:
0 strong and stiff enough to resist the pres-
sure exerted during cure;
0 dimensionally stable through repeated
heating and cooling cycles;
0 light enough to respond reasonably quickly
to the changes in cure cycle temperature
and to be moved in the shop;
0 leakproof so that the vacuum and pressure
cycles are consistent.
14 Introduction, composite basics and road map

The tool face is commonly the surface
imparted to the outer surface of the composite
and must be smooth, particularly for aerody-
namic surfaces. The other surface frequently
may be of lower finish quality and is imparted
by the disposable or reusable vacuum bag. This
surface can be improved by the use of a sup-
plemental metal tool known as a caul plate.
(Press curing, resin transfer molding, injection
molding and pultrusion require a fully closed
or two sided mold). Figure I. 6 shows the basic
components of the tooling for vacuum bag or
autoclave processed components and Table 1.7
shows the function of each part of the system.
Tooling options have been augmented by
the introduction of elastomeric tooling
wherein the thermal expansion of an elas-
tomer provides some or all of the pressure
curing cure, or a rubber blanket is used as a
reusable vacuum bag. The volumetric expan-
sion of an elastomer can be used to fill a cavity
between the uncured composite and an outer
mold. The use of elastomeric tooling can pro-
vide the means for fabricating complex
box-like structures such as integrally stiffened
skins with a co-cured substructure in a single
curing operation.
Tooling (Chapter 25) and the configuration
of the reinforcement have a great influence on
the curing process selected and vice-versa. The

2 3 4 5 6 7 8 9

12 13 14 9 10 11

Fig. 1.6 Typical vacuum bag lay-up components.

Table 1.7 Functions of vacuum bag components

Component * Functions
-
1 Bag sealant Temporarily bonds vacuum bag to tool
2 Vacuum fitting and hardware Exhausts air, provides convenient connection to vacuum pump
3 Bagging film Encloses part, allows for vacuum and pressure
4 Open weave breather mat Allows air or vacuum transfer to all of part
5 Polyester tape (wide) Holds other components of bag in place
6 Polyester tape (narrow) Holds components in place
7 Caul sheet Imparts desired contour and surface finish to composite
8 Perforated release film Allows flow of resin or air without adhesion
9 Non-perforated release film Prevents adhesion of laminate resin to tool surface
10 Peel ply Imparts a bondable surface to cured laminate
11 Laminate
12 1581-styleglass breather manifold Allows transfer of air or vacuum
13 1581 style glass bleeder ply Soaks up excess resin
14 Stacked silicone edge dam Forces excess resin to flow vertically, increasing fluid pressure
* numbers refer to Fig. 1.6
 Composite fabrication techniques 15

probable reinforcement configuration that Table 1.8 Common reinforcement configuration for
facilitates the completion of the finished com- the manufacturing process
posite is shown on Table 1.8.
The choice between unidirectional tape and Reinforcement Prepreg Prepreg Prepreg Other,
configuration tape or (dry) or (dry) woven
woven fabric has frequently been made on the tow woven preforms,
basis of the greater strength and modulus or non- chopped
attainable with the tape particularly in appli- woven fibers
cations which compression strength is fabric
important. There are other factors that should
be included in the trade, as shown in Table 1.9.
Handlay-up X x, (XI x
Automatic tape X
laydown
1.7.1 LAY-UP TECHNIQUE Filament x, (X) xm xm
winding
Lay-up techniques along with composite cure
control have received the greatest attention for Resin (XI (X) X
transfer
processing. In efforts to reduce labor costs of
molding
composite fabrication, to which lay-up
(Chapter 16) has traditionally been the largest Pultrusion (X) X
contributor, mechanically assisted, controlled Fiber X X
tape laying and automated integrated manu- placement

Table 1.9 Fabric compared with tape reinforcement

Tape advantages Tape disadvantages

_ _ _ _
Best modulus and strength efficiency
High fiber volume achievable
Low scrap rate
No discontinuities
Automated lay-up possible
Available in thin plies
Lowest cost prepreg form
Less tendency to trap volatiles
Fabric advantages
~ _ _ ~ _ _ _ - - ~ _ _
Better drape for complex shapes
Single ply is balanced and may be
essentially symmetric
Can be laid up without resin
Plys stay in line better during cure
Cured parts easier to machine
Better impact resistance
Many forms available
_ ~ - ~
Poor drape on complex shapes
Cured composite more difficult to machine
Lower impact resistance
Multiple plies required for balance and symmetry
Higher labor costs for hand lay-up
Fabric disadvantages
Fiber discontinuities (splices)
Less strength and modulus efficient
Lower fiber volume than tape
More costly than tape
Greater scrap rates
Warp and fill properties differ
Fabric distortion can cause part warping
16 Introduction, composite basics and road m a p

facturing systems have been developed. Table Generally, the percent matrix weight is higher
1.10 shows some of the considerations for before cure initiation; the matrix flows out of
choosing a lay-up technique. the laminate and takes the excess resin with
In addition to any cost savings by the use of the potential voids. An arbitrary 1%void limit
an automated technique for long production has been adopted for most autoclaved com-
runs, there are two key quality assurance fac- posites; filament wound and pultruded
tors which validate the automated techniques. composites will have higher void volumes
They are: greatly reduced chance that release depending upon the application.
paper or film could be retained, which would An autoclave is essentially a closed, pres-
destroy shear and compressive strength if surized oven; many common epoxy laminates
undetected, and reduced probability of the are cured at an upper temperature of 177°C
addition or loss of an angle ply which would (350°F) and 6 MPa (100 psi). Autoclaves are
cause warping due to the laminate’s lack of still the primary tool in advanced composite
symmetry and balance. processing and have been built up to 16 m (55
All curing techniques use heat and pressure feet) long at 6.1 m (20 feet) diameter. Since
to cause the matrix to flow and wet out all the autoclaves are expensive to build and operate,
fibers before the matrix solidifies (Chapter 26). many other methods of curing, compacting

Table 1.10 Considerations in composite lay-up technique

Considerat ion Manual Flat tape Contoured tape

Orientation accuracy Least accurate Automatic Somewhat dependent on
tape accuracy and
computer program
Ply count Dependent on operator, Dependent on Program records
count Mylars operator
Release film retention Up to operator Automatic Automatic removal
Labor costs High 86% improvement Additional improvement
quoted
Machine costs N/A Some costs Approximately 1M$ or
greater
Production rate Low (1.5 Ib/h) 10 lb/h Approximately same as flat
tape
Machine ’up’ time N/A Not a consideration Complex program and
machine make this a
consideration
Varying tape widths Not a concern Easily changed Difficulty in changing
Tape lengths Longer tapes more Longer is more Longer tape is more
difficult economical economical
Cutting waste Scrap on cutting Less scrap Least scrap due to back and
forth laydown
Compaction pressure No pressure Less voids Least voids
Programming N/A N/A Necessary
 Compositefabrication techniques 17

composites have been developed. The two a wind eye at speeds synchronized with the
newest and most attractive methods are fiber mandrel rotation, control winding angle of the
placement and resin transfer molding. reinforcement and the fiber lay-down rate.
The reinforcement may be wrapped in adja-
cent bands or in repeating bands that are
1.7.2 RESIN TRANSFER MOLDING
stepped the width of the band and that even-
Previous discussions have centered on moving tually cover the mandrel surface. Local
resin out of the laminate to reduce voids. Resin reinforcement can be added to the structure
transfer involves the placement of dry fiber using circumferential windings, local helical
reinforcement into a closed mold and then bands, or by the use of woven or unidirec-
injecting a catalyzed resin into the mold to tional cloth. The wrap angle can be varied
encapsulate the reinforcement and form a from low angle helical to high angle circum-
composite (Chapter 20). The impetus for the ferential or 'hoop', which allows winding from
use of this process comes from the large cost about 4"-90" relative to the mandrel axis;
reductions that can be realized in raw materi- newer machines can 'place' fiber at 0".
als and lay-up. The process can utilize low
injection pressures i.e. 55 MPa (80 psi), there-
1.7.4 FIBER PLACEMENT
fore, the tooling can be lower cost plastic or a
vacuum bag rather than metal. Fiber placement, initially developed by
Hercules Aerospace Co., is a cross between fil-
ament winding and automatic tape laydown,
1.7.3 FILAMENT WINDING
retaining many of the advantages of both. The
Filament winding is a process by which con- natural outgrowth of adding multiple axes of
tinuous reinforcements in the form of rovings control to filament winding machines results
or tows (gathered, untwisted strands of fiber) in control of the fiber laydown so that non axi-
are wound over a rotating mandrel. The man- symmetric surfaces can be wound. This
drel can be cylindrical, round or any other involves the addition of a modified tape lay-
shape as long as it does not have re-entrant down head to the filament winding machine
curvature. Special machines (Fig.
- 1.7) traversing
- and much more. The Cincinnati-Milacron
machine additions include in-process com-
paction, individual tow cut/start capabilities,
a resin tack control system, differential tow
f 1 payout, low tension on fiber and enhanced off-

I/iine programming (Chapter 22).

1.7.5 PULTRUSION
11 Pultrusion is an automated process for the
I manufacture of constant volume/shape pro-
I files from composite materials (Chapter 23).

cF The composite reinforcements are continu-

ously pulled through a heated die and shaped
and cured simultaneously. If the cross-sec-
p f
tional shape is conducive to the process, it is
r 4 the fastest and most economical method of
Fig. 1.7 The helical filament wound ply. (Courtesy composite production. Straight and cured con-
of Westinghouse Electric Co., Marine Division.) figurations can be fabricated with square,
18 Introduction, composite basics and road map

round, hat-shaped, angled 'I' or 'T'-shaped

cross-sections from vinylester, polyester, or
epoxy matrices with E and S-glass, Kevlar and
graphite reinforcements.. The curing is
effected by combinations of dielectric preheat-
ing and microwave or induction (with
conductive reinforcements like carbon
graphite) while the shape traverses the die.
I

3
1.7.6 BRAIDING, WEAVING AND OTHER
PREFORM TECHNIQUES Fig. 1.8 The unidirectional ply.
Braiding, weaving, knitting and stitching rep-
resent methods of forming a shape, generally be the same in any transverse direction. This is
referred to as preforming, with the composite the transverse isotropy assumption; it is
fibers before impregnation (Chapter 18). The approximately satisfied for most unidirec-
shape may be the final product or some inter- tional composite plies.
mediate form such as a woven fabric. The These properties are typically modified by
braiding process is continuous and is transformation relative to the laminate axis
amenable to round or rectangular shapes or where these may not be the same as the ply
smooth curved surfaces and can transition axes.
easily from one shape to another. In a multidirectional laminate there can be
The other fabric preforming techniques are as many as 21 stiffness constants. Strength pre-
weaving, knitting and the non-structural dictions are equally as complicated because of
stitching of unidirectional tapes. Stitching sim- directional differences, i.e. compression is not
ply uses a non-structural thread, such as nylon always equal to tension, and because the sev-
or Dacron, to hold dry tapes at selected fiber eral failure theories are complex. As the
angles. Preforming in this manner results in a complexity of the matrix calculations increase,
higher-cost raw material but saves labor costs it becomes evident that errorless mathematical
for orientation of individual lamina. The manipulations are impossible without the aid
stitched preform has known, stable fiber ori- of computers. Chapters 30 and 32 elaborate on
entations similar to woven fabric, without the the techniques of laminate analysis and the
crossovers which could reduce compressive applications of laminates to structures
strength.
1.9 DESIGN OF COMPOSITES
1.8 MECHANICS OF COMPOSITE MATERIALS
The design process for composites involves
The 1,2,3 axes in Fig. 1.8 are special and are both laminate design and component design
called the ply axes, or material axes. The 1 axis and must also include considerations of man-
is in the direction of the fibers, and is called the ufacturing process and eventual
longitudinal axis or the fiber axis. environmental exposure. These steps are all
The longitudinal axis is typically the high- interdependent with composites and the most
est stiffness and strength direction. Any efficient design must involve true concurrent
direction perpendicular to the fibers (in the 2,3 engineering. Figure 1.9 shows the various con-
plane) is called a transverse direction. cerns that should be a part of the composite
Sometimes, to simplify analysis and test design process at the initiation of the design
requirements, ply properties are assumed to process, and continuously from there on.

1.9.1 LAMINATE DESIGN
RECOMMENDATIONS
1. Take advantage of the orthotropic nature of
the fiber composite ply.
0 To carry in-plane tensile or compressive
loads align the fibers in the directions of
these loads.
0 For in-plane shear loads, align most
fibers at -c 45" to these shear loads.
0 For combined normal and shear in-plane
loading provide multiple or intermediate
ply angles for a combined load capabil-
ity.
2. Intersperse the ply orientations.
0 If a design requires a laminate with 16
plies at *45", 16 plies at 0", and 16 plies at
90°, use the interspersed design (90,/ -c
45,/0,),s rather than (90,/ .+ 45,/10,)s.
Concentrating plies at nearly the same
angle (0" and 90" in the above example)
provides the opportunity for large
matrix cracks to form. These produce
lower laminate allowables, probably
because large cracks are more injurious
to the fibers, and more readily form
delaminations than the finer cracks
occurring in interspersed laminates.
0 If a design requires all 0" plies, some 90"
plies (and perhaps some off-angle plies )
should be interspersed in the laminate to
provide some biaxial strength and stabil-
ity and to accommodate unplanned
Composite
Material
Environmental
Considerations
Component
Fig. 1.9 Design considerations for composites.
Design of composites 19
loads. This improves handling character-
istics, and serves to prevent large matrix
cracks from forming.
Locally reinforce with fabric or mat in
areas of concentrated loading. (This tech-
nique is used to locally reinforce pressure
vessel domes).
0 Use fabric, particularly fiberglass or
Kevlar, as a surface ply to restrict surface
(handling) damage.
Ensure that the laminate has sufficient
fiber orientations to avoid dependence
on the matrix for stability. A minimum
coverage of 6 to 10% of total thickness in
0, ?45", 90" directions is recommended.
3. Select the lay-up to avoid mismatch of
properties of the laminate with those of the
adjoining structures - or provide a
shear/separator ply.
Poisson's ratio: if the transverse strain of
a laminate greatly differs from that of
adjoining structure, large interlaminar
stresses are produced under load.
Coefficient of thermal expansion: tem-
perature change can produce large
interlaminar stresses if coefficient of ther-
mal expansion of the laminate differs
greatly from that of adjoining structure.
0 The ply layer adjacent to most bonded
joints should not be perpendicular to the
direction of loading. Thicken the com-
posite in the joint area, soften the
composite by adding fiberglass or angle
plies and select the highest strain-capa-
bility adhesive.
4. Use multiple ply angles.
Typical composite laminates are constructed
from multiple unidirectional or fabric layers
which are positioned at angular orientations
in a specified stacking sequence. From many
choices, experience suggests a rather narrow
range of practical construction from which
the final laminate configuration is usually
selected. The multiple layers are usually ori-
ented in at least two different angles, and
possibly three or four; (go, O0/&", or
20 Introduction, composite basics and road map

0 ° / ~ 0 / 9 0 cover
0 most applications, with 0 attempt to standardize the raw materials and
between 30 and 60 degrees). Unidirectional their test methods by publication of specifica-
laminates are rarely used except when the tions (Appendix A). However, these standards
basic composite material is only mildly have not reached the level of use to allow com-
orthotropic (e.g. certain metal matrix appli- plete dependence upon them without
cations) or when the load path is absolutely supplier-user interaction and user testing.
known or carefully oriented parallel to the The fabricators of composites will rely on
reinforcement (e.g. stiffener caps). specifications for control of fiber, resin and/or
the prepreg. Many prepreg resin and fiber
Further suggestions can be seen in Chapter 31. vendors will certify only to their own specifi-
cations which may differ from those shown;
1.10 COMPOSITE TESTING users should consult the vendors to determine
what certification limits exist before commit-
To ensure consistent, reproducible compo- ting to specification control.
nents, three levels of testing are employed: As part of raw materials verification, com-
incoming materials testing, in-process testing posite design effort and final product
and control and final structure verification. verification mechanical testing of composite
test specimens will be performed. The testing
1.10.1 INCOMING MATERIALS TESTING of composite materials offers unique chal-
lenges because of the special characteristics of
Incoming materials testing seeks to verify the composites. Factors not considered important
conformance of the raw materials to specifica- in metals testing are very important in testing
tions and to insure processibility. The levels of composites (Chapters 34,39).
knowledge of composite raw materials do not
approach those for metals, which can be
bought to several consensus specifications and REFERENCES
will appear generally identical although pur- 1. Foral, R.F. and Peters, S.T., Composite
chased from many manufacturers. Although Structures and Technology Seminar Notes, 1989
there are fewer suppliers for composite raw 2. Hercules Data Sheet for AS-4/3901-6 prepreg
materials, the numbers of permutations of H050-377/GF Prod Hdbk (4)/jc/2
resins, fibers and manufacturers prevents the 3. Agarwal, B.D. and Broutman, L.J., Analysis and
Performance of Fiber Composites 2nd edn, John
kind of standardization necessary to be able to Wiley and Sons, New York, 1990 p. 103
buy composite raw materials as if they were 4. Mayorga, G.D. in International Encyclopedia of
alloys. ASTM (American Society for Testing Composites, (ed. S.M. Lee) Vol 4, VCH
and Materials), SAE/AMS/NOMETCOM Publishers, N.Y., N.Y., 1991
(Society of Automotive Engineers, Aeronautical 5 . Tsai, S.W. and Pagano, N.J. in Composite
Materials Standards/ Nonmetallic Materials Materials Workshop, (eds. S.W. Tsai, J.C. Halpin
Committee) and SACMA (Suppliers of and N.J. Pagano), Technomic Publishing Co.,
Lancaster, PA, 1978, p. 249
Advanced Composite Materials Association)
POLYESTER AND VINYL ESTER RESINS
Frank A. Cassis and Robert C. Talbot
2.1 INTRODUCTION AND HISTORY
Organic polymers are divided into two types,
reinforced-thermoplastic and thermoset. With
thermoset polymers such as unsaturated poly-
esters and vinyl esters, a chemical reaction
cross links the material so that it cannot be
returned to liquid form. Other common ther-
mosetting polymers include epoxy and
phenolic resins. Thermoset plastics made with
polyester and vinyl ester resins represent the
major portion of the reinforced plastic com-
posites industry today.
Early workers on unsaturated polyesters
soon learned that despite the possession of
reactive double bonds, these resins were slug-
gish in reacting with themselves. Even with
effective catalysts, they still required high tem-
peratures and lengthy cure times to complete
the cross linking reaction. The key to modern
day application of unsaturated polyesters was
the discovery by Carlton Ellis in 1937l that the
addition of reactive monomers, such as styrene,
gave mixtures that would copolymerize many
times faster than homopolymerization. The
styrene addition produced the added benefit of
an easily handled liquid material that could be
pumped, transported and fabricated into a fin-
ished plastic by a myriad of molding processes.
Developments during the 1940s accelerated
the commercial applicability of unsaturated
polyesters to the position they hold today.
Styrene became readily available and lower in
cost as a result of the US Government's spon-
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
2
sored production of styrene-butadiene rubber.
At the same time, scientists found that styre-
nated polyesters could yield high strength,
light weight structures when reinforced with
glass fibers. They also learned that fiberglass-
reinforced polyesters had excellent electrical
properties and that large structures could be
molded at low pressures with low cost tooling.
As a result, commercial development pro-
ceeded rapidly after World War I1 with
materials and molding research moving in
many directions. In the 20 years that followed,
polyester and vinyl ester resins matured
rapidly and by the mid-l970s, the composites
fabricator and end user had numerous options
with these matrix systems to achieve the
desired properties in the finished part.
2.2 POLYESTER RESINS
The reaction of an organic acid with an alcohol
results in the formation of an ester. By using a
difunctional acid and a difunctional alcohol
(glycol)a linear polyester is produced (Fig. 2.1).
0 0
II II
H-(-0 - C - R - C - 0 - R -)" -OH
Fig. 2.1
Properties of polyesters can be varied by using
different combinations of diacids and glycols.
These products are thermoplastic polyesters
and they are made with various acids and
 Polyester resins 35

glycols such as the following:

- In the esterification reaction with maleic anhv-
Acids dride, the unsaturated acid isomerizes to the
GZycols
fumarate structure which copolymerizes with
Phthalic anhydride Ethylene glycol
styrene much faster than the maleate form. A
Isophthalic acid Propylene glycol
high degree of isomerization to the fumarate
Terephthalic acid Neopentyl glycol
structure is essential to produce an unsaturated
Adipic acid Diethylene glycol
polyester with high reactivity. Although the iso-
The reaction product of terephthalic acid and merization of maleic anhydride is usually from
ethylene glycol is the well known polyethyl- 65-95% in the esterification reaction, some com-
ene terephthalate (PET) which is used to make mercial resins are deliberately formulated with
polyester fibers and polyester plastics such as the more expensive fumaric acid to obtain max-
clear plastic bottles for soft drinks. imum reactivity with the monomer employed.
Unsaturated polyesters are produced by
replacing part of the saturated diacid with an
2.2.1 UNSATURATED POLYESTER CLASSES
unsaturated diacid such as maleic anhydride
or fumaric acid (Fig. 2.2). The former is vastly Unsaturated polyesters are divided into types
preferred since it is lower in cost, easily han- or classes depending on the structure of the
dled and produces only half the water that basic building block. These are orthophthalic,
would be generated in the reaction when isophthalic, terephthalic, bisphenol-fumarate,
fumaric acid is used. chlorendic and dicyclopentadiene.

Orthophthalic resins
CH = CH
t \ These are commonly referred to as ortho or
0 = c-0-c = 0
general purpose resins and are usually based
Maleic
anhydride on phthalic anhydride, maleic anhydride and
propylene glycol. Since the acid groups in
H H phthalic anhydride are on adjacent carbons of
I1 II the benzene ring, it is very difficult to produce
HOOC- C = C - COOH
resin molecular weights as high as those
Fumaric acid
achievable with isophthalic and terephthalic
acid. Accordingly, resins made from phthalic
anhydride have poorer thermal stability and
Fig. 2.2 chemical resistance than their iso/tere coun-
The resultant polyester contains reactive dou- terparts.
ble bonds (unsaturation) along the entire
polyester chain, which becomes the site for the Isophthalic resins
eventual cross linking to produce the cured
plastic (Fig. 2.3). These resins are produced from isophthalic
acid and are characterized by greater strength,
heat resistance, toughness and flexibility than
0 0 0 HO their ortho cousins. In isophthalic acid, the
It II II I II
HO ( C-R-C-O-R'-O-C-C=C-C-O-R'-O)n H acid groups are separated by one carbon of the
I benzene ring which increases the opportunity
H to produce polymers with greater linearity
and higher molecular weight in the esterifica-
Fig. 2.3 tion reaction (Fig. 2.4).
36 Polyester and viny ester resins
Phthalic lsophthalic
anhydride acid
0
c=o
‘OH
Terephthalic
acid
Fig. 2.4
Therephthalic resins
Unsaturated polyesters can be produced from
terephthalic acid with the expectation that the
resin property improvement obtained in going
from phthalic anhydride to isophthalic acid
will be matched in going from isophthalic to
terephthalic acid. This, however, is not the case
and terephthalic resins appear to offer only a
slight advantage in heat distortion tempera-
ture over their isophthalic counterparts. Other
important resin properties such as modulus,
hardness and overall chemical resistance favor
the is0 resins.
Because of its lower solubility and poorer
reactivity, therephthalic acid requires the use
of esterification catalysts or pressure process-
ing to produce a resin economically. Without
these, processing time for a terephthalic poly-
H H
I - CH2 - O
HO - C o l @ I - OH
0 - CH2 - C
I I
CH3
Fig. 2.5
ester can be three times longer than for an is0
resin. As a result of this, researchers have
turned to polyethylene terephthalate scrap
from the previously mentioned fiber and plas-
tic operations to develop an economical source
of terephthalic polyesters. This scrap can be
effectively depolymerized by using different
amounts of propylene glycol at elevated tem-
peratures. The glycolyzed product is then
reacted with maleic anhydride and diluted
with styrene monomer to produce a cost effec-
tive terephthalic polyester.
Bisphenol A fumarate resins
These resins are unsaturated rigid polyesters
made by reacting bisphenol A with propylene
oxide to produce the glycol shown in Fig. 2.5.
This propoxylated bisphenol A is then
reacted with fumaric acid to form an unsatu-
rated polyester. The bisphenol structure
illustrated above imparts a high degree of
hardness, rigidity and thermal stability to this
particular resin.
Chlorendic resins
These unique polyester resins are based on
HET acid (hexachlorocyclopentadiene) or the
anhydride shown in Fig. 2.6.
When reacted with an unsaturated acid and
a stable glycol such as neopentyl, an extremely
rigid unsaturated polyester results with out-
standing thermal stability and resistance to
oxidizing environments. The inherent chlorine
in the resin chain imparts some fire retardancy
as well.
..
CQ
;?!
CI CI-c-CI -c=o
CH3
Fig. 2.6
 Hydrocarbon Solvents 37

Table 2.72: Hexene-1 (4)

FORMULA cn2 = cn-cn2-cn2-cn2-cn,

RESEARCH PURE TECHNICAL

PROPERTIES
GRADE GRADE GRADE

'Literature values.

Table 2.73: cis-Hexene-2 (4) Table 2.74: Mixed 2-Hexenes (4)

1
_ _ _ _ _ _ ~

FORMULA cn3-c - c-cn2-cn2-cn, FORMULA -

cH3-cH cn-cH2-cn2-cn3
PURE TECHNICAL
RESEARCH PROPERTIES GRADE GRADE
PROPERTIES
GRADE
Composition, weight percent .. - - - -
Composition. weight percent
trxe 03
~

Hexenel .-
Hexene-1
___-_-.___~_-- 0.1 ~-
.
~

tranr-Hexene-2 - 0.2 - tiant-Hexene-2 i:it99Omin -

cis-Hexene.2 99.6 cis Hexene-2 __ 0.8 21
Hexener-3 ~ --- -
~~ ~

- -.
Hexe!Er-?p.- _ ~ ~

Normal Hexane
Normal Hexane - ~ -- - - -

_ _ lsoolefins
_ . _ ~ . 0.1 lsoolefins -_____ _ - - -

Heptene-l --__- -
__Heptene-l tranr-Heptene-3 . - _ ..
- tranr-Heptene-3
cis.Heptene.3 cis-Heptene3 .. - -
tranr-Heptene 2 -
tranr-Heptene.2 -~ ca-Heptene2
cis.Heptene2
Purity by freezing point, mol % 99.28 Purity by freezing point. mol % ~
.~ ~~~ ~- .
Freezing point, F -222.04' Freezing point. F ~~

-~ Boiling point, F _ _ _ -~ 156.00' Boiling point, F ~ -

__Distillation range, F Distillation range. F ____ __- . ~- ~-
Initial boiling point Initial boiling point 155.0
__.___.__ 155.0 .
Dry point Dry point 155.1 155.1
Specific gravity of liquid at 6076m 0.6 920*
_________ Specific gravity of liquid at 60160 F -. 0.684 ~ 0.686 ~

at 2014 C 0.68720' at2014 c - . . ~ ~ _ _ _ - . ~ -

API gravity at 60 F API gravity at 60 F 75.4 74.8
~- -.. - -
Density of liquid at 60 F. m a l 5.760' Density of liquid a t 60 F. Ibdgal 5.69 5.71 ~-.__
Vapor pressure at 70 F. psia 2.4' Vapor pressure a t 70 F. psis ____ 2.4 2.4 .
-___ 100 F, psia 4.9' 100 F, psia .
5.0 -~
... . -~
5.0 -
130 F, psia 9.1' 130 F, psia ~ .~~ !.2._. - -~.- ~ 9.2
_ _ Refractive
_ ._ index. 20/0- 1.39761. Refractive index, 2010 ~~
1.396 1.396 __
Color. Saybolt +30 Color, Saybolt +30
_
+30
Acidity, distillation residue Acidity. distillation residue -~ neutral ..
neutral ~

-__-Nonvolatile matter. gramdl00 ml Nonvolatile matter, gramdl00 ml _. 0.0005 .. -. 0.0005

Flash point. appoximate. F Flash point, approximate, F -5 -5
*Literature values.
38 Polyester and viny ester resins
In addition to tailoring the resin for specific
applications by varying the building blocks,
the properties of unsaturated polyesters can
often be altered significantly by selection of
the esterification process. This is particularly
true with isophthalic/terephthalic polyesters
which are slower reacting than phthalic anhy-
dride. By using a two stage or modified two
stage reaction with these aromatic diacids, the
molecular structure of the resultant polyester
can be changed to markedly improve heat dis-
tortion temperature, hydrolytic stability and
chemical resistance2.In the two stage process
the aromatic acid and glycol are fully or par-
tially reacted before the faster reacting
unsaturated acid is added to the cook. This
processing method, compared to charging all
ingredients at once (one stage method), also
leads to a more random distribution of the
unsaturation in the polymer chain which
changes the character of the final cross linked
network in the cured resin.
Cure plays one of the most important roles
in the chemical resistance developed by unsat-
urated polyester resins. Theoretically, the
curing reaction should go to completion at
room temperature with all the double bonds
converted to single bonds in the three-dimen-
sional network. However, complete cross
linking is rarely achieved at ambient tempera-
tures. This then will result in reduced chemical
resistance and, quite often, poorer than
expected mechanical properties. In addition,
unreacted diluent (styrene ) can remain in the
not-so-well cured polymer leading to major
problems when the polyester is used for food
grade applications. Accordingly, maximum
chemical resistance and certain other property
improvements can most often be achieved by
utilizing elevated temperatures for ‘post cure’
of the polyester resin finished product.
Unsaturated polyester resins are used in the
manufacture of a broad range of plastic prod-
ucts. A high percentage of these products
utilize reinforcing materials, particularly fiber-
glass. It is estimated that less than 20% of the
polyester resins produced are utilized in appli-
cations which do not involve reinforcing mate-
rials. These so-called casting applications
include buttons, bowling balls, putties, cul-
tured marble, gel coats and decorative
products. The marble industry and the more
recently developed polymer concrete industry
represent outstanding applications for highly
filled unsaturated polyesters which offer very
economical materials to the building and con-
struction industry. Fiberglass reinforced
polyesters (FRP) are used in the manufacturing
of boats, automobile and truck parts, building
panels, corrosion resistant equipment such as
pipes, tanks, ducts, scrubbers, etc., appliances
and business equipment, electrical equipment,
construction products such as grating and rail-
ing, sporting equipment and consumer
products that are almost endless. According to
the Composites Institute of the Society of
Plastics Industry (SPI), automotive, construc-
tion, marine and corrosion resistant
equipment are the four largest FRP markets, in
that order, in the United States which pro-
duces 2.5 billion pounds of FRP annually.
Mechanical properties are most often the
critical factor in the selection of a polyester resin
for a specific application. Testing of mechanical
properties for both resin castings and fiberglass
remforced composites is carried out using stan-
dardized ASTM (American Society for Testing
and Materials) tests for all plastics.
ASTM D-638 Standard Test Method for
Tensile Properties of Plastics
ASTM D-790 Standard Test Method for
Flexural Properties of Plastics
ASTM D-695 Standard Test Method for
Compressive Properties of
Rigid Plastics
ASTM D-256 Standard Test Method for
Impact Strength (IZOD) of
Plastics
ASTM D-648 Standard Test Method for Heat
Distortion Temperature of
Plastics
ASTM D-2583 Standard Test Method for
Barcol Hardness of Plastics
 Polyester resins 39

As mentioned earlier, glycol selection has a produce a rigid polyester which tends to be
significant effect on the properties of poly- hard, brittle and lower in tensile elongation.
esters. Ether glycols are of great value in Higher unsaturation also leads to higher heat
increasing tensile elongation and impact distortion temperature resins. The latter is also
strength which is of great importance in auto- achieved by formulating higher molecular
motive, casting and liner applications. A weight resins with the chlorendic, bisphenol A
principal deficiency of polyester resins is lack and dicyclopentadiene building blocks. As
of alkali resistance because the ester linkages expected, all of these resin classes are more
are subject to hydrolysis in the presence of brittle and have low tensile elongation. The
caustics. Accordingly, increasing the size of the major exception in this scenario are the
glycol has the same effect as reducing the con- iso/terepolyesters. Using the multi-stage pro-
centration of attackable ester linkages. Thus, a cessing methods described earlier, these resins
resin containing neopentyl glycol, propxylated can be formulated with reasonably high mole-
bisphenol A, or trimethyl pentanediol will cular weights (more linearity) to give very
exhibit improved water and chemical resis- tough resins having a good balance of ten-
tance which is highly important in gel coats, sile/flexural properties plus higher tensile
corrosion resistant equipment, construction elongation and heat distortion temperatures.
products and many consumer products. Obviously then, when the end use criteria
The major effect on polyester physical prop- requires the 'something more' than is offered
erties is, however, provided by the by general purpose polyesters (orthophthalics
unsaturation content in the polyester polymer. and dicyclopentadienes),the formulator turns
Higher unsaturation makes for more cross to iso/terepolyesters which have no disadvan-
linking and a stiffer cured composite. tages compared to general purpose resins
Accordingly, the formulators' selection of other than slightly higher cost.
unsaturated acid to saturated acid ratio which Table 2.1 summarizes the property and
determines cross linking density can move the application status for the various classes of
resin flexural modulus from rigid to resilient unsaturated polyesters.
to very flexible. In most cases, a 1/ 1 ratio will
Table 2.1 Properties and applications of unsaturated polyesters

Class Characteristics Uses

Orthophthalics, Rigid, resistant to
dicyclopentadiene crazing, light in color
Isophthalics/terephthalics Tough, good impact and
overall mechanical properties,
resistant to environmental
elements and moderate
chemical attack. Highly
resistant to aromatics
Chlorendic Rigid, high heat distortion,
highly resistant to oxidizing
chemical environments
Bisphenol A fumarates Rigid, high heat distortion,
highly resistant to most
chemical environments
particularly caustics
Boats, tub/shower, spas, marble,
consumer products, buttons, corrugated
sheet, building panels, seating,
decorative products
Automotive parts, gel coats,
electrical, bowling balls, trays,
gasoline, tanks, septic tanks, swimming
pools, tooling, aerospace products,
corrosion, construction products
Corrosion resistant tanks,
ducting, stacks, industrial vessels
Corrosion resistant tanks,
piping, stacks, industrial vessels
40 Polyester and uiny ester resins

2.3 VINYL ESTER RESINS Although vinyl esters have often been clas-
sified as polyesters, they should be designated
Vinyl ester resins are the most recent addition
to the family of thermosetting polymers. separately because they are typically diesters
Although several types of these resins were with a recurring ether linkage provided by the
synthesized in small quantities during the late epoxy resin backbone.
1950s, it was not until the mid-1960s that com-
mercialization, principally by Shell and Dow 2.3.1 VINYL ESTER RESIN TYPES
Chemical led the push to establish an
extremely important segment of today’s com- Aside from the fire retardant versions of vinyl
posite industry. Vinyl esters are unsaturated ester resins which are discussed in the next
resins made from the reaction of unsaturated section, there are two basic types of vinyl
carboxylic acids (principally methacrylic acid) esters having commercial significance. These
with an epoxy such as a bisphenol A epoxy are the general purpose lower molecular
resin. The typical structure of a vinyl ester weight vinyl esters and the higher heat resis-
resin is shown in Fig. 2.8. tant vinyl esters with greater cross link
The structure of vinyl ester resins shows density.
several important features which account for
the resultant exceptional properties of vinyl General purpose vinyl esters
ester resins. There is an epoxy resin backbone
with a high molecular weight that provides These are principally methacrylated epoxies
excellent mechanical properties combined made by the reaction of methacrylic acid with
with toughness and resilience. Secondly, vinyl a bisphenol A epoxy resin. When dissolved in
esters display terminal unsaturation which styrene monomer they provide a thermosetting
makes them very reactive. They can be dis- resin with good heat resistance, excellent
solved in styrene and cured like a mechanical properties (particularly high ten-
conventional unsaturated polyester to give sile elongation) and outstanding chemical
rapid green strength. Obviously, the vinyl resistance to acids, bases, hypochlorites and
ester structure also enables convenient many solvents.
homopolymerization which could lead to high
heat distortion products. Finally, vinyl esters
Heat resistant vinyl esters
have much fewer ester linkages per molecular
weight which combined with the acid resistant These vinyl esters have higher density cross
epoxy backbone, give outstanding chemical linking sites available which leads to a more
resistance (acids, caustics and solvents) to this heat resistant polymer network. They are pro-
class of resins. duced from novolac modified epoxy resins

OH OH
H - C-
I CH2- 0 G T O O - CH2-CI - H

0
7H2 CH3
7%
0
I I
c=o c = o
I I
C-CH3 C-CH3
II II
CH2 CH2

Fig. 2.8
 Vinyl ester resins 41

and methacrylic acid which provides more cal properties can be 'tailored' to meet the
unsaturation sites and higher molecular requirements of specific applications. Another
weight due to the epoxy backbone. These unique property of vinyl ester is the bondabil-
vinyl esters increase the heat resistance by ity of these resins to other surfaces. They are
17-27°C (30-50°F) over the general purpose not as good as epoxy resins in this character-
types. This often translates to higher useful istic, but obviously the epoxy resin
operating temperatures for vinyl ester based component gives them a boost over other
reinforced plastics even in corrosive environ- unsaturated polyesters in this area. A case can
ments. The higher-density cross linked vinyl also be made for vinyl esters providing better
esters are less resilient (lower tensile elonga- fiberglass wet out in FRP composites due to
tion) but still have excellent mechanical the backbone hydroxyl groups and their inter-
properties. Cure of the higher cross linked action with these groups on the fiber surface.
vinyl esters may require the use of different Some fabricators have reported that observ-
peroxide catalysts to reduce the peak able resin savings can be achieved with vinyl
exotherm and thereby prevent cracking/craz- esters because of this characteristic.
ing in resin rich areas. In other words, resins of However, vinyl esters such as bisphenol A
this type are more reactive and more caution is polyesters and chlorendic polyesters are made
required in the fabrication of FRP laminates. from higher cost materials and often require
extended process times which leads to higher
finished cost. Accordingly, the specifier/fabri-
2.3.2 PROPERTIES/APPLICATIONS
cator turns to commercial applications where
The development of vinyl esters has led to the the improved performance of vinyl esters can
fastest growing segment of the thermosetting justify the premium price of the finished com-
resin industry today. This is not surprising, posite.
since vinyl esters combine inherent toughness The foremost application for vinyl esters is
with outstanding heat and chemical resis- in glass reinforced laminates for corrosion
tance. In all other thermosetting resin types resistant equipment. Because of outstanding
one has to sacrifice some heat resistance and chemical resistance combined with excellent
often chemical resistance to increase resiliency mechanical properties, vinyl ester based FRP
and toughness. Unlike polyesters, vinyl ester tanks, piping, scrubbers, fans and ductwork
resins possess low ester content and low are being specified for waste water treatment
unsaturation which results in greater resis- plants, mining facilities, chemical processing
tance to hydrolysis, lower peak exotherms and storage units, semi-conductor chip opera-
during cure and less shrinkage during cure. tions, pulp and paper manufacturing and odor
They are easily dissolved in reactive control facilities. Since FRP corrosion resistant
monomers such as styrene which provides equipment is the fastest growing segment of
easy handling and transportation to the fabri- the US composites industry, the future for
cation site. As with polyesters, other reactive vinyl esters looks extremely strong. They are
monomers such as vinyl toluene, chlorostyrene comparable to other premium resins for chem-
and f-butyl styrene can be employed with few ical resistance and secondary bonding
problems. combined with a good balance of chemical
The toughness of vinyl esters comes from resistance (acids, bases, solvents) at the same
the epoxy resin backbone. Since the molecular or lower cost. As a result, chlorendics and
weight and structure of the epoxy resin can be bisphenol A polyesters have been reduced to
varied like the polyester resin building blocks, 'niche' applications where their specific prop-
physical properties such as tensile elongation, erty advantages such as heat resistance and
heat distortion temperature and key mechani- resistance to oxidizing environments demand
42 Polyester and viny ester resins
their use. Since iso/terepolyesters also give an
excellent balance of properties in corrosion
applications, these unsaturated polyesters and
vinyl esters now dominate the corrosion mar-
ket. The bonus provided by vinyl esters is of
course higher heat resistance and extended life
at higher operating temperatures, but at sig-
nificant additional cost compared with the
iso/ terepolyesters.
The next major market area for vinyl esters
utilizes the high tensile elongation characteris-
tics of these resins to produce linings and
coating with outstanding adhesion to other
types of plastics and conventional materials
such as steel and concrete. For example, vinyl
esters are an excellent barrier coat for fiberglass
boats and acrylic spas. Vinyl ester corrosion
coatings are used everywhere today for steel
tank linings and industrial flooring. In dual
laminate structures, a vinyl ester is often the
back up for exotic thermoplastics or the supe-
rior corrosion barrier for lower cost polyesters
in many FRP tank and pipe applications.
The growth of vinyl esters has also been
boosted by their excellent handling character-
istics and ease of cure. For example, vinyl
esters are much preferred by FRP fabricators
in filament winding operations because of
excellent glass wet out and in fabrication of
large structures because the resins are forgiv-
ing and provide predictable curing over a
wide range of temperatures. The latter situa-
tion has resulted in a virtual exclusive use for
vinyl esters in field fabrication of large FRP
structures.
Table 2.2 Resins for corrosion resistant applications
Tensile,
psi
General purpose vinyl ester 12 500
Heat resistant vinyl ester 13 000
Chlorendic polyesters 5 500
Bisphenol A polyester 10 000
Rigid isopolyester 8 500
Resilient isopolyester 12 500
Table 2.2 summarizes the resin casting
properties of the various resins used in corro-
sion resistant applications today.
The outstanding balance of properties pro-
vided by vinyl ester resins is obvious and
bodes well for continued strong growth in US
corrosion markets. Other significant markets
for vinyl esters includes pultruded construc-
tion and electrical components, automotive
structural applications, polymer concrete ves-
sels for mining and chemical operations,
grating, high performance marine applications
and sporting goods.
2.4 FLAME RETARDANT VERSIONS
The need for flame retardant polymers is
essential in many plastics applications today.
The combustibility of plastics has drawn so
much attention to the safety aspects of these
materials in construction applications, that
designers and specifiers have been pressured
by fire officials to provide fiberglass-rein-
forced construction materials that exhibit low
flame/low smoke characteristics. Since all
plastics are based on organic constituents, they
are inherently flammable and once ignited will
burn until they are completely consumed.
There are, however several methods available
for making thermosetting resin flame retar-
dant and these provide the capability to
supply fire retardant FRP and corrosion resis-
tant/fire retardant FRP for the numerous
applications that have a need for some degree
of fire retardancy.
Flexural, Elonga f ion HDT,
psi break, % OF
20 500 6.7 221
20 000 5.6 248
10 000 1.4 284
16 500 3.2 288
19 000 1.9 234
20 000 4.4 201
 Flame retardant versions 43

Flame retardancy can be achieved by using range of chemical environments, both acid and
numerous additives, both organic and inor- alkali, at operation temperatures similar to the
ganic. However, most of these have a negative general purpose vinyl esters. Brominated high
effect on mechanical and/or chemical resis- molecular weight isopolyesters offer economic
tance properties. Accordingly, the most widely advantages and are suitable for moderate cor-
used system for achieving optimum fire retar- rosion applications. These two resin types
dancy will be covered here, namely, have become the workhorses for the waste
halogenated thermosetting resin systems com- water/odor control FRP market and the chem-
bined with inorganic synergists. ical and pulp /paper industries because they
exhibit excellent impact properties combined
with good overall corrosion resistance.
2.4.1 CHEMISTRY AND APPLICATIONS
Variations of these resins are used to meet
Flame retardancy of unsaturated polyester MIL-R-21607 or MIL-R-7575 requirements.
and vinyl ester resin is an extension of the non- Dibromoneopentyl glycol formulated with
flame retardant systems (as discussed above). carefully selected chemical building blocks
Almost all of these resins can be reformulated provides resins for exposure to severe weather-
to include a halogen in the chemical composi- ing conditions. The construction industry uses
tion by either blending or by an in situ cook of these resin systems, which are specially formu-
the resin. There is an advantage to locking in lated to meet optimum fire retardance for the
the halogen in the original resin cook, in order continuous line products of corrugated and flat
to chemically tie in the halogen (Cl, or Br) to sheet panels. Such systems are formulated with
prevent migration of the halogen when sub- ultraviolet (W) stabilizers and acrylates to
jected to thermal degradation. While flame achieve excellent color stability with acceptable
retardancy can be achieved with additives low smoke and flame spread (FS)properties. In
(Dekabrom or Dechlorine), these additives most cases, these formulations offer good
have not been used for high performance chemical resistance for splash and spill on the
applications in either the corrosion or con- exposed surfaces. Highly filled halogenated
struction industries (corrugated FRP panels). resin systems are designed to accept high filler
The chlorendic resins were developed in the loading with aluminum trihydrate (ATH) and
1950s and were based on HET acid (hexa- other synergists to meet DOT requirements for
chloroxyclopentadiene). Other formulations low smoke, low flame spread properties
followed, based on either tetrabromo bisphe- (ASTM-E-662 and E-162 respectively). Values
no1 A (TBBPA) or dibromo neopentyl glycol of <150 smoke and 10 flame spread are
(DBNPG). These components react with achieved. Highly filled resins are specified for
maleic anhydride or fumaric acid in the pres- applicationswhere people could be exposed to
ence of a difunctional glycol, to produce flame indoor fires, such as underground transporta-
retardant unsaturated polyesters that can be tion. Low smoke allows visual capability to
combined with styrene monomer, or other exit an entrapped area.
monomers used for smoke control, such as Electrical applications often require the
methyl methacrylate. The use of bromine as addition of halogenated base resins to achieve
the halogen in the resin building block has flame snuffing properties resulting from high
proved to be the most efficient way of achiev- voltage shorting or sparking. Such fire retar-
ing optimum flame retardant thermosetting dant systems are used for compression
resins. Certainly a lower percentage of molding of complex electrical shapes, using
bromine than chlorine is required for satisfac- BMC or SMC molding materials. Wet mat
tory reduction of flame spread. molding is also used to produce flat sheet for
Brominated vinyl esters handle a wide electrical insulation components.
44 Polyester and viny ester resins
When compared to the non-flame retardant
versions, the addition of a halogen to the resin
formulation has very little, if any, effect on the
chemical or mechanical properties of a FRP
laminate, whereas the use of additives such as
aluminum hydrates, clays, carbonates or
fumed silica will have a direct and adverse
effect on the chemical resistance of FRP lami-
nates. In critical corrosion applications such
filler additions could result in early failure of
FRP laminates.
2.4.2 TESTING AND CLASSIFICATION
Most halogenated resin systems require a syn-
ergist such as antimony usually 3-5'/0 Sb,O, by
weight of resin in order to achieve a class I
flame spread rating. Other proprietary syner-
gists can be substituted, especially in
translucent laminates as used for siding and
roofing materials. Antimony oxide enhances
the flame spread rating by forming a char on
the burning surface of a laminate and effec-
tively subdues the rate of flame progression by
snuffing the flame out when the source of igni-
tion is removed or extinguished. Such flame
resistant FRP laminates will burn when sub-
jected to a high temperature flame source, but
the rate of burning is substantially less than for
non-flame retardant systems. The use of Sb,O,
will turn laminate opaque, which restricts
visual inspections of a laminate in production.
It is not a good idea to allow the addition of
Sb,O, in the corrosion resistant barrier. Alone,
Sb,O, will not improve a non-halogenated
resin; its use becomes an unnecessary expen-
sive filler with no flame retardant properties.
The most commonly used test method for
evaluating flammability is ASTM Method E-84
(the tunnel test) also known as NFPA 255. This
test method measures the comparative burn-
ing characteristics of a material by evaluating
the flame front propagation over the surface of
the test material, which is exposed to con-
trolled temperatures in a forced air chamber or
tunnel. A flame spread (FS) classification (FSC)
is obtained which measures the ignition time
and distance of the flame front advancing
down the test tunnel during a ten-minute
duration test and compared to those values
established for asbestos-cement board (at
0-FS) and red oak material (at 100 FS). This
test method establishes the rating at 0-25FS as
Class I, 25-75FS as Class I1 and 76-plus FS as
Class 111. During the test procedure, the
smoke emission is measured and can range
from 450 to 1000 or more for unfilled lami-
nates. When additives such as ATH are used,
smoke emissions of less than 450 can be
achieved.
Corrosion resistant FRP ducting exhibiting
low flame/low smoke characteristics is
required for waste water/odor control and
semiconductor applications. This can be
achieved with brominated vinyl esters or
brominated isopolyesters as the base for the
FRP duct which is then coated with an intu-
mescent paint to reduce smoke emissions.
Such systems are currently qualified by the
International Conference of Building Officials
(ICBO) with tunnel test ratings of <25FS and
<50 smoke development.
Unfortunately, many specifying engineer-
ing companies will request and specify
values that are not readily achievable for
most flame retardant resin systems. Ideally, a
Class I system with 25FS (max) to 450 (max)
smoke is acceptable for corrosion service,
when the use of additives cannot be toler-
ated. A FSC of <25FS is usually acceptable for
most applications. However, some specifiers
will claim that 15-20FS is better than 20-25FS,
when under actual burning conditions there
is a negligible difference in the combustibility
of FRP laminates. When selecting a flame
retardant resin, it is important to qualify a
system to meet the properties required. Flame
retardant resins are available in a wide vari-
ety of formulations, including lower cost
general purpose to premium grade types
with better high temperature properties.
Class I flame spread thermosetting resin
systems can also be achieved without the need
for a synergist like antimony oxide. These
 Design considerations 45

systems have a higher halogen content which product would essentially ’unzipper’ and fail.
obviously increases resin cost. However, these The polyester and vinyl ester resins described
materials allow for the production of translu- in this chapter offer a wide selection of materi-
cent FRP products that are desirable in many als which will accomplish the need to protect
construction applications. Such a resin system the fiberglass and, at the same time, provide
has been specified by Disney engineers for optimum performance properties dictated by
their architectural applications at Disney the end use application.
entertainment centers. The first agenda in proper resin selection
involves an analysis of the key performance
requirements of the end use application. This
2.5 DESIGN CONSIDERATIONS should be very thorough as follows:
Since most thermosetting resin systems are 0 strength requirements;
used with fiberglass reinforcements, it is 0 thermal requirements;
important to consider material selection and 0 chemical exposures;
the fabrication process in establishing the 0 electrical requirements;
design of the FRP composite. 0 color requirements;
0 surface requirements;
0 environmental exposures;
2.5.1 MATERIAL SELECTION 0 fire resistance needed;
0 smoke requirements;
The type of fiberglass reinforcement, place-
0 potential upset conditions;
ment in the composite and fiberglass content
0 number of parts required;
determines the strength of an FRP composite
0 life expectancy.
and provides the mechanical properties dic-
tated by the end use requirements. In any part Resin selection is obviously very important in
made of FRP, the strength of the part will any FRP application as the above list of design
increase directly in relation to the percentage criteria illustrates, but is absolutely vital in
of fiberglass in the total weight of the compos- corrosion applications. Corrosive attack on a
ite. In addition, the arrangement and type of FRP laminate along with fire is the most criti-
fiberglass will have important effects on the cal situation the composite will face. A
resultant physical properties since the strength fiberglass building panel properly made can
obtainable in the finished part will be in the perform for an indefinite number of years, but
direction of the fibers. even a properly fabricated FRP tank exposed
The selection of the thermosetting resin sys- to concentrated acids at elevated temperatures
tem will determine the chemical, electrical and may only be good for 10-15 years. The best
thermal performance of the FRP product. example of this is in the pulp and paper indus-
However, the most significant contribution by try where vigorous chemical attack on FRP
the resin relates to ‘life’ of the composite, equipment can dictate replacement on a rou-
since the resin must protect the fiberglass. tine basis, say every five years. In spite of this,
Accordingly, if the resin fractures or blisters in FRP equipment may still offer the most cost
any manner that permits an attack on the glass effective material of construction.
fibers, the composite will lose strength rapidly Although all FRP composites will be
or delaminate. An interesting way to visualize attacked in the same manner in a particular
this is to consider a FRP pipe made by the fila- environment, certain types (chlorendic,
ment winding process. If the continuous fiber bisphenol A, vinyl esters and isopolyesters)
strands providing the hoop strength to the are significantly more resistant. These then
product are severed by chemical attack, the make up the list of corrosion and heat resistant
46 Polyester and viny ester resins
resins to choose from in addressing a specific
application. A good rule to follow here is that
no single FRP resin can handle every kind of envi-
ronmental problem, so resin selection is of the
utmost important. It should also be under-
stood that knowledge of the molecular
structure of these higher performance resins
does not eliminate the need for actual testing
to determine resin suitability in a given appli-
cation. For example, certain vinyl esters are
reasonably resistant to alkaline exposure while
other types are poor. The corrosion fabricators’
guide for the suitability of a thermosetting
resin in a corrosive environment is ASTM C-
581. The procedure involves complete
exposure of a FRP test laminate for one year,
with intermittent strength testing, to establish
a curve which depicts loss of flexural strength
versus time. It is absolutely essential that the
resin selected for that environment form a
plateau during the one year test period.
Obviously, it is also important that this plateau
be achieved at a satisfactory retained flexural
strength. Table 2.3 summarizes a comparison
of FRP properties of various thermosetting
resin types versus carbon and stainless steel.
2.5.2 EFFECT OF PROCESS AND END USE
REQUIREMENT
There is an old saying in the FRP business that
heightens awareness of the fabrication
Table 2.3 Comparison of properties of various types of FRP
lsophthalic Orthophthalic Chlorendic Bisphenol A
Corrosion resistance
Acids B C
Alkalis B C
Peroxides C C
Hypochlorites C C
Solvents B C
Flame retardance C C
Structural strength A B
Thermal insulation A A
A = High, B = Moderate, C = Low
process. Simply, ’you can select the best resin
and fiberglass in the world and if you don’t
put them together correctly - failure will prob-
ably result’. Material selection added to design
and production requirements leads to a deter-
mination of the fabrication process. Many
methods of fabrication are used to manufac-
ture products for the numerous FRP markets.
These methods vary from hand lay-up/spray-
up, filament winding and resin transfer
molding which utilize low temperature curing
to various high temperature molding com-
pound (SMC), pultrusion, and continuous
panel. The designer must analyze the end use
property requirements such as color, surface
characteristics, strength and chemical resistance
requirements and then add-in cost factors,
part volume, part size and finishing to finalize
the selection of process. For example, trans-
portation body panels would be a high
volume application requiring outstanding sur-
face finish and excellent strength properties.
All of these can be satisfied with a isopolyester
sheet molding compound that is compression
molded under heat and pressure. This process
can be automated and delivers the highest vol-
ume and highest part uniformity of any
thermoset molding method. Lower part finish-
ing cost is achievable because subsequent
trimming machining is minimized.
Corrosion resistant equipment would be
fabricated,on the other hand, by either filament
Vinyl Carbon Stainless
fumarate ester steel steel
A A B C B
C A A B B
A B B C C
A B A C C
B B B A A
A C A A A
A A A A A
A A A C C

winding or hand lay-up/spray-up processing.
The former gives the highest strength to
weight ratio of any FRP manufacturing
process. However, the most important consid-
eration is that these two process methods
allow the easy creation of an effective resin-
rich corrosion barrier which is mandatory to
satisfactory FRP life expectancy in corrosion
applications. The purpose of this barrier is to
isolate the fiberglass reinforcements from
attack that would result in wicking, blistering
and delamination. The satisfactory corrosion
barrier should be about 125 mils (3175 pm)
thick, fabricated with glass or polyester veil on
the surface, backed up by 2-3 plies of type E
chopped strand mat. The resin-rich corrosion
barrier should be constructed with the very
best resin available in terms of chemical resis-
tance to the expected environment. For
example, the corrosion barrier for 26%
hydrochloric acid should employ a vinyl ester
and two layers of polyester veil. It is always
wise in dual laminate construction (different
liner and wall resins) to utilize the material
with the higher resiliency (higher tensile elon-
gation) in the liner portion of the laminate
structure.
A final example of process effect on lami-
nate properties should address the rapidly
growing world of FRP pultrusion. This fabri-
cation method provides very high strength
due to high fiber concentration and orientation
References 47
parallel to the length of stock. Pultrusion is an
automated, low labor system which can use
any type of thermosetting resin. However,
resilient resins such as isopolyesters and vinyl
esters are much preferred because of the very
high glass content in the finished part. Low
cost reinforcement is adaptable to putrusion
because the glass weight percentage is high.
Pultrusion is used for FRP structural and elec-
trical applications primarily, but the weight
and density of the finished product does pro-
vide moderate corrosion resistance properties.
The value received from good design based
on proper selection of materials and process
can be very rewarding for FRP composites.
The systematic analysis of end use require-
ments, economic requirements and
competitive materials will enable the compos-
ite designer/specifier to optimize the
cost/performance of FRP as a material of con-
struction. The matrix materials available today
give the fabricator sufficient opportunities to
meet his final objective of providing the right
product at the lowest cost.
REFERENCES
1. Ellis, C., US Patent 2 255 313; appl. August 6,
1937.
2. Amoco Chemical Company, Bulletin IP-70a,
Chicago, Illinois.
EPOXY RESINS
L.S. Penn and €3. Wang
3.1 INTRODUCTION
Epoxy resin systems have achieved acceptance
as adhesives, potting compounds, molding
compounds and as matrices for continuous fil-
ament composites used in structural
applications. In this chapter, we discuss epoxy
resins in their role as matrices in fiber compos-
ites. In this role, they possess several
advantages over other types of polymers. The
main advantages are:
0 inherently polar nature that confers excel-
lent adhesion to a wide variety of fibers;
0 relatively low cure shrinkage that makes
dimensional accuracy of fabricated struc-
tures easier to obtain;
0 no volatile by-products of the curing reac-
tion to cause undesired bubble or void
formation;
0 crossIinked structure that confers excellent
resistance to hostile environments, both
aqueous and nonaqueous.
In addition to these advantages, epoxy resins
have tremendous versatility because they can
be formulated to meet a broad range of specific
processing and performance requirements. To
know how to take advantage of the formula-
tion options, the engineer needs to have an
elementary understanding of epoxy resin
chemistry and structure-property relation-
ships. This chapter attempts to provide that by
presenting information about the resin system
constituents, how they react together to form a
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
3
crossllnked network and how they lead to dif-
ferent processing parameters and final
properties in the formulated system. The
chapter also describes the role of cure moni-
toring and property evaluation in epoxy resin
system technology.
3.2 GENERAL DESCRIPTION OF
THERMOSETTING SYSTEMS
3.2.1 DEFINITIONS
According to common chemical practice, mol-
ecules can be classified by the functional
groups they contain. Thus, a molecule contain-
ing the epoxide group (shown below) as part
of its structure is called an epoxide, regardless
of the remaining details of the molecule.
/O\
-c-c-
I I
In practice, other types of molecules are added
to the epoxide to formulate a thermosetting
system, i.e. one that will undergo a curing
reaction to harden into a rigid form. The con-
fusing practice has been followed of referring
to both the epoxide alone and the formulated
system as 'epoxy resin'. One must determine
which is truly intended by the context in
which it is used. For the purposes of clarity in
this chapter, we will use epoxide when refer-
ring to the epoxide constituent alone and will

use the term epoxy resin when referring to the
uncured or cured formulated system.
3.2.2 THE THERMOSETTING (CURING)
REACTION
The thermosetting reaction is the joining of
many small molecules by chemical reaction to
produce an extended network structure.
Although this process is a polymerization, it is
distinct from the type of polymerization that
forms many individual long chains; the ther-
mosetting reaction unifies all the constituent
monomers into a single large molecule extend-
ing to the boundaries of the material.
Epoxide molecules in the pure state at room
temperature normally do not react with each
other and can sit for years in a dry container
without mutual reaction. The types of chemi-
cals added to the epoxide to effect network
formation fall into two categories: curing
agents and catalysts. Curing agents, some-
times called hardeners, are added in
significant amounts to the epoxide and react
with it to become a part of the crosslinked net-
work. These curing agents can be aliphatic
amines, aromatic amines, or anhydrides.
Catalysts, on the other hand, are added in
extremely small amounts to cause the epoxide
molecules to react directly with each other, i.e.
to homopolymerize. Sometimes the chemicals
used as catalysts for homopolymerization can
be used for another purpose; when added in
small amounts to epoxide-curing agent mix-
tures, they will accelerate the curing reaction.
In this role they are called accelerators rather
than catalysts.
In the sections below, we discuss the chem-
ical reactions involved in network formation,
both when the different curing agents are used
and when homopolymerization occurs.
Amine curing
In amine curing agents, each hydrogen on an
amine nitrogen is reactive and can open one
epoxide ring to form a covalent bond 1-5.
General descripfion of thermoseffingsystems 49
When the amine nitrogen contains two hydro-
gens, each reacts with a different epoxide ring.
This scheme is shown in Fig. 3.1, where the
developing network is evident. This scheme
applies to both aliphatic and aromatic amine
curing agents. The reaction between epoxide
and amine produces a C-N bond, whose envi-
ronmental resistance is good, but whose
stability to elevated temperature is highly
dependent on the adjacent molecular structure.
- OH
I
CH-CH,
\ /
cH2-m-
OH
I
- I
OH
CH-CH2
/N-R-y OH
I
CH,-CH-
Fig. 3.1 Reaction scheme for the reaction between
epoxide and amine curing agent. Each hydrogen
reacts with an individual expoxide group. Thus the
primary amine group acts bifunctionally and the
secondary amine group acts monofunctionally. The
epoxide group acts monofunctionally.
From the reaction scheme, it is obvious that
the correct relative amounts of epoxide and
amine curing agent must be used. If there is ,an
imbalance, unreacted functional groups will
be present and the full properties of a com-
plete network will not be developed. The
correct amounts by weight to combine are
determined by computing the weight of cur-
ing agent that contains one chemical
equivalent of amine hydrogens and matching
that with the weight of epoxide that contains
one chemical equivalent of epoxide groups.
50 Epoxy resins

Anhydride curing functions as a catalyst to speed up the epox-

ide-curing agent reaction. (Acceleratorswill be
In anhydride curing agents, the anhydride
discussed later.) Figure 3.2 shows an idealized
groups themselves must be cleaved asymmet-
scheme, where the cleaved anhydride reacts
rically to start the r e a ~ t i o n ' ~Initial
, ~ . cleavage
with an epoxide ring carbon, opening the ring
is accomplished with the help of a small
in the process. The negatively charged oxygen
amount of accelerator,which is a chemical that
formed by the opening of the epoxide ring can
proceed to react with a different anhydride
group, perpetuating the reaction. In this ideal-
0 ized developing network, each anhydride
0-
II I group is bifunctional, i.e. it links to two differ-
NR3 (Accelerator) ent epoxide molecules. In practice, the high
temperatures required for anhydride cure, plus
C' the presence of accelerator, provides conditions
/I
0
+ for some extent of epoxide homopoly-
merization (described later) to take place,
0-
making the actual curing reaction much more
0-
I I complex than depicted in Fig. 3.2. The reaction
{c=o fC=O
between epoxide and anhydride produces pri-
marily ester linkages, which have good
L=o L += o stability to elevated temperatures and to most
+ /O\ hostile environments except bases.
Not surprisingly, the correct amount of
I anhydride curing agent relative to the epoxide
must be used to obtain a well developed net-
CC'O Cc=O
work and the associated good properties. The
L += o 'C= 0
+ correct amounts by weight to combine are esti-
mated by examining the reaction scheme and
0- 0- computing the weight of curing agent needed
I I to react completely with a given weight of
c= 0 epoxide. The simplified reaction scheme of
Fig. 3.2 proposes that one anhydride group
I
LI o reacts with two epoxide groups and one epox-
0 0 ide group reacts with two anhydride groups,
I I
o-cH~-c------c-cH*-o making the number of anhydride groups con-
I I sumed equal to the number of epoxide groups
c= 0 c= 0 consumed in the reaction.
(c=o
+ L + O
Catalytic curing (homopolymerization)
The remaining route to formation of a
crosslinked network from epoxide molecules
Fig. 3.2 Simplified reaction scheme for the reaction
requires homopolymerization'4~7.This can be
between epoxide and anhydride curing agent. After
cleavage, each anhydride group reacts with two brought about if small amounts of certain
epoxide groups and each epoxide group reacts with Lewis acids or Lewis bases are added. These
two anhydride groups. Thus both the epoxide operate as true catalysts by initiating a self-
group and the anhydride group act bifunctionally. perpetuating cationic (Lewis acid) or anionic
 Constituents used in formulated systems 51

/O\ +
R3N -I-CH2-m- +R,NCH2-CH-a2-
I
0-

/O\
CH2-CH- +
+ R3NCH2- CH- CH2-
I
P
cH2-CH-
I
0-
Fig. 3.3 Reaction scheme for the homopolymerization of epoxide. After ring opening, each epoxide group
reacts with two other epoxide groups. Thus the epoxide group acts bifunctionally.

(Lewis base) polymerization. A simplified 3.3 CONSTITUENTS USED IN FORMULATED

reaction scheme initiated by a Lewis base is
shown in Fig. 3.3. Homopolymerization
results in the formation of a network of ether
linkages, which has outstanding elevated-tem-
perature stability and resistance to hostile
environments.
SYSTEMS
3.3.1 EPOXIDES
Although many different types of epoxides are
available, only a few are favored for use in
matrices in fiber compositess-lO.These are
shown in Table 3.1.

Table 3.1 Structures and characteristics of commonly used epoxides

Epoxy equivalent Viscosity at 25"C, Comments
weighf, g/eq Pa s (cP)

Diglycidyl ether of bisphenol A (DGEBA)

171-177 3.5-5.5 May crystallize on storage.

(3500-5500) Example: DER 332 (Dow).
180-188 6.5-9.6 Contains small amount of higher polymer
(6500-9500) to prevent crystallization.Examples: DER 330
(Dow) Epon 826 (Shell).
185-200 10.0-19.0 Contains small amount of higher polymer to
(10 000-19 000) prevent crystallizalion.
Example: Epi-Rez 510 (Hi-Tek Polymers),
DER 331 (Dow), and GY 6010 (Ciba).
450-550 Melting point n = 2; used in prepregs. Examples: Epon 1001
65-76°C (149-167°F) (Shell)and DER 661 (Dow).
52 Epoxy resins

Table 3.1 Continued

Epoxy equivalent Viscosity at 25"C, Comments

weight, g/eq Pa s (cP)

Diglycidyl ether of bisphenol F (DGEBF)

/O\ /O\
CH2- CH- CH2- 0 0 - CH2 -CH- CH2

158-165 5.0-8.0 Isomeric mixture that will not crystallize on

(5000-8000) storage. Example: GY 281 (Ciba).

Polyglycidyl ether of phenol-formaldehyde Novolac

172-179 1.l-1.7 (1100-1700) Example: DEN 431 (Dow).

at 52°C (126°F)
176-181 20.0-50.0 (20 000-50 000) Example: DEN 438 (Dow).
at 52°C (126°F)
191-210 4.0-10.0 (4000-10 000) Example: DEN 439 (Dow).
at 52°C (126°F)

Polyglycidyl ether of o-cresol-formaldehyde Novolac

200 Melting point Used for high-temperature service: R represents

35°C (95°F) chlorohydrins, glycols, and/or polymeric ethers.
Molecular weight = 540. Example: ECN 1235
(Ciba).
225 Melting point Same as above, but molecular weight = 1080.
73°C (163°F) Example: ECN 1273 (Ciba).
230 Melting point Same as above, but molecular weight = 1170.
80°C (176°F) Example: ECN 1280 (Ciba).
235 Melting point Same as above, but molecular weight = 1270.
99°C (210°F) Example: ECN 1299 (Ciba).
 Constituents used in formulated systems 53

Table 3.1 Continued

Epoxy equivalent Viscosity at 25"C, Comments

weight, g/eq Pa s (cP)

N, N, N', N', - Tetraglycidyl methylenedianiline

117-133 10.0-15.0 (10 000-15 000) Used for prepregs. Example: MY 720 (Ciba).

Triglycidyl p-aminophenol
/O\
O-CH2-CH- CH2
I

I
/O\ / N\ /O\
CH2-CH-CH2 CH2-CH- CH2
95-107 0.55-0.85 (550-850) Used extensively for prepregs and adhesives.
Example: MY 0510 (Ciba).

Conspicuously, these epoxides all contain aro- achieve cure with amine curing agents fall in a
matic rings in their structures. Aromatic rings wide range, from 25°C to nearly 200"C,
confer mechanical rigidity and thermal stabil- depending on the chemical structure of the
ity to the crosslinked network. It is also worth amine. The first five entries in the table are
noting that some of the epoxides in the table aliphatic amines, which can cure epoxides at
have two epoxide functional groups, while room temperature or only slightly above.
others have three or four or more. Whether a Aliphatic amine-cured systems also tend to
network is developed by mixing the epoxide have low glass transition temperatures, T , (the
with a curing agent or is developed from epox- temperature at which the mechanical behavior
ide alone by catalytic homopolymerization, a changes from rigid to rubbery) and cannot be
large number of the molecules in a given for- used in composites that will experience high
mulation must be able to react with more than temperature use.
two other molecules in order to form a Most other entries in the table are aromatic
crosslinked network instead of merely form- amines, whose ring structures confer solidity
ing linear chains. and mechanical rigidity. These amine curing
agents require elevated temperature cure, but
the networks they produce have high glass
3.3.2 AMINE CURING AGENTS
transition temperatures and are suitable for
Table 3.2 presents commonly used amine cur- use in composites that will be exposed to ele-
ing agents. The temperatures required to vated temperatures in service.
54 Epoxy resins

Table 3.2 Structures and characteristics of commonly used amine curing agents

Amine hydrogen Viscosity at 25°C (77"F), Comments

equiv. weight, gleq Pa s (cP)

Diethylenetriamine (DETA)

HzN-CH2-CH2-NH- CH2-CH2 -NH2

20.6 0.00554.0085 Available from Dow as DEH 20.

5.5-8.5)

Triethylenetriamine(TETA)

H2Nf (CH2)z-NH CH2-CH2 -NH;!

24.4 0.020-0.023 Available from Dow as DEH 24.

(20-23)

Diethylaminepropylamine (DEAPA)

CH3- CH2,
- (CHZ)3- NH2
CH3- CH2
65 50 Available from Union Carbide.
(5000)

Tetraethylenepentamine(TEPA)

26-27 0.055 Available from Dow as DEH 26.

(55)

Aliphatic polyether triamine (APTA)

H2C f-0 - CH2- CH-(CH3) NH2

I
CH3 - CH2 - C - CH2 f-0 -CH2- CH-(CH,) NH2
Y
I
H2C f-0 - CH2- CH-(CH3) %NH2
77-82 0.072-0.080 x + y + z = 5.3. Available from Texaco as
(72-80) Jeffamine T 403.
 Constituents used in formulated systems 55

Table 3.2 Continued

Amine hydrogen Viscosity at 25°C (77"F), Comments

equiv. weight, g/eq Pa s (cP)

4,4'-Methylenedianiline (MDA)

50 Melting point Available from Ciba as HT 972 and from

89°C (192") Pacific Anchor as Ancamine DDM.

rn-Phenylenediamine (MPDA)
NH2
I

27 Melting point Available from E.I. duPont de Nemours &

60°C (140°F) Company.

44' -Diaminodiphenylsulfone (DDS)

0

62 Melting point 170-180°C Used mainly in prepregs; yields good shelf life and
(338-356°F) high-temperature properties. Available from
Ciba as HT 976.

3,3' -Diaminodiphenylsulf one

0

P- .S
It
I1
0

62 Melting point 174178°C Used mainly in prepregs; reacts more slowly than
(345-352°F) 4,4' analog. Available from Ciba as HT 9720.
56 Epoxy resins

Table 3.2 Continued

Amine hydrogen Viscosity at 25°C (77"F), Comments

equiv. weight, gleq Pa s (cP)

40% MPDA-60%MDA

38 1.50 Eutectic mixture. Available from UniRoyal

(1500) as Tonox 60-40

Dicyandiamide (DICY)

28 Melting point 207-209°C Slow reacting. Used for prepregs. Available from
(405408°F) Cytec Ind.

3.3.3 ANHYDRIDE CURING AGENTS Elevated temperature, typically in the range

Table 3.3 presents commonly used anhydride 100-200°C, is required to achieve cure with
curing agents. Their structures vary widely anhydride curing agents. The glass transition
and some are liquid at room temperature temperatures of anhydride-cured systems are
whereas others must be heated to liquefy. high.

Table 3.3 Structures and characteristics of commonly used anhydride curing agents

Anhydride equiv. Melting point, "C ("F) Comments

zueigkt, g/eq

Phthalic anhydride (PA)

148 130 (266) Available from Amoco.

 Constituents used in formulated systems 57

Table 3.3 Continued

Anhydride equiv. Melting point, "C ( O F ) Comments

weight, g/eq

Hexahydrophthalic anhydride (HHPA)

154 40 (104) Available from Pacific Anchor as Ancadride

MHHPA and from Ciba as HT 907.

Nadic methyl anhydride (NMA) maleic anhydride adduct of methyl cyclopentadiene

180 Liquid at 25°C (77°F) Widely used for prepegs. Available from Pacific
(0.200 Pa s) 200 cP Anchor as Anhydride METHPA and from
Ciba as HY 906.

Dodecenyl succinic anhydride (DDSA)

270 Liquid at 25°C (77°F) Available from Dixie Chemical and from
(0.200 Pa s) 200 cP Humphrey Chemical.
58 Epoxy resins

Table 3.3 Continued

Anhydride equiv. Melfing point, "C ( O F ) Comments

weight, g/eq

Chlorendic anhydride (CAI

371 231-235 Needs no cure accelerator, but is high melting and

(448445) hard to handle; good fire retardant. Available
from Velsicol.

Trimellitic anhydride (TMA)

,o

\\
0

193 161-1 64 Available from Buffalo Color.

(322-327)

Maleic anhydride (MA)

\\
0

100 53 (127) Available from Amoco.

Succinic anhydride (SA)

/p

l0
100 120 (248) Available from Buffalo Color.
 Constituents used in formulated systems 59

Table 3.3 Continued

Anhydride equiv. Melting point, "C ( O F ) Comments

weight, g/eq

Methyltetrahydrophthalicanhydride

166 Liquid at 25°C (77°F) Available from Lindau.

(0.06 Pa s) 60 cP

3,3', 4,4' - Benzophenone-tetracarboxylicdianhydride (BTDA)

0
0 II 0
\\
o/c~cy&o
C
'
// \\
0 0
161 221 (430) Used mainly in powder coatings; when used as
minor component in fiber composite matrix, it
improves high-temperature properties.Available
from Allco.

3.3.4 CATALYSTS FOR useful in prepregs that must be stored for

HOMOPOLYMERIZATION some time without cure advancement prior to
being used in fabrication of a structural com-
Table 3.4 presents some Lewis acids and Lewis
ponent.
bases that have been found effective as cata-
lysts for homopolymerization of epoxides.
Certain Lewis acids, such as boron trifluoride 3.3.5 ACCELERATORS FOR CURING AGENT
(BF,) produce rapid and very exothermic SYSTEMS
homopolymerization and need to be used in
blocked form. BF,, when blocked with Some Lewis acids and Lewis bases can also be
used as accelerators in epoxide-curing agent
monoethyl amine to form the complex
mixtures to speed up a sluggish reaction. They
BF,MEA, is latent at room temperature and
are added in small amounts, only a few weight
becomes active only above 90"C, the tempera-
per cent, empirically determined to give the
ture at which the complex separates. The
best results. Most often they are used to speed
epoxide homopolymerization that occurs
up the curing reaction in epoxide-anhydride
above 90°C is rapid, but has controllable
systems. Table 3.4 indicates which catalysts are
release of heat. Epoxides containing blocked
also used as accelerators and lists additional
Lewis acids as catalysts have been found to be
chemicals used as accelerators only.
60 Epoxy resins

Table 3.4 Structures and characteristics of commonly used catalysts and accelerators

Amine hydrogen Melting point, "C ( O F ) Comments

equiv. weight, g/e9

Benzyldimethylarnine (BDMA)

- Liquid at 25°C (77°F) Lewis base used as an accelerator mainly for

(0.1 Pa s, 100 cP) anhydride mixtures. Avalible from Ciba
as DY 062.

2,4,6-Tris(dimethylaminomethyl)phenol

Liquid at 25°C (77°F) Lewis base used as an accelerator for epoxide

(0.3Pa s, 300 cP) anhydride mixtures to provide room-temperature
cure. Available from Rohm & Haas as DMP-30 and
from Ciba as DY 064.

2-Ethyl-4-methylimidazole (EMI)

CH3- CH2 - C CH
\ /
N
H
Liquid at 25°C (77°F) Lewis base used as an accelerator for epoxide-
(4-8 Pa s, 4000-8000 cP) anhydride mixtures to provide long pot life and
good elevated-temperature properties. Available
from Air Products as EMI-24.
 Constituents used in formulated systems 61

Table 3.4 Continued

Amine hydrogen Melting point, "C ( O F ) Comments

equiv. weight, g/eq

Boron trifluoride-monoethylene amine (BF,MEA)

F
I
F -B:NHz- CH2- CH,
I
F
85-90 (185-194) Blocked Lewis acid; used as an accelerator for
epoxide DDS systems in high temperature
service; provides latency. Available from ATOTech.

3.3.6 DILUENTS epoxide groups. Some of these diluents are

monofunctional, i.e. have only one epoxide
For some types of processing the viscosity of
group, so they cannot form crosslinks in the
the uncured resin system needs to be lowered.
network like bi-, tri- and tetrafunctional mole-
When it is not advisable, as in the case of wet
filament winding or hand lay-up, to use cules do. However, by chemically attaching to
volatile solvents as diluents, reactive diluents the network, the reactive diluents become a
permanent and stable part of it. Other diluents
must be used. Table 3.5 lists some acceptable
are bifunctional and will form crosslinks.
diluents, all low viscosity liquids containing

Table 3.5 Structures and characteristics of commonly used, commerciallyavailable epoxide reactive dilutents

Epoxy equivalent Viscosify at 25"C, Comments

weight, g/eq Pa s (cP)

Butyl glycidyl ether (BGE)

/O\
CH3-(CH2)3 -0 - CH2- CH-CH2

130-149 0.002-0.003 Example: RD-1 (Ciba).

(2-3)

Octyl, decyl glycidyl ether blend

/O\
CH3-((CH2)7 - 0 - CH2- CH- CH2

215-235 0.005-0.015 Example: Epotuf 37-057 (Reichhold) and Dy 027

(5-15) (Ciba).
62 Epoxy resins

Table 3.5 Continued

Epoxy equivalent Viscosity at 25"C, Comments

weight,g/eq Pa s (cP)
___ ~~ . _ _ _ _ ~ ~

p - t - Butyl phenyl glycidyl ether

CH3
/O\
0 - CH2 - CH- CH2
I -

220-245 0.015-0.30 Example: Epi-Rez 5014 (Hi-Tek Polymers).

(15-30)

Phenyl glycidyl ether (PGE)

/O\
0 - CH2 -CH-CH2

150 0.006 Example: Heloxy WC-63 (Wilmington Chemical).

(6)

Cresyl glycidyl ether (CGE)

170-190 0.005-0.050 Less volatile than BGE. Example: Epotuf 37453

(5-50) (Reichhold), and by DY 023 (Ciba).

Diglycidyl ether of 1,4 - butanediol (BDE)

12@140 0.010-0.025 Example: RD-2 (Ciba); not a pure compound.

(10-25)
-~ _____ ~- ~~~~ ~~ ~-
 General principles of formulation 63

Table 3.5 Continued

Epoxy equivalent Viscosity at 25°C’ Comments

weight, g/e9 Pa S ( c ~ )
~

Diglycidyl ether of neopentyl glycol

CH3
13CL145 0.005-0.015 Example: AZ epoxy N (AZS Corp.);not a pure
(5-15) compound.

Diglycidyl ether of polypropylene glycol

r 1

175-205 0.30-0.060 (30-60) n = 4. Example DER 736 (Dow).

305335 0.55-0.100 (55-100) n = 9. Example DER 732 (Dow).

Vinyl cyclohexene dioxide

/O\
A CH - C H ~
O ’ W
76 0.20 Example ERL 4206 (Union Carbide).
(20)

3.4 GENERAL PRINCIPLES OF

FORMULATION
Epoxy resin systems must be formulated on a
rational basis and the chemical structure of the
constituents forms this basis. Many detailed
structure-property relationships can be
reduced to rules of thumb and some of those
we present in this section. The reader should
use these with caution, because often a more
detailed examination of the chemical structure
reveals conflicting trends and experimentation
is needed.
First, the presence of significant amounts of
aliphatic segments in the chemical structure of
the cured network results in lower rigidity and
lower Tg as compared to aromatic rings, or
even saturated rings. Thus, aromatic amine-
cured systems or homopolymerized systems
both have high stiffness and high Tg. whereas
an aliphatic amine-cured system will have a
lower stiffness and lower T,.
In terms of processing and cure, the flexibil-
ity and mobility of aliphatic segments imparts
low viscosity (if a liquid) or low melting point
(if a solid). Constituents whose structures are
mainly aliphatic react rapidly at room temper-
ature. Thus, an aliphatic amine-cured system is
recommended over an aromatic amine-cured
64 Epoxy resins
system if low viscosity for processing and a
room temperature cure are needed1’,12.
Constituents with aromatic ring structures
react sluggishly or not at all at room tempera-
ture13J4.Thus aromatic-amine cured systems
require elevated temperature cures.
As cited earlier in the discussion on cure
reactions, the relative amount of curing agent
to epoxide is important in achieving a well-
developed network. The formulations
presented in Table 3.6 are approximately what
would be used for some specific epoxide-curing
agent formulations. The reader should verify
the correctness of the formulations by comput-
ing the appropriate weight ratios from the
molecular structures given in Tables 3.1, 3.2
and 3.3.
Table 3.6 Formulations for selected epoxy resin
systems
Constituents Epoxide Curing agent
PbV Pbw‘
Diglycidyl ether of
bisphenol A triethylene
tetramine 100 14
Diglycidyl ether of
bisphenol A rneta-
phenylene diamine 100 16
Diglycidyl ether of
bisphenol A
hexahydrophthalic
anhydride 100 90
Parts by weight
Finally, through the chemistry of the constituents
and the network they form, the formulation
d u e n c e s the environmental resistance of the
resin. Thus the formulation must be selected
with the future environmental exposures in
mind. Figure 3.4 compares the environmental
resistance of four important types of epoxy resin
systems: aliphatic amine-cured,aromatic amine-
cured, homopolymerized epoxide (BF,MEA
catalyst) and anhydride-curedI5. The excellent
resistance of the crosslmked network is evident
in all but a few cases; the anhydride-cured sys-
tem is degraded in strong base due to basic
hydrolysis of its ester linkages and both the
anhydride-cured and the homopolymerized sys-
tems are vulnerable to swelling by the strong
solvent, trichloroethylene.
3.5 PROCESSING CONSIDERATIONS IN
EPOXY RESIN COMPOSITES
The goals of the processing procedures used to
make a good quality fiber composite are to
ensure that the resin forms a void-free contin-
uous phase, surrounds each filament, is evenly
distributed, is present in the desired amount
relative to the fiber and is fully cured. The ease
with which these goals can be achieved is
highly dependent on the rheological proper-
ties of the resin as it progresses through its
cure and on the engineer’s ability to evaluate
rheology and degree of cure throughout the
processing cycle.
In the early years of epoxy resin technol-
ogy, processing procedures were developed
by a trial and error approach. This is still a
viable approach, especially for engineers
skilled in the art of thermoset composite pro-
cessing. However, in recent years,
rheologica116-18 and chemorheologica119~20
models that relate viscosity, rigidity and
degree of cure to time and temperature have
been developed. These models predict rheo-
logical changes during cure and can serve as
an aid to processing and cure cycle develop-
ment.
3.5.1 PROCESSING VARIABLES EARLY IN CURE
One of the major concerns in the early stages
of composite processing is resin viscosity.
Sometimes, the freshly mixed, uncured resin
formulation is inherently fluid enough to pen-
etrate the fiber bundle and surround each
filament. (Tables 3.1, 3.2 and 3.3 give viscosity
values for several epoxides and curing
agents.) Often, however, the viscosity of the
uncured resin system is too high and must be
 Processing considerations in epoxy resin composites 65

100

75

50

ae
I 25
lm
n
.-C
VI
c1

9 0
$ Sodium hydroxide, 50% Sulfuric acid, 25% Hydrochloric acid, 25%
0 82°C (180°F) 82°C (180°F) 82°C (180°F)
L
E+
0
C
.-c0
C
W
w
E
-c3
c

i
0 100

-E
2
; 75
-
U
W

50

25

0
Distilled water Trichloroethylene Sodium hypochlorite, 6%
54°C (13CPF) 54°C (130°F) 54°C (130°F)
Exposure conditions

Fig. 3.4 Environmental resistance of common cured epoxy systems as indicated by flexural modulus reten-
tion after environmental exposure Is.
Aliphatic amine-cured (TETA),
Aromatic amine-cured (MPDA), @
reduced to achieve the desired flow require-
ments. The two major approaches to reducing
viscosity are thinning the mixture with low
viscosity organic solvents and adding low vis-
cosity reactive diluents, such as those
presented in Table 3.5.
Thinning with organic solvents, although
Homopolymerized (BF,MEA),
Anhydride-cured (PA), mrm
the simplest approach, can result in bubble or
void formation within the composite if the
solvent cannot escape completely. This could
be a problem for component fabrication by
wet filament winding, where layers contain-
ing the freshly mixed epoxy resin system are
placed sequentially on top of one another.
66 Epoxy resins

Filament winding processors do not use sol-
vents to reduce viscosity, rather selecting
lower viscosity resins, reactive diluents, or
diluting with heat. On the other hand, the use
By contrast, reactive diluents, being them-
selves epoxides, chemically react to become a
permanent part of the crosslinked network.
Figure 3.5 shows the relation between L'1SCOS-
'

of small amounts of solvent to reduce resin
viscosity during fabrication of prepreg
(pre-impregnated fiber) presents no prob-
lems, since prepreg is made in the form of
single, thin-layer sheet, tape or tow from
which solvent can vaporize easily and the
prepreg is heat treated to eliminate solvent
and to advance cure.
ity and the amount of diluent added to a
viscous epoxide. Ideally, the engineer wants to
use just enough diluent to lower viscosity as
needed without dramatically altering the
properties of the final cured network.
The length of time that an epoxy resin for-
mulation remains fluid is important.
Liquid-like flow becomes impossible once the
gelation stage, marked by an abrupt increase
in viscosity, is reached. Time to gelation is
called gel time, or sometimes pot life.

A
- 'T
1100
Aliphatic amine curing agents produce pot
lives of the order of minutes or a few hours,
while aromatic amine curing agents produce
pot lives of 24 h or more13,22,23.
Anhydride cur-
ing agents typically produce very long pot
- lives (e.g. two months for NMA) when mixed

- --
m with epoxides. This is because, as already
IS00
i
.- mentioned, the anhydride group is not very
ln
0
1100
reactive with epoxides unless it is cleaved with
, -
0
.-
ln
1100 the aid of an accelerator molecule. Once the
1000 - accelerator is activated, the pot life of the mix-
ture will be shortened to a few hours. Pot life
eo0 - can be controlled over a wide range by careful
800 - use of accelerators.
700 - Each resin formulation has a unique chem-
istry that imparts a set of processing variables
600 - with unique values. Standard laboratory test
500 - methods for processing variables that are
important early in cure are described by the
400 - American Society for Testing and Materials,
$00 - Philadelphia, Pennsylvania.ASTM numbers of
zoo - the procedures for determining resin viscosity,
gel time and melt flow are listed in Table 3.7.
100 -
I
0
l
lll
lrl
l
10
llTable 3.7 Laboratory test methods for measuring
20 30 40 SO 60 70 80 90 IOC

DILUENT, 'Io processing variables

Processing variable Reference

-
Fig. 3.5 Viscosity versus per cent of diluent in epox-
ide-diluent mixturesz1.The epoxide is DGEBA and Viscosity ASTM D2393
the diluent is BDE (diglycidyl ether of 1, 4-butane time (pot life) ASTM D2471
diol). Melt flow ASTM D3795, ASTM D4473
 Processing considerations in epoxy resin composites 67
3.5.2 MONITORING OF CURE
Once the cure is underway in an epoxy resin
system, all of the properties of the system
change rapidly until the final crosslinked net-
work is reached. Not only is flow decreasing
and rigidity increasing, but all other properties
(electrical, chemical, optical, etc.) are chang-
ing. When the curing epoxy resin system is
subjected to temperature and pressure
changes, the resin response will be characteris-
tic of its degree of cure at that moment. Cure
cycle events, such as temperature and pressure
changes, need to be carefully timed with this
in mind.
The degree of cure can be defined in terms
of any one of a large number of chemical or
physical (including mechanical) properties that
change continuously during the curing reac-
tion and reach a constant value at end of the
cure. Evaluation of the degree of cure is usually
based on one of these properties and full cure
is then defined as the point at which this
selected property reaches a constant value.
Originally, the only available methods for
evaluating cure were off-line laboratory meth-
1.24
1.22 -
+
1.20 -
$$ + s t + + $ + +
1.18-
\El
s 1.16 -
.-
c
v)
1.14-
Fig. 3.6 Specific gravity compared with cure time for an aromatic amine-cured epoxy system cured at
120°C26. Volume reduction (densification) during early network formation is rapid and levels off as cure
nears completion.
ods where samples were taken and tested at
intervals in the cure cycle. The time needed to
develop one data point depended on the par-
ticular laboratory method. Off-line testing has
been made more convenient with the develop-
ment of continuous monitoring techniques
(i.e. data points in real time) used on small
dedicated specimens of resin or prepreg.
Recently, real time, in situ methods where cure
can be monitored in the composite structural
component itself have been developed.
Traditional off-line methods
Intermittent off-line methods include chemical
titration of the unreacted epoxide groups pre-
sentz4jz5, specific gravity to measure
densificationzh and differential scanning
calorimetry to measure the residual cure
e~otherm*"~ Figure
~ ~ ~ ~3.6
* .shows a plot of spe-
cific gravity data obtained on specimens cured
for increasing lengths of time at a single tem-
perature. Figure 3.7 shows differential
scanning calorimeter scans for two epoxy resin
specimens of the same formulation, but with
different degrees of cure.
+ +
 Exotherm
A
. I
I I
I I
1 I

Energy
calls

1
Endotherm . I I I I I I I

Fig. 3.7 Differential scanning calorimeter scans for an epoxy resin system28.Scans for two different speci-
mens, each having a different original degree of cure, are shown, with scan A displaced upward from
scan B for graphical visibility. The height of the residual cure exotherm is inversely related to the original
degree of cure. The higher exotherm peak in B indicates an original degree of cure lower than in A.

Continuous off-line methods include infrared
s p e c t r o s ~ o p y ~ ,parallel
~ ~ , ~ ~ , plate-type bulk
diele~trornetry~’,~~ and dynamic mechanical
~ ” ~ . 3.8 shows the results
s p e ~ t r o m e t r y ~Figure
of infrared monitoring for five different neat
resin specimens, each cured at a different tem-
perature and Fig. 3.9 shows data obtained by
bulk dielectrometry.
The off-line methods, real time or not, are
useful for developing a cure schedule for a
new epoxy resin formulation, for optimizing
processing variables and for quality control of
incoming resins or prepregs. They have also
been used successfully for the development of
mathematical models of cure kinetics.
However, because they are off-line, they can-
not be used for process control.

Fig. 3.8 Degree of cure compared with time for an aromatic amine-cured epoxy systemz8.Data for five
specimens, each cured at a different temperature, are presented.
 Property data for cured epoxy resin systems 69

200 I 1
.1
I f f
I f
1
Decreasing molecular dipole mobility

150 Temperature profile - t

I
I \
0
I
-I
I

increasing molecular dipole mobility

w 100 er; elevation - %r
E C
.-c
0

--------
P
E m
F .-n
.-
v)

I-
v)

50
No further
cure at
temperature

0 I 1 I

0 2 4 6 8
Time - h
Fig. 3.9 Bulk dielectrometry data compared with time for an aliphatic amine-cured epoxy system28.
Dissipation factor (dashed line) is inversely related to rigidity in the developing network. The applied tem-
perature is shown by the solid line.

Modern in situ methods Other examples of in situ monitoring are

In situ methods for cure monitoring are real
time methods that require sensors small
enough to implant and leave in the composite
itself. When the information from in situ mon-
itoring is used as continuous input to an
appropriate process model, it can be used in
process control loops that adjust the process-
ing conditions automatically.
One example of an in situ method is low fre-
quency dielectrometry using a very small
assembly of interdigitated electrodes called a
fringe field sensor. This technique measures
changes in ability of permanent dipoles within
the resin chemical structure to align themselves
with the applied oscillating electric field and
also measures changes in the mobility of ions
present as impurities in the resin3941.Both of
these quantities correlate with resin viscosity in
the early stages of cure and with mechanical
rigidity in the later stages of cure39,40,42.
based on fluorescence spectroscopy of tag
molecules in the resin43,44 and on infrared45,46
and Raman47spectroscopies of the resin mole-
cules themselves. In these methods, optical
fibers are the sensors that transmit the appro-
priate wavelength of light into the curing resin
and also transmit the spectral information
back The spectral changes relate directly
to the chemical changes that occur as the cur-
ing reaction progresses to completion.
3.6 PROPERTY DATA FOR CURED EPOXY
RESIN SYSTEMS
Property data for cured, unreinforced epoxy
resin systems are needed for two purposes.
First, they are useful when selecting the best
fiber and matrix combination for a particular
application. Resin system choices can be
rapidly narrowed down to a few alternatives
70 Epoxy resins

when comparisons of key properties are made and many other properties of the composite can
from existing data tables or manufacturers’ be computed in advance, if one has the corre-
data sheets. sponding values for the fiber and the matrix.
Second, epoxy resin data are required in Tables 3.8, 3.9 and 3.10 present property
micromechanics computations of composite data for three major resin systems: aliphatic
properties. Elastic constants, thermal expansion amine-cured, aromatic amine-cured and anhy-
coefficients, moisture absorption coefficients, dride-cured. Property data for commonly used
Table 3.8 An aliphatic amine-cured epoxy resin system, room-temperature curable1228

Resin system constituents Parts by weight

Epoxy: DGEBA, eg., DER 332 (Dow) 100
Curing agent: APTA, e.g. Jeffamine T-403 (Texaco) 45
Cure cycle: 16 h at 60°C (140°F)for improved properties over room temperature cure
Viscosity at 25°C (77°F) Heat distortion temperature at
0.8 Pa s (800 cP) 1820 kPa (264 psi) 62°C (144°F)
Density of cured resin at 25°C (77°F) Coefficient of linear thermal expansion
1.16 g ~ m - ~ from 298 to 374 K 66x “C-’
Volumetric shrinkage Average specific heat from
After gelation 4.4% l
’ 286 to 367 K 1.75~10~Jkg-lK~~
After cure 4.4%
Coefficient of thermal conductivity
Water absorption, wt. gain after 2 h in At 298 K 0.133 W m-’ K-’ a
boiling water 0.75% a At 318 K 0.174 Wm-’ K-’ a

At 336 K 0.210 W m-l K-’

Impact strength
(Izod notched bar test)
Shear properties
Failure stress
Modulus of elasticity
Tensile properties
Modulus of elasticity
11.0 J m-’ of notch Compressive properties
Modulus of elasticity
3.48 GPa (504 ksi)
61 MPa (8.85 ksi)
1.27 GPa (184 ksi)
3.24 GPa (470 ksi)

120 I I I I
Cures: 16
._
r 16 h @ 60°C 4 m
Y

0
0 1 2 3 4 5 0 0.8 1.6 2.4 3.2 4.0

Tensile strain % Compressive strain %

~~ -~ ~~~ __

a Cured for 24 h at 60°C (140°F) + 24 h at 77°C (171°F).

 Property data for cured epoxy resin systems 71

Table 3.9 An aromatic amine-cured epoxy resin systemI3

Resin system constituents Parts by weight

Epoxy: DGEBA, e.g. Epon 826 (Shell) 100
Diluent: BDE, e.g. RD-2 (Ciba-Geigy) 25
Curing agent: MDA-MPDA eutectic, e.g. Tonox 6 0 4 0 (UniRoyal) 29
Cure cycle: 3 h at 60°C (140°F) + 2 h at 120°C (248°F)
Viscosity at 25°C (77°F) Water absorption, wt. gain
after 6 h in boiling water 0.93%
1.2 P a s (1200 CP)
Glass transition temperature
Time to reach 2.0 Pa s 6h
130°C (266°F)
Gel time for a 30-g mass at
25°C (77°F) 23 h Heat distortion temperature at
1820 kPa (264 psi) 121°C (250°F)
Density at 25°C (77°F)
Uncured 1.15 Mg m-3
Cured 1.21 Mg m-3 Coefficient of linear thermal expansion
from 298 to 3755 K 6.81 x 10-5oc-1
Volumetric shrinkage
After gelation 3.7% Specific heat
After cure 5.4% At 363 K 1.54 x lo3J kg-' K-'
At 424 K 1.71 x lo3J kg-'K-'
Tensile properties
Modulus of elasticity 2.68 GPa (389 ksi) Coefficient of thermal conductivity
At 325 K 0:243 W m-' K-'
At 356 K 0.244 W rn-' K-'
100 I I I I - 14 At 389 K 0.256 W m-'K-'
Shear properties
80 Failure stress 52 MPa (7.54 ksi)
- 10 Compressive properties
._ Maximum stress 111MPa (16.1 ksi)
h
H
60
- 8 %
VI
Strain at maximum stress 8.0 %
In
VI VI
E
Modulus of elasticity 2.9 GPa (420 Ksi)
E - 6 G
5 40

- 4
20
- 2

0
0 2 4 6 a io-
Strain YO

epoxy resin formulations are often available
from resin suppliers. Data for new or unusual
formulations must be generated by the user.
Whether the data are generated by the resin
supplier or the user, it is important that stan-
dard test procedures be followed. This will
ensure that the resin systems can be compared
on an equal basis. Where standardized test
procedures exist, e.g. as from the American
Society for Testing and Materials, they should
be followed. Where they do not exist, litera-
ture references are helpful. Table 3.11 lists
some commonly tested properties and the
standard methods (American Society for
Testing and Materials) describing the tests.
72 Epoxy resins

Table 3.10 An anhydride-cured epoxy resin systemI5

Resin system constituents Parts by weight

Epoxy: DGEBA, e.g. Epon 828 (Shell) 100
Curing agent: NMA 90
Accelerator: BDMA 1
Cure cycle: 3 h at 120°C (248°F) + 24 h at 150°C (302°F)

Viscosity at 27°C (81°F) 1.78 P a s (1780 cP)

Time to reach 100 Pa s (1000 cP) 556 days
Pot life of a 500 g mass at 23°C (73°F) 4-6 days
Heat distortion temperature at 1820 kPa (264 psi) 121°C (250°F)
Solvent absorption, wt. gain
After 24 h in boiling water 0.67%
After 3 h in boiling acetone 1.9%
Tensile properties At 23°C (73°F) At 100°C (212°F)
Maximum stress 72.4 MPa (10.5 ksi) 46.2 MPa (6.70 ksi)
Strain at maximum stress 2.7% 7.2%
Modulus of elasticity 3.45 GPa (500 ksi) 1.38 GPa (200 ksi)

Table 3.11 Standard test methods for cured epoxy resin systems

Property ASTM
Standard Method
___
Physical and chemical properties:
Specific gravity D792
Chemical resistance D543
Water absorption D570
Light and water exposure D1499
Electrical properties:
Volume resistivity D257
Surface resistivity D257
Dielectric strength D149
Dielectric breakdown voltage D149
Permittivity, dielectric constant D150
Dielectric loss D150
Thermal properties:
Heat deflection temperature D648
Glass transition temperature D4065
Coefficient of linear thermal expansion D696
Coefficient of thermal conductivity C177
Mechanical properties:
Tensile modulus and strength D638
Compressive modulus and strength D695
Flexural modulus and strength D790
Impact resistance D256
Dynamic mechanical properties:
Storage modulus D4065
Loss modulus D4065
Transition temperature D4065

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1. Lee, H. and Neville, K. Handbook ofEpoxy Resins,
Classical Re-issue, McGraw-Hill, New York,
1982.
2. Goodman, S’H. ‘Epoxy Resins’y ch’ in
Handbook of Thermoset Plastics, (S.H. Goodman,
Ed.), Noyes Publications~ Park New 19. Mijovic, J. and Ott, J. ’Modeling of chemorheol-
Jersey, 1986, pp. 132-182.
3. Tanaka, Y. and Bauer, R.S. ’Curing Reactions,‘
ch.3 in Epoxy Resins: Chemistry and Technology,
Dekkerr In‘., New
1988, pp. 285463.
4. Fischerf M.y F. and Schmid7 R’
’Struktureller Aufbau and Physikalisches 21. Product data sheet for Araldite RD-2, Ciba-
Verhalten venetzter Epoxiharze,‘ Makromol.
Chem., 1980,181,1251-1287.
5. Dusek* R. and B1ehar M. ‘Curing Of
resins: model reactions of curing with amines,’ J.
POlym. SCi., Polym. Chem. Ed., 1977~15,2393-2400.
6. Fisch, W. and Hofmann, W. ’ m e r den
Hartungsmeehanismu. der AthexY1i*arze,’ J. 23. Chiso, T.T., Jessop, E.S. and Perm, L.S.,
Polym. Sci. 1954,12,497-502.
7. Morgan, R.J. and Mones, E.T. ’Cure reactions,
netWork structure,and response Of
diamine sulfonecured tetraglycidyl
4,4‘-diamino methane epoxy matri-
ces,’ J. Appl. Polym. Sci., 1987,33,999-1020.
8. Resins and Hardeners Product Guide, Ciba-Geigy
Corporation, Hawthorne, New York, 1990.
9. Epoxy Resin Manual: Industry Edition, Dow
Chemical Company, Midland, Michigan, 1988.
10. Specification Guide for Epon and EpOnol Epoxy
Resins and Epon Curing Agents, Shell Chemical
Company, Houston, Texas, 1990.
11. Chiao/ T.T.r JessoP, E.S. and NeweYf H.A. ‘A
moderate- temperature-curab1e epoxy for
advanced composites,’ SAMPE Quart., 1975, 6, 27. Carpenter,
3842.
12. Chiao, T.T. and Moore, R.L. ‘A roOm-tempera-
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composites,’ 29th Ann‘ ‘Onf.I
PlasticslComposites Institute, SPI, Washington,
D.C., February 5-8,1974, section 16-B.
13. Chiao, T.T., Jessop, E.S. and NeweY H.A. ‘An
epoxy system for
Quart., 1974, 6,28-32.
14. Product data sheets, Ciba-Geigy, Hawthorne, 29, Damenberg, H. ‘Determination of functional
New York, 1993.
15. Epoxy Resins for Casting, Shell Chemical
Company, New York, 1967.
16. Springer, G.S., ’Resin flow during the cure of
fiber reinforced composites,’ J. Compos. Mater.,
1982,16,400410.
References 73
- - G.S. ’Heat of
17. Lee, W.I., Loos, A.C. and Springer,
reaction, degree of cure and viscosity of
Hercules 3501-6 resin,’ J. Compos. Mater.,
1982.16.510-520.
, ,
18. Springer, G.S., ‘Compaction and consolidation
of thermoset and thermoplastic composites,’
Compos. Polym,,1990, 3, 155-175,
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in advanced composites,’ J. Compos. Mater.,
1989,23,163-185.
20, Mijovic, J. and Wang, H,T, ‘Cure kinetics of neat
and graphite-fiber-reinforced epoxy formula-
tions,’ J. Appl. Polym. Sci., 1989,37,2661-2673.
Geigy, Ardsley, New York, 1979.
22. Penn, L.S. and Chiao, T.T. ‘A long pot-life epoxy
system for filament winding,’ in Proceedings of
the 7th National SAMPE Technical Conference,
Albuquerque, N~~ ~ ~October~ 14-16,i ~ ~
1975, vel. (1975), pp. 177-187.
‘Screening of epoxy systems for high perfor-
mance filament winding applications,~ in
Proceedings of the 7th National S M P E Technical
Conference, Albuquerque, New Mexico, October
1&16,1975, Val. 7 (1975), pp. 167-175.
24. Jay, R.R. ’Direct titration of epoxy compounds
and Aziridines,r ~ ~(-hem,~ 1964,
1 36,, 667468.
25. Jahn, H. and Goetzky, P.’Analysis of epoxides
and epoxy resins,, ch. 13 in E~~~~ ~ ~ ~ i
Chemistry and Technology, (C.A. May, Ed.),
Marcel Dekker, Inc. New Y’rk, 1988, pp.
1049-1087.
26. Chou, C.T. and Penn,L.S. ’Mechanism by which
an orthocarbonate reduces residual stress in a
composite,’ J. Compos. Mater., 1992,26,171-184.
J.F. and Bartels, T.T.,
’Characterization and control of composite
prepregs and adhesives,’ in Proceedings ofthe 7th
National SAMPE Technical Conference,
Albuquerque, New Mexico, October 14-16,
1975, vel, (1975),pp. 43-52.
28. Penn, L.S. and Chiao, T.T. ‘Epoxy resins,’ ch. 15
in ~ ~ n d b o oof kComposites, (George Lubin, Ed.),
Van Nostrand Reinhold, New York, 1982, pp.
57-88.
groups in epoxy resins by near infrared spec-
troscopy; SPE pans., 1963,3, 78-88.
30. Morgan, R. ’Structure-property relations of
epoxies used as composite matrices,’ Adv.
Polym, sei,, 1985, 72, 143.
74 Epoxy resins
31. Yalof, S. and Wrasidlo, W. 'Crosschecking
between dielectric measurements, DTA, and
other methods of thermal analysis in research
and production,' J. Appl. Polym. Sci., 1972, 16,
2159-21 73.
32. Delmonte, J. 'Electric properties of epoxy resins
during polymerization,' J. Appl, Polym. Sci. 1959,
2, 108-113.
33. Lewis, A. 'Dynamic mechanical behavior dur-
ing the thermosetting curing process,' SPE
Trans., 1963, 3,201-212.
34. Kreahling, R.P. and Kline, D.E. 'Thermal con-
ductivity, specific heat, and dynamic
mechanical behavior of diglycidyl ether of
bisphenol A cured with m-phenylene diamine,'
J. Appl. Polym. Sci., 1969, 13,2411-2425.
35. Arridge, R. and Speake, J. 'Mechanical relax-
ation studies of the cure of epoxy resins: 1.
Measurement of cure,' Polymer, 1972, 13,
443449.
36. Kline, D.E. 'Dynamic mechanical properties of
epoxy resins during polymerization,' J. Appl.
Polym. Sci., 1960,4, 123.
37. Babayevsky, P. and Gillham, J. 'Epoxy ther-
mosetting systems: dynamic mechanical
analysis of the reactions of aromatic diamines
with the diglycidyl ether of bispenol A,' J. Appl.
Polym. Sci., 1973,17, 2067-2088.
38. Enns, J.B. and Gillham, J.K. 'The time-tempera-
ture transformation (TTT) cure diagram:
modeling the cure behavior of thermosets,' J.
Appl. Polym. Sci., 1983,28,2567-2591.
39. Senturia, S.D. and Sheppard, N.F. 'Dielectric
analysis of thermoset cure,' Adv. Polym. Sci.,
1986, 80, 1 4 7 .
40. Day, D.R., Lewis, T.J., Lee, H.L. and Senturia,
S.D. 'The role of boundary layer capacitance at
blocking electrodes in the interpretation of
dielectric cure data in adhesives,' J. Adhesion,
1985,18,73-90.
41. Micromet Instruments, Inc., Cambridge,
Massachusetts, Technical literature, 1991.
42. Ciriscioli, P.R. and Springer, G.S. 'Dielectric cure
monitoring - a critical review,' S A M P E J., 1989,
25, 3542.
43. Sung, C.S.P., Pyun, E. and Sun, H.L.
'Characterization of epoxy cure by UV-visible
and fluorescence spectroscopy: azochromic
labeling approach,' Macromolecules, 1986, 19,
2922-2932.
44. Sung, C.S.P. and Mathisen, R. 'Cure characteri-
zation of an epoxy network by fluorescence
behavior of trans-diaminostilbene,' Polymer,
1987,28,941-945.
45. Compton, D.A., Hill, S.L., Wright, N.A. et al. 'In
situ FTIR analysis of a composite curing reac-
tion using a Mid-Infrared Transmitting Optical
Fiber,' Appl. Spectros. 1988,6,972-979.
46. Young, P.R., Druy, M.A., Stevenson, W.A. and
Compton, D.A. 'In situ composite monitoring
using infrared-transmitting optical fibers,'
S A M P E J., 1989,25,11-16.
47. Myrick, M.L., Angel, S.M., Lyon, R.E. and Vess,
T.M. 'Epoxy cure monitoring using fiber-optic
Raman spectroscopy,' S A M P E J., 1992, 28,
3742.
48. Mijovic, J., Kenny, J.M., Nicolais, L. and
Pejanovic, S. 'Present and future trends in in-
situ monitoring of processing of advanced
composites,' SAMPE J., 1992, 28, 3946.
HIGH TEMPERATURE RESINS 4
Hugh H.Gibbs

4.1 INTRODUCTION too much from their high temperature mechan-

The high temperature resins discussed in this ical properties and thermal-oxidative stability.
chapter are defined as a family of aromatic As a result of a extensive work on the part of
polyimides having glass transition tempera- polymer scientists, mostly within the USA, a
tures ( T J greater than 316°C (600°F). Other wide variety of products has been developed
resin systems such as the bis-maleimides and possessing various trade-offs between their
various aromatic thermoplastics (including processibility and properties. In writing this
lower Tg thermoplastic polyimides) are dis- chapter the author has attempted to explain the
cussed in Chapters 5 and 6 respectively. evolution of high temperature polyimides as
Over the years it has been found that the key matrix resins for advanced composites together
to achieving outstanding high temperature with a description of their processing character-
mechanical properties and thermal-oxidative istics (where available),physical properties and
stability is to have a polymer made with aro- long term high temperature performance.
matic heterocyclic repeat units where there is a
minimum aliphatic content (e.g. aliphatic C-H 4.2 CONDENSATION POLYIMIDE
and C=C groups). Such groups can contribute CHEMISTRY
to thermal-oxidative instability. Although
many types of aromatic heterocyclic polymers 4.2.1 GENERAL COMMENTS ON
are possible, one type, polyimides, has turned CONDENSATION POLYMERIZATION
out to be the most commercially successful.
The highly aromatic character achievable in Studies carried out in DuPont in the 1950s and
such polymers is the reason behind their ther- 1960s established that polyimides can be pre-
mal-oxidative stability. Also, provided that pared by the reaction of an aromatic
flexibilizinglinkages in the monomers are kept dianhydride and an aromatic diamine in a
to a minimum, the mherent rigidity of the polar solvent such as dimethyl acetamide or N-
repeat units results in the high T which is methyl-2-pyrrolidone (NMP). This is
essential if an adequate level of hi& tempera- illustrated in Fig. 4.1 for the polyimide based
ture mechanical property retention is to be on pyromellitic dianhydride (PMDA) and
achieved. 4,4'-oxydianiline (ODA). The intermediate
Over the past 25 years various strategies polyamide acid solution is the basis for
have been developed to introduce processibil- DuPont's Pyre ML@wire enamel. During the
ity into aromatic polyimides without detracting second step, the imidization of the polyamide
acid, 2 moles of water are eliminated per repeat
unit. Two other DuPont products, Kapton@
Handbook of Composites.Edited by S.T. Peters. Published polyimide film and Vespel@SP polyimide pre-
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 cision parts are also based on this chemistry.
76 High temperature resins

ti ti
Pyromellitic Dianhydnde
(PMDA)
4.4-Oxydianiline
(ODA)
i Heat
(-2H,O)
0 0 PMDAiODA Polyamide Acid n

(-solvent)

+ N : ~ ~ ; /
N ~C
' o +

II
0 0 n

PMDAiODA Polyimide

Fig. 4.1 Typical reaction sequence for a polyimide from a dianhydride and a diamine.

It turns out that the particular polyimide temperatures in excess of 100°C (212°F) are
shown in Fig. 4.1. is unsatisfactory for the pur- reached. Thus high solids monomeric solu-
pose of making prepregs for high temperature tions are possible which are ideal for
composite parts. For one thing the prepregging. If, on the other hand, the dianhy-
PMDA/ODA polyimide is too intractable, dride is the commercially available starting
having no detectable T , or melting point material then it must be converted in situ to
below its decomposition temperature which is the open ring diester diacid form by prereact-
well in excess of 500°C (932°F).In addition, the ing with an alcohol such as ethanol or
polyamide acid solutions which are immedi- methanol.
ately generated by dissolving the diamine in a
suitable solvent and then adding the reactive
4.2.2 CHEMISTRY OF SKYBOND'
dianhydride, are unsuitable for prepregging.
Ideally monomeric solutions are preferred that Skybond from Monsanto is a product which
possess modest viscosities even when the has been available commercially since the
solids contents are in the 50-60 wt.% range. mid-1960s. The chemistry of Skybond is illus-
This desired combination of properties cannot trated in Fig. 4.2. The relatively low cost
be achieved in polymeric solutions such as dianhydride, 3,3',4,4'-benzophenonetetracar-
polyamide acids. Instead, the solutions boxylic dianhydride (BTDA), is first
rapidly become unacceptably viscous when prereacted with ethanol using NMP as the sol-
solids contents in excess of 15-20% range are vent. Then, if m-phenylenediamine (MPD) is
reached thus making them too difficult for added to the solution, Skybond 700 results. If
prepregging using commercially available 4,4'-methylenedianiline (MDA) is employed,
equipment. then Skybond 703 is produced. During cure
In order to prepare polyimide binder solu- the application of heat causes the elimination
tions (or polyimide precursor solutions as they of the solvent along with 2 moles of water and
are sometimes called) it is necessary to have 2 moles of ethanol per repeat unit to produce
the aromatic dianhydride in either one of the the polyimide. The molecular weight initially
two possible open ring forms (tetraacid or achieved will depend on the monomer imbal-
diester diacid). If the tetraacid form is com- ance employed. It has long been speculated
mercially available then the binder solution that during the cure process branching can
can be made directly because there is essen- occur by the reaction of amine end-groups
tially no reaction with the diamine until with the bridging carbonyl group of the BTDA

3,3',4,4'-benzophenonetetracarboxylic
dianhydride
BTDA
I BTDE
1 m-phenylene diamine
Skybond700
Fig. 4.2 Chemistry of SkybondO binder solutions.
moiety leading to branching and intractability
of the matrix resin. This is probably one of the
reasons why it is difficult to fabricate low void
composites using this type of chemistry.
4.2.3 CHEMISTRY OF NR-150
The formation of DuPont's monomeric binder
solution NR-150 (used to make Avimid@N
prepreg) is illustrated in Fig. 4.3. The
2,2-bis(3',4'-dicarboxyphenyl) hexafluoro-
propane (6F tetraacid) is dissolved in a suitable
solvent (e.g. ethanol, diglyme or NMP) along
with a 95/5 mixture of p-phenylenedi-
amine/rn-phenylenediamineto form a low
viscosity, stable monomeric solution' suitable
for prepregging. During the cure both solvent
and 2 moles of by-product water per repeat
unit are eliminated to initially form the tran-
sient intermediate polyamide acid. According
to the studies of Sonnett et aL2, although a low
concentration of amide acid persists for a rela-
tively long time period during the early stages
of cure, most is rapidly converted to the imide
form by the thermally induced elimination of
water (2 moles per repeat unit). Since the
tetraacid and diamines are very pure, highly
Condensation polyimide chemistry 77
Diethyl ester of 3,3',4,4'-benzophenone
tetracarboxylic acid
4,4'-methylene dianiline +
Skybond703
reactive and present in stoicluometric propor-
tions, extremely high molecular weight
polyimide is ultimately produced. Also, since
the bridging hexafluoroisopropylidene group
is inert under normal cure conditions, the poly-
imide produced is essentially linear and & that
sense thermoplastic.
4.2.4 CHEMISTRY OF 3F/36F POLYIMIDES
One of the keys to success in producing an
essentially linear condensation polyimide is to
have a chemically inert flexibilizing linkage in
the dianhydride moiety. As indicated in
Section 4.2.3 one of the ways of doing t h s is to
employ a hexafluoroisopropylidene bridging
group. Since the phenyl group is also very
inert another approach is to replace one of the
CF, groups with a phenyl group3. This results
in the so-called 3F dianhydride. When the 3F
monomer is used along with PPD the poly-
imide produced is called 3F-PPD polyimide.
If, on the other hand, a mixture of the 3F and
6F monomers are employed along with the
same diamine the copolyimide is designated
36F-PPD.
78 High temperature resins

H O -O
C
II
0
- !/D
CF3

~ F D /~ - - OOH H +
C

0
00 NHZ

NH2
/ +
NH2

/ NH,

956 mixture PPDA4PD

+ Solvent

Monomeric binder solution

Intermediate transient polyamide acid J

(-2H20)

r 1

L NR-150 Polyimide

Fig. 4.3 NR-150 polymerization chemistry.

4.3 ADDITION POLYIMIDE CHEMISTRY
4.3.1 OVERALL CHEMISTRY OF ADDITION
POLYIMIDE PRECURSOR SOLUTIONS
One of the important concerns in the cure of
conventional condensation polyimides is the
proper management of the evolution of volatile
by-products. During the early stages prior to
pressurization the composite is generally some-
what porous and volatiles can readily diffuse
out. However, once pressure has been applied
and a low void state is achieved the diffusivity
dramatically decreases making it much more
difficult for these volatiles to escape. Therefore,
ideally one would want to eliminate all of the
volatiles prior to pressurization. In order to
accomplish this in a conventional condensation
polyimide it is necessary to have a high enough
monomer imbalance so that the polymer mole-
cular weight and melt viscosity will be low
enough to allow for complete consolidation.
The problem is that this molecular weight is
generally so low that the matrix resin properties
are adversely affected. Properties such as
strength, toughness and T, will be much lower
than desired.

A common way of making a low void com-
posite is to produce in situ an imide oligomer
having a low enough molecular weight so that
it has good melt flow and readily consolidates
when pressure is applied and then, with further
heating, can go on to produce much higher
molecular weight polymer without the further
evolution of volatile by-products. This can be
accomplished through the use of reactive end-
groups which are capable of reacting with one
another in various ways without the evolution
of volatiles. However, it must be pointed out
that such improvements in processibility are
only achieved with some sacrifices in other
properties. Because of the presence of cross-
links the toughness can be adversely affected.
Also, the kinds of linkages produced during
these addition polymerization reactions are
generally aliphatic in nature thus making them
much more prone to thermal-oxidative attack.
Many approaches, which are now discussed,
have been taken in order to achieve various
trade-offs in processibility against properties.
2 Moles NE 2 Moles MDA
PMR-15 Binder Solution
CrosslinkedPMR-15
Fig. 4.4 PMR-15 polymerization chemistry.
Addition polyimide chemisty 79
4.3.2 CHEMISTRY OF PMR-15
The first approach to a commercially successful
addition polyimide was PMR-15. The basic
PMR (Polymerizationof Monomeric Reactants)
chemistry was originally invented and devel-
oped at NASA Lewis Research CenteF. As
illustrated in Fig. 4.4 a monomeric solution is
first prepared consisting of the dimethyl ester
of BTDA (BTDE), the diamine, MDA and the
monomethyl ester of nadic anhydride (NE),the
reactive end-capping agent. The monomer
ratios are n:n+l:2 respectively. Because the high
solids solution is monomeric it is ideally suited
to prepregging. As a result of the application of
heat, solvent is eliminated along with the water
and alcohol of imidization to produce the inter-
mediate imide oligomer having a formulated
molecular weight of about 1500. This normally
occurs between 121°C (250°F) and 232°C
(450°F). At this point essentially all of the
volatile by-products have been eliminated. The
stage is now set for pressurization. At some-
1 Mole BTDE
80 High temperature resins
what higher temperatures the imide oligomer
undergoes melting and, if pressure is applied,
consolidation to form a low void structure
occurs. At temperatures in the 275-316°C
(527400°F) range ring opening of the nadic
end-groups takes place in a reverse Diels-Alder
type of reaction first discovered by Lubowitz9Jo
in 1970 and a complex series of reactions takes
place involving these end-groups leading to
high molecular weight polymer without the
further evolution of volatile by-products.
Hence the low void state originally achieved
during the initial consolidation is maintained
and a h g h quality laminate usually results.
PMR-I1 imide prepolymer
L
V-CAP imide prepolymer
$$
CH, -CH,
CYCAP imide prepolymer
L
AFR700B imide prepolymer
Fig. 4.5 Structures of 6F based addition polyimide prepolymers.
4.3.3 CHEMISTRYOF PMR-I1
During the early 1970s it became clear that
although composites based on PMR-15 pos-
sessed good enough properties to make them
a commercial success there was still room for
improvement. For instance, the relatively high
aliphatic content which came from the nadic
end-groups and the methylene group of the
MDA contributed to thermal-oxidative insta-
bility. Also, the relatively high cross-link
density in a polyimide with a formulated mol-
ecular weight of 1500 resulted in a rather
brittle matrix resin. In order to overcome these
deficiencies PMR-I1 was invented”-14(Fig 4.5).
For PMR-I1 polyimides the 6F dianhydride is
used in place of the BTDA and is converted in
situ to the diethyl ester diacid derivative
1 0
-l
 Addition polyimide chemistry 81

(6FDE)by pre-reacting with ethanol. The sin- 4.3.6 CHEMISTRY OF AFR700B

gle ring diamine, PPDJis employed in place of
With any of the reactive end-groups discussed
the MDA. The end-capping agent is still nadic
thus far in this chapter the concentration of
anhydride. The formulated molecular weight
end-capping agent has always been such that
was increased from 1500, which is what it is in
there are end-caps on both chain ends.
PMR-15, to the 3000-5000 range (yields
However, by adding just enough end-capping
PMR-11-30 and PMR-11-50 respectively). While
agent to cap one chain end only and assuming
the polymerization is basically the same in
that high molecular weight polymer can still
both PMR-I1 and PMR-15, since the aliphatic
somehow be obtained under reasonable pro-
content has been greatly reduced, significant
cessing conditions, a further significant
improvements in thermal-oxidative stability
improvement in thermal-oxidative stability
and toughness can be realized.
should be possible simply because the concen-
tration of unstable groups will have been cut
4.3.4 CHEMISTRY OF V-CAP in half. This is exactly what has been done
with AFR700B based on the work of Serafini et
Assuming that the 6F/PPD backbone has near al. at TRWz1-23.
optimal thermal-oxidative stability and formu-
In AFR700B the ratio of 6FDE:PPD:NE is
lated molecular weights in the 3000-5000 range 8:9:1 and the formulated molecular weight is
are about right from the stand-point of melt about 4400 (see Fig. 4.5 for its s t r ~ c t u r e )This
~~.
flow, if further improvements in stability are to means that the nadic end-group component is
be realized then one approach would be to only 3.7% of the overall weight compared with
make changes in the end-group chemistry. One 22% for PMR-15 and 6.5% for PMR-11-50).
effective method is the replacement of nadic During cure of AFR700B composites it is nec-
anhydride as the end-capping agent with p - essary not only to achieve the normal
aminostyrene The imide prepolymer
imidization and nadic end-group coupling
that is produced is illustrated in Fig. 4.5. In this
reactions but also other unspecified reactions
case there is only one weak bond per end-cap involving the amine end-groups undoubtedly
compared with eight for the nadic end-cap.
occur leading to the formation of the desired
During the addition polymerization phase of
strong, stiff, tough, high Tgpolyimide.
the cure free radical polymerization of the vinyl
(-CH=CH,) end-groups occurs leading to high
molecular weight polymer. 4.3.7 CHEMISTRY OF TRW-R-8XX
The most recent addition to the growing fam-
4.3.5 CHEMISTRY OF CYCAP ily of commercially available polyimides
comes from TRW and has been designated
Another approach to a more stable polymer TRW-R-8XXZ5.Although the chemical struc-
has been to replace the nadic end-capping ture of this polyimide has not yet been
agent with 2-amino-p-cyclophane (APC)19,20.disclosed it is reported to be a condensa-
The structure of the imide prepolymer con- tion/addition polyimide based on relatively
taining the CYCAP end-groups that is initially low cost monomers, making its cost compara-
produced is illustrated in Fig. 4.5. This type of ble to that of PMR-15. It is reported to be free
end-capping agent has only two weak bonds of the carcinogen, MDA.
per end-cap. Thermolytic cleavage of the
-CH,-CH,- groups during the final stages of
cure produces bi-radicals (-CH; CH,-) which
undergo coupling with other bi-radicals to
build up the molecular weight.
82 High temperature resins

4.4 COMMERCIAL AVAILABILITY OF BINDER Table 4.1 Typical properties of neat cured NR-150 ''
SOLUTIONS
Property Units Value
Most of the binder solutions described in this
chapter are not commercially available but "C 350-370
"F 662-700
rather are prepared by the prepregger on an Density g cm-? 1.43-1.45
as-needed basis just prior to prepregging. One Coefficient of thermal oc-I 5.6 x 10-5
notable exception is Monsanto's Skybond. The expansion OF-' 3.1 x
monomeric solutions (Skybond 700 and 703) Char yield % 60
have solids contents in the 45-52% range and Tensile strength MPa (ksi) 110 (16)
solution viscosities of 3000-7000 poisez6. Elongation, RT % 6
316°C (600°F) - 65
Fracture toughness J m-2 (in lb in") 2000 (11.4)
Rochwell hardness
4.5 COMMERCIAL AVAILABILITY OF
(E scale) 70
PREPREGS
At the time of writing of this chapter all of the
different polymide prepreg systems were com- Table 4.2 Typical properties of neat cured PMR-15
mercially available from one prepregger or
Property Units Value Reference
another. However, the reader should appreci-
ate the fact that as time goes by some prepreg T,
Density "C (OF) 335 (635) 28
types will disappear from the market place g ~ r n - ~ 1.30-1.32 28
Coefficient of oc-1 16x1O4 35
and others with an improved balance of pro- thermal OF-1 28X 10" 35
cessing characteristics, properties and expansion
economics will come along to take their place. Tensile strength MPa (ksi) 55 (8.0) 35
Also, some companies will go out of business Tensile modulus MPa (ksi) 3200 (470) 35
or will be bought out by other companies as Elongation "/o 1.5 36
consolidation in the industry occurs. Compressive MPa (ksi) 110 (16) 35
Therefore, if a given type of prepreg is yield strength
Compressive MPa (ksi) 186 (27) 35
required the reader should contact their
strength
favorite prepregger. If that particular company Equilibrium 96 4.2 28
does not offer the product the reader requires moisture
then advice should be obtained as to where absorption
such prepreg could be commercially pur- Fracture J m-2 500 (2.86) 37
chased, if at all. Another fruitful source of toughness (in lb i r 2 )
information would be to search the Internet.
In neat resin thermal-oxidative stability stud-
ies carried out by Sco1az7it was found that
4.6 NEAT RESIN PROPERTIES
after 24 h at 316°C (600°F) the NR-150 resin
The neat resin mechanical properties for cured had lost 9% of its weight compared with about
NR-150 and PMR-15 are summarized in Tables 76%for the PMR-15. Neat AFR700B, which has
4.1 and 4.2 respectively. One of the important been post-cured under nitrogen, has been
differences between these two resin systems is reported to have a room temperature tensile
their toughness. Cured NR-150 has been strength of 93.8 MPa (13.6 ksi) with 18% reten-
found to be dramatically tougher (2000 Jm-' tion of this value at 371°C (700°F). No
fracture toughness) compared with a value of properties were available for Skybond, PMR-11,
500 Jm-' for the cured PMR-15. Another signif- V-CAP and CYCAP. Very little information
icant difference is thermal-oxidative stability. was available for the 3F-PPD and 36F-PPD

polyimides except for neat resin densities (1.35
and 1 . 4 2 g ~ m -for
~ the 3F and 36F resins
respectively) and Tg of 365-370°C (689-698°F)
for both systems in the as-molded state and
405-410°C (761-770°F) for the post-cured
state3.TRW-R-8XX has been reported25to yield
polyimides having T g in the 400-426°C
(750-800°F) range and composite weight loss
characteristics at 371°C (700°F) up to 10 times
better than PMR-15. All of the resin systems
described in this chapter appear to possess
good strength and stiffness. Thus, provided
that complete cure is achieved during process-
ing and low void composites are produced
possessing good fiber/matrix adhesion, high
levels of composite mechanical properties
should be obtained with good retention (at
least 50%) of these properties to just below
their Tg.
4.7 PROCESSING CHARACTERISTICS
4.7.1 GENERAL COMMENTS
One of the features that can clearly differenti-
ate one resin system from another is the ease
with which a fully cured low void composite
can be produced having a specified fiber vol-
ume. Also, although all polyimides can have
their Tgincreased from post-cure, some sys-
tems respond much more readily than others.
In all cases there is a problem of properly man-
aging the release of a significant amount of
volatiles (normally 10-15% of the weight of
the prepreg). The ways in which this can be
accomplished can vary significantly from one
resin to another depending on the chemistry
involved. Factors such as the techniques
employed during lay-up of the vacuum bag
assembly, pressure, heat-up rate, maximum
cure temperature, vacuum application and
intermediate holds all must be carefully con-
trolled and optimized for each system.
Unfortunately the story on the processing of
the various systems covered in this chapter is
very incomplete. In a majority of cases infor-
mation on processing was simply not available
Processing characteristics 83
because such data was either considered pro-
prietary or classified as secret by the
Government Laboratories. In other cases,
where some processing information was avail-
able in the open literature, very little was
usually said about the quality of the part pro-
duced by a given cycle so it is difficult to
compare the processibility of one resin system
with another since the quality of the laminates
produced is generally unknown. To make mat-
ters worse there are also the issues of the
processing characteristics of thick compared
with thin sections and how processing can be
handled, if at all, when both thin and thick sec-
tions are present simultaneously in a given
part. It is, therefore, of paramount importance
for workers in this field to have as clear an
understanding as possible of the chemistry
involved at every stage of the cure so that they
can quickly and efficiently develop the opti-
mum cure cycle for a given part. The cure
cycles presented below will give the reader an
approximate idea of the kinds of conditions
that have been employed to produce a part.
4.7.2 SKYBOND PROCESSING CONDITIONS
The following autoclave cure cycle has been
recommended by MonsantoZ6for 12 ply
(3.2 mm, 0.125 in thick) 181 style E-glass (soft
A-1100 finish) fabric/Skybond 700 laminates:
0 apply full vacuum;
0 heat to 177°C (350°F) at 1.7-2.8"C/min
(3-5°F /min);
0 hold 5 min at 177°C (350°F);
0 apply 0.69 MPa (100 psi);
0 hold 30 min;
0 cool under pressure and vacuum.
In order to maximize high temperature prop-
erties it is recommended that a post-cure
should be carried out up to and including the
expected use-temperature. For laminates of
the type described above a post-cure is sug-
gested in which the part is heated to 200°C
(392"F), 225°C (437"F), 250°C (482"F), 300°C
(572"F), 325°C (617"F), 350°C (662°F) and
84 High temperattive resins
371°C (700°F) and held for 2 h at each temper-
ature. It is recommended that if thicker
laminates are involved the post-cure cycle
should be extended.
For the same type of laminate based on
Skybond 703 a similar autoclave cure cycle can
be employed. The only significant differences
are a slower heat-up rate (l.l-1.7"C/min,
2-3"F/min) with the pressure being applied at
121°C (250°F)on the way to the final cure tem-
perature of 177°C (350°F).Also a similar post-
cure cycle is suggested in order to achieve
maximum heat resistance.
While there is very little definitive informa-
tion on the void content of Skybond based
laminates it is believed that they are generally
in the 5-20% range. A most important feature
of this particular polyimide system is that the
maximum autoclave processing temperature
is only 177°C (350°F). No other resin system
described in this chapter can make that claim.
4.7.3 PMR-15 PROCESSING CONDITIONS
The following represents a typical autoclave
cure cyclez8cited for PMR-15:
apply 7-21 kPa (1-3 psi) vacuum;
raise autoclave temperature to 227°C
(440°F)at 0.83-1.l0C/min (1.5-2.O0F/min);
at 163-177°C (325-350°F) apply full vacuum;
dwell at 227°C (440°F) for 1 4 h depending
on part thickness (up to 2.8 mm, 0.11 in =
1 h, 2.8-6.4mm, 0.11-0.25 in = 2 h,
6.4-12.8 mm (0.25-0.50 in) = 3 h);
raise temperature to 238°C (460°F) at
1.1"C/ min (2.0°F/ min);
hold at 238°C (460°F) while 1.38MPa
(200 psi) autoclave pressure is applied.
Do not hold longer than 15 minutes while
pressure is being- applied
__
raise temperature to 316°C (600°F) at
2.2-3.3"C / min (46°F/min);
dwell at 316°C (600°F) for 3 h;
cool to room temperature. Vent autoclave
pressure below 204°C (400°F) It should be
noted that pressurization does not occur
until a temperature of about 238°C (460°F)
is reached. At that temperature essentially
all of the solvent and imidization volatiles
have been eliminated. Normally PMR-15
laminates are subjected to an oven post-cure:
0 heat from room temperature to 204°C
(400°F) at 5.6"C/min (10"F/min);
0 heat from 204°C to 288°C (400°Fto 550°F) at
1.1"C/min (2"F/min);
0 dwell at 288°C (550°F)for 1 h;
0 heat from 288°C to 316°C (550°F to 600°F) at
1.1"C/ min (2"F/min);
0 dwell at 316°C (600°F)for 10-16 h;
0 cool to room temperature at 2.8"C/min
(5"F/min) maximum.
4.7.4 PMR-I1 AND V-CAP PROCESSING
CONDITIONS
The autoclave cure cycles for PMR-I1 and
V-CAP based composites are similar to that of
PMR-15. The main difference is that the maxi-
mum processing temperature has been
increased from 316°C to 371°C (600°F to
700°F). The following typical autoclave cure
and post-cure cycles for graphite reinforced
PMR-I1 composites has been rep~rted'~?
0 apply full vacuum at room temperature;
0 heat to 149°C (300°F) at 3.9"C/min
(7.O"F/ min);
0 hold for 30min at 149"C, then apply
172 kPa (25 psi);
0 heat to 288°C (550°F) at 3.9"C/min
(7.O0F/min) with the pressure being
increased to 344 kPa (50 psi) at 177°C
(350°F) and then to 1.38MPa (200psi) at
232°C (450°F);
0 heat from 232°C to 371°C (450°F to 700°F) at
2.8"C/min (5"F/min);
0 cool under full pressure and vacuum to
232°C (450°F)slowly;
cool from 232°C to temperature
rapidly.
As with PMR-15, a post-cure is normally car-
ried out in a circulating air oven:
 Mechanical properties before and after air aging 85

heat from room temperature to 260°C their high T , (377418"C, 710-785°F) the reten-
(500°F) at 20"C/min (36"F/min) tion of properties was excellent out to
0 heat from 260°C to 385°C (700°F to 725°F) at temperatures as high as 360°C (680°F).
l"C/min (1.8"F/min) with 2 h holds at 316°C At the writing of this chapter the long term
(600"F),343°C (650°F)and 20 h hold at 385°C. air aging characteristics of laminates of this
particular type had not been completed.
However, because of its all aromatic character,
4.7.5 PROCESSING CONDITIONS FOR OTHER
ultra-high molecular weight and the complete
RESIN SYSTEMS
absence of any aliphatic character from reac-
At the time of the writing of this chapter no tive end-capping agents it should air age well
unclassified processing information was avail- and the matrix in Avimid N-150 has been pre-
able for CYCAP, AFR700B, TRW-R-8XX or the viously shown to possess outstanding
3F/36F polyimides. The compression molding thermal-oxidative stability30.
conditions used by DuPont to make the lami-
nates whose properties are described in
4.8.3 3F/36F POLYIMIDES
Table 4.4 were not disclosed. However, details
concerning the autoclave processing of Although this family of all aromatic poly-
Avimid N have been previously discussedz9. imides is relatively new, preliminary data
indicates that high quality laminates possess-
ing good mechanical properties and excellent
4.8 MECHANICAL PROPERTIES BEFORE AND long term thermal-oxidative stability can be
AFTER AIR AGING produced. According to the work of Scola3
both the 3F-PPD and the 36F-PPD systems
4.8.1 SKYBOND resulted in G40-600 laminates having the
The most common type of reinforcement that expected good room temperature mechanical
has been employed with Skybond binders is properties (flex strength and short beam shear
E-glass fabric. The mechanical properties of strength) with excellent retention of these 'dry'
as-molded and air aged laminates based on properties out to at least 371°C (700°F). Also,
Skybond 700 are summarized in Table 4.3. This after 100 h in air at 371°C (700°F) these lami-
particular resin system has been tailored for nates retained at least 100% of these properties
extended exposures at temperatures up to with weight loss values ranging from 1.4%for
371°C (700°F). For 343°C (650°F) applications the 36F-PPD resin and 2.4% for the 3F-PPD
Skybond 703 is recommended by the manu- polyimide. Surprisingly neat resin studies car-
facturer. It is interesting to note that in spite of ried out by Scola have similarly shown that
the relatively high porosity levels (5-20%) the 36F-PPD polyimide appeared to be some-
Skybond binders are still in demand for cer- what more stable than the 3F-PPD polymer.
tain specialty applications. For instance, after 100 h exposure at 371°C
(700"F), the 36F-PPD copolyimide had lost
about 2% of its weight compared with 3.2% for
4.8.2 AVIMID N the 3F-PPD polymer. Much more work needs
to be carried out on polyimides based on the
Some mechanical properties for compression
3F monomer before any final decision can be
molded/post-cured Celion G30-500 miweave/
made as to its long term viability in the market
Avimid N laminates are tabulated in Table 4.4.
place and how it will ultimately compete with
All laminates had a very low void content
the 6F based polyimides such as Avimid N,
(4'30)and, therefore, high levels of mechanical
PMR-11, V-CAP, CYCAP and AFR700B.
properties at room temperature. Because of
86 High temperature resins

Table 4.3 Mechanical properties of Skybond@700/181 style E-glass laminates (Soft A-1 100 Finish) 26

Property High temperature, Vacuum bag

high pressure
Flex strength, MPa (ksi)
24 "C (75 OF) 517-586 (75-85) 524-576 (76-84)
371°C (700°F)after 0.5 h at 371°C 310414 (45-60) 152-221 (22-32)
371°C (700°F) after 100 h at 371°C 138-241 (20-35) 138-166 (20-24)
316°C (600°F) after 500 h at 316°C 200 (29)
316°C (600°F)after 860 h at 316°C 138 (20)
316°C (600°F) after 1850 h at 316°C 76 (11)
288°C (550°F)after 2300 h at 288°C 283 (41)
288°C (550°F)after 4500 h at 288°C 221 (32)
288°C (550°F) after 9000 h at 288°C 103 (15)
Flex modulus, GPa (msi)
24°C (75°F) 22 (3.1) 19 (2.8)
299°C (570°F) after 335 h at 299°C 22 (3.1) -

371°C (700°F) after 100 h at 371°C - 12 (1.8)

316°C (600°F) after 500 h at 316°C 18 (2.6)
316°C (600°F) after 860 h at 316°C 18 (2.6)
316°C (600°F)after1850 h at 316°C 14 (2.1)
288°C (550°F) after 2300 h at 288°C 18 (2.6)
288°C (550°F) after 4500 h at 288°C 20 (3.0)
288°C (550°F)after 9000 h at 288°C 14 (2.0)
Ultimate tensile strength, MPa (ksi)
24°C (75°F) 393 (57) 347 (50.1)
299°C (570°F)after 335 h at 299°C 290 (42) -
24°C (75°F) after 100 h at 250°C (482°F) - 336 (49)
24°C (75°F) after 100 h at 300°C (572°F) - 332 (48.2)
Elongation, YO
24°C (75°F) 1.9 2.0
299°C (570°F) after 335 h at 299°C 1.4 -
24°C (75°F) after 100 h at 250°C (482°F) - 1.7
24°C (75°F) after 100 h at 300°C (572°F) - 2.0
Weight loss, YO
After 100 h at 371°C (700°F) 3.0
After 500 h at 316°C (600°F) 2.2
After 860 h at 316°C (600°F) 3.4
After 1850 h at 316°C (600°F) 7.9
After 2300 h at 288°C (550°F) 3.6
After 4500 h at 288°C (550°F) 5.0
After 9000 h at 288°C (550°F) 12.0
 Mechanical properties b$ore and after air aging 87

Table 4.4 Mechanicalproperties of compression molded Celion@G30-500 Uniweave/Avimid@N laminates 39

No. ofplies Orientation Tf "C (OF) Temperature, Property

"C (OF)

Short beam shear strength, MPa (ksi)

16 0" 418 (785) 24 (75) 98.6 (14.3)
218 (425) 61.4 (8.9)
316 (600) 46.2 (6.7)
360 (680) 38.6 (5.6)
Flex strength, MPa (ksi)
16 0" 418 (785) 24 (75) 1344 (195)
316 (600) 731 (106)
360 (680) 565 (82)
Flex modulus, GPa (msi)
16 0" 418 (785) 24 (75) 126 (18.0)
316 (600) 123 (17.9)
360 (680) 117 (17.0)
In-plane shear strength, MPa ( h i )
16 (k45") 418 (785) 24 (75) 174 (25.2)
371 (700) 104 (15.1)
Tensile strength, MPa (ksi)
10 0" 377 (710) 24 (75) 1261 (183)
416 (780) 1027 (149)
Tensile modulus, GPa ( m i )
10 0" 377 (710) 24 (75) 124 (18.0)
416 (780) 104 (15.1)
Open hole tensile strength, MPa (ksi)
10 0" 377 (710) 24 (75) 1027 (153)
416 (780) 854 (124)
Open hole tensile modulus, GPa (msi)
10 0" 377 (710) 24 (75) 132 (19.1)
416 (780) 114 (16.5)
Tensile strength, MPa (ksi)
16 0,90,i45" 377 (710) 24 (75) 460 (66.7)
360 (680) 314 (45.5)
416 (780) 236 (34.3)
Tensile modulus, GPa (msi)
16 0,90,+45" 377 (710) 24 (75) 56.5 (8.2)
360 (680) 46.8 (6.8)
416 (780) 30.3 (4.4)
Open hole tensile strength, MPa (ksi)
16 0,90,45" 377 (710) 24 (75) 389 (56.5)
360 (680) 250 (36.3)
416 (780) 177 (25.5)
Open hole tensile modulus, GPa (msi)
16 0,90,i45" 377 (710) 24 (75) 54.4 (7.9)
360 (680) 46.8 (6.8)
416 (780) 38.3 (5.7)
Compressive strength, MPa (ksi)
16 0,90,i45" 377 (710) 24 (75) 389 (56.5)
Compressive strength, MPa ( h i )
16 0,90,+45" 377 (710) 24 (75) 458 (66.4)
360 (680) 312 (45.4)
416 (780) 270 (39.2)
Compressive strength, MPa (ksi)
16 0" 377 (710) 24 (75) 868 (126)
316 (600) 448 (65.1)
360 (680) 409 (59.4)
Interlaminar fracture toughness
J m-2 (in Ib in-')
16 0" 418 (785) 24 (75) 630 (3.6)
316 (600) 682 (3.9)
343 (650) 718 (4.1)
88 High temperature resins

Table 4.5 Mechanical properties of fiber reinforced PMR-15 laminates 35

Reinforcement
High strength High strength
Property 7781 Style E-glass fabric 1>3447 MPa (500 ksi)] 1>3447 MPa (500 ksi)]
(50-55 Vol. %fibers) Standard modulus Standard modulus
/228 GPa (33 msi)] class 1228 GPa (33 msi)] class
Carbon fiber unidirectional tape Carbon fiber 8-harness
(57-63 Vol. %fibers) satin fabric
(55-60 Vol. %fibers)
Compressive
strength
MPa (ksi)
23°C (73°F) 517-586 (75-85) 827-965 (120-140) 552-689 (80-100)
288°C (550°F) 758-896 (110-130) 414-552 (60-80)

Compressive
modulus
GPa (msi)
23°C (73°F) 28-34 (4-5) 97-117 (14-17) 62-76 (9-11)
288°C (550°F) 83-110 (12-16) 48-62 (7-9)

Flex strength
MPa (ksi)
23°C (73°F) 483421 (70-90) 965-1103 (140-160)
288°C (550°F) 689-896 (100-130)
316°C (600°F) 414-552(60-80)

Flex modulus
GPa (msi)
23°C (73°F) 21-34 (3-5) 5 5 4 9 (8-10)
288°C (550°F) 5 5 4 9 (8-10)
316°C (600°F) 21-34 (3-5)

Tensile strength
MPa (ksi)
23°C (73°F) 1241-1448 (180-210) 689-896 (100-130)
288°C (550°F) 1241-1448 (180-210) 758-965 (110-140)

Tensile modulus
GPa (msi)
23°C (73°F) 117-138 (17-20) 62-76 (9-11)
288°C (550°F) 103-124 (15-18) 62-76 (9-11)

Interlaminar
shear strength
MPa (ksi)
23°C (73°F) 62-76 (9-11) 5 5 4 9 (8-10)
288°C (550°F) 34-48 (5-7)
316°C (600°F) 34-48 (5-7)
 Mechanical properties before and after air aging 89
4.8.4 PMR-15 perature and either 232°C (450°F) or 288°C
From the data cited in Table 4.5 it can be seen (550°F) at heat-up and cool-down rates of
that PMR-15 based composites reinforced with 278°C (532"F)/min (achieved by employing a
either E-glass or graphite fibers are character- heated fluidized sand bed) significant microc-
ized by good room temperature strength racking was detected at 5000 thermal cycles
properties with excellent retention of these and beyond. The data plotted in Fig. 4.6
properties at temperatures in the 288-316°C clearly indicate that cycling to the higher tem-
(550-600°F) range. perature resulted in a much higher
Over the past 20 years a great deal of effort concentration of microcracks.According to the
has gone into the study of the weight loss results plotted in Fig. 4.7 the development of
characteristics of PMR-15 composites at vari- microcracks was found to have a very delete-
ous temperatures and air pressures and the rious effect on the matrix-dominated
effects of these exposure conditions on the compressive strength of the graphite fabric
laminate mechanical properties. One of the laminates. However, GE also showed that the
significant new property features to be uncov- fiber-dominated tensile strength was not
ered has been the effects of temperature affected by the presence of the microcracks.
cycling on the development of microcracks There is every reason to believe that compos-
and the effects of these microcracks on the ites based on other resin systems will also
strength and stiffness properties. In acceler- undergo microcracking from temperature
ated thermal cycling studies3I carried out at cycling and can be expected to exhibit
General Electric - Aircraft Engines in which improved microcracking performance to the
the cycling was carried out between room tem- extent to which they possess improved tough-
ness compared with PMR-15.

35 c I

A
A A
A

15 1 A

.-c
u)

n
Y
u
RT - 288 "C (550 'F) Data

2
0 5 RT - 232 "C (450 OF) Data

1-
0
0 5000 10000 15000 20000 25000
Number of Cycles

Fig. 4.6 Crack density compared with accelerated thermal cycles for graphite fabric/PMR-15 laminates. 31
90 High temperature resins

100 1 I 1 I I

0
P
P
0 P

A
A
A

A -
RT 288 "0(550 OF) Data
t A
I I
O A I I I

0 5000 10000 15000 20000 25000

Number of Thermal Cycles

Fig. 4.7 Effect of accelerated thermal cycling on the compressive strength of PMR-l5/graphite fabric lam-
inate~.~~

4.8.5 PMR-I1 the 343°C (650°F) interlaminar shear strength

increased for the first 200-400 h of aging. Even
The greatly improved weight loss performance
after 600 hours aging the interlaminar shear
of PMR-I1 based composites compared with
strengths were about the same as they were at
PMR-15 as a result of aging in air at elevated
the beginning. However, the reader must be
temperatures (343"C, 650°F) is illustrated in
aware that there has been a considerable
Fig. 4.814,15.
Note that very little difference in
weight loss (about 8%) with the resulting
weight loss was found between PMR-11-30 and
shrinkage and induced stresses. Also, the
PMR-11-50. Although a stability improvement
matrix resin has presumably become embrit-
would have been expected with the higher for-
tled. Therefore, in assessing the useful lifetime
mulated molecular weight it usually is not
of a composite at elevated temperatures it is
detected because of the difficulty in making
important to not only consider the changes in
low void laminates with the higher viscosity
various strength and stiffness properties but
resin. Porosity itself, of course, can contribute
also the effects that weight loss itself can have
to thermal-oxidative instability.
on dimensional stability and matrix resin
As a general rule, for any of the polyimides
toughness.
discussed in this chapter, the high temperature
Carbon fiber selection can also be an impor-
mechanical properties tend to increase as a
tant factor in determining the overall high
result of the air aging process. This is presum-
temperature performance of a composite. As
ably because the oxidative crosslinking that
illustrated in Fig. 4.1032PMR-11-50 laminates
occurs during the aging process tends to
reinforced with Celion@G40-600 or ThomeP
increase the T,. In Fig. 4.9I4J5
it can be seen that
650-35 retained a higher level of flex strength
 Mechanical properties before and after air aging 91

I I I I I I I

I
12 A PMR-15
0 PMR-11-30
10
0 PMR-i1-5(i

0 100 200 300 400 500 600 700

Time, Hours
Fig. 4.8 Weight loss of Celiona 6KJPMR laminates at 343°C (65O0F).l4Js

60 I I I I I I I 1 8.70

0 .-
G
0 7.25 y"
5 0 OA

r;p 40 0
?!
3i

I 4.35 !

I I I I I I
0 '

0 100 200 300 400 500 600 700

Time, How

Fig. 4.9 Interlaminar shear strength of Celiona 6K/PMR laminates after aging in air at 343°C (650°F).14,15
92 High temperature resins

2 00 180

160
160
.-
u)
Q Y

k! 120 120 5-
tl,
s'
0
C
?!?
-
C
!
cy)
X
80 *O
z
x
-@
8 u,
ii
40 40

0 0

Initial After 500 Hours

at 371 OC (700 O F )

Fig. 4.10 Effect of fiber selection on the flex strength of PMR-11-50 laminates air aged at 371°C (700°F).32

100 rI I

1I 1 800 Hours' Exposure I

T40R G4U-600 G40-700 G40-800 T650-42 T650-35

Fiber

Fig. 4.11 Thermal-oxidative stability of various graphite fibers exposed to 371°C (700 O F ) air. 32
 Mechanical properties before and after air aging 93

after 500 h at 371°C (700°F)than laminates rein-
forced with other fibers such as Thornel 40R,
Thornel 650-42, Celion G40-700 and Celion
G40-800. It is of interest to note that according
to the data in Fig. 4.1132there was not a one-to-
one correlation with the basic carbon fiber
stability. While Celion G40-600 had one of the
lowest weight losses in 371°C (700°F) air aging
the Thornel 650-35 had one of the highest.
4.8.6 V-CAP AND CYCAP
As a result of the reduced aliphatic character
of the reactive end-groups in CYCAP, Meador
et a l l 9 have reported improved weight loss
performance in comparison with PMR-11.
These same researchers have also shown that
V-CAP/graphite compositespossess improved
thermal-oxidative stability compared with
PMR-11-50. However, with the advent of
AFR700B where significant improvements in
thermal-oxidative stability have been realized
by simply capping one end only with the low
cost nadic anhydride, it is not clear whether
either the V-CAP or CYCAP polyimides with
their more expensive end-capping agents will
be successful in the market place.

Table 4.6 Mechanical properties of unidirectional AFR700B/S2 glass tape laminates 24

Material Fiber VOl. % Test temperature, "C ( O F )

condit ion or ien f af ion fibers 23 (73) 316 (600) 371 (700)
Flex strength, MPa (ksi)
As-molded 0" 55 1123 (163) 634 (92) 496 (70)
Air aged 100 h 0" 55 958 (139) 517 (75)
at 371°C (700°F) (1atm)
90" Flex strength, MPa (ksi)
As-molded 0" 55 48 (6.9) 29 (4.2) 27 (3.9)
Air aged 100 h 0" 55 23 (3.3) 13 (1.9) 23 (1.7)
at 371°C (700°F) (1 atm)
Flex strength, MPa (ksi)
~~~

Cycled 100 x from 0" 55 972 (141) 421 (61)

RT to 371°C (700°F) in air
50 h total at 371°C
In-plane shear strength, MPa (ksi)
~~~

As-molded k 45 59 81 (11.8) 53 (7.7) 41 (5.9)

Air aged 100 h f 45 59 29 (4.2) 21 (3.0) 26 (3.7)
at 371°C (700°F) (1 atm)
Tensile strength, MPa (ksi)
As-molded 0" 54 1103 (160) 917 (133) 834 (121)
Air aged 100 h 0" 55 814 (118) 703 (102) 676 (98)
at 371°C (700°F) (1atm)
0" Compression strength*, MPa (ksi)
.~

As-molded 0" 58 662 (96) 386 (56) 303 (44)

Air aged 100 h 0" 58 621 (90) 352 (51) 331 (48)
at 371°C (700°F) (1atm)
* Non-standard test; open hole compression fixture used with no-hole specimen. For comparison the room temperature
IITRI compression strength (D3410) was 1152 MPa (167 ksi)
94 High temperature resins

2 1 I I I I I I I II

1.6

%
0 1.2
E
.-0
2" 0.8

0.4

0
0 1000 2000 3000 4000 5000 6000 7000 8000
Time, Hours
Fig. 4.12 Effect of air aging at 260°C (500°F) on the weight loss of AFR700B composites.24

4.8.7 AFR700B one can also expect significant improvements

in both matrix resin toughness and thermal-
One of the most promising new resin systems
oxidative stability compared with PMR-15.
that has come along in the last several years is
AFR700B. One indication of this is the excel-
lent properties tabulated in Table 4.624which 4.8.8 TRW-R-8XX
had been obtained on unidirectional S2
Although very little unclassified property data
(933 finish) glass tape laminates, both as-
was available at the time of the writing of this
molded as well as after 100 h in air at 371°C
chapter, according to TRWZ5,the room temper-
(700°F).
ature mechanical properties of composites
In long term isothermal air aging studies24
based on TRW-R-8XX have been found to be
carried out at 260°C (500°F) the weight loss
equivalent to those based on PMR-15 but with
performance of AFR700B laminates reinforced
superior toughness, higher Tg (371°C to >
with AstroquartzO I11 fibers was superior to
449"C, 700°F to >840"F), superior retention
that exhibited by either S2-glass or Thornel
(>70% compared with <20% for PMR-15) of
650-42 laminates (Fig. 4.12). The retention of
properties at 371°C (700 OF) and up to 10 times
the 260°C (500°F)flex strength of S2-glass lam-
better weight loss characteristics after 100 h at
inates is illustrated in Fig. 4.13. Similar results
371°C (700 O F ) compared with PMR-15. Based
were obtained with Astroquartz I11 and
on these results and assuming reasonable pro-
Thornel 650-42. Overall, composites based on
cessibility, TRW-R-8XX could turn out to be a
AFR700B offer the promise of reasonable
serious contender in the world of high tem-
processability, cost and excellent mechanical
perature polyimides, especially in view of the
properties in the dry-as-molded state out to
about 371°C (700°F). Based on its chemistry projected low cost.
 Electrical properties 95

n
90 I 1 I 90
t
I I I

80 80

I? .-ua
I Y
€ 70 70 i
UJ UJ

E \
C C
?! ! !
3 3
v
i
60 6o x
8
ii
50 50

40 40

0 1000 2000 3000 4000 5000 6000 7000

Time, Hours

Fig. 4.13 Effect of air aging at 260°C (500°F) on the flex strength of AFR700B/S2-glass laminates."
4.9 ELECTRICAL PROPERTIES
One of the useful properties of aromatic poly-
imides is their good all around electrical
properties. Low dielectric constants and dissi-
pation factors have been measured in quartz
fabric reinforced Avimid N and Skybond
based composite^^^. For instance, the room
temperature dielectric constants for Avimid N
and Skybond Astroquartz laminates have been
reported to be 3.2 and 3.7 respectively.Also, in
the same types of laminates the dissipation
factors have been measured to be 0.001 for
Avimid N and 0.015 for the Skybond. The par-
tial fluorocarbon character of the 6F monomer
is undoubtedly the reason behind the
improved properties of Avimid N compared
with Skybond. Some other miscellaneous elec-
trical properties26 of E-glass reinforced
Skybond based composites are tabulated in

Table 4.7 Electrical properties of Skybond@700/181 style E-glass fabric laminates 26

Property Units Value

Dielectric strength
short time parallel to laminate volt 55 000
step by step parallel to laminate volt 38 000
short time volts/pm 179
stepwise volts/pm 140
Dielectric constant (1MC) 4.1
Dissipation factor (1MC) 0.0045
Insulation resistance megohm 1.9 x 107
Volume resistivity ohm-cm 2.47 x 1015
Surface resistivity Ohm 3.35 x 1014
96 High temperature resins

Table 4.7. Skybond 700/E-glass fabric lami- there were also definite indications that voids
nates have been shown to have a dielectric in the composite could serve to facilitate the
constant and dissipation factor measured at drying out process, thus resulting in a higher
X-band (8.5 KMC) frequency at room temper- apparent 'wet' T . This means that although
ature of 3.74 and 0.016 respectively. When voids are well known to adversely affect
measured at 300°C (572°F) there was essen- mechanical properties their presence could
tially no change. conceivably result in significant improve-
ments in a composite's hot/wet properties to
the point where an overall better balance of
4.10 HYGROTHERMAL PROPERTIES
properties might be possible.
All of the mechanical properties discussed In the design of high temperature poly-
thus far in this chapter, either before or after imide parts it is strongly suggested that
air aging, have been determined on 'dry' spec- moisture effects be fully taken into account. It
imens. Although there are many reports in the seems apparent that the full potential of poly-
literature on the absorption of water by a wide imide composites will not be realized until
variety of polymers and the effects that this effective ways are found to reduce the adverse
water can have on the Tg,strangely there have effects of moisture at elevated temperatures
been relatively few reports of the effects of without seriously affecting the other impor-
moisture on polyimide composites. Hot/wet tant properties such as strength, toughness
properties are normally reported for epoxy and thermal-oxidative stability.
and bismaleimide composites, but usually not
those based on polyimides. Unfortunately for
4.11 END-USE APPLICATIONS
polyimide composites water absorption is to
be expected since the equilibrium water con- In spite of their recognized limitations (e.g.
tent of the neat resins being normally in the microcracking and hygrothermal problems)
2 4 % range. polyimide composites have been successfully
One of first references to moisture effects employed i i ~a wide variety of applications.
occurred in 1976%in which studies at DuPont For instance, autoclave molded PMR-15
on Avimid N composites indicated that low graphite fabric composite has been employed
void (<lo/,) E-glass fabric laminates under- in the manufacture of ducts for the F-404
went an almost 100°C (212°F) reduction in the engine used in the United States Navy's F-18
Tg when that property was measured on a fighter (Fig. 4.14). Other successful applications
water saturated laminate by thermal mechani- for PMR-15 include a fire wall for the GE-90
cal analysis at a heat-up rate of 50°C
(90"F)/min. The original 'dry' Tg of 342°C
(648°F)might have indicated good mechanical
property retention out to at least 316°C
(600°F).However, the 'wet' Tgof 245°C (473°F)
indicated a dramatically lower projected end-
use temperature (<<245"C). It was also
reported in the same reference that at the
slower heat-up rate of 5°C (9°F) per minute a
much higher apparent 'wet' Tg was possible
(305"C, 581°F). Thus, if a part can be heated up
slowly enough, it can dry out as it is heated
and the deleterious affects of absorbed mois- Fig. 4.14 PMR-15 /graphite duct for the F-404 jet
ture can be greatly reduced. In this same paper engine.

Fig. 4.15 AvimidO N/graphite jet engine variable
stator vane bushings.
engine as well as various splitters and fairings
for the F-110 engine.
Compression molded Avimid N/graphite
variable stator vane bushings (Fig. 4.15) and
washers, now available from DuPont/Tribon
Composites, have been extensively employed
since the early 1980s in conjunction with the
Fig. 4.16 NO-CHX@Take out jaws based on Avimid N/graphite.
End-use applications 97
variable stator vanes in a variety of military
and commercial jet engines. Parts of this type
have also been made using PMR-15 and
PMR-11. Another interesting non-aerospace
application for Avimid N from DuPont has
been the product, NO-CHX@takeout jaws (Fig.
4.16), which have been used in the glass bottle
industry to grab the hot blow-molded glass
bottles to transport them during fabrication
without cracking or checking.
Other applications for polyimide compos-
ites have been radomes, missile fins, jet engine
nozzle flaps, fairings, cowls and inlet guide
vanes, gear cases for helicopters and heat
shields.
98 High temperature resins
REFERENCES
1. Gibbs, H.H. 20th Natl. SAMPE Symp. Exhib.,
April 1975.
2. Sonnett, J.M., McCullough, R.L., Beeler, A.J. and
Gannett, T.P. 24th Intern SAMPE Tech. Conf.,
October 1992, p. T735.
3. Scola, D.A. United Technologies, private com-
munication.
4. Serafini, T.T., Delvigs, P. and Lightsey, G.R. 1.
App. Polym. Sci., 1972,16, 905.
5. Serafini, T.T., Delvigs, P.and Lightsey, G.R. US
Patent 3 745 149 (July 1973).
6. Serafini, T.T. and Delvigs, P. Appl. Polym. Symp.,
1973, 89, (22).
7. Serafini, T.T. Proc. 1975 Intern. Conf. Composite
Materials, AIME, New York, 1976,1,202.
8. Serafini, T.T., Delvigs, P. and Lightsey, G.R.
NASA TN D-6877 (1972).
9. Burns, E.A., Lubowitz, H.R. and Jones, J.F.
NASA CR-72460 (1968).
10. Lubowitz, H.R. US Patent 3 528 950 (1970).
11. Serafini, T.T., Vannucci, R.D. and Alston, W.B.
NASA TMX-71984 (1976).
12. Vannucci, R.D. 32nd Intern. SAMPE Symp.
Exhib., April 1987.
13. Vannucci, R.D. and Cifani, D. NASA TM-100923
(1988).
14. Vannucci, R.D. and Cifani, D. 20th Intern.
SAMPE Tech. Conf., Sept. 1988.
15. Serafini, T.T., Delvigs, P. and Vannucci, R.D.
36th Ann. Tech. Conf. SPI Reinforced
Plastics/Composites Inst., Feb. 1981.
16. Vannucci, R.D., Malarik, D.C., Papadapoulos
D.S. and Waters J.F. NASA TM 103233.
17. Vannucci, R.D., Malarik, D.C., Papadapoulos,
D.S. and Waters, J.F. 22nd Intern. SAMPE Tech.
Conf., Nov. 1990.
18. Malarik, D.C. and Vannucci, R.D. NASA CP-
10039,15-1 (1989).
19. Meador, M.A., Cavano, P.J. and Malarik, D.C.
Proc. Sixth Ann. ASM/ESD Adv. Comp. Conf.,
Oct. (1990).
20. Sutter, J.K. et al., NASA CP-10039,12-1 (1989).
21. Serafini, T.T. et al., US Patent 5 091 505 (Feb.
1992).
22. Serafini, T.T. et al., US Patent 5 149 760 (Sept.
1992).
23. Serafini, T.T. et al., US Patent 5 149 772 (Sept.
1992).
24. Johnson, K.M. Air Force Materials Laboratory,
private communication.
25. Serafini, T.T. TRW-Redondo Beach, private com-
munication.
26. Monsanto trade literature.
27. Scola, D.A. 34th Intern. SAMPE Symp., p. 246
(1989).
28. Hexcel trade literature.
29. Gibbs, H.H. 10th National SAMPE Tech. Conf,
1978, p. 21.
30. Gibbs, H.H. 1. Appl. Poly. Sci., Appl. Poly. Symp.,
1979, 35,207.
31. Ward, D. General Electric -Aircraft Engines, pri-
vate communication.
32. Meador, M.A. NASA Lewis Research Center,
private communication.
33. Tanikella, M.S. Mosco, J.A. and Rafalski, T.J.,
24th Intern. SAMPE Tech. Conf., 1992, p. 687.
34. Gibbs, H.H. 21st Natl. SAMPE Symp. Exhib.,
1976, p. 607.
35. Fiberite trade literature.
36. Engineered Materials Handbook - Composites,
1987,1, 79.
37. Wilson, D. High Performance Polymers, 1991,3(2).
38. DuPont trade literature.
39. Iuliano-Picho, D. DuPont Composites, private
communication.
SPECIALITY MATRIX RESINS
David A.Shimp
5.1 INTRODUCTION
Bismaleimide (BMI) and cyanate ester (CE)
resins were first commercialized in the 1970s as
250-300°C Tgclass laminating resins for circuit
board substrates. In the early 1980s structural
prepregs were introduced to an aircraft indus-
try searching for primary structure composites
with higher service temperatures and
improved damage tolerance relative to multi-
functional epoxy based composites. Both BMI
and CE resins have since evolved as easy-to-
process thermosetting resins qualified for
177°C (350°F) hot-wet service. Toughening
technologies provide compression-after-impact
ratings approaching or matching the damage
tolerance of thermoplastic resin composites.
Bismaleimides, with higher modulus values
and established higher thermal ratings, earned
a strong position in military aircraft primary
structures with recent selection for the F-22
fighter. Cyanate esters, with superior dielectric
loss properties and lower moisture absorption,
are strong contenders for radomes, skins cover-
ing phase-array antennae, advanced Stealth
composites and space structures.
5.2 RESIN CHEMISTRY
Cyanate ester monomers are prepared by react-
ing bisphenols or polyphenols with cyanogen
chloride in the presence of an organic base
(Rottloff, 1977).Crystalline monomers are ther-
mally advanced to amorphous prepolymer
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
5
resins by resin suppliers accomplishing from
1550% of the cyclotrimerization curing reac-
tion using closely controlled reactor processing.
Figure 5.1 illustrates formation of the s-triazine
ring (cyanurate trimer) by the cycloaddition of
three cyanate groups. Formulators catalyze
amorphous monomers or prepolymer resins
with latent catalysts which promote full con-
version to the thermoset polycyanurate with
subsequent heating to 177-250°C. Cyanates
also serve to cure epoxy resins, forming cost-
effective hybrids retaining an anomalously
high fraction of CE homopolymer properties
(Shimp, 1992).
Bismaleimide monomers are prepared by
the reaction of aromatic diamines with maleic
anhydride in the presence of dehydrating
agents (Stenzenberger, 1990). Homopolymers
of BMI monomers are excessively brittle and
in practice are co-reacted with chain-extending
diamines, diallyl bisphenols or dipropenyl
phenoxides to develop toughness via reduced
cross link density. Figure 5.2 illustrates chain
extension with aromatic diamine (Bargain,
1971) to form longer linear segments which
ultimately crosslink by homopolymerization
of maleic double bonds. Kerimid@resins and
Fiberite PI molding compounds are examples
of commercial BMIs using aromatic amine
modification.
Figure 5.3 depicts a series of reactions
whereby o-allyl-phenols add across the maleic
double bond via the 'ene' reaction and a second
maleimide enters into a Diels-Alder ring-form-
ing reaction with the now conjugated propenyl
residual double bond. The proposed reaction
100 Speciality matrix resins

0 0

I
MICHAEL ADDITION
VI

I
HOMOPOLYMERIZATION
VI
Prepolymer resin
0 0 0 0

Curing via
cyclotrimerization

Y Y

X = alkylidene Y = alkyl or H

Fig. 5.2 Sequence of chemical reactions for advanc-

ing BMI monomers with aromatic diamines to resin
adducts by chain extension and ultimately to
toughened thermoset plastics.
0
R
mechanism includes isomerization to form the
i aromatic ring. Crossllnking can occur by a con-
Thermoset plastic
(polycyanurate) tinuation of these reactions (difunctional
components) or via residual maleic double
Fig. 5.1 Dicyanates cure by forming triazine rings bond homopolymerization. The chemistry by
on heating, advancing to prepolymers (up to 50% which o,o'-diallyl bisphenol A coreacts with and
conversion) and to thermoset plastics at -O-C=N toughens 4,4'-bismaleimido-diphenylmethane
conversions >60-64%. (BMI-DAB) is described by Zahir (1978) and
 Matrixformulation 101

King (1984). Allyl functional phenoxy com- 5.3 COMMERCIAL RESINS

pounds follow the same reaction path while
The chemical structure of seven commercial
propenyl functional phenoxides eliminate the
di(po1y)cyanate ester monomers is shown in
'ene' reaction step (Stenzenberger,1990).
Table 5.1 along with supplier information,
physical state and key homopolymer proper-
ties. The three crystalline monomers are
r! Ri usually supplied only as amorphous prepoly-
I mers in semisolid, hard resin, or ketone
+ laminating solution form. CE homopolymer

@-OH I
properties are not affected by prepolymer
advancement, which is only an interruption of

I "ENE" REACTION

Ri
the ring-forming curing reaction to alter phys-
ical state and rheological properties. Monomer
asymmetry, e.g. AroCy@L-10, can yield low RT
viscosity. CEs have a low toxicity profile and

bv2b
storage stability comparable to epoxies.
Table 5.2 describes several BMI monomers,
advanced resins, reactive tougheners with
OH allyl and propenyl functionality and RTM

1 yy Ri resins. Most BMI monomers have a crystalline

DIELS-ALDER I physical state. Eutectic blends of monomers
REACTION are available as resolidified melts of lower
melt point. Resins prepared by prereacting a
molar excess of BMI with tougheners have a

e.
9
% db
MERIZATION - HOMOPOLY-
powder or hard resin physical state. Allyl and
propenyl functional reactive tougheners are
usually viscous liquids which serve to dissolve
crystalline BMIs at temperatures below 110°C
to offer convenient melt processibility.

1I
OH
AROMATIZATION
5.4 MATRIX FORMULATION

-
HoMoPoLY-
MERIZATION
Fig. 5.3 Sequence Of reactions between Phe-
nols and BMI monomers involves grafting via the
'ene' reaction and fused ring formation via
Diels-Alder. Crosslinking with di(po1y) functional
components involves completion of these reactions
and/or maleic double bond homopolymerization.
5.4.1 MEETING RHEOLOGICAL
REQUIREMENTS
Both resin classes offer a wide selection of
monomers and prepolymers enabling the
fomulator to satisfy the rheological properties
of fluid RTM compounds, tack and cohesive
integrity of compliant prepreg and the short
flow of compression molding compounds.
Figure 5.4 illustrates the limiting direct rela-
tionship in families of thermosetting resins
between fluid monomer (150 mPa s viscosity)
temperature and Tg On curing. High
temperature polyimides locate Off-sCalein the
102 Speciality matrix resins

Polycyanate monomer structure/ Trade name/ Homopolymer property

arecursor supplier/ T.2 wt.% Dk G,
physical state O e H,O MHz J m-2
~~

AroCy B
e c - ~ c ~ ~ + c ECibaNSpecialty Chem.*
CH3 BT-2000 289 2.5 2.91 140
Mitsubishi GC

Bisphenol A Crystal

943 p 3 AroCy M
N E c - o o { *)N Ciba Specialty Chem. 252 1.4 2.75 175
$ Crystal
dH3 CH3
Tetramethylbisphenol F

AroCy F
,oOcP*ZN Ciba Specialty Chem. 270 1.8 2.66 140
CF3
Crystal
Hexafluorobisphenol A

AroCy L-10
Ciba Specialty Chem. 258 2.4 2.98 190

Liquid
Bisphenol E

XU-366
Ciba Specialty Chem. 192 0.7 2.64 210

Semisolid
Bisphenol M

Primaset PT 270
Lonza, Inc.
to 3.8 3.08 60
XU-371
Ciba Specialty Chem. >350
Novolac resin Semisolid

XU-71787
*CZN Dow Chemical 244 1.4 2.80 125

Dicyclopentadienyl bisphenol Semisolid

~

* The complete name of the Ciba company supplying AroCy cyanate resins is Ciba Specialty Chemicals Corp.,
Performance Polymers Group.
 Matrix formulation 103

Table 5.2 Commercial BMI monomers, resins (adducts), reactive tougheners and compounds

Supplier Trade name/structure Description

~

Basic BMI monomer

Ciba Crystalline powder
m.p. 150-160°C
0 0

Matrimidm5292A

o,o'-DiallylBisphenol A
Ciba Reactive toughener
12 000-20 000 mPa s at 25°C

Matrimid 5292B

Inspec CornpimidemMDAB Basic BMI monomer

Inspec Compimide 353 Resolidified BMI melt

Eutectic monomer blend 400-1400 mPa s at 110°C

Inspec Compimide 796 Resolidified BMI resin melt

Proprietary BMI adduct 10004500 mPa s at 110°C

Bisallyl polyphenoxide
Inspec Reactive toughener
Compimide TM 121 120-250 mPa s at 71°C

a r' Bispropenyl phenoxy

benzophenone
Reactive toughener
Inspec 1000-1600 mPa s at 71°C
0
Compimide TM 123

Inspec Compimide 15 MRK Powder for molding compounds

Inspec Compimide 65 FRW Resolidified melt for filament

winding and RTM
Ciba designates Ciba Specialty Chemicals Corp., Performance Polymers. Inspec designates Inspec Fine Chemicals Co.

Table 5.1 (on facing page) Commercial cyanate ester monomers, suppliers, physical states and homopoly-
mer properties. Water absorption is wt.% at saturation. D, = dielectric constant
104 Speciality matrix resins

400

300
I BM' I
0
d,
0
AROCY R T ~ T m -

-
I- L-10
366 EPOXIDE
z 200
v)
n
U
w
[r DlEPOXlDE
O
w VINYL
a
2100 -
POLYESTER

0
0 50 100 150
MONOMER TEMP. ( " C ) at 150 MPA.S

Fig. 5.4 Relationship between fluid monomer tem-

perature and cured T g in families of thermosetting - 21 0 0 20 40 60 80 1
10
resins.Higher service temperature is normally asso- AROCY L-10, WEIGHT %
ciated with increasing processing difficulties.
Fig. 5.5 The asymmetric structureof AroCy L-10 dis-
upper right quadrant. AroCy L-10, derived rupts crystallinity, permitting optional use of this
from an asymmetric bisphenol, breaks the pat- ring-forming resin as a reactive diluent.AroCy num-
tern and can be used as a 250°C T g resin or as bers are the % cyanate conversion of prepolymers.
a reactive diluent of 120mPas viscosity
(Fig. 5.5). but predissolving in 2-6 phr (parts per hun-
dred resin) alkyl phenol, e.g. nonyl or dinonyl
phenol, forms stable liquid packages which
5.4.2 CURE CATALYSTS
are readily miscible (Shimp, 1988). The alkyl
Catalysts are not required to cure BMI resins at phenol provides the active hydrogen co-cata-
temperatures above 200"C, but several types lyst and can serve as a monofunctional
provide effective cure acceleration. Tertiary reactant to increase conversion and resistance
amines, imidazoles and free radical generators to boiling water at marginal cure temperatures
are noted by Zahir (1978). Boyd (1987) (Fig. 5.6). Extension of this principle to AroCy
describes the preferred latency of tri- XU-366 enables this monomer to convert satis-
phenylphosphine and its phosphonium halide factorily at 121°C for use with high modulus
derivatives as prepreg catalysts. polyethylene fibers (Shimp, 1994a) and with
Cyanate esters require catalysis to cure at composite tools.
practical rates. Copper (most active at low
temperatures) and cobalt (latent) acetylaceto-
5.4.3 TOUGHENING TECHNIQUES
nates provide 295% conversion within 2-6 h at
post cure temperatures in the range of Concentrated effort over the last decade has
200-250°C. Metal coordination catalysts in produced composite toughening techniques
general are difficult to solubilize in neat resins, which satisfy damage tolerance requirements

I L
' I
".
0 2 4 6
NONYLPHENOL CONC. (phr)
I I I 5.4.4 EPOXY RESIN MODIFIERS
0 10 20 30 40
Meq OHIOCN
Fig. 5.6 Increasing concentrations of alkyl phenols
in cyanate ester homopolymers increase conversion
(numbersat right) for a given cure temperature and
increase resistance of 3 mm thick castings to hydrol-
ysis in boiling water. Cure temperature: a: 250°C;
A,:210°C; 0 :177°C. (for AroCy B)
of primary aircraft structures and microcrack
resistance in earth orbit and cryogenic service.
BMI resins earlier required the development of
allyl, propenyl and amine functional reactants
to achieve >2% tensile elongation-at-break, a
minimum requirement for efficient secondary
toughening with thermoplastic polyimides.
Boyd (1990) describes the development of
improved chain extending reactants by cou-
pling 2- or 4-propenyl phenol with diepoxides.
Incorporation of thermoplastic polyimide fine
particles of 5-15 pm diameter, described by
Boyd (1991a),increased the compression-after-
impact (CAI) performance of BMI composites
to 2276 MPa (240 ksi). Further toughening to
Matrix and composite properties 105
the CAI performance level of 245 ksi was
demonstrated (Boyd, 1993a) by combining in
situ epoxy extension of o,o'-diallylbisphenol A
with thermoplastic polyimide particles.
CE monomers and prepolymers dissolve
powdered amorphous thermoplastics (Tps) of
the polysulfone, polyethersulfone, polyether-
imide, polyphenylene oxide and copolyester
families, then subsequently phase separate
these thermoplasticsduring cure. Co-continuous
morphologies are developed at Tp concentra-
tions 215% which increase GI, values in a non-
linear response to concentration (Shimp,
1994a). Lee (1991) describes the development
of a CE matrix formulation toughened with
polyoxazolidinones, polyethersulfone and co-
polyester Tp resins. Table 5.3 lists a number of
Tp resins used to toughen both CE and BMI
resins as well as reactive rubbers used to elim-
inate microcracking in orbital service.
Epoxy resins derived from epichlorohydrin
co-react with CE resins at equivalent ratios of
up to 1.2 epoxides per monomer cyanate.
Hybrids with typical epoxy weight fractions of
50-70'/0 develop Tg values in the 180-200°C
range and retain dielectric constants 13.1 with
loss tangents generally below 0.010 (Shimp,
1992). The use of diepoxides to toughen BMI
resins via chain extension of alkenyl (bis)phe-
nols was described in the previous section.
Epoxides can also react with the secondary
amine formed by the Michael addition of aro-
matic diamine to the BMI maleic double bond.
5.5 MATRIX A N D COMPOSITE PROPERTIES
The following acronyms will be used to
denote BMI resin system properties in figures
used thoughout this section:
BMI-MDA = the reaction product of 4,4'-bis-
maleimidodiphenyl methane (molar excess)
with methylene dianiline.
BMI-DAB = the equimolar reaction product of
106 Speciality matrix resins

Table 5.3 Thermoplasticand reactive rubber tougheners

Classification Product Used Supplier

with

Soluble T,"
Polyethersulfone Victrex 5003P 203 CE ICI/Mitsui
Polysulfone Udel P-1700 175 CE Amoco
Polyetherimide Ultem lOOO(P) 215 CE General Electric
Polyphenyleneoxide PPO 202 CE General Electric
Polyimide Matrimid 5218 300 CE Ciba
Elastomeric T,
Copolyester Vitel PE-307 14 CE Bostik
Reactive rubbers
Solublea(OH) ATX-013 <25 CE Echo Resius
Soluble"(Epoxy) Hycar ETBN <25 CE B.F. Goodrich
Preformed Core/Shellb CRS (exp.) <25 CE Dow Chemical
Polysiloxanes
Epoxy functional Experimental <25 CE Proprietary
Maleimide functional PAP Series <25 CE National Starch
Particulate T,"
Polyimide P-84 290 BMI Lenzing AG
Polyimide Matrimid 5218 300 BMI Ciba
Polyamide 1002 D NAT 85 CE Atochem Corp.
a Initially soluble but phase separate during cure.
Small particles swell but do not completely dissolve with cure.
Note: Most of this toughening technology is described in patents.

4,4'-bismaleimido diphenylmethane with Although CE resins demonstrate higher tem-

o,o'-diallylbisphenol A (Matrimid 5292).
5.5.1 MECHANICAL PROPERTIES
Table 5.4 compares properties of representa-
tive CE and BMI castings. Significant
differences are the higher room temperature
modulus values of BMI matrices (superior
stress transfer to fiber) and higher CE elonga-
tion-at-break values.
perature onsets of rapid thermal degradation
in TGA tests, available long term isothermal
aging tests in air indicate superior BMI perfor-
mance. Boyd (1993b) classifies 1-year CAI
retention life of BMI composites as >177 but
<205"C. Stenzenberger (1991) rates 2000 h life
of BMI castings as >2OO0Cbut <250"C based
on retention of shear and flexure strengths.
CE/E-glass laminates are rated at 162-180°C
for 25 000 h retention of flexure strength at
50% of the unaged values (Shimp, 1989).

5.5.2 THERMAL PROPERTIES 5.5.3 DIELECTRIC PROPERTIES

T , values average about 20°C higher for BMI Figure 5.7 ranks the dielectric constant (D,)
matrices (Table 5.5). CTE values below T,are and dissipation factor (D,) or loss tangent of
comparable while CE resins retain higher char thermoset matrix resin castings compared
yields as a result of increased aromaticity. with reference thermoplastics. Effects of
 Matrix and composite properties 107

RESIN DIELECTRIC PROPERTIES

25 O C DK 'I,
DK Df

HOMOPOLYMER

BMI-DAB
AroCy 6 , L
AroCy B AroCy M ,F

F
AroCy M
AroCy F
XU - 366

2 1
POLYETHYLENE
PTFE
0 20 40 60 80 11 0
RESIN CONTENT, Volume %
Fig. 5.8 Effect of reinforcement and concentration

1 1
AIR
I
I oe5
on dielectric constant of AroCy M composites. Test
data at 25°C and 1 MHz.

tems. Moisture locates primarily in the CE free

Fig. 5.7 Thermosetting and thermoplastic resins are
volume fraction, resulting in less swelling
ranked for dielectric constant (D,) and dissipation
factor (D,) at 1 MHz frequency. (Fig. 5. 10) than is caused by association with
strong dipoles. Plasticization of moisture-con-
moisture absorption, test temperature and fre- ditioned matrix castings, compared as a
quency are summarized by Shimp (1994b). function of flexural modulus retention at ele-
Low D , values of CE homopolymers and vated test temperatures, is minimized by the
CE/epoxy hybrids are attributed to the sym- low absorption of AroCy M o-methylated CE
metrical arrangement of electronegative resin (Fig. 5.11). Hydrolysis of AroCy M cya-
oxygen and nitrogen atoms around a central nurate linkages in 121°C steam requires >600 h
electropositive carbon atom in these struc- exposure (Fig. 5.12).
tures, resulting in weak dipoles. Dielectric
constants of CE composites compared with
5.5.5 PROPERTIES OF UNIDIRECTIONAL
fiber type and loading are plotted in Fig. 5.8.
COMPOSITES
D, and loss tangent values of quartz reinforced
BMI, CE and epoxy composites are compared Properties of intermediate modulus carbon
at four radar bandwidths in Fig. 5.9 (Speak, fiber reinforced BMI composites (Table 5.6)
1991). and CE composites (Table 5.7) indicate good
translation of fiber strength for both classes.
Damage tolerance ratings based on CAI
5.5.4 MOISTURE ABSORPTION AND EFFECTS
results at 6.7 KJ m-l impact energy fall in the
CE homopolymers absorb less moisture than 200-345 MPa (30-50 ksi) class, approaching or
BMI and TGMDA/DDS epoxy matrix sys- equaling the damage resistance of thermoplastic
108 Speciality matrix resins

Table 5.4 Mechanical properties of CE and BMI resins

AroCy AvoCy AroCy Matrimid

B M L 5292

Composition (PBW)
- -
AroCy B-30 100 -

AroCy M-20 - 100 - -

AroCy L-10 - - 100 -

Matrimid 5292A - - - 100

Matrimid 5292B - - - 85
Nonylphenol 2 2 2 -

Cobalt acetylacetonate 0.13 0.13 0.13 -

Property of casting"
Tensile strength, MPa 88 76 87 82
ksi 12.7 11.0 12.6 11.9
Tensile elongation, YO 3.2 2.7 3.8 2.3
Flexure strength, MPa 174 159 187 167
ksi 25.2 23.0 27.1 24.2
Young's modulus Flexure Flexure Flexure Tensile
25"C, GPa 3.17 2.97 3.24 4.28
msi 0.46 0.43 0.47 0.62
149"C, GPa - - - 2.42
msi - - - 0.35
163"C, GPa 2.55 2.35 2.28 -

msi 0.37 0.34 0.33 -

204"C, GPa - - - 2.00

msi - - - 0.29
G,,, J m-2 140 175 190 170
in lb in-2 0.80 1.00 1.08 0.97
aStep-cure with post cure of 2 h at 250°C for CE; 6 h at 250°C for BMI. Data courtesy of Ciba Specialty Chemicals Corp.,
Performance Poiymers Group.

composites. BMI composites have demon- KorexTMaramid/phenolic honeycomb core

strated hot-wet performance in 177°C rated
aircraft. CE composites may attain that goal
with AroCy M resin, but insufficient 177°C
hot-wet compression data has been published
for commercial materials of this class.
5.6 DESIGN CONSIDERATIONS
5.6.1 SELECTION OF ARAMID FIBER AND
CORE
Aramid fiber and core reinforcements for CE
composites should be selected from second
generation materials wluch absorb <2% mois-
ture in the workplace. Kevlar@aramid fiber and
(DuPont) are recommended for use with CE
resins catalyzed with copper or cobalt acety-
lacetonates to eliminate blistering associated
with post cures >190°C. (Shimp, 1993; 1994a).
5.6.2 GALVANIC CORROSION
Both BMI and CE carbon fiber composites
have been reported to undergo resin degrada-
tion in accelerated galvanic cell tests
producing strongly alkaline conditions at
cathodic sites (Boyd, 1991b; Olesen, 1991).
Figure 5.13 compares the onsets and rates of
alkaline hydrolysis (etching) for CE and BMI
matrix castings. (See also Boyd, 1991b).
 Suppliers of prepreg and other formulated products 109

Table 5.5 Thermal properties of CE and BMI resins

AroCy AroCy AroCy Matrimid

B M L 5292

Composition (PBW)
AroCy B-30 100 - - -
AroCy M-20 - 100 - -
AroCy L-10 - - 100 -
Matrimid 5292A - - - 100
Matrimid 5292B - - - 85
Nonylphenol 2 2 2 -

Cobalt acetylacetonate 0.13 0.13 0.13 -

Property of casting"
HDT, "C
Dry 254 252 249 273
Wet 197 226 183 217
T,' "C
by DMA 289 267 270 295
by TMA 257 255 259 273
CTE by TMA, ppm/"C
40 to 200°C 64 66 64 63
TGA at 10"C/min
Onset in air, "C 411 406 408 371
Char in N,, Yo 41 46 43 29
Specific gravity at 25°C 1.201 1.151 1.228 1.232
aStep-cure with post cure of 2 h at 250°C for CE: 6 h at 250°C for BMI. Data courtesy of Ciba Specialty Chemicals Corp.,
Performance Polymers Group.

Effective design practices for susceptible com-
posites are use of titanium rather than
aluminum rivets, placement of a fiberglass
reinforced insulating ply and/or modification
of CE resin with 55-70% epoxy resin.
5.6.3 MICROWAVE TRANSPARENT
COMPOSITES
Composite design for radomes, antennas and
advanced stealth structures should utilize low
dielectric loss materials (Speak, 1991; Shimp,
1994b; Stonier, 1991a,b). Figure 5.14 summa-
rizes microwave interactions with a radome
wall. Reflection weakens returning signals and
overheats emitter sources; refraction distorts
signal quality; absorption decreases signal
strength and generates destructive heat, limit-
ing power and range. CE composites curing at
121°C (250°F), e.g. Bryte Technologies'
EX-1515, are thermally compatible with high
modulus polyethylene reinforcement. Such
composites are characterized by D, values as
low as 2.6 and D, values as low as 0.004 when
measured at 10 GHz.
5.7 SUPPLIERS OF PREPREG AND OTHER
FORMULATED PRODUCTS
Table 5.8 lists suppliers of BMI and/or CE
prepreg, adhesive, syntactic foam, RTM/fila-
ment winding systems and chopped fiber
reinforced molding compounds formable by
compression, injection or transfer processes.
110 Speciality matrix resins

4.0 I 1
IIELECTRIC I I
CONSTANT

3.5

3.0 J
XBAND KaBAND UBAND WBANC
8-12 26-40 40-60 75-100
GHz GHz GHz GHz
0.030

TANGENT
0.020

0.0 10

CE tI
0.000 '
XBAND KaBAND UBAND W BAND

Fig. 5.9 Comparison of typical quartz reinforced radome composites for dielectric loss properties measured
at four radar bandwidths. Redrawn from Speak, S.C., Sitt, H and Fuse, R.H.. 1991. Novel cyanate ester
based products for high performance radome applications. Int. S A M P E Symp., 36 pp. 336-347.

i
I +
P

10' 1o2 1o3 1o4

Hours at 25°C & >95% RH
Fig. 5.10 Changes in 3 mm thick bar volumes during water immersion for a period of one year indicate
swelling rates and limits of thermoset resins. The ratio of volume increase to total volume of water
absorbed (numbers on right) indicates the fraction of water associated with dipoles.
A: BMI-MDA; X: BMI-DAB; 0: TGMDA-DDS; 0:AroCy B; 0 :XU-366
 Suppliers of prepreg and other formulated products 111

Table 5.6 Properties of BMI/IM-7 unidirectional composites

Mechanical st rengtk Rigidite Rigidite

5250-4" 5260b

0" Tensile, MPa (ksi)

25°C 2618 (380) 2691 (390)
0" Compression, MPa (ksi)
25°C Dry 1820 (235) 1746 (253)
105°C Wet - - 1346 (195)
149°C Wet - - 1276 (185)
177°C Dry 1310 (190)
177°C Wet 966 (140)
0" Compressive modulus
25"C, GPa (msi) 158 (23) 152 (22)
Open hole compression, MPa (ksi)
25°C Dry 420 (61) 352 (51)
177°C Dry 351 (51) 269 (39)
191°C Wet 303 (44) 221 (32)
Compression after impact
At 4.5 kJ m-l, MPa (ksi) 248 (36) 380 (55)
At 6.7 kJ m-l, MPa (ksi) 214 (31) 345 (50)
Edge delamination, MPa (ksi)
25°C 241 (35) 358 (52)
~~

a Data courtesy of Cytec. Post cure 6 h at 227°C; 60% fiber vol.

Data courtesy of Cytec. Post cure 6 h at 215°C; 60% fiber vol.

Table 5.7 Properties of CE unidirectional composites

Cytec Fiberite Hexcel

5245C 954-2 HX-1562

Reinforcementhre
Carbon fiber IM-6 IM-7 IM-7
Max. cure temp., "C 210 232 177
Mechanical strength
0" Tensile, MPa (ksi) 2439 (356) 2814 (408) 2610 (378)
0" Compression, MPa (ksi)
25"C, Dry 1690 (245) 1573 (228) 1700 (246)
121"C, Wet 1350 (196) 1331 (193) - -
132"C, Wet 1310 (190) - - 1140 (165)
149"C, Wet 987 (143) 1290 (187) - -

CAI, MPa (ksi)

At 6.7 kJ m-I 214 (31) 262 (38) 317 (46)
Edge delamination, MPa (ksi) 262 (38) 269 (39)
112 Speciality matrix resins

Fig. 5.11 (left) Moisture plasticization of cast

matrix systems is inversely related to the percent-
age of dry room temperature flexural modulus
0 ° 1 1 O0
retained at elevated test temperatures.
79
74 : at 149°C wet;
: at 177°C wet.
61

Fig. 5.12 (below) Hydrolysis of unsubstituted CE

(bisphenol A dicyanate) homopolymer begins to
reduce mechanical properties after 200 h exposure
~
to 121°C steam autoclave at 15 psig. Ortho-methy-
AroCy AroCy BMI/ lation is an effective technique for increasing
hydrolytic stability of cured CE resins in aggressive
environments. 0: AroCy B; 0:AroCy M.

% WEIGHT GAIN
121

91 AROCY B

0 200 400 600

TIME, HOURS

Table 5.8 Sources of formulated/compounded CE and BMI products

Supplier Prepreg Adhesive Syntactic RTM Compression molding

foam compound compound

Bryte Technologies CE CE CE CE -
Cytec BMI, CE BMI, CE BMI, CE BMI -
Hexcel BMI, CE BMI - - -

Fiberite, Inc. CE - - - BM1,CE

YLA CE CE CE CE -
 AppIications 113

+1.0
AROCYBIEKXY

w H.5
P3 -I
AROCYM
I

0 10 20 30 40 50 60
DAYS IMMERSION IN 20% NaOH AT 50°C
Fig. 5.13 Cured CE and BMI resins hydrolyze (etch)
in strongly alkaline solutions, as indicated by the
onset of weight loss. Ortho-methylated CE resin
and blends with epoxy resin (50/50 blend shown)
increase resistance to alkaline environments gener-
ated in galvanic cells.
5.8 APPLICATIONS
Toughened BMI/carbon fiber composites have
been specified as the principal composite mate-
rial for F-22 fighter primary and secondary
structures (Fig. 5.15).BMI service temperatures
are sufficiently high for cowlings, nacelles and
thrust reversers of jet engines. CE composites
t
Y
TRANSMISSION
Fig. 5.14 Interactions of microwaves with a radome
wall.
were used to construct EFA (Eurofighter) pro-
totypes and are used in construction of the
Dassault Rafale. Both materials are candidates
for HSCT (High speed civil transport) use.
Principal applications for CE composites
(McConnell, 1992) include radomes for mili-
tary aircraft, fighter aircraft retrofitted with
improved tracking systems, skins over phase
array radar, weather tracking aircraft radar
and missile nose cones. CE prepreg reinforced
with high modulus pitch-based carbon fibers
are preferred materials for earth orbit service,

Fig. 5.15 F-22fighter constructed with BMI composites. Photograph courtesy of Lockheed.
114 Speciality matrix resins
demonstrating low outgassing, microcrack
resistance and resistance to lo9rads of ionizing
radiation (Willis, 1991). Applications in space
include communication satellites, solar arrays,
parabolic antennas, optical benches and preci-
sion segmented reflectors.
BMI film adhesives are employed in jet
engine or high speed aircraft sandwich panels
where hot-wet service up to 190°C is required.
CE film and paste adhesives are used together
with syntactic foams in the construction of
radomes. BMI molding compounds reinforced
with up to 65 wt.% of chopped reinforcements
are used to mold ducts, drive sprockets for
heated rolls in copy machines, helicopter gear
boxes and missile strongback mounting sup-
ports.
REFERENCES
Bargain, M. et al. 1971. US Patent 3 562 223.
Boyd, J.D. and D.A. Shimp. 1987. US Patent
4 644 039.
Boyd, J.D. and Hon-Son R. 1990. US Patent
4 923 928.
Boyd, J.D. 1991a. US Patent 5 037 689.
Boyd, J. et al. 1991b. Galvanic corrosion effects on
carbon fiber composites. Int. S A M P E Symp.,
36,1217-1231.
Boyd, J.D. and L.N. Repecka. 1993a. US Patent
5 189 116.
Boyd, J.D. and G.E.C. Chang. 1993b. Bismaleimide
composites for advanced high temperature
applications. Int. S A M P E Symp., 38,357-369.
King, J.J., Chaudhari M. and Zahir. S. 1984. Nat.
SAMPE Conf., 29 392.
Lee, F.W. and K.S. Baron. 1991. US Patent 5 045 609.
McConnell, V.P. 1992. Tough promises from cyanate
esters. Adv. Comp., May/June pp. 28-37.
Olesen, K. 1991. Degradation of graphite/polymer
composites in the presence of a corroding metal.
Read at the High Temple Workshop, 11, Reno,
Nevada, 4 Feb 1991.
Rottloff, G. et al. 1977. US Patent 4 028 393.
Shimp, D.A. 1988. US Patent 4 785 075.
Shimp, D.A., S.J. Ising and J.R. Christenson. 1989.
Cyanate esters: a new family of high tempera-
ture thermosetting resins. SPE/Case Western
Conf. on High Temperature Polymers and Their
Uses, 1, 127-140.
Shimp, D.A. and J.E. Wenhvorth. 1992. Cyanate
ester-cured epoxy resin structural composites.
Int. SAMPE Symp., 37,293-305.
Shimp, D.A and M. Southcott. 1993. Controlling
moisture effects during the curing of high T
cyanate ester/aramid composites. lnt. S A M P f
Symp., 38,370-379.
Shimp, D.A. 1994a. Technologically driven applica-
tions. In Chemistry and Technology of Cyanate
Ester Resins (I. Hamerton Ed.) Chap 10. Blackie,
Glasgow, pp. 282-327.
Shimp, D. and B. Chin. 1994b. Electrical properties
and their significance for applications. In
Chemistry and Technology of Cyanate Ester Resins
(I. Hamerton Ed.) Chap 8. Blackie, Glasgow, pp.
230-257.
Speak, S.C., H. Sitt and R.H. Fuse. 1991. Novel
cyanate ester based products for high perfor-
mance radome applications. Int. S A M P E Symp.,
36,336-347.
Stenzenberger, H.D. 1990.Chemistry and properties
of addition polyimides. In Polyimides (D.
Wilson, P.M. Hergenrother and H.D.
Stenzenberger, Eds) Chap 4. Blackie, Glasgow.
Stenzenberger, H.D. et al. 1991. BMI/bis(allylphe-
noxy phthalimide)-copolymers: improved
thermal oxidative stability. Int. S A M P E Symp.,
36 pp. 1232-1243.
Stonier, R.A. 1991a. Stealth aircraft and technology
from World War I1 to the Gulf, Part I. SAMPE
Journal, 27(4), 9-16.
Stonier, R.A. 1991b. Stealth aircraft and technology
from World War I1 to the Gulf, Part 11. S A M P E
Journal, 27(5), 9-18.
Willis, P.B. and D.R. Coulter. 1991. Applications of
cyanate resins to spacecraft composites. Paper
read at 8th Int. Con$ Composite Materials,
ECCM/VIII, Honolulu, 15-19 July 1991.
Zahir, Sheik A-C. and A. Renner. 1978. US Patent
4 100 140.
THERMOPLASTIC RESINS 4
Lars A.Berglund

6.1 INTRODUCTION posites offer advantages. They have very low

Thermoplastic composites form a fairly new toxicity since they do not contain reactive
group of materials. Commercial prepreg tape chemicals (therefore storage life is infinite).
such as CF/PEEK (carbon fiber/polyether Because it is possible to remelt and dissolve
etherketone) and later CF/PPS (polyphenyle- such thermoplastics, their composites are also
nesulfide) was introduced in the early 1980s. easily recycled or combined with other recy-
However, as early as 1966, Menges reported on cled materials in the market for molding
improved static strength and fatigue resistance compounds.
when epoxy was replaced by polyamide 6 as In the aerospace market, composites based
a composite matrix (Menges, 1966).In the mid on toughened epoxies dominate. The poten-
tially cheaper manufacturing of thermoplastic
1970s there was interest in CF/PSU (Po1YSu1- composites has not yet been realized to the
fone) due to expectations of better processing
methods and improved toughness characteris- extent necessary to motivate large-scale invest-
tics. However, solvent resistance was found to ment in new manufacturing equipment.
be a problem. Composites later introduced However, for the next generation of aircraft,
based on semi-crystalline thermoplastics, such interest in thermoplastic composites is high.
as PEEK and PPS, which have been introduced Higher flying speeds require higher tempera-
more recently, have excellent chemical resis- tures in the materials than the maximum
tance and are superior to epoxy-based temperature available from epoxy-based com-
posites in use today. Since the release of gases
composites in this respect.
Enthusiasm for thermoplastic composites is during processing and inherent brittleness are
serious disadvantages of thermoset polyimides,
generated for, basically, three different rea-
sons. First, processing can be faster than for thermoplastic composites are of great interest.
In the automotive market, thermoplastic
thermoset composites since no curing reaction
is required. Thermoplastic composites only composites are used extensively. Matched-die
require heating, shaping and cooling. compression molding of glass mat thermo-
Secondly, the properties are attractive, in par- plastics (GMT), primarily based on glass
ticular, high delamination resistance and fiber/polypropylene (GF/PP), is common,
because it permits fast processing cycles for
damage tolerance, low moisture absorption
fairly large components. In the established
and the excellent chemical resistance of semi-
crystalline polymers. Thirdly, in light of field of injection molded components, materi-
als are used with long fibers (5-10mm) in
environmental concerns, thermoplastic com-
molding pellets. This leads to improved
mechanical properties compared with materi-
als based 0; shorter fibeis (Truckenmueller
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman &Hall, London. ISBN 0 412 54020 7
and 1991).
116 Thermoplastic resins

6.2 MANUFACTURING METHODS processing, for conversion into a high-viscos-

ity melt. Shaping then takes place and the
The principles for thermoplastic composites
material solidifies on cooling. In Table 6.1,
processing are very different from those for
different manufacturing methods used for
thermoset composites. During the processing
thermoplastic composites are outlined.
of thermosets, the polymer is initially a liquid
Further discussion of thermoplastic compos-
which then solidifies due to the formation of
ites processing is available in Chapter 24 of
a three-dimensional molecular network from
this book and in previous reviews (Carlsson
chemical reactions. Thermoplastics are in the
1991; Cogswell, 1992; Kausch, 1993).
solid state before processing because of their
As with thermoset composites, materials
high molecular weight. They are heated
with low fiber volume fractions show ease of
above their softening temperature during

Table 6.1 Manufacturing routes for composites based on thermoplastic resins

-

Manufact zi ring ro ii te Outline of fabrication and processing methods

Open mold processes
1. Autoclave Unidirectional or woven fibers pre-impregnated by the resin (prepreg) are
used. Other forms of prepreg have reinforcing fibers in combination with
the resin as fibers or as powder. The prepreg layers are stacked on the
mold surface and covered with a flexible bag. Consolidation is obtained by
external pressure applied in an autoclave at elevated temperature.
2. Filament winding Prepreg tape or tape with the resin as fibers or powder are wound onto a
mandrel at pre-determined angles. Heat and pressure are applied to the
tape in order to continuously weld it onto the underlying material.
3. Folding Preconsolidated sheets are heated. Simple fixtures are then used to shape
the sheets into the desired geometry.
Closed mold processes
4. Injection molding A mixture of molten thermoplastic and short fibers is injected into a colder
(short fibers, 0.1-10 mm) metal mold at very high pressure. The component is allowed to solidify
and is automatically ejected.
5. Compression molding Semi-finished sheets of glass mat thermoplastics are heated and placed in
(short fibers, 5-50 mm) the lower part of the mold in a fast press. The press is quickly closed and
pressure is applied so that the material can flow to fill the mold.
Technology is also available where the hot molding compound reaches the
mold from an extruder.
6. Compression molding The same principle as for short fiber materials.
(continuous fibers) Continuous fibers require special clamping fixtures for the sheets and can
primarily be used for simple geometries.
7. Diaphragm forming A stack of prepreg is placed inbetween two diaphragms (superplastic
aluminium or polymer film). The diaphragms are fixed whereas the
prepreg can move freely. The material is slowly deformed by external
pressure and the mold.
8. Pultrusion Prepreg tape or tape with the resin as fibers or powder is pulled through
a heated die to form beams or similar continuous structures with constant
cross-section geometry. The material is allowed to cool and solidify.
9. Resin injection Dry reinforcing fibers are placed in the mold. Monomers and/or low
molecular weight polymer with low viscosity are injected, the
reinforcement is impregnated. Polymerization to a high molecular weight
thermoplastic occurs by mixing of reactive components and/or thermal
activation.

processing but low stiffness and strength. On
the other hand, materials with high fiber con-
tent have high stiffness and strength but
require slow processing and are difficult to
shape into geometrically complicated struc-
tures. For high fiber content materials, the high
viscosity of a molten thermoplastic usually
requires some kind of prepreg fabrication step
before final processing. The prepregs may need
to be combined into the consolidated, semi-fin-
ished sheets before the final processing step.
Regular autoclave processing can be used
for thermoplastic composites. For most high-
performance thermoplastics, however,
temperatures have to be higher than the typi-
cal 177°C used for epoxy-based composites.
Often, the composite manufacturer must pur-
chase a new autoclave if this is the preferred
processing route. Autoclave processing of
thermoplastics has been modeled (Lee and
Springer, 1987). Consolidation of the prepreg
layers is an important issue. At a given tem-
perature, sufficient time must be available for
the polymer molecules to diffuse from one
prepreg layer into the other and form strong
physical entanglements (Howes, Loos and
Hinkley, 1989). In addition, the air initially
present in the material must be displaced.
For thermoplastic composites, filament
winding has demonstrated good economic
potential (Egerton and Gruber, 1988). The
major problem is in the welding of filaments or
the tape onto the underlying composite layers.
Heat has been applied by means of a gas flame,
IR, laser beam or simply from a hot metal sur-
face. Pultrusion of thermoplastic composites
offers potential for faster processing than with
thermoset composites (Astrom, Larsson and
Pipes, 1991), due to the absence of exothermal
heat generation from chemical reactions.
Profiles may also be produced by roll-forming
techniques similar to those used in metal-
working. The shape of existing profiles can be
changed. The low-cost folding technique (GE
Plastics, 1990) has been used commercially by
Fokker and TenCate in Holland for quite large
components of fairly simple geometry.
Material forms 117
Compression molding of glass mat thermo-
plastics (GMT) is a wide-spread process of
great sigruficance in the automotive industry
(Berglund and Ericson, 1994).Resin injection of
polymerizing prepolymer molecules of low
viscosity is in principle the same process as for
thermosets although the chemical reactions
lead to increased molecular weight rather than
to cross-linking. Such a process does not pro-
vide the advantages of infinite storage life
materials with low toxicity. Diaphragm form-
ing is a processing route where the problem of
low extensibility of prepreg-based materials is
addressed (Mallon, O’Bradaigh and Pipes,
1989).
6.3 MATERIAL FORMS
Thermoplastic composites are usually sup-
plied as semi-finished materials, with the
exception of resin injection materials. In Table
6.2, material forms for thermoplastic compos-
ites are presented. Prepregs of high fiber
volume fractions (V, = 0.6) may be prepared
by solvent-, melt-, prepolymer- or powder-
impregnation of the reinforcing fibers.
Solvent-impregnation is limited to amorphous
resins with high solubility. Melt-impregnation
is a technique successfully developed by IC1
(Cogswell, Hezzell and Williams, 1981) pro-
ducing high-quality prepreg. The resulting
prepreg is considered too stiff, for some pro-
cessing situations with little drapability in
comparison with CF/EP (epoxy) prepreg. This
problem is addressed in prepolymer- and
powder-impregnated prepreg. One example is
the FIT-technology where small tubes contain-
ing reinforcing fibers and polymer powder are
used (Thiede-Smet, 1989). In addition, com-
mingled weaves (prepregs) are available. The
resin is present in the form of fibers which are
melted during processing to form a matrix.
Composites produced from commingled
material forms may have a fairly inhomoge-
neous distribution of fibers (Olson, 1990).
Film-stacking is a simple method often
used for preparation of laboratory samples
118 Thermoplastic resins

Table 6.2 Material forms for composites based on thermoplastic resins

Material forms Outline of preparation procedure

Prepregs
1. Solvent impregnated Reinforcing fibers are impregnated by a mixture of solvent and
thermoplastic. The solvent is removed by evaporation.
2. Melt impregnated Reinforcing fibers are impregnated by thin molten films to which pressure
is applied.
3. Prepolymer impregnated Low viscosity prepolymers are used to impregnate the fibers.
Polymerization to high molecular weight thermoplastic takes place during
processing.
4. Powder impregnated Fibers are enclosed by thermoplastic powder, either in small tubes
containing reinforcing fibers and powder or by powder particles adhering
to the fibers from partial melting in a fluidized bed.
Other material forms
5. Film stacked composites Stacks with alternating layers of dry fibers and polymer film are heated
and compressed.
6. Fiber hybridized weaves Roving of commingled reinforcing fibers and the matrix in fiber
and roving form. Weaves are produced from the roving.
7. Prepolymer liquid and Reinforcing weaves are impregnated by prepolymer liquid and
dry reinforcement polymerized to a thermoplastic composite.
8. Semi-finished glass mats Supplied as sheets prepared in belt press by extrusion and melting of
(low fiber content) films which impregnate fiber mats. Porous sheets are produced from slurry
of fibers and thermoplastic powder in water, by technology similar to
manufacturing of paper. Recycled material can be used.
9. Pellets Often prepared by pultrusion of unidirectional fibers and matrix
(low fiber content) followed by chopping into pellets. Used in injection molding or in
plasticizing and/or compounding unit combined with compression
moulding. Recycled material is easily incorporated.

(Hartness, 1982) although the technique has
also been used commercially. In the category
of materials with low fiber volume fraction
(V,=: 0.2), semi-finished sheets of GMT-materi-
als are available. They usually have random,
chopped or continuous fiber mat reinforce-
ments. Unidirectional prepreg may be used in
order to selectively provide additional stiff-
ness, strength a n d creep resistance. A n
interesting step forward is provided by extru-
sion compounded GMT (Composite Products
Inc, 1994; Hoechst AG, 1994). No semi-finished
sheets are used, instead a special extruder is
used to produce a hot, soft 'cake' constituted
of chopped fibers and the polymer matrix,
often PP. The cake is placed in a press and
molded. The investment in technology is
higher than for conventional GMT molding.
On the other hand, the material cost and
energy consumption is reduced, greater free-
dom in materials selection is obtained and
recycling is facilitated. Suppliers of thermo-
plastic composites are listed in Table 6.3.
6.4 THERMOPLASTIC RESINS
Thermoplastics have either amorphous or
semi-crystalline structure (Sperling, 1992). The
large, chain-like polymer molecules do not
show long-range order in amorphous thermo-
plastics, which may be viewed as polymer
glasses and, in the absence of color pigments,
are usually transparent. Thermosets are also
amorphous. In contrast, crystalline polymers
have regions of molecular order. In melt-
processed crystalline polymers, a spherical
 Thermoplastic resins 119

Table 6.3 Suppliers of thermoplastic composites

Supplier Materials
Ba ycomp Unidirectional tapes. Matrices PP, HDPE, PA12
Burlington, Ontario, Canada PC, PEI, PBT, PES, PPS, PEEK, ABS, PPO. Fibers: glass, carbon,
aramid and stainless steel.
CYTEC, Anaheim Commingled yams. Carbon fiber with PEEK, PEKEKK, PA6,6, TPI
CA, USA (Aurum@).GF/PA6,6.
DuPont de Nemours Prepreg based on Avimid@K,thermoplastic polyimide, and
Bad Homburg, Germany and carbon fiber. Sheets laminated of continuous fiber thermoplastic
Newark, DE, USA composites or unidirectional discontinuous fibers. Molding
compounds of lower fiber content. Matrices: PA6,6, PEKK, PET and
others. Fibers: carbon, glass and aramid.
Electrostatic Technology Prepreg fabrication by deposition of polymers in powder form
Branford, C, USA on tow and fabrics. Wide variety of resins and fibers.
GE Plastics GMT-materials based on glass fiber mats and PP, PBT, PC and
Amsterdam, Netherlands and blends PC/PBT. Unidirectional GF/PP.
Pittsfield, MA, USA
Hoechst Unidirectional prepreg of GF/PP, GF/PA6, GF/PE, CF/PPS,
Frankfurt, Germany CF/PA6. Pellets > 12 mm for use in plasticating extruder combined
with compression moulding.
Huls GF/PA12 fabric prepreg.
Marl, Germany
ICI/Fiberite APC-2 (CF/PEEK) prepreg tape and tow and developmental
Monchengladbach, Germany materials, primarily for high-temperature applications.
and Laguna Hills, CA, USA
Porcher Textile FIT-weaves (Thiede-Smet, 1989).Matrices PA12, PEI, PEEK. Glass
Lyon, France and carbon fibers. Enichem, Milano, Italy reportedly produces
GF/PP, PET, PBT with FIT-technology.
Quadrax Corp Prepreg fabrics and unidirectional tape, consolidated sheets.
Portsmouth, RI,USA Matrices PA6,6, PMMA, PEI, PPS and PEEK. Carbon, glass and
aramid fibers.
Schappe Techniques Spun yarns combining reinforcing and matrix fibers for subsequent
Charnoz, France weaving. Matrices PP, PA6, PA6,6, PPS, PC, PEI, PEEK. Carbon, glass
and aramid fibers.
Symalit AG Glass mat thermoplastic sheets based on GF/PP.
Lenzburg, Schweiz
TenCate Advanced Composites Prepreg fabrics and unidirectional tape, consolidated sheets.
Nijverdal, Netherlands and Matrices PES, PEI and PA12. Carbon, glass and aramid fibers.
Fountain Valley, CA, USA
120 Thermoplastic resins
morphology, termed spherulitic, is often
observed (Bassett, 1981). Crystalline lamellae
are present within the spherulites although
disordered regions exist between and within
the lamellae. This is because the large size of
polymer molecules inhibits perfect crystalliza-
tion. The crystalline thermoplastics are
therefore more correctly described as semi-
crystalline, since the degree of crystallinity
never reaches 100%. Semi-crystalline thermo-
plastics can be viewed as two-phase materials
with a crystalline and an amorphous phase.
To illustrate the difference in behavior of
semi-crystalline and amorphous thermoplas-
tics, polyethylene terephthalate (PET),may be
used as an example. PET is a thermoplastic
polyester which crystallizes fairly slowly.
Therefore, upon rapid cooling from the
molten state, crystallization can be sup-
pressed and an amorphous polymer is
obtained (similar behaviour is shown by
PEEK). Samples of PET with different degrees
of crystallinity can be produced by changing
the conditions of cooling. The shear modu-
lus G' (obtained from dynamic mechanical
thermal analysis, DMTA) is plotted against
temperature for such samples in Fig. 6.1. The
I I I
I
50 100
Temperature ("C)
Fig. 6.1 Shear modulus (G') compared with temperature for PET of different degrees of crystallinity.
amorphous sample shows a dramatic drop in
modulus at the Tg (glass transition tempera-
ture). The drop in modulus for semi-crystalline
samples is less dramatic: the higher the crys-
tallinity, the slower the drop. Above T,,
material modulus is maintained by the crys-
talline phase (although strength usually
decreases dramatically). Another effect of
reduced degree of crystallinity is reduced
chemical resistance.
A disadvantage with semi-crystalline poly-
mers is the high processing temperature, see
Tables 6.4 and 6.5, compared with the heat
deflection temperature (see next section, Table
6.11). The melting temperature, Tm,of the crys-
talline phase must be exceeded during
processing, although the maximum use tem-
perature, as for amorphous polymers, is still
below T,.
Characteristic temperatures of thermoplas-
tics used in applications where only moderate
temperatures are experienced are presented in
Table 6.4. These materials are available from
many different chemical companies, therefore
trade names and suppliers are not listed. In
Table 6.5, thermoplastics for applications at
higher temperatures are listed. These polymers
I
I
I I
150 200 250
 Thermoplastic resins 121

Table 6.4 Characteristic temperatures for thermoplastic resins with T,< 90°C

Polymer Chemical Structure T T,,, Processing

type name ("C) ( "C) temp. ("C)
___ ~ - ___
Polyolefin Polypropylene Crystalline -10 165 200-240
(PP)
Polyamides Polyamide 6,6 Crystalline 55 265 270-320
(pA6,6)
Polyamide 12 Crystalline 35 180 220-260
(PA12)

Polyesters Polyethylene Crystalline 70 265 280-310

terephthalate
(PET)
Polybutylene Crystalline 20 240 260-290
terephthalate
(PBT)

Table 6.5 Characteristic temperatures for thermoplastic resins with T, 290°C

Polymer Chemical Trade name Structure T, Processing

fYPe name and supplier ("Ci temp. ("C)
~~ ~~ ~~

Polyester Polycarbonate Lexan, GE Amorphous 150 none 280-330

(PC) Makrolon, Bayer
Polyarylene Polyphenylene Ryton, Phillips crystalline 90 280 300-340
ether or sulfide
sulfide (PPS)
Polyarylene PAS-2, Phillips Amorphous 215 none 330
sulfide
PEEK Victrex PEEK, IC1 Crystalline 143 343 380400
PEEKK Hostatec, Hoechst Crystalline 165 365 390-415
PEKK Declar, DuPont Crystalline 155 340 380400
PEKEKK Ultrapek, BASF Crystalline 175 375 400420
Polyketone Victrex HTX, IC1 Crystalline 205 385 420430

Poly- Polysulphone Udel P1700, Amoco Amorphous 190 none 300-350

sulfones (PSU)
Polyether- Victrex 4100G, IC1 Amorphous 220 none 300-320
sulfone (PES) Ultrason E, BASF

Polyamide- Polyamide- Torlon C, Amoco Amorphous 275 none 350400

imides imide (PAI) Torlon AIX-159 Amorphous 290 none 350400
Amoco

Polyimides Polyetherimide Ultem, GE Amorphous 217 none 335420

(PW
Polyimide (TPI) Avimid KIII, Du Pont Amorphous 250 none 340-360
Polyimide (TPI) Aurum, Mitsui Crystalline 260 390 400420
Toatsu
122 Thermoplastic resins

are more expensive and are often termed ’high- of static mechanical properties of the resins is
performance’ resins. The higher cost of these given in Table 6.6. Resins with low Tg,such as
materials is due to small material volumes, PP and PA12, have lower modulus and
more expensive monomers and more difficult strength. Their fracture toughness is high and
polymerization procedures. valid data according to linear elastic fracture
Many resins used in injection molding are mechanics are difficult to obtain. Among poly-
so called blends, physical mixtures between mers with T, well above room temperature, the
two thermoplastics. In the field of commercial modulus is fairly similar. It is controlled by
composite materials, this technology is pri- weak physical forces between the molecules.
marily used for GMT-materials, where Viscoelastic effects such as creep and stress
composites based on PC/PBT blends are relaxation during loading will affect the data.
available (Table 6.3). However, for high-per- Tensile strength varies more widely than mod-
formance resins, blending amorphous with ulus between different resins. As a material
semi-crystalline thermoplastics is an interest- property it is unfortunately not very reliable. It
ing route to improved chemical resistance. is sensitive to loading rate, specimen geometry,
Most polymer mixtures form immiscible two- specimen preparation and the presence of
phase structures although PEEK and PEI may microscopic flaws on the specimen surface. In
be mixed to form a miscible blend (Crevecoeur addition, uniaxial resin tensile strength is dif-
and Groeninckx, 1992). ferent from resin strength in the composite
where the stress state is different.
Thermoplastics have higher fracture toughness
6.5 PROPERTIES AND DESIGN
than epoxy and other thermosets, although
CONSIDERATIONS
epoxy fracture toughness can be improved by
In contrast to thermoset resins, thermoplastics addition of a thermoplastic (Bucknall and
can be dissolved and melted. In general, vis- Gilbert, 1989) or other means. Although not
coelastic and plastic effects are more apparent from the table, epoxy modulus is usu-
pronounced in thermoplastics. A presentation ally slightly higher than for thermoplastics.

Table 6.6 Mechanical properties of thermoplastic resins

Material Tensile Tensile Fract lire

modulus strength toughness
E (GPu) 0,( M W G,? (kJ m-2)
-__
PP 1.l-1.6 3040 -

PA6,6 2.5-3.8 50-80 -

PET 2.74.0 50-70 -
PC 2.3-3.0 60-70 -

Amorph. PA a-2) 3.2 100 1.6

PPS (Ryton) 3.5 80 0.5-0.9
PAS (PAS-2) 3.2 100 -
PEEK 3.1-3.8 90-100 4.0
PSU (Udel P1700) 2.5 70 2.5
PES (Victrex) 2.6 80 1.9
PA1 (Torlon) 2.84.4 90-190 3.4
PEI (Ultem) 3.0 105 3.3
TPI (Avimid K-111) 3.5 100 1.5
TPI (LaRC-TPI) 3.7 120 1.8
EP(thermoset) 2.8-3.5 40-120 0.1-0.5
 Properties and design considerations 123

Many mechanical properties of composites
are dominated by the influence of fiber mod-
ulus, fiber strength and fiber volume fraction.
This is usually true for longitudinal tensile
modulus and strength as well as flexural
modulus and strength. For thermoplastic
composites based on AS-4 carbon fiber, typi-
cal tensile data are: longitudinal tensile
modulus E,= 130 GPa, longitudinal tensile
strength (5, = 1950 MPa. In the present con-
text, we are more interested in properties
dominated by the matrix and the fiber/matrix
interface. One such property is the transverse
tensile strength of unidirectional laminates.
When a multidirectional laminate is loaded in
in-plane tension, the first major damage
mechanism is likely to be matrix cracking in
the plies with transverse orientation to the
maximum load direction. This reduces lami-
nate stiffness and initiates other damage
mechanisms such as delamination. In Table
6.7, transverse strength and modulus are pre-
sented for different thermoplastic composites.
Fiber volume fractions are high, V ,= 0.5-0.6,
For composites based on brittle epoxies, typi-
cal transverse strength is 40 MPa. Composites
based on LaRC-TPI, J-2, PAS-2 and K-111 show
transverse strengths in the range 3 2 4 1 MPa.
Otherwise, typical transverse strengths for
thermoplastic composites are in the range
60-90 MPa. Toughened epoxy composites also
show fairly high transverse tensile strengths,
typically around 75 MPa.
The use of transverse tension data in failure
criteria will lead to conservative estimates.
Data are higher for transverse plies in multidi-
rectional laminates (Berglund, Varna and
Yuan, 1991). The modulus data for carbon
fiber composites in Table 6.7 appear insensi-
tive to small differences in matrix modulus.
Variations in fiber volume fraction and trans-
verse fiber modulus between the materials
mask any such effect. The detrimental effect of
glass fiber as opposed to carbon fiber is appar-
ent from the GF/PA6,6 and CF/PA6,6 data.
GF/PP shows very poor performance, proba-
bly due to poor fiber/matrix interfacial
adhesion (note the low V, ). Interfacial weak-
ness is also likely to explain the low strength
for Kevlar / PEKK. For thermoplastic compos-
ites based on AS-4 carbon fiber, Table 6.7 can
be used to estimate typical data: transverse

Table 6.7 Transverse tensile properties of thermoplastic composites

Material Transverse modulus Transverse strengfh

ET (GPa) (MPa)
~~~ -
GF/PP Plytron (V, = 0.35) 4 11
GF/PA6,6 E-glass/Ultramid 8.6 48
CF/PA6,6 G30-500/Ultramid 7.2 72
CF/Am. PA AS-4/J-2 9 35
CF/PPS AS-4/Ryton 7.6 72
CF/PAS T 650-42/Rade18320 8.4 61
CF/PAS AS-4/PAS-2 8.3 32
CF/PSU AS-4/Udel P1700 7 59
K49/PEKK Kevlar/PEKK LDFTM 6.2 21
CF/PEKEKK G30-500/Ultrapek 10.3 90
CF/PEEK AS-4/PEEK (ICI) 8.9 80
CF/PAI T650-42/PAI-696 7.6 67
CF/TPI AS-4/K-III 9 41
CF/TPI G30-500/’NewTPI’ 8.3 59
CF/TPI AS-4/LaRC-TPI 33
CF/EP AS-4/3501 (thermoset) 9 52
CF/EP HTA/6376C (thermoset) 9.9 75
124 Thermoplastic resins

tensile modulus E, = 8.6 GPa, transverse ten-
sile strength (T, = 75 MPa.
High interlaminar toughness is desirable
since this suppresses the tendency for delam-
ination crack formation during loading.
Interlaminar fracture toughness is determined
on double cantilever beam specimens (DCB),
usually unidirectional materials are used
(Whitney, Browning and Hoogsteden, 1982).
In Table 6.8 such data are presented.
CF/PEEK shows the highest fracture tough-
ness. All thermoplastic composites show
higher toughness than the thermoset compos-
ites. There is a difference between crack
initiation and crack propagation data (Davies,
Benzeggagh and de Charentenay, 1987). The
data presented here are crack propagation
data; crack initiation data are in general much
lower. For tough matrices one may question
the applicability of the data to design prob-
lems. In DCB experiments, the crack opening
displacement (COD) is very high, whereas the
COD at small central cracks in stiff laminates
is much smaller. Local stress fields and dam-
age mechanisms may therefore be different
and affect the measured fracture toughness.
At present, delamination fracture toughness
from DCB tests are therefore preferentially
used to compare material. It has been pointed
out that composite data are significantly
lower than resin data (Hunston, 1984).In tests
on neat resins, energy is absorbed by yielding
and other types of damage when the volume
of material is relatively large. In a composite,
the presence of fibers tends to limit this mate-
rial volume. For shear strength, no
comparable data for different thermoplastic
composites appear to be available in the liter-
ature. The interlaminar fracture toughness in
mode I1 shear loading, Glrc,is higher for ther-
moplastic than for comparable thermoset
composites (Cantwell and Davies, 1993). This
also indicates a higher shear strength for the
thermoplastic composites. A typical value for
the in-plane shear modulus of thermoplastic
composites based on AS-4 carbon fiber is
4.8 GPa which is similar to toughened CF/EP
systems but slightly lower than for brittle
matrix CF/EP composites.
Compressive strength is lower for thermo-
plastic than for thermoset composites
(Table 6.9). Most of the thermoplastic compos-
ites are in the range 900-1100MPa whereas
typical thermoset composite data are
1700 MPa. Fiber misalignment, shear stiffness
and strength have been shown to affect com-
pression strength based on plastic kink band
formation (Budiansky, 1983). Compression
modulus data in Table 6.9 are similar, in sup-
port of similar fiber volume fractions for the
materials compared. The composite based on
PA6,6 has the lowest strength; PA6,6 also has

Table 6.8 Interlaminar fracture toughness of thermoplastic composites

Material Trade name Fracture toughness

_ _ ~
-~ ~ ~
qc(kJ~m-2)
CF/Amorph. PA AS-4/ J-2 1.3
CF/PPS AS-4/Ryton 0.9
CF/PEEK AS-4/Victrex PEEK 2.1
CF/PEEK IM7/Victrex PEEK 2.5
CF/PSU AS-4/Udel P1700 1.2
CF/PAI T650/Torlon AIX-159 1.3
CF/PEI T300/Ultem 1000 0.9
CF/TPI AS-4/Avimid K-I11 1.8
CF/TPI AS-4/ LaRC-TPI 0.8
CF/EP AS-4/3501-6 (thermoset) 0.2
CF/EP IM7/8551-7 (thermoset) 0.5
 Properties and design considerations 125

Table 6.9 Compressive properties of unidirectional thermoplastic composites

Material Trade name Compression Modulus

strength (MPa) (MPa)
__ -~
CFDA6.6 G30-500 /Ultramid 700 110
CF/Amorph. PA AS-4/ J-2 1100 -

CF/PPS AS-4 / Ryton 940 130

CF/PAS AS-4/ PAS-2 900 120
CF/PEEK AS4/Victrex PEEK 1100 120
CF/PEEK IM7/Victrex PEEK 1140 -

CF /PEKEKK AS-4/Ultrapek 1310 127

CF/PSU AS-4/Udel P1700 1040 -
CF/PAI C-3000/Torlon C 1380 -

CF/TPI AS-4/Avimid K-111 1000 110

CF/EP AS-4/ 3501-6 (thermoset) 1720 140
CF/EP HTA/6376C (thermoset) 1720 130

the lowest creep modulus and yield stress of superior performance to first generation ther-
the investigated matrices. It is interesting to moset composites (AS-4/3501-6). This is
note that AS-4/PEEK and IM-7/PEEK have because the delaminated area due to the
roughly the same strength although the IM-7 impact event is more limited for the thermo-
fiber has higher modulus. The smaller diame- plastic composites. However, toughened
ter of the IM-7 fiber appears to have a negative epoxy resin composites combined with tough-
effect as expected from Euler-buckling consid- ened interlayers between the plies do in
erations. general show as good compression strength
Compression strength after impact, a mea- after impact as thermoplastic composites. In
sure of laminate and material damage fatigue, delamination resistance is higher for
tolerance (Dorey, 1989), is presented in AS-4/PEEK compared with epoxy composites
Table 6.10. A quasi-isotropic laminate of given (Gustafsson, 1988). However, in uniaxial ten-
lay-up and geometry is subjected to impact of sion, brittle CF/EP was found to be superior to
a certain energy. Internal damage mechanisms both toughened CF/EP and the thermoplastic
such as matrix cracking and delamination composite (Curtis, 1987). Claims have been
occur in the laminate. The plate is then sub- made that this observation is due to heating
jected to compressive load and the stress and effects in the thermoplastic composite speci-
strain at failure can be determined. The data mens from testing at high frequency (Moore,
show that thermoplastic composites have 1991).

Table 6.10 Compression strength after impact of thermoplastic composites

Material Trade name Compression strength after impact

(impact energy)
(28 J) (42 1) (571)
o (MPa) o (MPa) o (MPa)
CF / PPS AS-4 /Ryton 221 179 -
CF/PEEK AS-4/Victrex PEEK 331 310 290
CF / PA1 C-3000/Torlon C 365 345 317
CF/EP AS-4/3501-6 (thermoset) 179 145 131
CF/EP AS-4/8551-7 (thermoset) - 303 -
126 Thermoplastic resins

Table 6.11 Glass and heat deflection temperatures Table 6.12 Glass melting and heat deflection tem-
for amorphous thermoplastics peratures for semi-crystalline thermoplastics

Material T, ("C) HDT ("C) Material T, ("C) T,,,

("C) HDT ("C)
PC 150 132 PP -10 165 60
Amorph. PA 160 154 PA6.6 55 265 75
PSU 190 175 PET 70 265 41
PES 220 203 PPS 90 280 135
PA1 290 278 PEEK 143 343 160
PEI 217 200 TPI (Aurum) 250 388 238
EP (thermoset) 200 180

Increased market need for polymer compos-
ites with good performance at elevated
temperature has generated interest in thermo-
plastic composites. Materials with continuous
use temperatures above 150°C are of particular
interest since they perform better than epoxies.
One question is how maximum use tempera-
ture relates to Tg. In Table 6.11, Tg and the heat
deflection temperature (HDT) for amorphous
thermoplastics are presented. HDT is deter-
mined by subjecting the material to static load
(typically 1.8 MPa) and slowly increasing the
temperature. HDT is determined as the tem-
perature at which a critical deflection of the
sample is obtained. Table 6.11 shows HDT to
be 620°C below the T of amorphous poly-
6
mers. In comparison with room temperature
strength, the strength of the composite is sig-
nificantly reduced above the HDT. The reason
is that molecular mobility in the polymer is
increased dramatically as the temperature
approaches T .
In Table 8.12, similar data to those in
Table 6.11 are presented for semi-crystalline
thermoplastics. HDT is usually somewhat
higher than Tg. However, for some semi-
crystalline polymers, HDT is below T (as for
amorphous polymers). Creep effects 'will be
very strong close to and above Tg.For this rea-
son the maximum temperature for continuous
service under significant load is unlikely to
exceed a temperature of 20°C below T' for
semi-crystalline thermoplastics. The primary
advantage of crystallinity is therefore chemical
resistance. This is apparent from Table 6.13,
where chemical resistance for different ther-
moplastics is indicated in a qualitative way.
Semi-crystalline thermoplastics have much

Table 6.13 Chemical resistance of thermoplastics

Material Structure Hydraulic Chlorinated Ketones Esters H,O abs.

fluid kydro- (Yo)
carbons
PA6,6 Crystalline - 0 0 0 8
PEEK Crystalline 0 0 0 0 0.5
PPS Crystalline 0 0 0 0 0.5
PEI Amorphous 0 D A A 1.2
PSU Amorphous A D A A 0.9
PA1 Amorphous 0 0 0 0 2 4
PES Amorphous A D A A 0.3
Am.PA Amorphous A A A 5
PC Amorphous - D A A -

0 = no effect, A = is absorbed, D = is dissolved


better chemical resistance than the amorphous
polymers. A notable exception is the high
water absorption in PA6,6 caused by
hydrophilic groups in its chemical structure.
The solvent resistance of a large selection of
different thermoplastic composites has been
reported (Johnston, Towel1 and Hergenrother,
1991). For most thermoplastics, e.g. PEEK,
moisture expansion coefficients of the carbon
fiber composite may be taken as 0. Thermal
expansion coefficientshave been characterized
(Barnes et al., 1990) and are similar to epoxy
composites. For AS-4/PEEK, the composite
density is 1600 kg m-3.
For polymers with high Tg, exposure to ele-
vated temperature may lead to increased
density not connected with crystallinity but
with the amorphous state. The phenomenon is
termed physical aging and leads to a more
brittle behavior of the polymer (Kemmish and
Hay, 1985). Further work is needed to eluci-
date the importance of physical aging to
composite fracture behavior under practical
service conditions. For composites processed
at high temperatures, residual stresses will
also affect fracture behavior. The magnitude of
the residual stresses and, consequently, detri-
mental effects will increase with increasing
cooling rate (Manson and Seferis, 1992).
Thermoplastic composites can be joined by
the same methods as thermoset composites.
Bolted joint performance has been compared
for thermoset and thermoplastic composites
(Walsh, Vedula and Koczak, 1989) with results
in favor of thermoplastic composites. With the
semi-crystalline thermoplastics, adhesive
bonding requires careful surface preparation
(Kinloch and Taig, 1987).This is because of the
good chemical resistance and limited solubil-
ity of these polymers. However, with careful
surface preparation, as good adhesive bonds
are obtained as with thermoset composites.
The thermoplastic nature of the matrix offers
another possibility: fusion bonding. Different
methods have been compared (Davies and
Cantwell, 1993), including hot gas, IR, laser,
ultrasonic, vibration, electrical resistance and
Applications 127
induction welding. There are difficulties in con-
trolling the processes and very few methods
offer the promise of portable equipment.
Various bonding technologies for PEEK com-
posites have been compared (Silverman and
Criese, 1989).The study favored a technique for
fusion bonding with a polyetherimide film.
This approach can also be used in repair of
damaged structures, since the temperature
needed is below the T, of PEEK.
6.6 APPLICATIONS
Thermoplastic composites can be used in sim-
ilar applications to thermoset composites. The
following examples will demonstrate some of
the reasons for choosing a thermoplastic com-
posite material. In Europe, the automotive
market for GMT composites is significant.
Rapid processing by compression molding,
cycle times of typically 30s even for large
structures, results in cheaper components. In
addition, more functions can be integrated
into each component compared with sheet
metal structures. Bumper beams dominate the
automotive market in the US whereas, in
Europe, a wider variety of applications are in
commercial production. Typical components
are subjected to minor loads or impact and
surface appearance is not important. Battery
trays, beams supporting the hood, seat sup-
ports, oil trays, engine shields and even the
complete front end have been produced for
Volvo, Volkswagen and others.
In the aerospace market, DuPont has sup-
plied thermoplastic polyimide composites to
the prototype programs for the F-22 fighter
aircraft. In the supersonic civil aircraft pro-
gram, the same thermoplastic polyimide is
considered for wing skins. The main reason
for this particular thermoplastic composite is a
continuous high maximum temperature.
AS-4/PEKK (unidirectional discontinuous
fibers) was used by Bell Helicopter Textron in
a V-22 tiltrotor thermoplastic wing rib for bet-
ter open hole compression behavior than
thermoset composites for high proportions of
128 Thermoplastic resins

Bike helmets are also produced (Fig. 6.2). A

semi-finished sheet is heated by IR, transfered
to heated dies where a selective clamping sys-
tem is used to hold the sheet. Forming and
consolidation pressure is applied and the
mold is cooled before demolding. Hoechst in
Germany present applications made by wind-
ing, a pressure vessel, tubes, sealings and
support rings (Fig. 6.3). Matrices include PA6
and PPS with carbon and glass fibers.
In the field of biomedical applications, such
as hip prostheses, semi-crystalline thermo-
plastic matrices offer good potential due to
their chemical stability (Williams and
Fig. 6.2 Bike helmet, an example of a commercial McNamara, 1987).
application of thermoplastic composites (Courtesy:
DuPont Europe).
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3: 66-80.
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Bassett, D.C. 1981. Principles of Polymer Morphology.
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Berglunh L.A., Varna J. and Yuan J. 1991. Effect of

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1
Fig. 6.3 Thermoplastic composite applications
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Carlsson, L.A., ed. 1991. Thermoplastic Composite
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Chang, I.Y. 1992. Thermoplastic Matrix Composites
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Cogswell, EN. 1992. Thermoplastic Aromatic Polymer
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Crevecoeur, G. and Groeninckx G. 1992. Melt-
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(TLCP) in a Miscible Matrix of Polyether ether-
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Curtis, P.T. 1987. In Investigation of the Tensile
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Davies, I? and Canhvell W.J. 1993. Bonding and
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Dorey, G. 1989. Damage Tolerance and Damage
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Egerton, M, and Gruber M. 1988. Thermoplastic
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Gustafsson, C-G. 1988. Initiation and Growth of
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Development in Thermoplastic Resins and
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Simulated Laminate (PSL): A Methodology for
Internal Stress Characterization in Advanced
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Mallon, P.J., O'Bradaigh C.M. and Pipes R.B. 1989.
Polymeric Diaphragm Forming of Continuous
Fibre Reinforced Thermoplastic Matrix
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Menges, G. 1966. The reinforcement of plastics.
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Elsevier.
Olson, S.H. 1990. Manufacturing with
Commingeled Yarns, Fabrics and Powder
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Pultruded Materials with Direct Addition of
130 Thermoplastic resins

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FIBERGLASS REINFORCEMENT* 7
Dennis J. Vaughan

7.1 INTRODUCTION (2300°F). The molten glass then flows directly

The history of glass is ancient, but its engi- to the fiber-drawing furnace in a direct melt
neering scientific development is recent. flow process (Fig. 7.1) or into a marble making
machine. These marbles can be sorted and can
Glass was first produced some 4000 years
ago, probably in Egypt in the furnaces used to eventually be remelted and drawn into fibers.
produce pottery. Its first application was as a Continuous glass fibers are produced when
form of adornment in jewelry and as added molten glass from the fiber-drawing furnace is
decoration to vases and drinking vessels. gravity fed through numerous tiny openings
The use of glass in fiber form dates back to in a platinum alloy tank called a bushing
the early seventeenth century when the (Fig. 7.2). The droplets of molten glass that
extrude from each of the bushing’s openings
Venetians utilized it to create specialized
(Fig. 7.3) are gathered together, mechanically
gowns. However, commercial fiberglass did
attenuated to the correct dimensions, passed
not become a reality until in 1939 the joint
through a water spray and over a revolving
research efforts of Owen-Illinois and Corning
belt that applies a protective and lubricating
Glass Works, resulted in the formation of
coating known as a size or binder. The fibers
Owens-Corning Fiberglas Corporation.
are then gathered together in a suitably
Textile fiberglass has now grown into a
shaped shoe to form a bundle called a strand
multi-million dollar industry. Glass fiber can
which is wound onto a core at approximately
be obtained as a continuous fiber on staple or
190 km/h (120 mile/h). This package of fibers
discontinuous fiber. Both forms are made by
is then dried or conditioned prior to further
the same manufacturing process until the fiber
processing and eventually sold as a continu-
drawing operation.
ous filament yarn.
Staple fibers are produced by passing a jet of
7.2 FIBERGLASS PRODUCTION air across the openings at the base of the bush-
ing, which pulls individual fibers of
The production of glass fibers starts with the
approximately2040 cm (8-15 in) long from the
dry mixing of silica sand and limestone, boric
molten glass that is extruding from each open-
acid and a number of other products such as
ing. These filaments are collected on a rotating
clay, coal and fluorspar. These materials are
vacuum drum, sprayed with size and gathered
melted in a high-refractory furnace, the temper-
into a strand. This package of filaments is again
ature of the melt being dependent on the glass
conditioned or dried prior to processing into a
composition, but is generally about 1260°C
specific product for further use.

Handbook of Composites. Edited by S.T. Peters. Published * Significant portions of this article appeared in Handbook
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 of Composites, 1982, (G. Lubin ed.) Van Nostrand
Reinhold, New York.
132 Fiberglass reinforcement

,CLAY , RAW MATERIALS

,C OA L , F,LMRSPAR ,
LIMESTONE SILICA SAND BORIC ACID

FORYUUTION

U I
I I I

W
DECORATIVE AND
INDUSTRIAL YARN

-1
INSPECTION
AND

r
WEIGHING
TWISTING

OVEN HEAT TREATING

J
STRAND W
CHOPPING
7-77-

A capsule view of the fiber glass

manufacturing process lor yarn.
roving and chopped strand takes
PACKING the fiber from raw rnalerflals batch
slage lo 'inished products

Fig. 7.1 Direct-melt fiberglass manufacturing process.

 Glass composifion 133

Fig. 7.2 Molten glass flows from tiny orifices in Fig. 7.3 Molten glass flows from tiny orifices in
platinum bushings (Courtesy of PPG industries). platinum bushings (Courtesy of Owens-Corning
Fiberglas Industries).
Each individual fiber is drawn from the
bushing opening and must be controlled so that Table 7.1 Fiberglass filament designations
reproducible filaments, strand dimensions and
properties are obtained. This control is Filament Filament diameter
achieved by the regulation of the melt viscosity, designation
i n ~ l O - ~ Pm
temperature and drawing speed. It is possible,
B 1.5 3.8
therefore, to obtain a large number of filament C 1.8 4.5
diameters by varying the number of openings D 2.1 5
in the bushing and the drawing conditions. DE 2.5 6
As demand has dictated over the years, the E 2.9 7
fiberglass industry has established a number G 3.6 9
of standard filament diameters (Table 7.1). H 4.2 10
K 5.1 13

7.3 GLASS COMPOSITION

Glass is generally defined as an amorphous
material, being neither solid or liquid.
Chemically glass is made up of elements such
as silicon, boron and phosphorus that are con-
verted into glass when combined with oxygen,
sulfur, tellurium and selenium. The molecular
arrangement is conducive to formation of an
intricate three-dimensional network of oxygen
tetrahedra with a silicon atom in the middle,
bonded to each oxygen atom. Silicon by itself
requires extremely high temperatures for lique-
faction. Therefore, other elements are added to
the mix to reduce temperatures and to produce
134 Fiberglass reinforcement

a viscosity in the molten glass that will allow
easy drawing.
A number of glass compositions are avail-
able depending on the properties desired from
the resulting fibers (Table 7.2).
A-glass: A high alkali or soda glass is made
into fibers for use in applications where
good chemical resistance is needed.
E-glass: A low alkali glass, based on alu-
minum borosilicate. This glass possesses
excellent electrical insulation properties
and is the premium fiber used in the major-
ity of textile fiberglass production.
C-glass: A material based on soda borosili-
cate that produces a fiber that offers
excellent chemical resistance.
S-2 glass: This glass is made up of magne-
sium, aluminum silicate and offers higher
physical strength.
-~ - Fibers produced from
this glass have an approximate per-
cent strength improvement Over
those of E-glass composition.
D-glass: This fiber made from a low dielec-
tric composition has dielectric loss
properties 'Onstant Of 3.8 at
mc s-l) superior to that of E-glass (6.O at
1mc s-l).
R-glass: A 'Pecial glass that
produces fiber that is alkali resistant and is
used in reinforcing concrete.
Low K: An experimental fiber produced to
Table 7.2 Fiberglass compositions (wt.%)
improve dielectric loss properties in electri-
cal applications (similar in performance to
D-glass).
0 Hollow fiber: A special glass whose fibers
are tube-like or hollow; the material has
specific applications in reinforced aircraft
parts where weight could be significant.
0 Te glass: A Japanese manufactured S-glass,
for higher strength structural application.
7.4 FIBERGLASS PROPERTIES
The composition of the original glass melt
probably plays the biggest role in determining
the properties of the fiberglass. The continuing
widespread use of fiberglass in numerous and
diverse applications can be directly related to
its inherent unique properties (Table 7.3). The
suppliers of these materials in the USA are
shown in Table 7.4.
0 High tensile strength: Fiberglass has an
exceptionally high tensile strength corn-
pared with other textile fibers. Its strength
to weight ratio exceeds steel wire in
applications.
0 Heat and fire resistance: Because fiberglass
is inorganic it does not burn or support
combustion.
0 Chemical resistance: Fiberglass has excel-
lent resistance to most chemicals and is
impervious to fungal, bacterial or insect
attack.

Components Grade of glass

~____._ ___
A C E s
(high alkali) (chemical) (electrical) (high strength)
Silicon oxide 72.0 64.6 54.3 64.2
Aluminum oxide 0.6 4.1 15.2 24.8
Ferrous oxide - - - 0.21
Calcium oxide 10.0 13.2 17.2 0.01
Magnesium oxide 2.5 3.3 4.7 10.27
Sodium oxide 14.2 7.7 0.6 0.27
Potassium oxide 1.7
Boron oxide 4.7 8.0 0.01
Barium oxide - 0.9 0.2
Miscellaneous 0.7
 Fiberglass properties 135
Table 7.3 Properties of fiberglass

Grade of glass
-
A C E 5
-
Physical properties
Specific gravity 2.50 2.49 2.54 2.48
Mohs hardness - 6.5 6.5 6.5
Mechanical properties
Tensile strength, psi x lo3 (MPa)
At 72°F (22°C) 440 (3033) 440 (3033) 500 (3448) 665 (4585)
At 700°F (371°C) - - 380 (2620) 545 (3758)
At 1000°F (538°C) - - 250 (1724) 350 (2413)
Tensile modulus of elasticity at
72°F (22"C),psi X lo6 (GPa) - 10.0 (69.0) 10.5 (72.4) 12.4 (85.5)
Yield elongation, % - 4.8 4.8 5.7
Elastic recovery, % - 100 100 100
Thermal properties
Coefficient of thermal linear
expansion, OF-' x lo4
("C-1) 4.8 (8.6) 4.0 (7.2) 2.8 (5.0) 3.1 (5.6)
Coefficient of thermal
conductivity, Btu in h-' f f 2 OF-'
(Wm-' K-I 1 - - 72 (10.4) -
Specific heat at 72°F (22°C) - 0.212 0.197 0.176
Softening point, "F ("C) 1340 (727) 1380 (749) 1545 (841) -

Electrical properties
Dielectric strength, V/mil - - 498 -
Dielectric constant at 72°F (22°C)
At 69 Hz - - 5.9-6.4 5.0-5.4
At lo6 Hz 6.9 7.0 6.3 5.1
Dissipation (power) factor at 72°F (22°C)
At 60 Hz - - 0.005 0.003
At lo6 Hz - - 0.002 0.003
Volume resistivity at 72°F (22°C)
and 500 V DC, ohm-cm - - 1015 10'6
Surface resistivity at 72°F (22°C)
and 500 V DC, ohm-cm - - 1013 1014
Optical properties
Index of refraction - - 1.547 1.523
Acoustical properties
Velocity of sound, ft/s (m/s) - - 17 500 (5330) 19 200 (5850)

0 Moisture resistance: Because fiberglass does
not absorb water, it neither swells, stretches
nor disintegrates. Fiberglass does not readily
rot and continues to maintain its mechanical
strength in humid environments.
0 Thermal properties: Due to its low coeffi-
cient of thermal linear expansion and high
coefficient of thermal conductivity, fiber-
glass exhibits excellent performance in
thermal environments.
136 Fiberglass reinforcement

Table 7.4 Summary of available fibers from manufacturers

Type of glass S uppl ier

OCF PPG Nitto Boeski Vetrotex NEG
-- ___ __ --
E X X X X X
S X X
5-2 X
D X
R X X
A X
C X
Low K X
Te X
Hollow fiber X X

0 Electrical properties: Fiberglass being non- 7.5 FIBERGLASS TYPES

conductive is an ideal choice for electrical
insulation, where designers can make use of 7.5.1 FIBERGLASS ROVING
the high dielectric strength and low dielec- Fiberglass roving is a collection of parallel con-
tric loss properties. tinuous strands or filaments. Conventional
The user may take advantage of one or more rovings are manufactured by winding together
of the above properties in manufacturing rein- the number of single strands necessary to pro-
forced composites. By utilizing both the high duce the required yield (the number of yards of
strength and the excellent electrical properties roving weighing one pound). Single strand
of glass fiber, the aircraft industry has found roving, as the name implies, consist of a single
fiberglass an excellent reinforcement for strand of fiberglass filaments. These filaments
radome applications. are drawn from a bushing that has the correct
The printed circuit board industry has used number of openings, so that the single strand
the combination of electrical properties and will have the correct yield.
superior dimensional stability of fiberglass to Rovings are generally manufactured from
manufacture circuit boards that can be used G or K filaments (see Table 7.1), larger diame-
under the various adverse environmental con- ters are also available. Roving yields can vary
ditions. from 1800 to 225 yd/lb (276 to 222 Tex). The
In numerous applications glass reinforce- use of the word Tex indicates a unit of fiber
ment is chosen because it allows composites to fineness that is assessed by the weight in
retain maximum properties in high moisture grams of 1000 m of yarn, the lower the num-
environments. E-glass fibers are the material ber, the finer the yarn.
of choice because of their excellent water resis-
tance. (E-glass fibers exhibit only a 1-7%
7.5.2 WOVEN ROVING
weight loss when exposed to boiling water for
60 min.) This water resistance helps maintain A number of rovings are woven into heavy,
the physical and electrical characteristics of coarse weave fabrics for use in materials that
the composite over prolonged time exposure require a quick build-up of composite thick-
to aqueous atmospheres’. ness over relatively large areas, such as various
marine products and different types of tooling.
Woven rovings are manufactured in
weights ranging from 400-1400 g/m2 (1240
 Fiberglass types 137

oz/yd2) and thicknesses of from 0.7-1.5 mm wet layup techniques or by impregnating and
(0.02-0.04 in) (see Table 7.5). applying low pressure (RTM) (see Table 7.5).
The fiberglass rovings can be used in con-
junction with ~.polyester resins in hand lay-up 7.5.3 FIBERGLASS MAT
techniques that
typically be used in the The three basic forms of fiberglass mat, are
manufacture of boats. Woven roving reinforced
chopped strand, continuous and surfacing or
laminates can be made by using conventional
veil.
Table 7.5 Woven roving and polyester laminate data

Woven roving constructions and properties

Count, Weight, Thickness, Weave
per in oz/yd2 in
(per em) (g / m2) (mm)
5x8 18.0 0.031 Plain
(2 X 3.2) (610) (0.787)
5x8 24.0 0.038 Plain
(2 X 3.2) (814) (0.965)
5x6 30.0 0.049 Plain
(2 X 2.4) (1020) (1.24)
5x8 36.0 0.052 Plain
(2 x 3.2) (1220) (1.32)

Laminate properties - 24 oz (814 g ) woven roving reinforced

Resin type" FR Epoxy FR Epoxy GI' Epoxy
Resin content, wt.% 49.0 45.6 42.5
Thickness, in (mm) 0.299 (7.59) 0.265 (6.73) 0.263 (6.68)
Cureb RT P+T P+T
Flexural strength, psi (MPa)
Cond. A' 34 200 (235.8) 49 800 (343.4) 73 100 (504.0)
Cond. D2/100d 38 800 (267.5) 44 400 (306.1) 59 600 (410.9)
Flexural modulus, psi (GPa)
Cond. A 20.6 X lo6 (14.2) 2.41 X lo6 (16.6) 2.92 X 106(20.0)
Cond. D2/100 2.12 X lo6 (14.6) 2.31 X lo6 (15.9) 2.83 X lo6 (19.5)
Compressive strength, psi (MPa)
Cond. A 29 700 (204.8) 25 700 (177.2) 47 300 (326.1)
Cond. D2/100 27 300 (188.2) 25 200 (173.8) 40 100 (276.5)
Tensile strength, psi (MPa)
Cond. A 42 000 (289.6) 48 900 (337.2) 51 400 (354.4)
Cond. D2/100 40 600 (279.9) 47 400 (326.8) 50 400 (347.5)

"FR = Fire Retardant; GP = General Purpose

"RT = Room Temperature; P + T = Pressure and Elevated Temperature
'Cond. A = as-received condition
dCond. D2/100 = immersion for 2 h in water at 100°C.
138 Fiberglass reinforcement
Chopped strand mat is a non-woven mater-
ial which the fiberglass strands are chopped
into 2-5 cm (1-2 in) lengths and evenly distrib-
uted at random onto a horizontal plane, bound
together with some type of chemical size. The
mats so produced weigh from 2.6-12g/m2
(0.7-3.0 oz/ft2)and are available in a variety of
widths, 60-230 cm (24-90 in) with 9.6 cm (38
in) width being the most typical.
Continuous strand mat is made of
unchopped continuous strands of fiberglass
deposited and interlocked in spiral fashion.
This mat is open and flexible, but due to its
mechanical interlocking does not require
much application of size to achieve adequate
handling strength.
Surface mat, or veil as it is sometimes
called, is a very thin mat of single continuous
filaments used frequently as a decorative sur-
face reinforcing layer in hand lay-up or press
molding processes in order to minimize sur-
face defects and to prevent ’weep’ in
pressurized wound tanks.
7.5.4 TEXTILE FIBERGLASS YARN
A yarn can be described as an assembly of
fibers or strands which can be woven into
some form of textile material.
The continuous individual strand as it
emerges from the bushing opening represents
the simplest form of textile fiberglass yarn and
is designated ’singles’ yarn. However, to
ensure the correct and efficient utilization of
this yarn in a weaving operation, additional
strand integrity has to be added by twisting
the yarn slightly (less than one turn per inch).
A number of woven fabrics, however, require
heavier yarns than can be drawn from the
bushing. These heavier yarns can be achieved
by combining single strands using a twisting
and plying operation. This simply involves
twisting one or more single strands together or
subsequently plying together two or more of
the twisted strands.
A yarn can be defined as having an ‘S’
twist if when it is held in a vertical position,
the spirals conform in shape to the central
position of the letter ’S’. Alternatively, a yarn
is said to have a ’Z’ twist if the spiral con-
forms in shape to the central position of the
letter ‘Z’.
Strands that have a simple twist (greater
than one turn per inch) will kink, corkscrew
and unravel, because their twist is in only one
direction. The plying operation will normally
eliminate this problem by countering the twist
in a twisted ’singles’ yarn with an opposite
twist in the plied yarn. For instance, a ’singles’
yarns which have a ’Z’ twist are plied with an
’S’ twist that will result in a balanced yarn. The
twisting and plying operations allow the
yarn‘s strength, diameter and flexibility to be
varied, which in turn allows scope in produc-
ing a wide range of suitable woven fabrics.
7.5.5 TEXTURED YARN
’Singles’ or plied yarn can be textured by using
a jet of air directed onto the yarn’s surface
which results in random but controlled break-
age of surface filaments, producing a general
increased loft to the fiber surface. The term
used to describe such a process is texturizing
or bulking and the degree to which it occurs
can be controlled by regulating the air pres-
sure and yarn feed rate. The texturing process
opens the fiber bundles resulting in some
mechanical damage to the surface filaments.
The increased surface area allows higher resin
absorption during impregnation and produces
low glass-to-resin ratios, resulting in more eco-
nomical laminates.
7.5.6 YARN NOMENCLATURE
Because of the wide variety of fiberglass yarns
produced, it is necessary to have a precise sys-
tem for yarn identification. The standard
fiberglass yarn nomenclature is based on both
alphabetical and numerical designations.
The first alphabetical letter identifies the
glass composition (E-glass), the second letter
indicates filament type (C = continuous) and
 Fiberglass types 139

the third and fourth letters identify filament ECG 150 4/2 3.8s
diameter (E 7 micron) [for details see Table 7.11. E = E-glass; C = Continuous filament; G =
The first series of numbers in the numerical Filament diameter
designation represents 1/1OOth of the basic 150 4/2 = Four basic strands of 150 1/0 are
strand yield, the second number series speci- twisted together to form 150 4/04
fies the number of single strands twisted 150 4/2 3.8s = Plying two strands of EGG
together and the number of twisted yarns 150 4/04 (using 'S' twist to create balance)
plied together. The total number of basic
The above yarn contains 8 (4 x 2) basic 150
strands in a plied yarn is found by multiplying
strands with a glass yield of 1875 (15 000 + 8)
these two figures. The yield of the yarns is
yards/pound.
obtained by dividing the basic strand yield by
The nomenclature and typical properties of
the total number of strands in the yarn. A third
commercially available weaving yarns can be
number combined with either the letter 'S' or
seen in Table 7.6.
'Z' (designating the type of twist) will some-
times also be included. For example:

Table 7.6 Commercially available fiberglass weaving yarns

Yarn designation Yield Minim um breaking strength

~. - ___
Glass system Tex system ydhb Tex Ib N
-~ ~~ -
E-glass Yarns
ECD 1800 1/0 EC5 2.75 1 x 0 180 000 2.75 0.25 1.11
ECD 1800 1/2 EC5 2.75 1 X 2 90 000 5.5 0.5 2.22
ECD 900 1/0 EC5 5.5 1 x 0 90 000 5.5 0.5 1.11
ECD 900 1/2 EC5 5.5 1 x 2 45 000 11 1.1 4.89
ECD 450 1/0 EC5 11 1 x 0 45 000 11 1.1 4.89
ECD 450 1/2 EC5 11 1 X2 22 500 22 2.2 9.79
ECD 450 1/3 EC5111x3 15 000 33 3.3 14.7
ECD 450 2/2 EC5112x2 11 250 44 4.4 19.6
ECD 450 3/2 EC5 11 3 X 2 7500 66 6.6 29.4
ECD 225 1/0 EC5 22 1 x 0 22 500 22 2.2 9.78
ECD 225 1/2 EC5 22 1 x 2 11250 44 4.4 19.6
ECD 225 1 / 3 EC5 22 1 X 3 7500 66 6.6 29.4
ECD 225 2/2 EC5 22 2 x 2 5625 88 8.8 39.1
ECD 225 2/3 EC5 22 2 X 3 3750 132 14.4 64.1
ECDE 150 1/0 EC6 33 1 X 0 15 000 33 3.5 15.6
ECDE 150 1/2 EC6 33 1X 2 7500 66 7.0 31.1
ECG 150 1/0 EC9 33 1x 0 15 000 33 3.5 15.6
ECG 150 1/2 EC933 1 X2 7500 66 7.0 31.1
ECG 150 1/3 EC9 33 1 x 3 5000 99 9.0 40.0
ECG 150 2/2 EC9 33 2 X 2 3750 132 12.0 53.4
ECG 150 2/3 EC9 33 2 x 3 2500 196 18.0 80.1
ECG 150 2/4 EC9 33 2 x 4 1875 264 24.0 107
ECG 150 3/3 EC9 33 3 x 3 1667 297 27.0 120
ECG 150 4/4 EC9 33 4 X 4 938 528 48.0 214
Continued on next page
140 Fiberglass reinforcement

Table 7.6 Continued

Yarn designation Yield Minimum breaking strength

Glass system Tex system
ECDE 75 1 / 0 EC6 66 1 X 0 7500 66 5.7 25.4
ECG 75 1/0 EC9 66 1 X 0 7500 66 5.7 25.4
ECG 75 1 / 2 EC9 66 1 X 2 3750 132 11.4 50.7
ECG 75 1 / 3 EC9 66 1 X 3 2500 198 17.1 76.1
ECG 75 2/2 EC9 66 2 X 2 1875 264 22.8 101
ECG 75 2/3 EC9 66 2 X 3 1250 396 34.2 152
ECG 75 2/4 EC9 66 2 X 4 938 528 45.6 203
ECH 55 1/0 EClO 90 1 X 0 5500 90 9.5 42.3
ECDE 37 1/0 EC6 134 1 X 0 3700 134 11.2 49.8
ECG 37 1/0 EC9 134 1X 0 3700 134 11.2 49.8
ECG 37 1/2 EC9 134 1 X 2 1850 268 22.8 101
ECG 37 1 / 3 EC9 134 1 X 3 1230 403 34.2 152
ECH 25 1/0 EClO 198 1 X 0 2500 198 17.0 75.6
ECK 18 1 / 0 EC13 275 1 X 0 1800 275 23.0 102
S-glass Yarns
s c 5 11 1 x 1 22 500 22 - -
SCD 450 1/2
SCG 150 1/2 s c 9 33 1 x 2 7500 66 8.2 36.5
SCG 150 2/2 s c 9 33 2 x 2 3750 132 16.4 72.9
Textured Yarns
ETDE 150 1/0 ET6 33 1 X 0 14 200 35 1.24 5.52
ETDE 75 1/0 ET6 66 1 X 0 7100 70 2.2 9.79
ETDE 37 1/0 ET6 134 1 X 0 3450 144 4.7 29.0

7.5.7 FIBERGLASS FABRIC There is a variety of weave patterns

The effect that fiberglass fabrics have on the
properties of composite material is largely
dependent on the fabric’s construction, which
involves fabric count, warp and filling yarn
construction, weight and weave pattern.
The fabric’s count is made up of the number
of warp yarns (’ends’) per inch (cm) in the
width and the number of filling yarns (’picks’)
per inch (cm) in the lengthwise direction.
The warp yarn is the yarn that lies in the
lengthwise (machme) direction of the fabric.
The filling yarn is the yarn lying in the cross-
wise direction of the fabric. The physical
parameters of the fabric, such as weight, thick-
ness and tensile strength are directly
proportional to the types and numbers of yarns
used to weave it (see Table 7.7)
(Fig. 7.4) that can be used to combine warp and
filling yarns to form a fabric. This weave pat-
tern controls the handling characteristics of the
fabric and to a large extent the properties of the
composite that uses it as a reinforcement.
(a) Plain weave: This fabric is constructed so
that one warp yarn passes over and under
one filling yarn (and vice versa). While the
resulting fabric exhibits the greatest degree
of stability in respect to yarn slippage and
fabric distortion, this stability is also a func-
tion of the fabric count and yarn content.
(b) Basket weave: A basket weave fabric has
two or more warp yarns interlocking over
and under two or more filling yarns. While
a basket weave is less stable than a plain
weave, it is more pliable and will conform
or drape more readily to simple contours.
 Fiberglass types 141

Table 7.7 Glass-fabricconstruction and properties: physical properties for loomstate fabrics (without finish)

Style Count, Warp yarn, Filling yarn, Weave Weight, Thickness, Bveaking
/cm Tex system Tex system g/m2 mm stvengtlz,
/in US system US system ozf yd? in N/5 cm
lb/in

104 23.6 x 20.5 5 5.5 1x 0 5 2.75 1 x 0 Plain 19.7 0.030 350 x 130
60 x 52 D 900 1/0 D 1800 1/0 0.58 0.0012 40x15
106 22.0 x 22.0 D 5.5 1x 0 5 5.5 1x 0 Plain 24.7 0.038 394 x 350
56 x 56 D 900 1 / 0 D 900 1 / 0 0.73 n.nni
- _ -,5- 4.5
. x 40
.-

1Q7 236x138 D5.51~2 55.51~0 Plain 35.6 0.043 613x 175

60x35 D9001/2 D9001/0 1.05 0.0017 Mx20
108 23.6~18.5 D5.51~2 55.51~2 Plain 4.8.8 0.051 613x350
60x47 D9001/2 D9001/2 1.44 0.0020 70x40
1 151Fx95.4 5111x2 5111x2 Plain 71.9 0.076 718x700
6x39 I D4501/2 D4501/2 2.12 0.003 82x80
1 23.6x25.2 5111x2 5531x2 Plain 83.7 0.076 1077 x 525
60x64 DW1/2 D9001/2 2.47 0.003 123x60
116 236~22.8 D111x2 511 1 x 2 Plain 107 0.102 1095x1050
60x57 D 450 1/2 D 450 1/2 3.16 0.004 125x120
120 23.6 x 22.8 5 111x 2 5 1 11x 2 Crowfoot 107 0.102 1095 x 1050

220 23.6 x 22.8 7 22 1x 0 7 22 1x 0 Crowfoot 109.2 0.0889 1096 x 1051

60 x 58 E 225 1 / 0 E 225 1 / 0 3.22 0.0035 125 x 120
341 118~19.3 5111x2 5223x2 Crowfoot 298 0.229 438x5250
30x49. D4501/2 D2253/2 8.78 0.009 50x600
1070 23.6 x 13.8 5111x0 55.51~0 Plain 35.6 0.043 613 x 175
60 x 35 D 450 1/0 D 900 1/0 1.05 0.0017 70x20
1080 23.6 x 18.5 5111x0 5111x0 Plain 48.8 0.051 613 x 350
60 x 47 1.44 0 002 70 x 40
1 0.060 700x613
0.0024 80x70
1 0.089 788x1
0.0035 9 D x 1
1165 23.6 x 20.5 5111x2 9 331 x 0 Plain 124 0.109 1310 x 1180
60 x 52 D 450 1/2 G 150 1/0 3.66 0.0043 150 x 135
Continued on next page
142 Fiberglass reinforcement

Table 7.7 Continued

Style Count, Warp yarn, Filling yarn, Weave Weight, Thickness, Breaking
/cm Tex system Tex system g/m2 mm strength,
/in US system US system oz/yd2 in N/5 em
lb/in
-
-. _. - . _ - -
1560 1 9 . 3 ~16.5 7511x0 7511x0 Plain 167.8 0.132 2285 x 515
49x42 E 110 l / O E 110 1/0 4.95 0.0052 261x253
1501 18.2 x 12.7 751 1/0 751 1 x 0 Rain 166.1 0.127 2145 x 2102
46x45 E 110 1/0 E 110 1/0 4.90 o m 245x240
1504 23.6x19.7 6331x0 6331x0 Plain 147.8 0.127 2 6 8 8 ~2233
60x50 DE 150 1/0 DE 150 1/0 4.36 0.01)50 307x255
1522 9.1x 8.7 9331x2 9331 x 2 Plain 125 0.140 1400 x 1180
24 x 22 G 150 1 / 2 CG 150 1/2 3.70 0.0055 160 x 135
1523 11.0 x 7.9 9333x2 9333x2 Plain 403 0.356 4595 x 3500
28 x 20
-_ - G 150
...3.,/ 2
~
G 150 3 / 2 11.9 0.014 525 x 400
1526 13.4 x 12.6 9331x2 9331x2 Plain 185 0.165 1970 x 1705
34 x 32 G 150 1/2 G 150 1/2 5.45 0.0065 225x195
1527 6.7 x 6.7 9333x3 9333x3 Plain 437 0.381 4375 x 4245
17 x 17 G 150 3/ 3 G 150 3/ 3 12.9 0.015 500 x 485
1528 17.3 x 12.6 9331x2 9331x2 Plain 203 0.178 2185 x 1750
44 x 32 G 150 1/2 G 150 1/2 6.00 0.007 250 x 200
1543 19.3 x 11.8 9662x2 7221x2 Crowfoot 298 0.229 5250 x 525
49 x 30 G 75 2/2 D 225 1/2 8.34 0.009 600x60
1557 22.4 x 11.8 9331x2 7221x0 Crowfoot 184 0.140 3240 x 525
57 x 30 G 150 1 / 2 E 225 1/0 5.42 0.0055 370 x 60
1564 9241x2 9241x2 9334x2 Plain 431 0.406 4375 x 3940
G 37 1/2 G 37 1/2 G 150 4/2 12.7 0.016 500 x 450
1581 22.4 x 21.3 9331x2 9331x2 Satin 302 0.216 2975 x 2885
57 x 54 G 150 1/2 G 150 1 / 2 8.92 0.0085 340 x 330
1582 23.6 x 22.0 9331x3 9331x3 Satin 454 0.356 4595 x 4375
60 x 56 G 150 1/3 G 150 1/3 13.4 0.014 525 x 500
1583 21.3 x 18.9 9332x2 9332x2 Satin 570 0.457 5690 x 5165
54 x 48 G 150 2/2 G 150 2/2 16.8 0.018 650 x 590
1584 17.3 x 13.8 9684x2 9684x2 Satin 861 0.686 8315 x 7005
44 x 36 G 75 2/2 G 75 2/2 25.4 0.035 950 x 800
1588 16.5 x 14.2 9334x4 9334x4 Satin 1756 1.27 16 635 x 11820
42 x 36 G 150 4/4 G 150 4/4 51.8 0.050 1900 x 1350
1614 11.8 x 5.51 933 1x 0 968 1x 0 Len0 79.0 0.127 657x744
30 x 14 G 150 1 / 0 G 75 1 / 0 2.33 0.005 75 x 85
1652 20.5 x 20.5 9331x0 9331x0 Plain 141.7 0.114 2154 x 1926
52 x 52 G 150 1/0 G 150 1/0 4.18 0.00454 246 x 220
1665 15.7 x 9.5 9331x0 6681x0 Plain 141.7 0.114 2154 x 1926
40 x 24 G 150 1/0 DE 75 1/0 3.50 0.0049 180 x 180
1674 15.7 x 12.6 9331x0 9331x0 Plain 95.6 0.107 1225 x 832
40 x 32 G 150 1/0 G 150 1/0 2.82 0.0042 140 x 95
1675 15.7 x 12.6 6331x0 6331x0 Plain 95.6 0.107 1225 x 832
40 x 32 DE 150 1 / 0 DE 150 1/0 2.82 0.0042 140 x 95

1677 15.7 x 15.7 6331x0 6331x0 Plain 108 0.114 1225 x 1135
40 x 40 DE 150 1/0 DE 150 1/0 3.20 0.0045 140 x 130
Continued on next page
 Fiberglass types 143
Table 7.7 Continued
.
..

Style Count, Warp yarn, Filling yarn, Weave Weight, Thickness Breaking
/cni 7ex system Tex system g/m’ mrn strength,
/in US system US system oz/yd2 in N/5 cm
lb/in
-~ ~~~ _ _ _ ~ _ _ ~ _ ~ ~
1678 15.7 x 15.7 9331x0 9331x0 Plain 108.5 0.109 1839 x 1751

16 x 14 K 18 1 / 0 R 18 1 / 0 9.66 0.014 o.
431 x 41_
2112 15.7 x 15.4 7221x0 7221x0 Plain 71.2 0.086 788x700
40x39 E2251/0 E2251/0 2.10 0.0034 90x80
2il3 23.6 x 22.0 7221x0 5111x0 Plain 80.7 0.081 1225X!i2B
60x56 E225L’O E4501/0 2.38 0.0032 14Ox~
2116 23.6 x 22.8 7221x0 7221x0 Plain 107 0.102 1095 x 1050
60 x 58 F 225 1/11 c 225 I / i ) 1.16 u.001 125 x 120
2117 26~21.6 7221x0 7221x0 Plain 20.4 0.085 1182xlfM9
66x55 E2251/0 R2251/0 3.18 0.0037 135x115
23.20 23.6~228 5221x0 5221 Crowfoot 107 002 1095XlW
60x58 D2251Jf) 0 2 2 5 3.16 0.004 W x 120.
2123 15.7x15.4 5221x0 9331x0 Plain 888 0.094 rnXlP35
80x39 D225 l / O G 150 1/0 2.62 0.0051 9ox13Q
2165 23.6x20.5 5221x0 9331x0 Plain 225 0.114 1095x1220
60 x 52 D 225 1/0 G 150 1/0 3.70 0.0045 125x140
2313 13.6 x 25.2 7221 x 0 511 1 x 0 Plain 80.7 0.81 3 1226 x 525
60 x 64 E 225 1 / 0 D 450 1 / 0 2.38 0.0032 140 x 60
2523 11.0 x 7.9 10 198 1x 0 10 198 1x 0 Plain 403 0.330 5075 x 3370
28 x 20 H 25 1 / 0 H 25 1/0 11.9 0.013 580 x 385
2532 6.3 x 5.5 10 198 1x 0 10 198 1x 0 Plain 246 0.254 2625 x 2450
16 x 14 H251/0
~ H251/0 7.25
~. n.nin 3nn x 2x13
3070 276x76 6 16.5 1 x 0 6 165 1 x 0 Plain 92.1 0.0788 1226xk26
70 x 70 DE 300 1/0 DE 300 1/0 2.74 0.0031 lLPoxlg0
3313 2.3.6 x 24.4 6 16.5 1 x 0 6 16.5 1x 0 Plain 81.4 0.0076 1050x2094
60x62 DE 300 1/0 DE 300 11’0 2.40 0.0030 120x125
34 1 91341 crowfoot 431 0.390 5900x3700
371 G 37 1 12.7 0.0134 571x423
3733 7 1 x7.1 91341x0 91341x0 Plain 197 0.203 2185 x 1750
18 x 18 G 37 1/0 G 37 1/0 5.80 0.008 250 x 200
3743 19.3 x 11.8 9 134 1x 0 5 22 1x 0 Crowfoot 286 0.203 5250 x 525
49 x 30 G 37 1/0 D 225 1/0 8.45 0.008 600 x 60
3783 21.2 x 18.9 9 134 1x 0 9 134 1x 0 8Harness 556 0.406 4816 x 4290
54 x 48 G 37 1/0 G 37 1/0 16.4 0.0160 550 x 490
4522 9.4 x 8.7 9331x2 9331x2 Plain 123.4 0.130 1226 x 1130
(6522) 24x22 G 150 1/2 G 150 1/2 3.64 0.0051 140 x 129
4533 7.1 x 7.1 9681x2 9681x2 Plain 200.7 0.188 2382 x 2601
(6533) 1 8 x 18 G 75 1/2 G 75 1/2 5.92 0.0071 272 x 297
Continued on next page
144 Fiberglass reinforcement

Table 7.7 Continued

~~ ~

Style Count, Warp yarn, Filling yarn, Weave Weight, Thickness, Breaking
/cm Tex system Tex system g/m2 mm strength,
/in US system US system oz/ydZ in a N/5 em
1b/in
- - - - - - -
4700 5.5 x 5.1 9681x0 9681x0 Rain 147.5 0.1% 2189x1445
14x 13 G 37 1/0 G 37 1/0 4.30 0.0077 250x165
6060 23.6x23.6 6 8 . 2 7 1 ~ 0 68271x0 Plain 39.0 0.0019 656.7 x 718
60x60 DH l b 0 DE 600 5 / 0 1.19 0.048 75x82
6581 22.4x21.3 9331x2 9331x2 8ws 301.8 0.228 3520x2846
57x54 f;1 9 1/2 G 150 112 8.90 0.90 400x325
6781 22.4 x 21.3 9681x0 9681x0 X HS 301.X 0.28 3320 x 28-36
57 x 54 S2C6 75 1 / 0 S2CG75 1 / 0 8.90 0.0090 400 x 325
7500 6.3 x5.5 9682x2 9682x2 Plain 327 0.356 3940 x 3590
16 x 14 G 75 2/2 G 75 2/2 9.66 0.014 450 x 410
7520 7.1 x 7.1 9681x3 9681x3 Plain 294.3 0.304 2890 x 2890
18 x 18 G 75 1/3 G 75 1/3 8.68 0.0120 338 x 330
7532 6.3 x 5.5 9681x3 9681x3 Plain 254 0.254 2930 x 2765
16 x 14 G 75 1 / 3 G 75 1 / 3 7.50 0.010 335 x 316
7533 7.1 x 7.1 9681x2 9681x2 Plain 193 0.203 2010 x 1925
18 x 18 G 75 1/2 G 75 1 / 2 5.70 0.008 230 x 220
7544 11.0 x 5.5 9682x2 9682x2 2xlBSK. 610 0.559 6520 x 7265

7626 13.4 x 12.6 9681x0 9681x0 Plain 183 0.168 1970 x 1750
34 x 32 G 75 1/0 G 75 1/0 5.40 0.0066 225 x 200
7628 17.3 x 12.6 968 1 x 0 968 1 x 0 Plain 203 0.178 2190 x 1750
44 x 32 G 75 1/0 G 75 1/0 6.00 0.007 250 x 200
7629 17.3 x 13.3 9681x0 9681x0 Plain 211.9 0.178 2190 x 1883
44 x 34 G 75 1 / 0 G 75 1 / 0 6.25 0.007 250 x 215

44 x 20 G 75 1/0 G 37 1/0 (Tex) 6.85 0.011 250 x 120

59 x 54 DE 75 1/0 DE 75 1 / 0 9.15 0.010 340 x 330

76281 17.3 x 12.6 968 1 x 0 9 6 8 1x 0 Crowfoot 203 0.173 2190 x 1750
44 x 32 G 75 1/0 G 75 1/0 6.00 0.0068 250 x 200

Shaded items may be obsolete or not in all vendor current catalogues

 Fiberglass types 145

Notes to Table 7.7

All fabrics listed in Table 7.7 which contain D 225 5 22 yam can also be woven with the original E
2257 22 yarn equivalents.
Breaking strength of fabrics in SI units: N was determined by testing a specimen of 5 cm width and is
for loomstate fabrics. Finishing reduces fabric strength.
This thickness is an estimate for dry ply thickness and is an average of several tests. The manufacturer
usually reports a range of thicknesses. To estimate the cured ply thickness, divide the dry estimate by
the expected fiber volume, i.e. if the dry thickness is 0.1 mm and the fiber volume is 0.5 then the
estimated cured ply thickness is 0.1/0.5 or 0.20 mm. See introduction for methods of converting
between weight and volume percent.
Styles 4522 (6522) and 4533 (6533) are S-2 glass; Styles 6581 and 6781 are S-glass.
a Data from Reference 3

Fig. 7.4 (a) Plain weave; (b)basket weave; (c) twill weave; (d) crowfoot satin (four harness weave; (e) eight-
harness satin weave.

(c) Twill weave: This fabric consists of one or
more warp yarns over and under two or
more filling yarns in a regular pattern. This
produces either a straight or a broken diag-
onal line in the fabric, which produces
greater drapeability and stability.
(d) Crowfoot satin weave: This weave pattern
has one warp yarn interlocking over three
and under one filling yarn in an irregular
pattern. The fabric that results is extremely
pliable and lends itself to conforming to
complex contours.
(e) Eight-harness satin weave: A fabric con-
structed with one warp yarn interlocking
over seven and under one filling yam in an
irregular pattern. The resulting fabric is
very pliable and readily conforms to com-
pound contours. Because this weave
pattern allows comparatively high fabric
counts, it contributes maximum strength to
composites reinforced by it.
(f) Unidirectional fabrics: Fabrics produced
with heavy warp yarns and light filling
yarns, in either crowfoot or long shaft satin
weaves. The filling yarns can also be com-
posed of yarns other than glass. These
fabrics offer high strength reinforcements
in the heavy yarn direction.
146 Fiberglass reinforcement
(g) Non-woven: Unidirectional fabrics that can
be produced by sticking the 'warp' and 'fill-
ing' yarns together chemically. Although
this chemical bonding contributes to the
fabric's stability, these fabrics have a firm
hand and do not drape over complex con-
tours.
7.5.8 OTHER WOVEN FORMS
Fiberglass yarns can also be woven into tapes,
contoured fabrics, fluted core fabrics and three
dimensional fabrics.
Tapes are usually narrow fabrics [less than
30 cm (12 in) wide], with a secured selvedge to
prevent unravelling. Contoured fabrics are
woven into a specific geometrical shape.
Fluted core fabrics are two parallel layers of
fabric tied together by stringers of woven fab-
rics so that the cross-section is triangular or
rectangular. Three dimensional fabrics are
really planar or fabrics woven with yarns in
three distinct directions within the fabric plane.
That is, yams are interwoven in: (i) the machine
direction, (ii) +45" from the machine direction,
or (iii) -45" from the machine direction.
7.5.9 MILLED FIBERS
Continuous fiberglass strands can be hammer
milled into very short fiber lengths [approx.
2-6 mm ( H 6 - X in) long]. The actual fiber
lengths are determined by the diameter of the
screen openings through which the fibers pass
during milling. These milled fibers are usually
used as inert fillers for thermoplastic and ther-
moset resin systems.
7.6 SURFACE TREATMENTS
7.6.1 ROVINGS
In order for fiberglass rovings to be compatible
with processing methods and materials, a
chemical size is applied during the basic fiber
forming operation. The formulation of this size
is designed to hold the individual glass fila-
ments together, lubricate the roving for contact
with various processing equipment, and to
permit the glass filaments to be thoroughly
wetted when combined with other materials.
Fiberglass roving sizes consist of polyvinyl
acetate, polyvinyl alcohol, or PVA/starch as a
film former with the addition of such chemi-
cals as chrome complexes, organosilane
antistatic agents and lubricants that impart the
desired strand characteristics.The film former
aids in adhering the filaments together and
giving strand integrity that will reduce fila-
ment abrasion during fiber drawing, strand
conversion and the end use of the rovings by
the fabricator.
An organosilane or coupling agent is
added, that can react with hydroxyl groups on
the glass fiber surface and also possesses one
or more reactive groups to react with other
materials, specifically those present in thermo-
plastic and thermosetting resins. The silane
produces a form of chemical bridge between
the glass surface and the resin matrix.
The inclusion of antistatic agents and lubri-
cants improves the softness and choppability
of the roving. The selection of a roving size is
based on its resin compatibility, processing
and the expected end use performance.
The largest percentage of rovings are used in
processes that require relatively short fiber
lengths (1-5 cm, 0.5-2.0 in). This type is used in
processes such as spray-up, preform molding,
bulk molding compounds and continuous
lamination.
Rovings suitable for chopping are available
in varying degrees of softness; the softer rov-
ings are generally more difficult to chop, but
they are recommended for use in applications
that require intricate shapes, sharp comers
and difficult radii. Conversely, the harder
types of rovings are generally recommended
for use where the choppability is of prime
importance and they are used in simple parts
with minimum contours and radii.
Single strand rovings that are commonly
used in filament winding and pultrusion
should have good strand integrity, controlled

level of broken filaments, good wettability and
uniform processability under controlled ten-
sion.
S-glass based rovings have been used in
applications where the composite needs
increased physical properties ( e g filament
wound pressure vessels).
7.6.2 FIBERGLASS TEXTILE YARNS
The continuous fiberglass strands that will be
used in weaving are treated at the bushing
with a starch-oil binder; the general formula
for such a binder can be a partially or fully
dextrinized starch or amylose hydrogenated
vegetable oil, a cationic wetting agent, emulsi-
fying agent and water. These sizes or binders
are intended to protect the fibers from damage
during their formation and subsequent opera-
tions of twisting, plying and weaving.
7.6.3 FIBERGLASS FABRICS
Fabrics directly from the loom still have the
original binders that were applied at the yarn
bushing; the warp yarns have also been treated
with a polyvinyl alcohol solution to help pro-
tect them during weaving. These binders and
sizes are not compatible with the resins used
by the composite manufacturers and must be
removed prior to impregnation with other
polymers. This is usually accomplished by
treating the fabric to carefully controlled
time-temperature cycles, which results in com-
plete removal of all organic material. However,
after this heat treatment no suitable interface
exists between the fiberglass surface and the
resin matrices that will eventually be used. An
improved interface with resulting good adhe-
sion even in adverse environment conditions
can be achieved by the application of a cou-
pling agent to the glass fiber surface.
The most commonly used coupling agents
in current use are those termed silanes. The
coupling agent mechanism of these
organofunctional silanes depends on a link
between the organofunctional group (desig-
Design considerations 147
nated Y) and hydrolyzable groups (designated
X) in materials with a generic structure X,SiRY.
The hydrolyzable groups are intermediaries in
the formation of silanol groups that bond to
the glass surface, whereas the organofunc-
tional groups are designed for reactivity or
compatibility with the polymer to be used by
the composite manufacturer. (Table 7.8)
The chemical functionability of the cou-
pling agent can determine the resistance to
varied environments, chemical, physical and
thermal (Table 7.9). There are many functions
that may be attributed to coupling agents at
the glass-resin interface. They may provide
lubrication to protect against abrasion during
fabrication. The coupling agent mechanism
can protect against stress corrosion as a result
of water incursion and can help improve the
mechanical and electrical properties of rein-
forced composites.
7.7 DESIGN CONSIDERATIONS
It is only recently that the engineering and
design criteria in the combination of such dif-
ferent materials as thermosetting and
thermoplastic polymers with reinforcing of
glass were properly understood. There are a
number of basic considerations that are com-
mon to the use of fiberglass as a reinforcing
media in the production of composites. The
type form, weave pattern, weight, permeabil-
ity and alignment of the fibers have direct
bearing on the mechanical properties of the
composite. Also in some instances the chemi-
cal, thermal and electrical properties may also
be influenced by the judicious choice of rein-
forcing material (Table 7.10).
7.7.1 GLASS COMPOSITION
The chemical composition of the glass can
have a direct bearing on the fiber properties
which can indirectly affect composite perfor-
mance.
It has been noted that 'E' glass composition
fibers can contribute 210 000-225 000 psi to the
148 Fiberglass reinforcement

Table 7.8 Commercial coupling agents

Organofunctionalgroup Clzemical structure

Vinyl CH,= CHSi(OCH,),
Chloropropyl ClCH,CH,CH,Si(OCH,),

/”\
EPOXY CH2CHCH20CH2CH2CH2Si(OCH3)3
CH2
I
Methacrylate (CH2=C-COOCH2CH2CH2Si(OCH3)3
Primary amine H,NCH,CH,CH,Si(OC,H,),
Diamine H,NCH,CH,NHCH,CH,CH,Si(OCH,)3
Mercapto HSCH,CH,CH,Si(OCH,),
Cationic styryl CH,=CHC,H,CH,NHCH,CH~NH(CH~),Si(OCH,),HCl
CH3 c1
I I +
Cationic methacrylate CH2=CXOOCH2CH2- N(Me2)CH2CH2CH2Si(OCH&

CH3
I
CH,=C
I
Chrome complex

CH2
I
Titanate (CH2=C-C00)3 TiOCH(CH&
Cross-linker (CH,O), SiCH,CH,Si (OCH,),
Mixed silanes C,H,Si(OCH,), + F
Formulated Melamine resin + C

tensile strength of a composite which they 7.7.2 FILAMENT DIAMETER

reinforce. A number of different ’E’ glass filament diam-
Other glass compositions/ ’” and eters have been evaluated comparing the
’2’ glass, have produced even greater strength influence of filament diameter on resulting
improvements in reinforced composites. laminate properties. The fabrics evaluated
were woven with the same count and weave
pattern as Style 1581, using both plied and sin-
gles yarn containing different filament
diameters (Tables 7.11 and 7.12).
 Design considerations 149

Table 7.9 Effect of coupling agents on the mechanical strength properties of laminates

Finish Loomstate 112 Volan A1 72 A174,26030

Polyester laminates reinforced with style 1581 glass fabric
Flexural strength,
psi X lo3 (MPa)
Cond. A 40.4 (278.6) 32.3 (222.7) 73.2 (504.7) 68.8 (474.4) 75.5 (520.6)
Cond. D2/100 25.3 (174.4) 31.8 (219.3) 59.0 (406.8) 66.1 (455.8) 77.3 (533.0)
Compressive strength,
psi X lo3 (MPa)
Cond. A 23.8 (164.1) 40.4 (278.6) 48.0 (331.0) 47.1 (324.8) 66.2 (456.4)
Cond. D2/100 12.5 (86.2) 12.1 (83.4) 38.9 (268.2) 44.9 (309.6) 58.8 (405.4)
Tensile strength,
psi X lo3 (MPa)
Cond. A 48.1 (331.6) 20.6 (142.0) 49.9 (344.1) 50.0 (344.8) 52.2 (359.9)
Cond. D2/100 48.8 (336.5) 51.2 (353.7) 50.7 (349.6)
Epoxy laminates reinforced with style 1581 glass fabric
Flexural strength,
psi X lo" (MPa)
Cond. A 78.2 (539.2) 76.0 (524.0) 80.9 (557.8) 71.3 (491.6) 85.7 (590.9)
Cond. D2/100 76.7 (528.8) 72.4 (499.2) 83.1 (573.0) 68.9 (475.1) 82.4 (568.1)
Compressive strength,
psi X lo3 (MPa)
Cond. A 64.3 (443.3) 63.4 (437.1) 70.7 (487.5) 63.0 (434.4) 67.5 (465.4)
Cond. D2/100 58.5 (403.3) 54.1 (373.0) 64.7 (446.1) 62.9 (433.7) 59.5 (410.3)
Tensile strength,
psi x lo3 (MPa)
Cond. A 56.9 (392.3) 48.8 (336.5) 57.8 (398.5) 50.9 (351.0) 58.2 (401.3)
Cond. D2/100 55.8 (384.7) 47.2 (325.4) 56.1 (386.8) 49.4 (340.6) 52.2 (359.9)

Filament diameter does not appear to play
an important role in the determination of the
mechanical properties of such plied yarn fab-
rics as Style 1581 woven with ECG 150 1/2
(EC 9 33 1 x 2 yarn and style) and Style 1281
woven with ECB 150 1/2 (EC 3.8 33 1 x 2
yarn). However, in comparison with commer-
cially available singles yarn Style 7781 woven
with ECDE 75 1 / 0 (EC 6.66 1 x 0) yarn, sin-
gles yarn Style B 7781 woven with finer
filaments [ECB 75 1/0 (EC3 8.66 1 x 0 yarn)]
gives laminates with higher flexural
strengths, flexural modulus and tensile
strengths. Conversely a singles yarn G 7681
woven with coarser filaments [ECG 75 1/0
(EC9 66 1 x 0 yarn)] gives composites with
improved compressive strengths.
The effect of variation in the available sur-
face area for stress transfer is affected by the
coupling agent-resin interaction. Larger sur-
face areas with poor coupling agents reduces
specific shear loading on the interface and so
produces high laminate flexural strengths. But
with improved interfacial bonding the surface
areas effect disappears because other failure
modes appear first. Singles yarns produce
higher composite strengths due to the smaller
angle between fiber axis and load axis in the
lower twist yarns. This produces less tensile
loading across the interface; the magnitude of
this effect will vary with the resin coupling
agent efficiency and the function of the twist of
the yarn or the angle of the spiral of the fila-
ments.
150 Fiberglass reinforcement

Table 7.10 The effect of fabric construction on laminate mechanical properties2

Fabric construction
Fabric no. E1581 51581 YM31A"
Count/in (cm) 57 X 54 (22.4 x 21.3) 57 x 54 (22.4 x 21.3) 57 x 54 (22.4 x 21.3)
Warp yarn
Glass system ECG 150 1/2 SCG 150 1/ 2 MCG 150 1 / 2
Tex system EC933 1 x 2 SC933 1 x 2 MC9 33 1 x 2
Filling yarn
Glass system ECG 150 1/2 SCG 150 1/2 MCG 150 1/2
Tex system EC9 33 1 x 2 s c 9 33 1 x 2 MC9 33 1 x 2
Weave Long-shaft satin Long-shaft satin Long-shaft satin

Laminate mechanical properties

Fabric no. E1581 S1581 YM31A"
Flexural strength,
psi x lo" (MPa)
Cond. A 88.6 (610.9) 87.1 (600.6) 89.8 (619.2)
Flexural modulus of elasticity,
psi x loh (GPa)
Cond. A 3.78 (26.1) 3.79 (26.1) 5.00 (34.5)
Compressive strength,
psi x lo3 (MPa)
Cond. A 64.8 (446.8) 56.4 (388.9) 61.0 (420.6)
Tensile strength,
psi x lo" (MPa)
Cond. A 60.0 (413.7) 61.4 (423.4) 64.5 (444.7)

a Data from Reference 4

7.7.3 WEAVE PATTERN or more yarns lying 90 degrees to it), the

The amount of yarn and the pattern of the
weave often determine the handling character-
istics of a fabric. If a fabric is too tightly woven,
it will not readily drape and conform to vari-
ous contours during molding; a tight weave
can also adversely affect impregnation of the
fabric by the resin. If a fabric has a weave pat-
tern that is very open, this can produce a
weaker reinforcement due to insufficient fiber,
a tendency to distort and in horizontal treater,
difficulty in impregnation.
A general assumption can be made in the
longer the float (Le. the portion of a warp or
filling yarn that will extend unbound over two
higher the reinforced composite strength. So
by extending the length of the float which
reduces the interlocking frequency, the result-
ing composite's strength will be increased.
Changing the weave, for example from a plain
weave to a crowfoot weave, will also achieve
improved composites strength properties
(Table 7.13).
7.7.4 GLASS-TO-RESIN RATIO
In general, approximation of physical proper-
ties for fiber glass reinforced composites
follows the 'rule of mixtures'. The calculation of
loads stresses and strains parallel to the fibers
 Design considerations 151

Table 7.11 Composite mechanical properties as a function of glass-filament diameter

Plied-yarn fabrics
~-
Fabric style 181 1581 1281
Count/in (cm) 57 x 54 (22.4 x 21.3) 57 x 54 (22.4 x 21.3) 57 x 54 (22.4 x 21.3)
Warp yam
Glass system ECE 225 1/3 ECG 150 1/2 ECB 150 l / 2
Tex system EC7 22 1 x 3 EC9 33 1 x 2 EC3.8 33 1 x 2
Filling yarn
Glass system ECE 225 1 / 3 ECG 150 1 / 2 ECB 150 1/2
Tex system EC7 22 1x 3 EC9 33 1 x 2 EC3.8 33 1x 2
Weave Long-shaft satin Long-shaft satin Long-shaft satin
Flexural strength,
psi x lo3 (MPa)
Cond. A 93.0 (641.2) 88.6 (610.9) 92.4 (637.1)
Flexural modulus of elasticity,
psi x 106(GPa)
Cond. A 3.88 (26.8) 3.78 (26.1) 4.06 (28.0)
Compressive strength,
psi x lo3 (MPa)
Cond. A 58.1 (400.6) 64.8 (446.8) 64.9 (447.5)
Tensile strength,
psi x lo3 (MPa)
Cond. A 60.0 (413.7) 60.0 (413.7) 64.8 (446.8)
~.

Singles-yarn fabrics
~ _ _ _ _

Fabric style G7681 DE7781 B7781

Count/in (cm) 60 x 54 (23.6 x 21.3) 60 x 54 (23.6 x 21.3) 60 x 54 (23.6 x 21.3)
Warp yarn
Glass system ECG 75 1/0 ECDE 75 1/ 0 ECB 75 1/0
Tex system EC9661x0 EC6 66 1x 0 EC3.8 66 1 x 0
Filling yarn
Glass system ECG 75 1/0 ECDE 75 1/0 ECB 75 1/0
Tex system EC9 66 1 x 0 EC6 66 1 x 0 EC3.8 66 1 x 0
Weave Long-shaft satin Long-shaft satin Long-shaft satin
Flexural strength,
psi x 10’ (MPa)
Cond. A 92.6 (638.5) 94.9 (654.3) 101.1 (696.4)
Flexural modulus of elasticity,
psi x lo6 (GPa)
Cond. A 3.78 (26.1) 3.90 (26.9) 4.02 (27.7)
Compressive strength,
psi x 10’ (MPa)
Cond. A 76.7 (528.8) 67.7 (466.8) 69.9 (482.0)
Tensile strength,
psi x lo1 (MPa)
Cond. A 64.2 (442.7) 66.3 (457.1) 69.4 (478.5)
152 Fiberglass reinforcement

Table 7.12 Mechanical properties of S-glass fabrics-epoxy composites as a function of plied compared
with unplied yarn

Fabric style S1581 S7682 57681

~~~ ~~ - -~
-
Finish Volan A Volan A CS-310
Flexural strength,
psi x lo3 (MPa)
Cond. A 84.8 (584.7) 120.0 (827.4) 116.0 (799.8)
Flexural modulus of elasticity,
psi x 10" (GPa)
Cond. A 3.10 (21.4) 4.18 (28.8) 5.21 (35.9)
Compressive strength,
psi x lo3(MPa)
Cond. A 61.3 (422.7) 55.8 (384.7) 73.9 (509.5)
Tensile strength,
psi x lo1 (MPa)
Cond. A 70.6 (486.8) 87.5 (603.3) 86.4 (595.7)

Table 7.13 Effect of weave pattern on composite mechanical properties

Fabric style 7628" 76281h 16-149' 7781d

Finish Volan Volan A Volan A Volan A
Resin Polyester Polyester Polyester Polyester
Plies 18 18 12 12
Resin content, wt.% 37.1 36.7 36.5 37.6
Thickness, in (mm) 0.124 (3.15) 0.121 (3.07) 0.120 (3.05) 0.120 (3.05)
Flexural strength,
psi X 10' (MPa)
Cond. A 53.8 (371.0) 84.7 (584.0) 63.2 (435.8) 87.0 (600.0)
Flexural modulus of elasticity,
psi x 1Oh (GPa)
Cond. A 3.89 (26.8) 3.41 (23.5) 3.81 (26.3) 3.24 (22.3)
Compressive strength,
psi X lo1 (MPa)
Cond. A 25.7 (177.2) 57.0 (393.0) 48.0 (331.0) 64.3 (443.3)
Tensile strength,
psi x 103(MPa)
Cond. A 45.9 (316.5) 59.2 (408.2) 58.7 (404.7) 60.0 (413.7)

Plain weave, data from Reference 3 A 5-shaft satin weave version of Style 7781
Crowfoot satin weave, data from Reference 3 li An 8-shaft satin weave
 Design considerations 153

and perpendicular to the fibers is quite differ-
ent. Also, the stress transfer across the material
boundaries is greatly affected by the degree of
adhesion at the reinforcement-resin interface.
A more subtle effect is the possibility that
wall effects at the surface may alter the matrix
orientation and mechanical properties.
It must also be assumed that there will be
sufficient resin present to fill all of the spaces
between the fibers. Internal voids have been
shown to produce considerable stress concen-
trations resulting in premature mechanical
failure of the laminate. Woven fiberglass fabrics
by virtue of the weave interlocking reduce the
effective glass-to-resin ratio below those of fila-
ment wound structures. The optimum glass to
resin ratio then becomes dependent on weave
pattern, weave density and yarn diameters. The
optimum strengths of laminates are obtained
with the lowest practical resin content.
With coarse plain weave fabrics using hand
lay-up, laminates can be produced with resin
contents of 36-38%; with other weaves using
less twist in the yarn and optimum yarn spac-
ing, excellent physical properties can be
achieved in the 25% resin content range. Plain
weave fabrics with higher twist yarn will
require higher resin contents than low twist
singles fabrics of equivalent weave.
In filament winding applications parallel
strands of fiberglass are wound around a cylin-
drical mandrel, the resulting cross-section of
round filaments provides a close packing,
resulting in low resin contents of the final part.

Table 7.14 Laminate mechanical properties as a function of glass-to-resin ratio (Style 181 glass
fabric-epoxy resin composites)

Plies 7 9 11 13 14 16 18 20
~ ~ ~ ___
Resin content, wt.% 55.0 49.2 44.0 35.6 31.2 28.0 22.5 22.2
Thickness, in 0.117 0.126 0.127 0.126 0.125 0.131 0.132 0.147
mm 2.97 3.20 3.23 3.20 3.18 3.33 3.35 3.73
Flexural strength,
Cond. A
psi x103 45.6 58.8 64.8 83.0 81.2 92.1 87.4 91.9
MPa 314.4 405.4 446.8 572.3 559.9 635.0 602.6 633.7
Flexural modulus
of elasticity,
Cond. A
psi x l o h 2.26 2.62 2.92 3.33 3.82 4.04 4.37 4.64
GPa 15.6 18.1 20.1 23.0 26.3 27.9 30.1 32.0

Compressive strength,
Cond. A
psi x lo3 45.2 47.9 44.7 53.2 56.9 52.4 54.3 67.8
MPa 311.7 330.3 308.2 366.8 392.3 361.3 374.4 467.5
Tensile strength,
Cond. A
psi x 103 30.8 35.7 40.5 51.3 53.7 61.0 64.7 65.1
MPa 212.4 246.2 279.2 353.7 370.3 420.6 446.1 448.9
Tensile load/ply,
lb 514 494 468 498 480 500 476 480
N 2286 2197 2082 2215 2135 2224 2117 2135
154 Fiberglass reinforcement

For example, resin contents of 25-30% with
glass fiber content of 70-75% product final
composites with high physical strengths. But, if
there is any variation from the parallel align-
ment of the glass fibers, this will reduce the
degree of packing and inevitably the optimum
glass-to-resin ratio. The weaving of glass fab-
rics will of course reduce the effective
glass-to-resin ratios because of the weave inter-
locking. The correlation between glass-to-resin
ratios and composite strength is well known,
the composite's strength increases as resin con-
tents are reduced (see Table 7.14 and Fig. 7.4).
7.7.5 FIBER DISTRIBUTION
Reinforced composites that have the glass
strands aligned parallel to each other have
their maximum strength and stiffness in the
direction of the alignment. This type of paral-
lel alignment is conducive to certain filament
winding and pultrusion operations.
When the reinforcement is aligned at right
angles to itself (half of the strands are laid at
right angles to the other half), the resulting
mechanical strengths at either angle is less than
that of the parallel alignment. As the distribu-
tion of strands varies between 0" to 90"
alignment to a +45" to a 45", this further
reduces mechanical strength in the primary
direction, but shows an increase in the +45"and
4 5 " directions. Of course the yarn distribution
can be varied from 0" and 90" directions as part
of the fabric design. A so called %balanced' fab-
ric, that is one with equal yarn distribution in
the warp and filling directions, will have com-
parable composite properties in both directions.
When fiberglass yarn is woven with yarn
primarily in the warp direction with only the
minimum amount of filling yarn (enough to
give the fabric stability), the result is a unidi-
rectional fabric. Composites reinforced with
this type of fabric have the maximum mechan-
ical strength in the direction of the greatest
concentration of yarn5.
The differences between the mechanical
properties, bidirectional and unidirectional
reinforced composites, can be seen in Table 7.15.

Table 7.15 Effect of fabric yarn distribution on laminate mechanical properties

Fabric type (style) Bidirectional (2582) Unidirectional (7743)

_ _ ~ ~

Test direction Warp Filling Warp Filling

Yarn content, 'lo 52 48 90 10
Flexural strength,
psi x lo3 (MPa)
Cond. A 84.2 (586.0) 78.2 (539.2) 95.0 (655.0) 23.3 (160.6)
Cond. D2/100 75.5 (520.5) 68.5 (472.3) 87.4 (602.6) 24.1 (166.2)
Flexural modulus of elasticity,
psi x loh (GPa)
Cond. A 4.02 (27.7) 3.65 (25.2) 4.95 (34.1) 2.47 (17.0)
Cond. D2/100 3.87 (26.7) 3.41 (23.5) 4.80 (33.1) 1.46 (10.1)
Compressive strength,
psi X lo" (MPa)
Cond. A 62.7 (432.3) 63.4 (437.1) 64.5 (444.7) 28.9 (199.3)
Cond. D2/100 51.8 (357.2) 54.5 (375.8) 51.1 (352.3) 23.6 (162.7)
Tensile strength,
psi X lo3 (MPa)
Cond. A 57.9 (399.2) 54.9 (378.5) 94.0 (648.1) 12.1 (83.4)
Cond. D2/100 55.7 (384.0) 50.2 (346.1) 91.6 (631.6) 11.7 (80.7)
 References 155

Table 7.16 Mechanical properties of polyester lam- Fiberglass remforcement aligned in a ran-
inate reinforced with chopped strand mat dom manner within the polymer matrix (e.g.
chopped strand mat) produces composites with
Resin content, wt.'%, 69.8 fairly uniform mechanical strengths in all direc-
Thickness, in (mm) 0.238 (6.05) tions. However, this also tends to produce
Flexural strength, psi (MPa)
composites that have relatively low physical
Cond. A 26 400 (182.0) properties in all directions (Table 7.16).
Cond. D2/100 30 400 (209.6)
Flexural modulus of elasticity, REFERENCES
psi (GPa)
1. Pitt, C.F. and Harvey J. 20th Anniversary
Cond. A 0.99 x lob (6.83)
Technical Conference, SPI Reinforced Plastics
Cond. D2/100 0.94 x lo6 (6.48)
Division, 1965, Section 9-C.
Compressive strength, psi (MPa) 2. Knox, C.E. Non-Metallic Materials (SAMPE) 4,
Cond. A 27 600 (190.3) 127 1972.
Cond. D2/100 23 200 (160.0) 3. Horton, R.C. and Adams, R.G. 21st Annual
Conference, SPI Reinforced Plastics Division,
Tensile strength, psi (MPa) 1966, Section 10-A.
Cond. A 14 100 (97.2) 4. Knox, C.E. New Horizons in Materials and
Cond. D2/100 13 800 (95.1) Processing (SAMPE) 18, 527 1973.
5. Peterson, G.P. Properties of High Modulus
Reinforced Plastics, S.P.E.J., 57, 1961 January.
BORON, HIGH SILICA, QUARTZ 8
AND CERAMIC FIBERS
Anthony Marzullo

8.1 INTRODUCTION tinuous. Continuous fiber or whisker is capa-

ble of being manufactured to an indefinite
Boron, high silica, fused quartz and ceramic
length. Discontinuous fiber can be chopped
fibers are used in demanding industrial, auto-
continuous fiber, or a short fiber called staple.
motive, electronic, aircraft and aerospace
Discontinuous whisker is manufactured to a
environments. Boards made of ceramic fibers
definite length in batch type processing, while
such as alumina, alumina-silica or zirconia are
continuous whisker is produced by melt
used as supplemental linings to insulate high
processes such as the laser-heated floating-
temperature furnaces. Ceramic tiles contain-
zone process.
ing alumina and silica fibers protect the
Summarizing, there is continuous fiber
aluminum skin of USA's space shuttle orbiter
(indefinite length), continuous whisker (single
during re-entry, where the tile's surface may
crystal, indefinite length), discontinuous fiber
be aerodynamically heated to 1260°C (Banas,
(chopped continuous fiber or staple fiber) and
McCormick and Creedon, 1991). Other appli-
discontinuous whisker (single crystal, definite
cations of these fibers involve reinforcing
length).
polymer-, glass-, ceramic-, or metal-matrix
composites. If the composite is well designed,
it will be tougher than the matrix material by 8.2 MANUFACTURE
itself. As an example, the fracture toughness of
Sic is 1.5 MPa m-2,but 8-15 for Sic reinforced Melt, vapor deposition and chemical processes
with Sic fibers (Richerson, 1992). are used to manufacture fibers and whiskers.
Fibers and whiskers that are made by melt
Fibers can be classified according to struc-
processing include continuous quartz fibers
ture, diameter (or cross sectional width) and
by drawing from a fused quartz rod, alu-
length. In general, a material is classified as a
mina-silica staple by atomizing a molten
fiber if its diameter or cross sectional width is
ceramic stream and continuous alumina
less than 0.0254 m (0.010 in) and 1ength:diam-
whiskers by drawing from a melt. Vapor depo-
eter ratio is greater than 1O:l.Most commercial
sition processes include chemical vapor
fibers meet these requirements easily. A fiber is
deposition of silicon carbide or boron onto a
called a whisker if its microstructure is pre-
dominantly single crystal. Fibers or whiskers tungsten core to make continuous fibers and
can be subclassified as continuous or discon- the vapor-liquid-solid (VLS) process to make
discontinuous whiskers. Chemical processing
called sol-gel technology is used to create alu-
mina-based continuous fiber. Other chemical
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 processes include the creation of polymer
 Continuous fibers 157

precursor fiber that is later pyrolyzed into sili- fibers with a minimum of surface flaws, the
con, carbon and nitrogen-based continuous rod’s surface should be flame polished with an
fiber and the reaction between silica and car- oxy-hydrogen flame, as is done in optical fiber
bon to make discontinuous whiskers. manufacturing (Blyler and DiMarcello, 1991).
The manufacturing processes are summa-
rized in Table 8.1.
8.3.3 CONTINUOUS FIBERS BY CHEMICAL
VAPOR DEPOSITION
8.3 CONTINUOUS FIBERS Producing silicon carbide fibers by chemical
8.3.1 HIGH SILICA FIBERS vapor deposition (CVD) begins by pulling a
melt-spun carbon fiber through a mercury seal
Amorphous high silica fibers can be manufac- and into a tubular reactor. The carbon fiber is
tured by leaching sodium oxide from sodium heated by coupling the mercury seals on the
silicate glass fibers. The glass fibers, made by top and bottom of the reactor to a source of
using conventional glass fiber production tech- electricity. The melt-spun carbon fiber is called
niques, are composed primarily of 74.5%)silica a substrate or a core because silicon carbide is
and 24.2% sodium oxide. The fibers are held in vapor deposited onto it. The deposited silicon
a perforated basket, which is suspended within carbide is produced by the reaction of a gas
a cylindrical tank. A solution of HC1 and water mixture of silanes and hydrogen that enters
is pumped from the bottom of the tank up to the reactor through a port. Details of produc-
and over the glass fibers for several hours. The ing silicon fibers by CVD are found in
HCl/water/fiber mixture is stirred periodi- Wawner, Jr. (1988) and Textron Specialty
cally. The HCl and water are drained away, the Materials (1993b). Producing boron fibers by
fibers rinsed and a second leaching and rinsing CVD is a similar process (Tsirlin, 1985;
cycle is performed. The fibers are dried at a low Wawner, Jr., 1988; DeBolt, 1982).
temperature (Price and Kielmeyer, 1980).Other
techniques used to make high silica fibers
include spinning from solutions and spinning 8.3.4 PYROLYSIS OF POLYMERIC PRECURSOR
from a gel (Cooke, 1991). FIBER
Several ceramic fibers composed of various
combinations of silicon, carbon, nitrogen,
8.3.2 DRAWING CONTINUOUS FUSED
boron and titanium have been produced by
QUARTZ FIBERS
the pyrolysis of polymeric precursor fiber. The
Amorphous fused quartz fibers are made from process consists of four major steps: synthesize
preforms of fused quartz rods. The end of a a spinnable polymer, spin the polymer into
fused quartz rod is heated with an oxy-hydro- precursor fiber, cross-link (cure) the precursor
gen flame and the fiber is drawn, sized and fiber and pyrolyze the cured precursor fiber
either taken up on a spool or combined with into ceramic fiber.
other simultaneously drawn fibers to form a The synthesis of a polymeric precursor is
strand. Fused quartz rods are made by fusing known as Preceramic Polymer Chemistry.
chemically purified ground quartz crystal or Many spinnable polymers have been synthe-
quartz sand. Fused quartz rods are classified sized, including polycarbosilane as a
as Type I or Type I1 vitreous silica depending precursor for silicon carbide fiber (Yajima,
on the fusion technique. Type I signifies that 1985),polytitanocarbosilane as a precursor for
fusing was done in an electrically heated cru- Si-Ti-C-0 fiber (Yamamura et al., 1988) and
cible, while Type I1 implies fusing with an hydridopolysilazane as a precursor for silicon
oxy-hydrogen flame. To obtain fused quartz carbonitride fiber (LeGrow et al., 1987). In
158 Boron, high silica, quartz and ceramicfibers
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 Staple 159

general, the polymeric precursor is melt spun. operation. They claimed that the fiber proper-
But other spinning methods, such as dry spin- ties were improved due to uniform heating and
ning, have been used. even fiber tensioning (Koba et al., 1989).
The spun precursor fiber is cross-linked to Sumitomo Chemical Co invented a fiber
prevent melting during the subsequent pyroly- with 85% gamma or delta-alumina and 15%sil-
sis step. Yajima cross-linked his polycarbosilane ica by calcining dry-spun fibers. The spinnable
precursor fiber by heating it in air to 200°C. mixture was formed by mixing an aluminum
Later research showed that silicon carbide fiber compound in a solvent and adding water to
properties were improved after curing the poly- get polyaluminoxane. A silica containing com-
carbosilane precursor fiber with electron beam pound, an organic polymer to improve
radiation (Takeda et al., 1992). spinnability and a compound such as lithium
The pyrolysis step consists of heating the to improve fiber properties were added. The
cured precursor fiber to a temperature gener- solvent was removed by distillation. The mix-
ally above 800°C in order to create a ceramic ture is spun into fiber and the fiber is calcined
fiber. (Kadokura, Harakawa and Matumoto, 1991).
Minnesota Mining and Mfg. Co. (3M)
makes fibers composed of alumina, boria and
8.3.5 ALUMINA BASED FIBER
silica by drying and sintering fiber that is spun
E.I. du Pont de Nemours patented a process to from concentrated aqueous solutions. The
make continuous alumina fibers that involved aqueous solution can be composed of an alu-
spinning a viscous slurry. One slurry composi- mina and boria precursor such as a basic
tion was prepared by dissolving an alumina aluminum acetate, silica sol and water. The
precursor such as aluminum chlorohydroxide 14%boria in 3M’s Nextel 312 fiber mhibits the
in water and then adding solid alumina parti- formation of alumina crystals and aluminum
cles. An organic polymer might be added to borosilicate is the predominant crystalline
the slurry to aid its spinnability by modifying species. The 2% boria in Nextel 440, however,
its viscosity. The viscous slurry was extruded is not enough to inhibit alumina, with eta-
through a spinneret and the green (unfired) alumina being the predominant crystalline
fibers were wound onto a bobbin. The fibers species (Sowman, 1988).
were fired at a temperature below the sinter-
ing temperature (calcining) to remove water
8.4 STAPLE
and volatile material. The calcined fibers were
sintered (densified) to remove porosity and The process to make alumina staple is similar
convert the alumina precursor to the stable to the processes that are used in making alu-
alpha-alumina structure. mina-based continuous fibers. An aqueous
This slurry-spinning process was advanced and viscous solution of an alumina precursor,
by Mitsui Mining Co. where the fiber was spun, silica and an organic polymer is extruded
dried, calcined and sintered in a continuous through apertures into a high velocity gas
stream, creating green (unfired) staple. The
green staple is sintered. The silica is added to
toughen the resultant staple by inhibiting alu-
Footnotes for Table 8.1
mina crystal growth while the green staple is
a Most of the trade names are registered trademarks. Each

trademark belongs to the manufacturer listed to its left.

being sintered (Bunsell et al., 1988).
All data on composition for the continuous and staple Imperial Chemical Industries (ICI) has a
fibers, except for Tyranno Fiber, are from the commercial alumina staple called Saffil. Saffil
manufacturers’ product literature. Tyranno Fiber is 3 ym in diameter and its length is 1-5 cm in
composition is from Weddell (1990). the mat form. Saffil comes in six grades ranging
160 Boron, high silica, quartz and ceramicfibers

from the catalytic grade with an eta-alumina the end of a polycrystalline feed rod is melted
structure, to an aerospace grade with a delta + with a CO, laser, a grain free seed crystal is
alpha-alumina or an alpha + delta-alumina + brought in contact with the melt and a whisker
mullite structure. is drawn. The LHFZ process can be used to
Alumina-silica staple, also called alumi- produce whiskers with diameters as low as
nosilicate staple, is made by atomizing a 10 pm or as high as 10 pm (Haggerty,Wills and
molten ceramic stream. The raw material for Sheehan, 1991).
the melt is a clay mineral or a blend of alumina
and silica. The melt is atomized by pouring it 8.5.2 DISCONTINUOUS WHISKERS BY THE VLS
into the path of a high velocity air stream or by PROCESS
feeding it onto a rotating wheel that throws
out the melt by centrifugal force. The former is VLS stands for vapor feed gases-liquid cata-
called the blowing process, while the latter is lyst-solid crystalline whisker growth. In a
called centrifugal spinning. One commercial particular VLS process to make single crystal
alumina-silica staple called Fiberfrax ranges Sic whiskers, uniformly sized catalyst particles
in length from 70-1000 pm and is made by The are applied to carbon substrates. The carbon
Carborundum Co. substrates and catalyst are placed within a
growth chamber. Also within the chambers are
Si0 generators, made by impregnating porous
8.5 WHISKERS brick with carbon and SiO,. The chamber is
placed within a furnace and heated to a growth
8.5.1 CONTINUOUS WHISKERS
temperature of 1300-1450°C. During t h s time,
Single crystal continuous alumina whiskers can gases such as CO, CH,, N, and H, are fed into
be grown from a pure melt by using a modifi- the chamber. The catalyst particles melt and
cation of the Czochralski method. The modified become supersaturated with material supplied
method is still classified as a moving crystal from the vapor and carbon from the substrate.
techruque, but, unlike Czochralslu’s technique, Solid Sic precipitates from the liquid catalyst
uses a die to shape the growing whisker. A cap- onto the growth substrate. As precipitation con-
illary tube draws the melt up to and over a die. tinues, the whisker grows, lifting the catalyst
The melt flows to the die’s vertical edges and ball from the substrate (Petrovic and Hurley
stops; so the die’s vertical edges control the 1990; Milewski et al., 1985).
shape of the subsequently drawn whisker. A The time necessary to produce Sic whiskers
grain free seed crystal is brought in contact with by the VLS process can be reduced by under-
the melt surface and a whisker is drawn. A lin- cooling or pre-alloying the catalyst balls. After
ear temperature distribution is maintained reaching the growth temperature, the catalyst
along the axis of the growing crystal to avoid balls are undercooled by 150”C,initiating pre-
defects by lowering thermal stresses (LaBelle, cipitation. The chamber is brought back up to
Jr, 1980; Antonov, 1990). Saphikon Inc. grows the growth temperature and held there until
whiskers in many shapes using a similar whisker growth is completed. Another tech-
process that they call EFG (edge-defined,film- nique to reduce the growth time is to pre-alloy
fed growth). One of the shapes is a hollow tube the catalyst particles with carbon and silicon
that may be used as a waveguide (Harrington so that whisker growth occurs immediately
and Gregory 1990). upon reaching the growth temperature
Another moving crystal technique to make (Shalek, 1987; Shalek, Katz and Hurley, 1988).
continuous alumina whiskers is called the Other whiskers produced by the VLS
laser heated floating zone directional solidifi- process include A1,0,, boron, MgO and Si
cation process (LHFZ). In the LHFZ process,

(Wagner, 1970); Tic by using TiC1, and CH, as
the primary feed gases and a nickel catalyst
(Pearson and Easley, 1992; Narasimhan and
Bhat, 1992);Si,N, by using Si,Cl, and NH, as the
primary feed gases and an iron catalyst
(Motojima et al., 1989);and TiB, by using TiC1,
and BC1, as the primary feed gases and Au or Si
as the catalyst (Withers, Loutfy and Lee, 1988).
8.5.3 OTHER DISCONTINUOUS WHISKER
GROWTH PROCESSES
An early vapor phase growth process to make
alumina whiskers involved hydrogen reduc-
tion. Wet hydrogen was passed over heated
aluminum powder. Whisker lengths and
diameters were from 1-30 mm and 3-50 pm,
respectively. Hydrogen reduction of methyl-
trichlorosilane was used to produce p-Sic
whiskers (Milewski, 1991).Other vapor phase
growth techniques are evaporation-condensa-
tion and vapor phase reaction. These and
other growth techniques, are discussed in
Bracke, Schurmans and Verhoest (1984).
Some commercial processes to make Sic
whiskers use a chemical reaction between silica
and carbon powders. Tokai Carbon manufac-
tures p-Sic whiskers by heating a mix of
pulverized silica gel, carbon black and a metal
catalyst. The mix is heated in a nonoxidizing
atmosphere at 1300-1700°C and the whiskers
grow within the pores of the mix (Yamamoto,
1985).The whiskers are under 1.0 pm in diame-
ter and under 300 pm in length.
Other companies have produced Sic
whiskers by chemical reactions: the J.M.
Huber Corp. passed perforated trays filled
with ground rice hulls over heated carbon pel-
lets and through a horizontal furnace. Ground
rice hulls were used as the reactant material
because they contain both silica and carbon
(Tanaka, Kawabe and Kobune, 1986).
Silicon nitride whiskers have been pro-
duced by heating a silica and carbon mix or
rice hulls in a nitrogen atmosphere (nitriding),
or by heating silica powder in a gas mixture of
ammonia gas and hydrocarbon gas.
Forms 161
8.6 PROPERTIES
Boron, h g h silica, quartz and ceramic fibers
have a high thermal and chemical stability rela-
tive to organic fibers. Maximum use
temperatures of boron, h g h silica, quartz and
ceramic fibers, except for boron fiber in an oxi-
dizing atmosphere, all are over 1000°C. These
fibers have a good balance of specific strength
(tensile strength/density ratio) and specific
modulus (elastic modulus/density ratio) com-
pared with other materials. Tsirlin’s (1985)
graphs of specific strength against specific
modulus for boron or Sic fibers with cores
illustrate this point. In Table 8.2 note the low
coefficient of thermal expansion for quartz
fibers, which allows them to be used in parts
that are subjected to high temperatures, such as
in high speed printed circuit boards.
8.7 FORMS
The form that a fiber can take depends on its
length, diameter and mechanical properties,
such as elastic modulus and tensile strength.
In general, discontinuous whiskers are too
short to be spun into yarn, however, VLS
whiskers about 75-100 mm long might be
spun into staple yarn (KO, 1989).A fiber’s flex-
ibility is related to its diameter, elastic
modulus and tensile strength. A measure of
flexibility is l / [ d ( E / o- l)]where d = diameter,
E = elastic (Young’s)modulus and cs = tensile
strength. A greater value indicates a greater
flexibility. Obviously, the greater a fiber’s flex-
ibility, the easier it is to twist, braid and weave
into complex shapes without breakage.
As an example, l / [ d ( E / o - l)]is about 126
for continuous Sic fiber with a core (d =
80 pm), 533 for continuous alumina fiber, 1298
for continuous Sic fiber (d = 12 pm) and 10 101
for continuous fused quartz fiber. The Sic
fiber with a core, having a lower flexibility rel-
ative to other fibers, is generally used for
unidirectional reinforcement. The fiber might
also be used in a material-geometric hybrid to
axially reinforce a woven preform of finer
162 Boron, high silica, quartz and ceramic fibers
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diameter Sic fiber (KO, 1989). Fine diameter
(less than 20 pm) continuous ceramic fiber is
more flexible, can be formed into nontwisted
strands (sometimes called nontwisted yarn)
and braided or woven into two- or three-
dimensional shapes. The quartz fibers, being
the most flexible, can be twisted into filament
yarn and braided or woven into two- or three-
dimensional shapes.
Figure 8.1 shows some of the many forms
that fibers can take. Each strand of the fine
diameter ceramic fibers can contain anywhere
from 250 to 1000 filaments per strand, depend-
ing on the product. The strands may be
bundled to form roving. Fused quartz
untwisted strands are formed into roving that
contains either 2880 or 4800 filaments per rov-
ing. As mentioned earlier, fused quartz fibers
may be twisted into yarn at 4 turns per inch,
with 120, 240, 480, 960, or 1920 filaments per
yarn and in a variety of yarn constructions.
Fine diameter ceramic and fused quartz fibers
can be formed into many multidimensional
structures, such as orthogonal nonwoven fab-
rics (Fiber Materials, Inc., 1993; KO, 1989).
Orthogonal nonwoven fabrics are so-called
because there is no interlacing of fibers. Other
names for these fabrics are xyz fabrics, multi-
directional preforms and 3D, 4D, 5D, 7D or
11D woven blocks. The 5D, 7D and 11D blocks
have strands going in the three orthogonal
directions and in diagonal directions. The 4D
blocks have strands going in two orthogonal
Footnotes for Table 8.2
aAll values, except those for silicon carbide whiskers, are
from the manufacturers’ product literature.
Test methods may varv between manufacturers.
i ,
All values are averages, are for reference only and are
not to be taken as a specification.
Most fibers are under continual development. Contact
the manufacturers for the most up to date property values.
DNA = Data Not Available.
The silicon carbide whisker values are from Petrovic and
Hurley (1990).
This value in metric units was converted from a value
that was given in English units.
Most of the tradenames are registered trademarks. Each
trademark belongs to the manufacturer listed to its left
Applications 163
and two diagonal directions. Figure 8.1 shows
the 3D and 5D fabrics. See Ngai (1990) for dia-
grams of 4D, 7D and 11D fabrics.
Continuous boron fibers are supplied in the
form of borodepoxy prepreg tape and
boron/aluminum preform sheets. The
boron/aluminum preform sheets are made by
resin bonding the boron fibers to the side of
aluminum foil. The fibers can be aligned in
any direction. These preform sheets are used
in solid state (low temperature, high pressure)
diffusion bonding processes (TextronSpecialty
Materials, 1993a).
Continuous Sic fibers with a core are
formed into plasma-sprayed aluminum or
titanium preform sheets for hot molding (a
low pressure, hot pressing process) and into
’woven fabric’ for investment casting or diffu-
sion bonding. In diffusion bonding, the fabric
is placed between two metal foils prior to con-
solidation. The ’woven fabric’ is similar to
nonwoven roving because the fibers are
aligned in one direction and held together by a
cross-weave of metallic ribbons (Textron
Specialty Materials, 199313; Mittnick 1990).
Continuous high silica fibers are processed
into a variety of forms such as cloth, tape,
sleeving, yarn, cordage, rope, nonwoven mat,
blanket, felt, rigid tile and sewing thread.
Alumina-silica staple fibers are made into
paper, rigid board and cylinders, other rigid
three-dimensional shapes and into most of the
high silica fiber forms. Alumina staple fibers
are processed into paper, mat, felt, blanket,
rigid board and cylinders and other rigid
three-dimensional shapes.
8.8 APPLICATIONS
Table 8.3 provides a sampling of the many
applications for boron, high silica, fused
quartz and ceramic fibers. For other applica-
tions, see Bracke, Schurmans and Verhoest
(1984), Mortensen and Koczak (1993),
Schwartz (1992) and the other chapters within
this handbook.
164 Boron, high silica, quartz and ceramicfibers
0
U
0
mI
U
0
0-
I N
$3
mz
2
m
z
0
B

Fig. 8.1 Schematic of some fiber forms.

ui
Y
O
h z
W
3
Fig. 8.1 Schematic of some fiber forms.
Applications 165
166 Boron, high silica, quartz and ceramic fibers
8.8.1 NONCOMPOSITES
Alumina and alumina-silica staple fibers and
the continuous high silica fibers are used in
high temperature applications in many indus-
tries. Forms of these fibers are used for
thermal insulation, personnel protection and
gasketing. See Carborundum (1991) for the
many applications of high silica fibers and
Carborundum (1989) for the many applica-
tions of alumina-silica fibers.
8.8.2 COMPOSITES
Fibers and whiskers have been used to rein-
force polymers, epoxies, glasses, metals, or
ceramics. The reinforced materials are called
composites in general and, more specifically,
polymer, epoxy, glass, metal, or ceramic
matrix composites. The reinforcements are
either discontinuous whiskers or continuous
fibers for the applications in Table 8.3, but sta-
ple fiber and continuous whisker may be used
as a reinforcement material as well. Usually
the fiber or whisker is coated to cover its sur-
face flaws, provide a diffusional barrier
between it and the matrix material and protect
the fiber or whisker from oxidation. In addi-
tion, the coating provides a weak interface that
deflects cracks propagating through the
matrix in ceramic matrix composites
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Tomorrow’s Ceramics, ed. P. Vincenzini, pp.
2889-98. Amsterdam: Elsevier Science
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Blyler, Jr., L.L. and DiMarcello, F.V. 1991. Optical
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Brown, A.S. 1993. High-temperature materials
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Milewski, J.V., et al. 1985. Growth of Beta-silicon
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CARBON FIBERS 9
Khalid Lafdi and Maurice A. Wright

9.1 INTRODUCTION microstructural features developed in the spin-

Carbon fibers exhibit truly outstanding prop- ning process that also influence the stiffness,
erties. As shown in Table 9.1, their strength, 0, strength and the thermal and electrical proper-
competes with the strongest steels; they can ties of pitch can be optimized. Nevertheless,
have stiffness, E , greater than any metal, the tensile strength of PAN-based fibers has
ceramic or polymer; and they can exhibit ther- always been superior to pitch-based fibers;
since PAN fibers were developed before pitch
mal and electrical conductivities that greatly
exceed those of competing materials. If the fibers, most structural materials and compo-
strength or stiffness values are divided by the nents use PAN-based fibers.
-
low density, p, 1800-2200 kg m-3, then their
cal
The most
properties
important mechanical and physi-
exhibited by carbon fibers are the
huge specific properties (o/p, E/p) make this
class of materials quite unique. elastic modulus, tensile strength and the electri-
All carbon fibers sold commercially are fab- cal and thermal conductivities. These
ricated from polyacrylonitrile (PAN) or from a properties are sensitive to the crystallite size
coal, petroleum or synthetic pitch. PAN-based and perfection of the graphene layers devel-
fibers are produced from a solubilized mixture oped within the carbon fiber and depend for
the most part on the degree of molecular align-
that is wet or dry spun to produce a fiber,
ment with respect to the fiber axis. Growth and
ostensibly for use in the textile industry. This
alignment of such layers occur within the pre-
fiber is stabilized and carbonized to produce a
cursor and within the solid carbon fiber when it
carbon fiber. Aerospace grade material can be
is heated to high temperature. However, it can
obtained in tows that contain between 3000
be argued that the most extensive structural
and 12 000 fibers. Lower performance materi-
rearrangement occurs when the basic structural
als are usually formed using larger tows that
units (BSUs) present in the original precursor
contain up to 320 000 fibers. PAN-based car-
are large and plate-like so that the shear stresses
bon fibers are cheaper when produced from
generated during spinning can align these large
larger tows.
areas more easily. Heating the fiber to high tem-
Pitch fibers are melt spun products obtained
in small tow sizes varying from 2000 to 4000 perature after spinning relaxes the spinning
stresses and allows the oriented regions to
fibers. They are usually of larger diameter
grow. Compared to PAN, the basic structural
(- 10-15 pm) than fibers formed from PAN.
units in an original mesophasic pitch are much
The spinning process is controlled by the
larger in area and length and are not twisted to
pitch-based carbon fiber producer; thus,
the same degree. The resulting ease of graphiti-
zation and alignment of the graphene layers
and the development of large crystallites, pro-
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 duces a large elastic modulus and electrical and
170 Cnrbon fibers

thermal conductivity parallel to the fiber axes.
Unfortunately, large graphitized regions tend to
produce high local stress concentrations, espe-
cially if they are misaligned (Reynolds and
Sharp, 1974; Reynolds and Moreton, 1980).
'rhus, pitch-based fibers tend to exhbit high
modulus and high electrical and thermal con-
ductivities, but low strength. PAN-based fibers
tend to be of intermediate modulus and rela-
tively high strength.
The mechanical properties of structural met-
als generally vary in direct proportion to
density. Thus, as shown in Table 9.1, the specific
properties (o/p, E/p) tend to remain relatively
constant; structures designed to resist a given
set of loads tend to weigh the same irrespective
of whether they are made from aluminum, tita-
nium or steel. These mechanical property/
density relationships are not followed by car-
bon fibers; so, compared with metals, similar
structures made from carbon fiber reinforced
composites will be lighter.
The most successful use of carbon fiber rein-
forced materials has been for military
purposes, especially aeronautical structures
(Schwartz, 1984; Hadcock, 1982). Composite

Table 9.1 Physical and mechanical properties of typical carbon fibers

-
Siipplier/Fiber name Tensile Elastic Fracture Density, dp. E/P >
strnzgth, rnoduliis, elongation, p ( k g / ~ ~ IOp
) rn? s-: I O h rn2s-'
a (GPd E (CPal %
Pitch Type
Amoco /Thornel PlOO 2.2 690 0.3 -2150 1.02 321
P120 2.4 830 0.3 -2150" 1.11 386
Petoca /Carbonic HM50 2.8 490 0.6 -2000" 1.40 245
HM60 3.0 590 0.5
HM80 3.5 790 0.4 -2000" 1.75 395
PAN Type
Amoco/Thornel T-300 3.45 231 NA 1760 1.96 131
T-50 2.9 390 NA 1810 1.60 215
T-40 5.65 290 NA 1810 3.12 160
Akzo / Fortafil F-~(c) 2.76 345 NA 1800 1.53 192
F-3(c) 3.80 227 NA 1700 2.24 133
RK Fibers/RK RK30 ~3.0 -230 NA 1780 1.68 129
RK25 >2.5 -230 NA 1780 1.40 129
Toray/Torayca M46J 4.2 436 0.5
T300 3.5 230 1.2 1750 1.71 143
T800 5.5 294 2.0
Toho/Besfight ST-1 3.6 240 1.5 -1800b 2.00 160
ST-2 4.0 240 1.7 -1800b 2.20 141
ST-3 4.4 240 1.8 -1800b 2.38 133
Metals
Aluminum' 0.172 73 NA 2720 0.063 27
Titanium' 0.324 110 NA 4500 0.072 24
Steel' 0.414 199 NA 7860 0.052 25
"Estimated from Tanabe et al. 1987; hEstimated from Johnson 1987; 'Eshbach and Souders, 1974;
NA, Not Available.
 Overview 171

use in civilian aviation has been more limited,
largely because of cost. However, in 1985 the
European Airbus consortia used carbon/epoxy
vertical stabilizers on their A310 and, since
1993, delivered their A340 and A330 models
equipped with composite tail sections, floor
panels, landing gear doors and carbon-carbon
brakes. The new Boeing 777 and the projected
McDonnell-Douglas MD-12 contains similar
composite structures (High-Performance
Composites, 1994).
9.2 OVERVIEW
Ln this chapter we have chosen to combine,
rather than separate, the discussion of the
preparation of carbon fibers from PAN or from
pitch. This style of presentation is attempted
since the methods used to fabricate carbon
fibers from either of these precursor materials
seem to be almost identical, as shown in
Fig. 9.1; for example, both methods involve the
preparation, spinning and subsequent thermal
degradation of organic precursors. Essentially,
a precursor material is prepared, spun into a
fibrous shape, stabilized to change it from a
thermoplastic to a thermoset, then heated until
all unwanted elements are expelled. Depending
on the final heat treatment temperature, a fiber
is produced that is primarily carbon. A strik-
ingly similar production technique is used to
produce either type of fiber; however, the initial
pretreatment and the chemical reactions that
occur within either PAN or pitch during stabi-
lization and carbonization are markedly
different. These differences are discussed in the
following sections since they determine the
ultimate properties and the cost of the carbon
fibers that are produced.
9.2.1 POLYACRYLONITRILE
The chemical composition of PAN-based pre-
cursors tends to be proprietary; however, in
general it consists of small diameter linear
molecules that are made up from nitrogen,
hydrogen and carbon (Fig. 9.2). Spinning
tends to orient these molecules parallel to the

Pitch Polyacrylonitrile
precursor
I
Particulate removal
I
Pretreatment
(chemical, thermal, mechanical)

I
Fiber spinning
Wet or dry spinning
I
Solvent extraction

I
Stabilization
at 200-260°C
I
Carbonization
to 1500°C
I
Graphitization
to 2500°C

Fig. 9.1 Schematic illustration of process to produce carbon fibers from polyacrylonitrile and pitch.
172 Carbon fibers

\ ,CH2\ /CH2\ /CH2\ /CH2\ /

CH CH CH CH CH
n a a n a
C C C C C
NN NN NN NN NN
Fig. 9.2 Structure of the ideal PAN molecule (Eggs, 1976).

fiber axis, but they continue to be randomly
oriented transverse to that direction. Thus, a
fiber with a twisted fibrillar structure is pro-
duced. This fiber is supplied by the textile
industry to the carbon fiber fabricator who sta-
bilizes it under tension before converting it
into a carbon fiber using a controlled heat
treatment process. Apart from the obvious
generation of the fibrous shape, the impor-
tance of the spinning process to the fabrication
of carbon fibers from PAN is relatively minor;
more important is the chemical makeup of the
PAN and the presence of small amounts of
other constituents that influence the complex
chemical reactions that occur during stabiliza-
tion and carbonization. Stabilization involves
cyclization of the oriented molecules and
results in the release of most of the hydrogen
and part of the nitrogen as NH, and other
nitrogen compounds (Fig. 9.3). The role of the

Initiation Cyclization

Abnormal structures
end structures
impurities
N N

H intra- or
n = 0, 1 , 2 ... Abstraction intermolecular
m = 0,1,2. transfer

reactions scission

I \
2. Transfer
1.Cyclization
I re-initiation

Fig. 9.3 Release of HCN and NH, during cyclization of PAN fiber (Grassia and McGuchan, 1971b).

retained nitrogen is very important to both the
crosslinking process and to the development
of optimum properties during carbonization.
9.2.2 PITCH
A pitch precursor taken from a petroleum or
coal tar feedstock initially contains individual
molecules that exhibit appreciably different
molecular weights. These untreated precur-
sors have been used to produce fibers;
however, they are isotropic and exhibit rela-
tively poor mechanical and physical
properties. Conversely, the carbon fiber pro-
ducer can pretreat the pitch to develop a
continuous anisotropic phase (similar to a
mesophasic liquid crystal) or a two phase mix-
ture that becomes highly oriented during the
subsequent spinning process. In contrast to the
chemical changes occurring in PAN, physical
changes are responsible for the final properties
of pitch-based carbon fibers. Essentially, the
precursor isotropic pitch is pretreated to pro-
duce a two phase mixture that is
predominantly anisotropic. During spinning
and drawdown, this mixture is very strongly
oriented both parallel and transverse to the
fiber axis. Oxygen added during stabilization
tends to crosslink these large molecules in a
simple way before being released on car-
bonization as CO, CO, and H,O. More recent
interest has centered on producing fibers from
synthetic pitches. These require no extensive
pretreatment and they stabilize faster at a
given temperature. Fibers made from these
pitches should cost less to produce.
Precursor materials that have been used to
produce carbon fibers include: polyamides,
polyesters, polyvinyl alcohol, polyvinylidene
chloride, poly-p-phenylene, phenolic, naptha-
lene, naphthalene-phenanthrene, alkylbenzenes,
rayon, polyacrylonitrile (PAN) and various
petroleum, coal tar and synthetic pitches
(Ezekiel, 1969; US Patent 3 533 741, 1970;
Shindo, Nakanishi and Soma, 1969; Boncher,
Cooper and Everett, 1970; French Patent 1535
800, 1968; Kawamura and Jenkins, 1970;
Pitch precursor treatments 173
Mochida et al., 1988; Lewis and Nazem, 1987a).
Today, fibers are produced commercially from
rayon, PAN and the various pitches. However,
the process to produce fibers from rayon is
very expensive because it involves stretching
at very high temperatures and the yield of car-
bon after carbonization is small. Rayon-based
fibers are therefore fabricated in such small
amounts that they are really of no commercial
importance. Additional information can be
obtained from: Yanagida et al., 1991; Bacon,
1973; US Patent 3107152, 1963; Yoneshoga
and Teranishi,l970.
9.3 PITCH PRECURSOR TREATMENTS
A typical pitch precursor material is obtained
from either the distillation products involved
in the chemical treatment of decanted oil or as
a by-product of the production of metallurgi-
cal coke from coal. In a conventional
as-received pitch, basic structural units (BSUs)
are already present to a degree that pitch can
be considered a random suspension of highly
aromatic molecules similar to coronene (mole-
cular weights between 600 and 900)
surrounded by a liquid of smaller molecular
weight. Heating such a system initially
reduces the viscosity. Eventually, however, the
viscosity increases as the BSUs grow and coa-
lesce to form larger entities (molecular weights
between 1000 and 4000) with a specific long
range anisotropy called 'mesophase' (Brooks
and Taylor, 1965). Continued heating eventu-
ally causes an inversion in which the
mesophase spheres become the continuous
anisotropic phase within which are suspended
spheres of the isotropic low molecular weight
material. The rate of viscosity increase is very
slow at low temperatures, but accelerates as
the temperature is increased. At temperatures
greater than 350°C, the pitch begins to form
coke by a process of thermal degradation and
gas evolution. The variation in viscosity with
temperature for numerous pitch fractions has
been documented (Bathia, Fitzer and
Kompalik, 1984) and is shown in Fig. 9.4. As
174 Carbon fibers

60
I- lS
CTP A240 1:1 1:4

I
I
I
I
45 - I
v) I
B I
>. I
.-
c
I
v)
30- I
0
.->
v) I
I
U
C I
EQ I
P 1s-

50 100 150 200 250 300 350 b 00 1so 500 550

Temperature OC
Fig. 9.4 The variations of apparent viscositv w ~ t l temperature
i o f T ariotii pitch fractions (Batha, Fitzer and
Kompalik, 1984)

can be noted, at a given temperature, the vis-
cosity of any pitch is greater the more
anisotropic phase it contains. By cooling after
partial reaction, it is possible to produce a two
phase pitch with a viscosity appropriate for
spinning or infiltration.
A number of experiments have been carried
out designed to accelerate the process of pro-
ducing two phase pitch mixtures. These
involved heating, stirring, bubbling an inert
gas through the liquid (sparging), or the com-
bination of stirring and sparging (US Patent
3 629 379, 1971; US Patent 3 919 383, 1975; US
Patent 3 974 264, 1976; US Patent 4017327,
1977). In this way, an appropriate anisotropic
concentration can be produced in much shorter
time periods (hours instead of days) with
improved spinning characteristics. This latter
characteristic seeins to be associated with the
smaller molecular size existing within the two
phase mixtures formed by stirring and sparg-
ing and the smaller variation of molecular size.
A 1980 patent (US Patent 4 208 267, 1980)
discussed a different method of producing
isotropic/anisotropic pitch mixtures. The
method essentially consists of dissolving part
of the original isotropic pitch in an organic sol-
vent such as benzene, toluene, xylene, etc. The
material that is insoluble can then be con-
verted, by heating, into a material that is
greater than 75% anisotropic. The efficiency of
this process is quite poor however, since only
a \Tery small amount of this 'neomesophase'
can be produced from a given pitch. For
instance, using Ashland A260 pitch, about
75-90% of the initial pitch will dissolve.
Using Ashland A240,80-905:1 of the pitch dis-
so1v es.
Variations of the gas-sparge process fpossi-
bly associated with a chemical fractionation)
can be made to change the characteristics of a
resultant pitch. Lafdi, Bonnamy and Oberlin
(1991a; 1991b; 1991c; 1992) and Lafdi and
Oberlin (1994a;1994h) have indicated that

some pitches exposed to a nitrogen sparge at
atmospheric pressure or a hydrogenation
treatment at high pressure produce a continu-
ous strongly anisotropic material that contains
small particles of a weakly anisotropic mater-
ial. During spinning, the second phase
becomes completely absorbed (or trans-
formed) to produce a uniformly anisotropic
fiber. They believe that sparging disturbs the
formation of an anisotropic phase that
exhibits large differences in molecular weight.
Indeed, they suggest that the spheres of
anisotropic material contain BSUs that are
only weakly associated. In contrast to the
strong molecular orientation exhibited by the
Brooks and Taylor type of ’mesophase’
(Brooks and Taylor, 1968), the common orien-
tation of this new anisotropic material results
from the statistical orientation of small units.
The pitch then behaves as a two component
gel which exhibits a long range anisotropy in
the bulk. The short range change in orientation
of the carbon units produces sharp changes in
orientation similar to grain boundaries. Such
regions produce a zig-zag nanotexture in the
resultant carbon fiber that prevents inter-sheet
gliding and provides a crack inhibiting func-
tion that contributes to relatively high ultimate
strength values.
9.4 SPINNING CONDITIONS
9.4.1 POLYACRYLONITRILE
Dry and wet spinning of polyacrylonitrilepre-
cursors have been used. In the dry process the
polymer is solubilized and spun into a current
of hot air that removes the solvent.
Unfortunately, solvent removal tends to be
quite rapid and can cause the outer portion of
the fiber to solidify before the solvent can dif-
fuse from the fiber’s center. The large diffusion
gradient that develops can seriously affect the
final shape of the fiber (Edie and Diefendorf,
1993). The more common wet spinning
method involves solubilizing the polymer
with a polar solvent such as dimethyl
Spinning conditions 175
acetamide before extruding it into a ’coagula-
tion’ bath through a spinneret. In the
wet-spinning process, the fiber is solidified by
using a coagulant (such as ethylene glycol)
which extracts the solvent from the polymeric
fiber. In a manner similar to the dry spinning
process, the rate at which the solvent is
extracted from the polymer as it passes
through the coagulation bath governs the final
shape of the fiber. The temperature, concentra-
tion and circulation rate of the fluid in the
coagulation bath are known to affect the struc-
ture and hence the physical and mechanical
properties of as-spun fiber. Many companies
have added a supplemental stage to the spin-
ning process that is designed to reduce the
water content. This additional step tends to
increase the molecular orientation within the
fiber (US Patent 3846833, 1975; US Patent
3 841 079,1974).
A typical acrylonitrile-based precursor con-
tains several percent of various co-monomers
such as methyl acrylate or vinyl acetate which
improve the precursor’s spinnability or fabric
properties. Though not added to aid car-
bonization specifically, they have been found
to influence the properties of the resulting car-
bon fiber. Many modified PAN polymers such
as acrylonitrile-hydroxyethylene, acryloni-
trile-vinyl chloride-itaconic acid (French
Patent 2 328 723), polyacrylomidoxium (US
Patent 3 767 773,1973) have been investigated
to obtain a suitable as-spun fiber capable of
producing a fiber with a large carbon yield
after carbonization.
9.4.2 PITCH
According to Singer (US Patent 3919383
(1975)), in order to spin a fiber, pitch must be
heated to produce a viscosity between 10 and
200 poise (1-20 Pa s). However, temperatures
greater than about 35OOC cannot be used to
obtain the required viscosity because thermal
decomposition of the pitch will occur. In addi-
tion, spinning should be carried out above a
minimum temperature of about 200°C since
176 Carbon fibers

this determines the maximum temperature
that can be used in the subsequent stabiliza-
tion step. These temperature requirements
define a processing window into which suit-
able pitches must fall. Using literature data
(Lewis and Nazem, 1987a;Mochida et al., 1988;
Yanagida et al., 1991), White (1992) has shown
that the smallest window exists for 100%
anisotropic pitches processed from coal or
petroleum. A larger window exists for material
partially transformed from the same precur-
sors; however, as shown in Fig. 9.5, the largest
window exists for synthetic pitches.
The spinning of two phase mixtures is not
an easy commercial operation since the phases
exhibit different viscosities and densities. The
strongly anisotropic continuous phase con-
tains within it a less anisotropic (or isotropic)
phase which exists as spheres. If the diameter
of the spheres is large relative to the spinning
orifice, localized weak sections of extrudent
can be produced that can break and make it
difficult to maintain a continuous fiber thread.
In addition, since the stabilization rates of each
phase differ, one phase may be over stabilized
relative to the other and it becomes difficult to

Temperature ("C)
450 400 350 300 250 200

4 c Window Boundaries

h
In
(d
4
Sol
poi
11 lU"
In
h

(d

8
>
.-
In

In
5
I lo2
4
>
.-
c
In
0
0
In
5

A
B
7/////
TC \ Lowest viscosity pitch 1'"'
I that can be stabilized
\ High temperature limit, to
avoid pitch decomposition
-

I l l l l l t l l l l l l l l ,
10-3
1.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2

Inverse Temperature, I/Tx lo3 (K-l)

Fig. 9.5 Processing window for injection of mesophase pitch (White, 1992).
A A : The lowest viscosity reported for mesophase pitch prepared from petroleum or coal-tar pitch by
pyrolysis to 100% mesophase.
BB': The lowest viscosity reported for a petroleum- or coal-tar-based mesophase pitch only partially
transformed but with the mesophase acting as the continuous phase.
CC': The lowest viscosity reported for a chemically-derived fully-transformed mesophase pitch.

generate optimum properties in the resulting
carbon fiber. This fact seems to have been rec-
ognized early, since Singer (US Patent
3 919 383, 1975) describes methods to remove
the isotropic component from the two phase
fiber immediately after spinning.
Due to the proprietary nature of the various
procedures, little is known of the spinning
process itself, however, a number of patents
have been awarded (US Patent 4 331 620,1982;
Matsumoto 1985; US Patent 4 504 454, 1985).
These have been discussed in other publica-
tions (Wright, 1989; Wright and Palmer, 1994);
most deal with attempts to combat the two
phase nature and non-Newtonian behavior by
stirring the pitch in the spinneret. Apparently,
agitation of mesophase within the spinneret is
part of the technique used by the Petoca Oil
Company to randomize the cross sectional
microstructure and produce the folded
graphene layers that are thought responsible
for the relatively high strengths exhibited by
their ’carbonic’ carbon fiber (Guigon, Oberlin
and DesarmotJ984a; 1984b). As seen previ-
ously in Table 9.1, for similar modulus
materials, the strength of Petoca’s carbonic
fibers (HM-series), while still not as good as
PAN based fibers (T-series),is appreciably bet-
ter than other commercially available pitch
material (P-series).
The flow of pitch through the spinneret
(Matsumoto, 1985), the geometry of the die
hole (Singer, 1978; Yamada et al., 1984; US
Patent 4 504 454, 1985), pitch viscosity, die
swell and drawdown are all known to affect
the microstructure of the resulting pitch-based
fiber. Indeed, the above authors illustrate their
comments with fiber microstructures that vary
from circumferential through random, radial
or radial with a crack (Fig. 9.6).
Spinning experiments using 100%
’mesophasic’ synthetic pitches produced
from napthalene (Ohtsuka, 1988),
napthalene-phenanthrene (Lewis and
Nazem, 198%) and alkylbenzenes (Yanagida
et al., 1991) have been reported. The viscosity
of these materials is appropriate for spinning
Stabilization of polyacrylonitrile 177
Fig. 9.6 Typical pitch-based carbon fiber
microstructures (Edie, 1990): (a) radial; (b) onion-
skin; (c) random; (d) flat-layer; (e) radial-folded;(f)
radial with wedge.
at temperatures lower than those necessary to
spin anisotropic-isotropic mixtures obtained
from petroleum or coal tar pitch; thermal
decomposition during spinning is therefore
not a problem. Stabilization of such pitches
must be performed at correspondingly low
temperatures; however, when they are com-
pared to petroleum and coal tar mesophasic
pitches, stabilization at a given temperature
occurs at a significantly faster rate. This fea-
ture, when combined with the fact that no
pitch pretreatment is necessary, should
enable fibers to be produced at significantly
lower cost.
The result of all spinning processes is a PAN
or pitch fiber that can be changed into a carbon
fiber by heating at a very slow rate to a tem-
perature of about 1500°C. A higher rate of
heating will usually melt the fiber unless it is
first converted from a thermoplastic to a
thermoset. This conversion or stabilization
treatment is done by heating to a relatively low
temperature for an extensive time period in an
atmosphere containing oxygen (usually air).
9.5 STABILIZATION OF POLYACRYLONITRILE
This process converts the thermoplastic,
as-spun polymer into a thermoset that is capa-
ble of maintaining its shape during
178 Carbon fibers
carbonization (Lavin, 1992; Yooh, Korai and
Mochida, 1994).The operation is identical for
both PAN and pitch based fibers. However,
the stabilization of anisotropic pitches
involves simple cross linking of plate-like
molecules whereas the stabilization of PAN
involves many different chemical reactions.
Stabilization of both PAN and pitch is an
exothermic process, so great care must be
taken to control the rate of reaction and to
avoid thermal runaway which melts the fiber
and is a fire hazard.
Commercial stabilization is carried out by
heating the PAN fiber in air between 200 and
I
CN CN CN
PAN
CYCL’ZATloN
Fig. 9.7 The process of PAN stabilization and subsequent carbonization (Fitzer and Heine, 1988).
260°C for a period of time that varies between
thirty minutes and several hours. During sta-
bilization, several interdependent chemical
reactions occur. The reaction that dominates is
primarily determined by the chemical compo-
sition of the initial precursor, the spinning
history, the final composition of the as-spun
fiber and the stabilization heating schedule.
A PAN polymer mainly consists of acry-
lonitrile entities -CH,CH(CN)- which are able
to cyclize (Johnsonet al., 1972)with the help of
an initiator into a presumably linear ’ladder
polymer’ similar to that shown in Fig. 9.7. In
general, the pendant nitrile groups of PAN
 Stabilization of polyacrylonitrile 179

first become crosslinked to form a ladder poly-
mer. Initiation of this process is catalyzed in
some cases by the presence of a small amount
of reactive copolymer such as itaconic acid.
Oxygen is then incorporated into the ladder
polymer under a number of possible schemes
which have been described by Watt and
Johnson (1975) and by Clarke and Bailey
(1973) and are shown in Fig. 9.8. Cyclization
and stabilization induce tremendous shrink-
age into the polymer. Longitudinal shrinkage
is resisted mechanically; however, the diame-
ter of the fiber is allowed to decrease.
A balance should be kept during stabiliza-
tion as to hydrogenation degree. A large
hydrogen content can result in a small N/C
ratio which increases the temperature at which
the local molecular ordering occurs.
Conversely, increasing the available oxygen
decreases the size of and the temperature at
which the units of local molecular order
(LMOs)are formed. In addition, since the vis-
cosity increases as crosslinking (stabilization)
proceeds, the mobility and growth rate of the
LMOs decrease; hence their final size remains
small. The smaller the size of the LMOs, the

la
c c c c
Ill Ill Ill Ill
N N N N

H H H H H H

I I I I

H H
H
/:\>
%
;\/;\;/: 'LL,
I l l 1 IV
/c\N/c\N/c\N/c\N /
+ + + +
0 0 0 0
Fig. 9.8 Incorporation of oxygen into cyclized PAN fiber (Clarke and Bailey, 1973).
180 Cavbonfibers
less graphitizable is the carbon and the lower
the properties of the fiber. In order to ensure
appropriate N/C ratios at reasonable temper-
atures, stabilization should result in only a
moderate degree of crosslinking. In addition,
slow heating rates during precarbonization
should permit hydrogen and delay nitrogen
emissions; both of these effects lower the tem-
perature at which extensive formation and
growth of LMOs occur.
A commercially acceptable rate of stabiliza-
tion requires the use of as high a temperature
as possible. However, since the reactions that
occur during stabilization are exothermic, it is
most important to limit the oxidation rate and
to prevent uncontrollable temperature
increases. These conflicting requirements have
resulted in the development of alternative
methods of stabilization. These include stabi-
lization in: hydroxylamine solution (US Patent
3 767 773, 1973), aminophenoquinones (US
Patent 4 004 053, 1976), aminosiloxanes (US
Patent 4 009 248,1977), amine salts (US Patent
4 009 248, 1977; US Patent 4 024 227, 1978; US
Patent 4 031 288, 1978) or stabilization in gas
phases such as mixtures of NO and NO,, Br,
and 0,, or HC1 and 0,. Other stabilization
processes have been proposed that are
designed to reduce the cost and/or decrease
the stabilization time. It seems possible to
reduce the time by stabilizing the fibers in per-
sulphate (US Patent 3 650 668, 1972), cobalt
salt (US Patent 3 656 882,1972), nitric acid (US
Patent 3814377, 1974; US Patent 3 656 883,
1972), or to control the final quality of the fiber
by stabilizing in carboxylic acid (US Patent
3 814 377, 1974; US Patent 3 656 883,1972), or
nitrophenol. Processes designed to produce
fibers of larger modulus have also been devel-
oped. These involve stretching the precursor
during stabilization (US Patent 3 917 776,1975;
US Patent 3 677 705,1976).
Fiber manufacturers attempt to fit the
physico-chemical conditions of the various
operations cited above (nature and proportion
of the co-monomers, cyclization, stretching,
stabilization, carbonization) to obtain an opti-
mal product, i.e. forming the LMOs at the
smallest reasonable temperature, retaining the
largest nitrogen content beyond the tempera-
ture of LMO formation and incorporating an
optimum amount of oxygen during stabiliza-
tion to prevent polymer melting without
inducing too small a LMO size.
It is known that the overall oxygen content
should be between 8 and 12 wt.% in order to
completely stabilize PAN fibers (US Patent
4069 297, 1978). Less than 8 wt.% oxygen
gives a large weight loss on carbonization due
to excessive evolution of gases from the
incompletely stabilized central core; more than
12 wt.% oxygen degrades surface layers and
the properties of the final fiber (Johnson, Rose
and Scott, 1970). Exactly what an average
value of 8 wt.% translates into for the specific
oxygen content of the surface layers and the
core region is unknown, but it would obvi-
ously depend on fiber diameter and the
kinetics of the stabilization process (diffusion
or reaction controlled). A large diameter PAN
fiber containing an average of 8 wt.% oxygen
exhibiting diffusion controlled stabilization
kinetics would probably be composed of
highly degraded surface layers with perhaps
an under-stabilized central core. Conversely, a
very thin fiber exhibiting reaction controlled
stabilization kinetics might be completely and
homogeneously stabilized with an average
oxygen content of less than 8wt.%.
Presumably a similar statement can be made
for the stabilization of pitch fibers. In the sta-
bilization process, the effect of fiber diameter
on the rate of oxygen uptake is important. The
three curves shown in Fig. 9.9 illustrate the
slower rate of oxygen uptake exhibited by fat-
ter fibers. In addition, larger diameter pitch
fibers tend to exhibit a diffusion controlled sta-
bilization that produces an under-stabilized
central core and an over-stabilized fiber skin.
Smaller diameter pitch fibers appear to exhibit
reaction controlled stabilization since no skin-
core type microstructures are observed.
 Chemical changes during carbonization 181

.................... ________---------

Solid line - mesophasic particles

-4.881 ( O x i d i z e d Oxygen, 388 Deg

-5.08 " " I ' " ' I " " I '

8.68
Time (hours)
Fig. 9.9 Effect of diameter on the stabilization of mesophasic particles and pitch-based fibers (Kowbel,
Wapner, Wright, 1989).
9.6 CHEMICAL CHANGES DURING rate of emittance are important control para-
CARBONIZATION meters since they affect the strength of the
The carbonization of stabilized PAN and pitch resultant carbon fibers.
A stabilized polyacrylonitrile fiber which
involves controlled heating to a temperature
contains about 11wt.% oxygen can be ther-
of about 1500°C.The majority of gases emitted
from either the PAN or the pitch are emitted mally degraded by heating at a slow heating
before a temperature of 1000°C is reached and rate (Riggs, Shuford and Lewis, 1982) in an
the emission is primarily from unstabilized inert atmosphere such as nitrogen or a reactive
environment where nitrogen gas is bubbled
regions (Jain and Alhiraman, 1987; Lewis,
through acid (US Patent 3 972 984, 1976) or
1982). Indeed, the quantity of gases emitted
water (US Patent 3 677 705,1976; US 3 656 903,
from an unstabilized central core of either
1972; US Patent 4 039 341, 1976).As the tem-
PAN or pitch can be so large that the fiber can
disintegrate. Great care should therefore be perature increases, many complex reactions
taken to determine the optimum heating rate take place resulting in the evolution of volatile
products. For example, when the fiber is ini-
for stabilized or under-stabilized fibers. In
tially heated, cyclization occurs with the
some cases, hold times should be incorporated
into the heating cycle. Both materials emit a release of large amounts of HCN and NH,. Up
variety of gas molecules containing oxygen, to 450°C, HCN, acrylonitrile, propionitrile,
NH, and H,O are emitted. Subsequently, at
hydrogen and carbon; however, a major differ-
around 500°C and 700°C copious quantities of
ence between PAN and pitch involves
nitrogen containing compounds which are HCN and water vapor are emitted, respec-
tively. All of these emissions are believed to
only emitted from PAN. The temperature and
182 Carbon fibers

come from reactions involving crosslinking of

individual molecules. Evolution of nitrogen
starts near 700°C; so fibers produced after
being heated to 1000°C retain only about 40
.1-
5.8 wt.% nitrogen and have lost about 50 wt.% 3.5 -
100
of the original PAN precursor fiber.
Results obtained from experiments involv-
ing slow pyrolysis at 4"C/min indicate that 3.0-
.-
c

optimum mechanical and physical properties 0-

=
I)

g too
n
are unobtainable unless high nitrogen contents (3

I I
are retained within the precursor until the later f 2.5- G2
stages of carbonization (Deurberque, 1990; z
W W

Deurberque and Oberlin, 1991). Therefore, a a

t;; E
large nitrogen content (large N/C ratio) should W
300
W
$
2.0-
be present when local molecular ordering z 2
w W
(LMO)begins and the carbon skeleton is being k t-

formed. Since the N/C atomic ratio depends

inversely upon the H/C ratio, LMO should
occur at large N/C and small H/C ratios.
Essentially, small amounts of aromatic hydro-
gen and a relatively large amount of nitrogen
present during the LMO stage allow the carbon
skeleton to remain flexible enough at high tem-
peratures that molecular rearrangement is
easy. Within this overall fibrous texture, the
nanotextural features of the carbonized fibers
are the consequence of the variations in
cyclization, stabilization, carbonization and
graphitization conditions. If the original pre-
cursor is CH- and NH-rich but oxygen-poor,
the corresponding carbonized fibers will have
low porosity, high compactibility and stacking
order and a relatively high strength. Likewise,
if two nitrogen atoms are present in two aro-
matic rings contained within adjacent sheets,
they are able to promote bonding of contacting
BSUs together with a N, release (Watt, 1972).
The ultimate strength value of the fibers
increases as the compactibility and the avail-
ability of 'efficient' nitrogen (i.e. the nitrogen
remaining at the moment of LMO occurrence)
increases (Oberlin and Guigon, 1988; Guigon,
1985). Bright and Singer (1979) agreed with
others when they found that the tensile
strength of most heat treated fibers tends to
decrease with higher temperature exposures
and release of nitrogen (Fig. 9.10). The same
1.5 -
zoo
1.0 -
Fig. 9.10 Effect of heat treatment temperature on
the tensile strength of carbon fibers (Bright and
Singer, 1979).
authors argue that if adequate nitrogen exists
within the fiber after LMO occurs, then a
greater potential for bonding exists and an
improved rather than a diminished strength
will result. This conclusion is based on the
observation that, in contrast to other fibers, the
strength of (nitrogen containing) commercially
available Toray T-300 fibers increased from 2.2
to 3.2GPa after heat treatment to 2800°C.
Tension also increases cyclization and nitrogen
elimination which increases the tensile
strength of the final carbon fiber (Watt, 1972).
Exactly what influence nitrogen has on the
development of high tensile strength is still
being debated. However, the texture of the
graphitic layers, the amount of nitrogen pre-
sent in the original precursor and the
temperature at which misshapen layers touch -
 Microstructural changes during carbonization 183

and hence are available to bond and emit nitro-

gen - are obviously important.
Up to lOOO"C, carbonization leads to an
effluentloss and increasing aromatization. As a
result, the solid residue transforms from a vis-
coelastic into a brittle solid material. The
stabilized PAN normally carbonizes into a sta-
tistically isotropic but nanoporous carbon
material which, because of the small dimen-
sions of the initial LMOs, is inherently
non-graphitizable (Joseph and Oberlin, 1983a).
Continuing pyrolysis up to 1500°C eliminates
most of the residual nitrogen and completes the
conversion of the PAN molecules into sheets of
carbon that are appreciably anisotropic (Mair
and Mansfield, 1987).Continued heating elimi-
nates the remaining nitrogen and, since the
material is then only made of pure carbon, fur-
ther modifications are only structural.
Graphitization is the name of the process
that involves heating the carbonized fiber to
approximately 2500°C in times as short as a
minute (US Patent 4 005 183,1977).Graphitized
pitch fibers exhibit a larger, more graphitic and
better oriented crystal structure than
PAN-based carbon fibers which are inherently
non-graphitizable. Parallel to the fiber axes,
pitch fibers have higher stiffness and thermal
conductivity values and a reduced thermal
expansion coefficient. These changes due to Fig. 9.11 Model of crumpled sheet-like structure
graphitization do not produce any significant (Guigon,Oberlin and Desarmot, 1984a).
increase in relative strength values. As a result
of the extreme temperatures required to temperatures, for the bonding of adjacent
process them, graphitized pitch-based carbon sheets. These sheets contain numerous vacancy
fibers are more expensive and are fabricated imperfections and are folded to enclose pen-
for specialized applications. cil-shaped voids oriented in the general
direction of the fiber axis. The lengths of each
block or sheet are relatively short, with each
9.7 MICROSTRUCTURAL CHANGES DURING
succeedingblock misoriented with respect to its
CARBONIZATION
neighbor. A schematic illustration of the
The initial heating of stabilized PAN fibers microstructure as it exists within the actual
causes growth of graphite-like ribbons by a fiber is shown in Fig. 9.12. This structure is typ-
dehydrogenation mechanism. Denitrogenation, ically exhibited by high strength PAN-based
which occurs as the temperature is increased, is carbon fibers.
responsible for the growth in area and the Further temperature increases tend to
transformation of these ribbons into thin sheet- decrease the void space by joining sequentially
like structures (Fig. 9.11) and, at higher oriented and touching graphite like layers and
184 Carbon fibers

fibre axis

Fig. 9.12 Model of microstructure within a high

strength PAN-based carbon fiber (Guigon, Oberlin
and Desarmot, 1984a).

aligning them more parallel to the fiber axis.

The distorted sheets of BSUs associated with
tilt and twist boundaries are bonded to each
other wherever the boundaries of adjacent
sheets touch. The more compact the fiber, the
larger the number of contact areas and the Fig. 9.13 Model of PAN-based high modulus car-
greater the chance for adjacent sheets to bond. bon fiber (Guigon,Oberlin and Desarmot, 1984b).
The lateral cohesion thus formed causes the
strength of the fiber to increase. Specifically,
the distortions within the polyaromatic centrations and, hence, weaker fibers
graphene layers or sheets tend to be removed (Reynolds and Sharp, 1974; Reynolds and
by accumulating any structural defects at their Moreton, 1980).
boundaries. This induces a progressive
increase of the width and the radius of curva-
9.8 ELECTRICAL AND THERMAL
ture of the aromatic layers which can be
PROPERTIES
correlated with the stiffness, stacking order
and the diameter of the graphitic layers Studies of microstructural features have been
(Oberlin, 1984).A schematic of this microstruc- carried out using techniques that include:
ture is shown in Fig. 9.13. The longer, better X-ray and electron diffraction, electron spin
oriented and more graphitic microstructures resonance, thermoelectric power, magneto
exhibit both higher values of moduIus and resistance, lattice fringe imaging, etc. All
thermal and electrical conductivities; unfortu- results indicated that carbon fibers are com-
nately, the misalignment of the larger posed of turbostratic layers of graphite
microstructural units causes large stress con- oriented preferentially at some angle to the
 Electrical and thermal properties 185

fiber axis. Increasing the heat treatment tem- PAN-based fibers is the lower maximum val-
perature results in a reduction of the ues of the elastic modulus and the electrical
interlayer spacing, a decrease in void space, a and thermal conductivities. Typical results
growth in thickness and area of the graphitic which compare the effect of heat treatment on
crystallites and an increase in the preferred the electrical and thermal conductivities are
orientation of the microstructure. All of these shown in Figs. 9.15 and 9.16.
changes increase the elastic modulus and the
electrical and thermal conductance. A corre-
sponding reduction of the tensile strength
also occurs by mechanisms that depend on
local defects as discussed in the previous
section.
A comparison of the g-value anisotropy of
pitch and PAN in Fig. 9.14 indicates that the
degree of anisotropy changes for both fibers
after heating to about 1700°C. Although pitch
based fibers become more anisotropic when
the temperature is increased further, the
anisotropicity of PAN seems to saturate at a
level which is comparable to that of a pitch
fiber heated only to about 2000°C. A simple
consequence of this inability to fully graphitize

-
x104

140
- I
t \
Long Heat Treatment 1
/
:120- I -------------
Single Crystal Graphite
----
0) /
I
/ 1000 1500 2000 2500 3000 35 0
dl 100- /
HEAT TREATMENT TEMPERATURE (OC)

Fig. 9.15 Schematic variation of the room tempera-

" 1800 2200 2600
Heat Treatment Temperature, deg C
Fig. 9.14 Variation in g-value anisotropy of
pitch-base and PAN-base carbon fibers as a func-
tion of heat-treatment temperature (HTT)
(Aggarival, 1977).
ture electrical resistivity against T,, for: (0)
ex-rayon; ( 0 )hot stretched rayon; (A and V) ex-PAN
fibers (Robson et al. 1972); (0) Ex-pitch fibers (Bright
and Singer, 1979)and (solid curve) benzene-derived
fibers (Chieu et al. 1983). The scatter of typical data
points about the mean give an indication of the
3000 uncertainty. The dashed line indicates the decrease
in resistivity produced by hot stretching the
ex-rayon fibers.
186 Carbon fibers

E. GPa

tiI '
0.01 1 '
20
I
30
I
40
I
u)
I
60
I
70
I
80
I
90
1

Ex 106 psi

Fig. 9.16 Conductivity of pitch-base, PAN-base and rayon-base carbon fibers as a function of the tensile
modulus of elasticity. (Courtesyof R. Gray, NSWC, Dahlgren, Virginia.)

9.9 MECHANICAL PROPERTIES OF FIBERS observation, have used electron diffraction

(Guigon, 1985) and lattice fringe imaging
The microstructural changes discussed above
(Oberlin and Guigon, 1988). This latter tech-
have been deduced using X-ray diffraction
nique is particularly powerful, because in
techniques. In addition, the mean length of
dark field, the parallel orientations (with
the graphite sheets oriented in the fiber direc-
respect to the imaging beam) of the convo-
tion La and their thickness Lc may be
luted graphite layers can be imaged. Sketches
computed using such techniques. It has been
of the possible layer convolutions, the images
found that both of these parameters increase
they can produce and the measurements that
with increasing temperature. The orientation
can be made are shown in Fig. 9.18. Most
of these layers also becomes increasingly
important is the realization that it may be
aligned with the fiber axis. The net effect is to
possible to classify the properties of commer-
increase the tensile modulus continuously as
cial samples in terms of decreasing either
shown in Fig. 9.17. Conversely, the tensile
transverse (rt) or longitudinal (r,) radius of
strength tends to decrease (Fig. 9.10).
curvature of the sheets. Such a classification,
More recent studies, which allow direct
based on these and other numerical values
 Mechanical properfies offibers 187

shown in Table 9.2, could form the basis of

empirical relationships between micro-tex-
ture and mechanical properties.
At increasingly higher heat treatment tem-
peratures, the scattering domains within high
modulus fibers become large and well
defined so that the length of the graphitic
sheets in the fiber direction, .La,,Cr can be mea-
sured directly (see Table 9.2) from the
observed Moire fringes. Correspondingly, the
radii r, and rI of the sheets are also measur-
able from 002 lattice fringes. The lateral
cohesion of the fiber is also ensured by bond-
ing between adjacent distorted sheets of
carbon wherever two grain boundaries are in
contact. The chances of such bonding increase
as r, and rI decrease, but decrease as La
I 1
1000 2000 3000 3500 increases. Hence the extent of lateral cohesion
THT ( ' C ) can be defined by a variable S = La [(l/rf)
(l/rt + l/r l) ] . As shown in Fig. 9.19, a linear
Fig. 9.17 Effect of heat treatment temperature on correlation has been observed between CY, and
the elastic modulus of PAN and pitch-based carbon 1/ S indicating that long, relatively unbonded
fibers. (Data from Johnson, 1969 and Aggarival, graphitic layers result in weak fibers.
1977). Conversely, Young's modulus and electrical

1 2 3

m n m n
2rr sin 37. 2r,sin37*

Fig. 9.18 Sketches of the possible dark-field images of a longitudinal section (lamellar model of Fig. 9.15)
as r decreases and the fold develops (Guigon, Oberlin and Desarmot, 1984b).
188 Carbon fibers

Table 9.2 Quantitative measurements which are suggested for use to classify microtexture and mechani-
cal properties

SAD patterns L'coo4

Half width of 004 reflections
L'd, [O]
Half width of 11[0] ring
__
002DF Lc
Thickness of elementary bright domain [BSU]
La Length of elementary bright domain
~ _ _ __
002LF N Number of fringes in a stack
L, Length of a perfect fringe
L?
Length of a distorted fringe
__ __
11DF Lall TF
Length of turbostratic Moire fringes
Lall Cr
Diameter of a domain showing
rotational Moire fringes
~-

ODP of 002LF P Arc opening

ADO,, Interfringe spacing spreading

,,
lt 11s
+ I 1 1 I " ' I I I 1 1 ' f i I I ' I I I
0 0.1 0.2 AA-
Fig. 9.19 Numerical relations between tensile strength and the microtexture oc = f(l/S). High modulus
fibers (full line). High tensile strength fibers heat treated at 2800°C (dashed line) (Oberlin and Guigon,
1988).

conductivity correlate well with La, as seen in According to the pioneering work of
Fig. 9.20. Griffith (1920), the following expression
describes the strength, oF,of a brittle solid,
containing a crack of length 2 4
9.9.1 MICROSTRUCTURAL CONSIDERATIONS
oF=d(Ey/4a) (9.1)
Carbon is a brittle solid; thus, since no plastic
deformation can occur, very high local stresses where E is the elastic modulus and y is the sur-
will develop at stress raisers, such as disconti- face energy. Inspection of equation (9.1)
nuities, changes of section size, cracks, etc. indicates that longer cracks are more effective

I I
longer cracks generate higher tip stresses, it
can be inferred that once a crack begins to
move it will continue to move (accelerate)
until it reaches the geometric boundaries of
the material. As a consequence of this, the fail-
ure of brittle solids is abrupt and depends on
the probability that a crack of some critical
length is present. If such a theory can be
applied to carbon fibers, then it can be argued
that the maximum length of cracks (or similar
microscopic stress raisers) that can be con-
tained is limited by the fiber diameter; so
small diameter fibers will be stronger than
large diameter fibers. In addition, since the
chance of a crack being present is greater, long
fibers will tend to be weaker than short fibers.
Mechanical properties offibers 189
(a)
I I iil
In a composite, many fibers are arranged more
or less parallel to one another and function as
a load bearing bundle. A number of publica-
tions have appeared (Herring, 1966; Wright
and Iannuzzi, 1973; Wright and Wills, 1974)
that discuss the distribution of strengths
exhibited by brittle fibers and how these dis-
tributions can be used to compute a mean
strength, om and a corresponding bundle
strength, ob.
For example, the above authors argued that
their individual fiber strength data tended to
obey a Weibull distribution characterized by
the expression,
G(o) = 1- exp{- a(o/oo)") (9.2)
where G(o) is the probability of failure of a
fiber subjected to stress o,oois the distribution
190 Carbon fibers
scale factor, w is the distribution shape factor
and a is a function of the length/diameter
(L/d) ratio of the fiber (Corten, 1967).
If many fibers are tested of different length
I, then a graphical method can be used to
deduce w, a and a. and, the mean strength and
the strength of a bundle of fibers can be com-
puted from
om=oo(i/d)-lw(i + i/c~), (9.3)
where r is the gamma function and
Gb=oo(acl)e)-'lY (9.4)
Bundles of twisted fibers would exhibit lower
strengths.
9.10 COMPOSITES FABRICATED FROM
CARBON FIBERS
Carbon fibers are very strong, stiff and light-
weight materials. In addition, their small
diameter (8-12 p)makes them extremely
flexible. Unfortunately, they exhibit little com-
pressive strength and they exhibit a poor
abrasion resistance. A solution to these prob-
lems, and to the problem of brittleness, is to
bond large numbers of fibers together to form
a composite solid. In this case, the glue or
bonding agent forms a continuous phase that
is usually defined as the matrix. The
matrix-fiber mixture is called a composite
material. The function of the matrix is to sup-
port and separate the fibers, to protect them
from reaction with the environment and to
transfer load. In a composite, the tensile and
compression properties parallel to the fibers
are much better than those measured on bun-
dles. The transverse properties are also
optimized, since the matrix serves to improve
the fiber-matrix connectivity. This function is
important since it affects the mechanical and
thermal properties in the transverse direction.
Fortunately, although the strength of individ-
ual fibers exhibits a pronounced size effect, no
size effect is exhibited by composites. In effect,
load is transferred around fiber breaks into
adjacent fibers and back into the unbroken sec-
tion of the same fiber by a shear process. The
length of matrix required to do this defines a
bundle of short fibers (or segment of compos-
ite) which must break in order to break the
composite. Such bundles can be modeled as
analogous to a link within a chain; failure of
the weakest link defines the failure load of the
composite. Nevertheless, since shorter fiber
bundles are stronger than longer, shorter links
are stronger than longer links.
The link length, 6, has been discussed by
Rosen (1964) and, for purposes of this discus-
sion can be approximated by,
6=~ d / 2 ~ (9.5)
where o = obthe stress in the fibers at failure of
the composite, d is the diameter of the fiber
and z is the shear strength of the matrix or
matrix-fiber bond as it exists in the composite.
For a given fiber strength distribution, the
stronger composites will all exhibit smaller
ineffective (link) lengths. This is accomplished
by using small diameter fibers, well bonded
using high strength glue.
9.10.1 SURFACE TREATMENT
A freshly prepared fiber does not bond well to
a polymeric glue (or to anything else for that
matter); however, the tendency to bond can be
significantly increased by subjecting the fiber
surface to a controlled oxidation. As discussed
by Eggs, Shuford and Lewis (1982) in the ear-
lier edition of this handbook, this treatment
essentially etches the surface, cleans it,
increases its surface area and produces polar
hydrophilic oxygen-containing groups which
bond to it. The process can be carried out in a
liquid or gaseous environment; for example,
heating in air or oxygen-nitrogen mixtures,
CO,, C1, NOz-NO, NH, and plasma-ionized
inert gases oohnson 1969; US Patent 3 754 957,
1973a; US Patent 3 723 150, 1973b; British
Patent 1341 161, 1973; U.S Patent 4 374 114,
1983; US Patent 3 627 466, 1971; US Patent
3767774, 1973; US Patent 3780255, 1973).
Direct wet chemical oxidation has been tried
 Mechanical properfies of unidirectional composites 191

using aqueous nitric acid, hypochlorite, chlo-
rate and dichromate in sulfuric acid.
Treatments have also been investigated using
electrolytes of hypochlorite, ammonium
hydroxide, sodium hydroxide and ammonium
sulfate (US Patent 3 660 140, 1972; US Patent
3 746 506,1973; US Patent 3 894 884,1975a; US
Patent 3 859 187, 197513; US Patent 3 746 450,
1973; US Patent 3989802, 1976; US Patent
3832297, 1974; US Patent 3671422, 1972;
British Patent 1371621, 1974; British Patent
2 071 702,1981) .
During oxidation, the strong carbon-oxy-
gen complexes which are formed bond
tenaciously to the fiber surface and will subse-
quently react with a matrix resin. In order to
preserve this reactivity a thin layer of the final
matrix resin is applied to the surface of the
fibers as a finish or size. This layer does dou-
ble duty in both protecting the fiber surface
against damage during transportation, further
processing and handling and in promoting
wetting when the sized fibers are bonded
together with the matrix resin.
Poor bonding is a sensitive function of the
surface morphology, anisotropicity, hetero-
geneity and the nature of the interphase layer
between the fiber and the matrix. For example,
it has been found that the greater the degree of
graphitization and the better the alignment of
the microstructure with respect to the fiber
axis, the poorer the fiber will bond.
Essentially, the higher modulus carbon fibers
will not bond easily in the absence of a surface
treatment. In some composites where the fail-
ure strain of the matrix is smaller than the
failure strain of the fibers (as it is for ceramics
or carbon), poor bonding is an asset since the
largest fiber-matrix bond strength is not
required. Conversely, if the failure strain of the
matrix is larger than that of the fibers, a strong
bond is desired. The reason for this apparent
dichotomy involves the fact that fibers are
added to brittle matrices primarily to toughen
them; only tough matrices (large failure strain)
can be strengthened. The mechanism of tough-
ening depends on the blunting of a running
crack by interaction with low strength
fiber-matrix bonds; strengthening depends on
load being transferred from the matrix to the
fibers through a strong fiber-matrix bond.
9.11 MECHANICAL PROPERTIES OF
UNIDIRECTIONALCOMPOSITES
The properties of unidirectionally reinforced
composites are strongly orthotropic.
Specifically, properties measured parallel to the
fibers are quite different from those measured
at right angles to them. More importantly per-
haps is the sensitivity of property
determination with respect to the direction of
the measurement. For example, Fig. 9.21 illus-
trates the change in elastic properties exhibited
when a unidirectionally reinforced composite
is loaded at some angle to the fiber axis. In this
case, it can be observed that the stiffnesses of
the composite (Qll,etc.) begin to change signif-
icantly when the load is misaligned only fifteen
degrees to the fiber axis.
9.11.1 MICROMECHANICS
Using micromechanics, various equations can
be used to estimate the properties that might
be exhibited by well bonded composites. For
example, parallel to the fibers, the modulus
and Poisson's ratio y2are
(E,), strength (0,)
given by;
E , =Vf E, + Vm Em (9.6)
ol=vfof+ vm0, (9.7)
'12 = Vfv12 + 'mum (9.8)
o2z om (9.9)
where V is the volume fraction of fibers (0 or
matrix (m) respectively, ofis the strength of a
bundle of fibers with length equal to the inef-
fective length (usually, due to lack of statistical
data ofis taken as the mean strength supplied
by the fiber processor). Also,
192 Carbonfibers

mechanics of composites; thus, the reader is

9.11.2 MACROMECHANICS OF LAMINAE
There are a number of excellent books and
monographs that have been written on macro-
directed to these for a more complete discus-
sion of this subject (Ashton, Halpin and Petit,
1969; Jones, 1975; Tsai and Hahn, 1980; Daniel
and Ishai, 1994).
When only plane stress conditions exist,
(e.g. 03=0 and E, is related to E, and E,), then it
is possible to relate stress to strain along the
principal axes of an orthotropic lamina,i.e. par-
allel (1)and perpendicular (2) to the fiber axis:

I 1
-8 I
01
30 60 90 ' -6
01 30 60 90

60 [ (42

01
I
30
I

60
a

90 - 8

Fig. 9.21 Transformed, off-axis modulus of T300/5208. The angle is the ply orientation and is positive for
counterclockwise rotation (Tsai and Hahn, 1980).
 Mechanical properties of unidirectional composites 193
(9.12)
or
(9.13) In addition to the variation of elastic proper-
where
and
Inspection of equations (9.12) and (9.13) indi-
cates that parallel and perpendicular to the
fiber axes, tensile (compressive)stress produces
tensile (compressive) strain and shear stress
produces shear strain. There is no coupling
between shear stress and tensile (compressive)
strain, e.g. Q,, = 0 = Q,, as shown previously in
Fig. 9.21 and the shear coupling coefficient
which is the ratio of tensile (compressive)stress
to shear strain, is zero. The above conclusion is
not valid when loads are applied at some angle
to the principal axes since appreciable shear
coupling can occur; Q,, and Q,, are not zero.
This means that tensile (compressive) stresses
produce shear strains in addition to the more
normal tensile (compressive strains). The
stress-strain relationships are then written,
(9.14)
where x and y are the orthogonal axes of the
composite test specimen that are oriented at
some angle to the fiber axes and where [Q] or
.xY
[SI, are the transformed matrixes of equabons
(9.12) and (9.13). The variation with angle of
the components of the [Q],, has already been
illustrated in Fig. 9.21.
(9.15)
ties, the strength of unidirectionally reinforced
composites has been found to be sensitively
dependent on the angle of loading. A typical
failure curve for tension and compression is
shown in Fig. 9.22. This type of curve can be
obtained by transforming the applied stresses
to directions parallel and perpendicular to the
fiber axes and then equating those stresses to
the failure strengths actually measured (or
computed using micromechanics) along those
directions. Failure of a composite is then con-
sidered to occur when the transformed stress
exceeds the failure stress actually measured in
that direction, i.e. when
F,,, = Fl,/(cos28);Fx,= F,, / (sin20);
F,, = F6/ (sine c o d )
and
Fxc = F J ( s i n 0 ~ 0 s 0 )
Fxtc = FlC/(~os20);
where Fl,(c,,F2t(c)
and F, are the measured failure
tensile (t) or compressive (c) loads measured
parallel (1)or perpendicular (2) to the fiber axis
and F, is the measured shear strength. These
failure criteria are collectively described as the
maximum stress failure criterion.
There are other failure criteria such as max-
imum strain, deviatorial strain energy
(Tsai-Hill) and Interactive Tensor Polynomial
(Tsai-Wu) that can be used, some of which
allow for interaction between the stresses.
However, for typical composite structures, the
maximum stress criterion give reasonably con-
servative estimates of expected failure
stresses.
9.11.3 MACROMECHANICS OF LAMINATES
In order to eliminate coupling and to reduce the
very strong change of mechanical properties
194 Carbonfibers
1.2
1.o
a 0.8
a .-
(3 0.6
LL' 0.4
g 0.2
F! = o
5 -0.2
-0.4
-0.6
-0.8
0 10 20 30
Fiber orientation, 8, deg.
Fig. 9.22 Uniaxial strength of off-axis E-glass/epoxy unidirectional lamina as a function of fiber orienta-
tion (Daniel and Ishai, 1994).
with the direction of applied load, composites
are usually fabricated from multiple layers,
each arranged at some angle to their neighbor.
The angles that are used can be arranged to
bring the fiber axes at some optimum angle to
the expected loads; however, there is a require-
ment for each lamina to be oriented very
precisely with respect to one another in order
to avoid tensile-shear effects and coupling
between in-plane loading and out-of-plane
deformation (tensile loads can be made to pro-
duce bending and twisting deformation, for
example). Various rules of angle-ply materials
have been worked out in order to avoid the
cross-coupling terms. For example, symmetric
laminates exhibit no coupling between
in-plane loading and out-of-plane deforma-
tion. (Symmetric laminates define a composite
in which for every lamina oriented at some
angle there is another layer of identical thick-
ness and orientation placed at an equal
distance from the mid-plane of the composite.)
And, composites which exhibit no shear cou-
pling are 'balanced laminates' (pairs of
identical layers oriented at a positive and an
equal negative angle with respect to the lami-
nate reference axes).
160
120
(I)
80 x-
LX
40 g-
m
O E
-40 i5
-80
40 50 60 70 80 90
Of particular interest is the quasi-isotropic
composite which is often specified for com-
mercial structures. The in-plane engineering
elastic constants of these materials are identi-
cal in all directions and there is no shear
coupling. Examples of such composites are
symmetric arrangements of [0/60/-601 or
[0/ +45/90] layers.
9.12 TESTING TECHNIQUES
A knowledge of the behavior of the constituent
phases allows the mechanical properties of the
resulting composites to be computed. These
calculations are made with the use of expres-
sions (9.6)to (9.11).The results of the following
tests should provide input to and in some cases
confirm these calculations. The following was
adapted from the excellent (and much more
extensive) discussion contained in Chapter 8 of
the book Engineering Mechanics of Composite
Materials (Daniel and 0.Ishai, 1994).
9.12.1 PROPERTIES OF FIBERS AND MATRICES
Determination of the elastic and failure prop-
erties of the fibers is described in ASTM
 Testing techniques 195

specification D3379. The difficulty is mostly verse Young’s modulus, tensile strengths and
involved in determining the elastic displace- strains and the major and minor Poisson’s
ment parallel to the fiber axis, since no ratio can all be determined from this type of
measurement device can be attached directly coupon test specimen. Similar properties can
to the fragile fiber. Since the fiber tends to shat- also be measured in compression; usually
ter and disintegrate when failure occurs, the however, short, thick specimens are used in
mean diameter measured before the test has to order to avoid buckling failure. ASTM D-3410
be used to calculate the failure stress. describes this test method.
The method involves attaching the fiber
across a slot cut into a paper tab. The compos-
Flexure testing
ite specimen is aligned coincident with the
load axis of the testing machine, the tab ends A far more expensive test is described in ASTM
are gripped and the sides of the tab are cut to C393. This requires a rather large
allow only the fiber to be loaded by the (22 in/l in/1.5 in) sandwich flexure specimen
machine. The measured compliance Cm is the which is tested in four point bending. The
sum of the compliance of the loading system dimension of the honeycomb core and the
C, and the compliance of the fiber C,. Thus composite face sheets are adjusted to cause fail-
ure in the approximate face sheet. Good results
,
Cm= C,+ C, = C, + (AE,)
can be obtained in both tension and compres-
where 1 is the fiber length and E , is the fiber sion; however, since failure might occur in the
modulus. A plot of measured compliance core or in either of the outer skins or at the
against fiber length allows calculation of the skin/core interface, care should be exercised in
loading system compliance and the fiber both determining the exact failure mode and in
modulus. reporting the appropriate failure stresses.
Polymer matrices are evaluated using In the above paragraphs the reader has
coupons cut from thin sheets. Typical geome- been cautioned about making sure that the
tries are described in ASTM specifications loading axis of the testing machine and the
D638, D638 and D882. symmetry axis of the specimen are coincident.
Indeed, consistent measurements will only be
achieved by eliminating any tendency to
9.12.2 PROPERTIES OF COMPOSITES develop complex stresses in any region of the
specimen. An additional effect not significant
Coupon tests
in designing or testing ductile materials is the
The determination of the tensile longitudinal tendency for composites to exhibit poor shear
and transverse properties of unidirectionally properties. Indeed it is common for engineers
reinforced composites can be obtained by test- designing metallic components to assume that
ing relatively long coupon specimens. These failure in shear will not occur if failure in ten-
specimens, as described in ASTM specifica- sion or compression is designed against.
tions D3039-76, are 9 in long, 0.5 in wide and Unfortunately, shear resistance of composites
from 0.02 to 0.10 in thick. The apparently is not directly related to tensile or compressive
excessive length requirement is an attempt to properties; thus, a separate shear failure crite-
minimize the effect of specimen misalignment rion must be used when designing with
with respect to the loading axis. Glass/epoxy composites. Shear failure can occur in-plane or
tabs are bonded to the specimen ends to shear interlamina.
the load into the specimen and to avoid dam-
age and failure of the specimen within the
gripped length. The longitudinal and trans-
196 Carbon fibers
In-plane shear testing
A reasonably simple test method which utilizes
a coupon with an eight layer symmetric +. 45
deg. layup is described in ASTM standard D35
18. If the specimen has strain gages oriented
parallel to the x and y axes of the specimen
(not the fibers), then the failure stress in shear
is given by (0JmaX/2, the shear failure strain is
( E ~- &Jmax and the shear modulus is given by
GI,= E J ~ ( E-~ E,)
A rail shear test has been described in
ASTM D4255-83. The shear stress and shear
strain can be obtained at intermediate and
maximum loads. Thus, GI, and the appropri-
ate failure parameters can be obtained.
Interlaminar shear strength
The interlaminar shear strength is a measure
of the strength of the bond that exists between
the various layers within the composite. It is
important to know such a value since bending
of beams can cause appreciable shear stresses,
which while not large enough to cause failure
of a traditional metallic structural material can
fail a composite. This occurs either within the
matrix or at the fiber-matrix bond line. The
test specimen, as discussed in ASTM D2344, is
a rather short, thick beam which is tested in
three-point bending. Basically, the test speci-
men is sized such that the ratio of the shear
stress generated at the midplane is maximized
with respect to the tensile or compressive
stresses generated in the outer fibers. If inspec-
tion of the failed specimen indicates that
failure by shear has occurred, then beam the-
ory indicates that a reasonably accurate
estimate of the interlaminar shear strength F,,
can be calculated from
F3,=3P/4wh
where P is the maximum load and w and h are
the width and depth of the beam.
Another way to measure the same maxi-
mum shear stress is by using the
double-notched specimen as described ASTM
D3846. This specimen contains two square
notches, each cut into an opposite face of a ten-
sile or compressive specimen. If the slots are
cut a reasonable distance, I, apart in order to
avoid interactions between the stress fields of
the cut slots, then the interlaminar shear
strength is given by
F,, = P/wl
9.13 CONCLUSION AND PERSPECTIVES
Low performance isotropic non-continuous
pitch-based fibers and anisotropic PAN-based
large tow fibers have been available for a num-
ber of years in the USA priced at $20/kg.
These fibers have been used to produce elec-
trically conducting flexible heating materials
to control the temperature of pipelines, to heat
human dwellings, hot-houses, etc. (Karpinos
and Izmalkov, 1982; Glushchenko and Griffen,
1982; Levit, 1986; Jakubowski and
Subramanian, 1979).In addition, low modulus
carbon fiber materials and their composites
have been used as abrasive, anti-friction, seal-
ing and heat-insulating materials. Other
nonstructural uses include activated carbon
fibers which can be used directly for the purl-
fication of nitrogen oxide-containing fumes,
chimney smoke, automobile air conditioners,
various respiratory, water purification
(Chupolov et al. 1983; Richter, Knoblauch and
Juntgen, 1984). In recent years carbon fiber
adsorbents have been used in medicine to
remove toxic substances from body fluids
(Ternovoiet al., 1985).
The high modulus/high strength continu-
ous carbon fibers have been available at a cost
of $60-80/kg. Thus, reinforced epoxies, poly-
esters and other polymers have demonstrated
properties that have enabled them to find use
in the aerospace and aeronautical fields.
Smaller quantities of fibers have been used in
high quality sports gear such as golf clubs,
fishing rods, tennis rackets, marine sports, ski
equipment, bicycle equipment, etc. Fibers
have also been used in many civil engineering

structures. These include short fiber reinforce-
ment of cement mortar and continuous
reinforcementof concrete. Some attempts have
been used to provide earthquake resistant
structures and fiber reinforced ropes and some
successes have been reported in fabricating
structures with carbon fiber reinforced alu-
minum and copper. Carbon fiber reinforced
carbon has been considered for high tempera-
ture load bearing structures and heat shields
in spacecraft and supersonic aircraft. And,
finally, similar materials are considered useful
in nuclear applications and disc brake materi-
als for aircraft, high speed trains and racing
cars. At the present time, there is a growing
interest in the use of very high thermal con-
duction properties to manage local
temperatures in sensitive electronic equip-
ment. Nevertheless, despite all these apparent
successes, it is vitally important to realize that
the expanded use of high performance carbon
fibers depends very sensitively on the lifetime
costs involved in substituting carbon and its
composites for competing metals, ceramics
and polymers.
It has been recognized for many years that
market penetration of carbon fibers will
always be limited to rather sophisticated
structures if the cost remains at the present
high level. However, the precursor PAN mate-
rial presently costs about $5/kg; thus, taking
into account the weight loss and processing
costs involved in converting PAN to carbon, it
is unlikely that large amounts of carbon fiber
made from such material will ever be less than
$10/kg. Conversely, the cost of the pitch pre-
cursor material is almost insignificant, since it
is the byproduct of a commercial process
established to produce other end products:
gasoline, metallurgical coke, etc. In addition,
since the fiber is fabricated using a melt spin-
ning process, the production rate can be much
faster than the wet or dry process used to pro-
duce PAN based fibers. The carbon yield from
pitch precursors can average up to 85%,
whereas the carbon yield produced from PAN
averages about 65%. Pitch based carbon fibers
Conclusion 197
can be made with modulus values much larger
than can be obtained from PAN precursors.
Unfortunately,rather sophisticated and expen-
sive pitch pretreaments must be applied to a
petroleum or coal tar pitch in order to produce
a high performance fiber. The pitch softening
temperature is much higher than PAN; thus
stabilization can potentially be carried out
quickly at higher temperatures. Nevertheless,
stabilization of both PAN and pitch materials
is exothermic and, in order to avoid overheat-
ing, thermal runaway and decomposition of
the precursor, a less than advantageous tem-
perature of oxidation must be used. Future
developments in these areas should therefore
involve methods to increase the stabilization
rate and the development of new precursor
materials. Specific topics might include stabi-
lization in thermally stable environments
(fluidized beds, liquids, etc.) and the develop-
ment of alternative synthetic precursor
materials (polymers and/or pitches).
Cost of the final component, while very sen-
sitive to the cost of raw materials, also
involves all of the design, fabrication and test-
ing costs. All of these component costs must be
tightly controlled if economically viable per-
formance increases are to be realized. When
using composites, it has been found to be
vitally important to pay strict attention to
detail design if a maximum expected weight
saving is to be realized. Designers must opti-
mize the total vehicle weight and not simply
substitute a carbon composite for a metal one.
It is rumored for instance that, due to overly
conservative design (i.e., the use of metallic
joining and fabrication techniques etc.), the
resulting weight of some composite structures
has, in the past, turned out to be as heavy as
similar components built from aluminum.
9.14 CONCLUSION
Many people appear to believe that despite
nearly thirty years of development, carbon
fibers are still an evolving space age material.
Until very recently, there was a production
198 Carbon fibers

over-capacity in the carbon fiber industry. For
example, in 1995 it was estimated that
10 000 000 kg of carbon fibers were sold from
an estimated capacity of 16 000 000 kg. Exactly
how accurate these estimates were is difficult
to assess; however, it can be concluded that the
market is small and cannot accommodate
many producers. For this reason, many pro-
ducers have seen fit to evaluate their position
in the industry. For example, Table 9.3 is a list-
ing of carbon fiber processors taken from
Chapman and Hall's directory, 'Carbon and
High Performance Fibers' which was pub-
lished in 1991. In 1996, only the first eight of
these were still producing significant commer-
cial quantities of PAN-based carbon fibers.
Table 9.4 is a similar listing for pitch-based
fibers. In this case only the first five appear to
be active.
At the present time, downsizing of the
industry, increasing use of low cost fibers and
the resurgence of orders for new commercial
aircraft that now use increased quantities of
carbon fiber has brought industrial capacity
and market requirements closer together.
Indeed, some fiber types are now difficult to
obtain. Nevertheless, any major growth of the
carbon fiber industry depends on the discov-
ery of a method to produce fibers for one-half
or one-third of the present projected large vol-
ume price and the development of new
inexpensive fabrication methods for struc-
tures. These developments will initiate major
new transportation based markets for the
material. At the present price, however, the
use of carbon fibers will always be limited to
competitive performance driven applications.

Table 9.3 PAN-based tow manufacturers

Company Country Trade name

Akzo Carbon Fibers Inc. (Fortafil Fibers Inc.) USA Fortafil
Amoco Performance Products Inc. USA Thomel
RK Carbon Fibres Limited UK RK
Mitsubishi Rayon Co. Ltd. Japan Pyrofil
Soficar SA (Toray Industries Inc.) France Torayca F
Toho Rayon Co. Ltd Japan Besfight
Toray Industries Inc. Japan Torayca
Zoltek Corporation USA Panex
Akzo NV (Fibres and Polymers Division)(Enka AG) Holland Tenax
Anglo-Soviet Materials Ltd USSR Sapem
Asani Kasel Carbon Fiber Co. Ltd Japan Hi-Carbolon
BASF Structural Materials Inc.' USA Celion
Formosa Plastics* Taiwan ?
Hercules Advanced Materials and Systems Company2 USA Magnamite
Korea Steel Chemical Co. Ltd Korea Kosca
Nikkiso Co. Ltd* Japan ?
N.W. Chemical Power Co.* China ?
Sigri GmbH Germany Sigrafil
Textron Specialty Materials USA Avcarb
* Not available.
Now Hexcel; * Now Toho.
 References 199

Table 9.4 Pitch-based tow manufacturers

Company Country Trade name

Amoco Performance Products Inc. USA Thomel
Mitsubishi Kasei Corporation Japan Dialead
Petoca Ltd (Kashima Oil Co. Ltd) Japan Carbonic
Tonen Corporation Japan Forca
Nippon Petrochemicals Co. Ltd Japan Granoc
Kawazaki Steel Co. Ltd Japan KMFC
Kobe Steel Ltd" Japan ?
Mitsubishi Oil Co. Ltd* Japan ?
Nippon Carbon Co. Ltd* Japan ?
Nippon Steel Co. Ltd" Japan ?
Osaka Gas Co. Ltd (Donac Ltd) Japan Donacarbo-F
Showa Shell Sekiyu Japan Carbonexel
* Not available.

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ORGANIC FIBERS 10
Linda L. Clements

10.1 INTRODUCTION A different type of h g h performance organic

Before the first aramid fibers were introduced fiber, extended chain polyethylene fibers, was
added in the 1970s. While inferior to inorganic
in the 1960s and 1970s, organic fibers were rel-
fibers in some properties, organic fibers provide
atively low performance materials, primarily
combinations of properties not available with
used in textile applications. Now several dif-
ferent types of high performance organic inorganic fibers and so have made possible new
fibers exist, all competitive with inorganic designs and applications.
In this chapter, only high performance
fibers in some or even most of their properties.
The market demand for these fibers exceeds organic fibers which are commercially avail-
one billion dollars (Adams and Farrow, 1993a). able will be discussed in detail, although fibers
The main applications for high perfor- which are nearing commercialization will be
mance organic fibers today are in asbestos discussed briefly. For a more complete review
replacement, ballistics, rubber reinforcement, of both commercially available and experi-
ropes and cables and composites. Most of the mental high performance organic fibers, see
Yang (1989, 1992).
usage is of aramid fibers, with over 18000
metric tons used each year. Both usage and
existing capacity for other organic fibers are 10.2 ARAMID FIBERS
only a fraction of this value (Adams and
Farrow, 1993a). 10.2.1 OVERVIEW
Tlus broad market for organic fibers is a
direct outgrowth of applying the basic princi- Aramid fiber is the generic term for a specific
ples of polymer science to produce a new and type of ’aromatic polyamide fiber.’ The US
exceptional engineering material. In the 1950sit Federal Trade Commission defines an aramid
was recognized that if a means could be found fiber as ‘a manufactured fiber in which the
to form certain intractable polymers into fiber-forming substance is a long-chain syn-
extended chain fibers, very high stiffnesses, thetic polyamide in which at least 85% of the
strengths and use temperatures could be amide linkages are attached directly to two
achieved. The difficulty of producing such aromatic rings.’
fibers was solved in the 1960sby spinning from Thus, in an aramid, most of the amide
liquid crystalline solutions. The first fibers pro- groups are directly connected to two aromatic
duced by t h s process were the aramids, which rings, with nothing else intervening. It should
have since been followed by other such fibers. not be surprising that aramids have quite dif-
ferent properties from nylons and other
conventional polyamides since the latter poly-
Handbook of Composites. Edited by S.T. Peters. Published
mers contain few if any aromatic groups in the
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 main chain of the polymer.
 Aramid fibers 203

Aramid fibers can be separated into two include DuPont’s KevlarO, Akzo’s TwarorP,
types: the para- aramids and the meta-aramids. Teijin’s TechnoraO and Kaiser VIAM‘s Amosa
In para-aramids, the chain-extending bonds are and S W @fibers, while meta-aramids include
in the para-position on the aromatic ring, as in DuPont’s Nomexs and Teijin’s TeijinconexO
poly-p-phenylene terephthalamide (PPTA) (Fig. fibers. Hoechst AG also markets a para-aramid
10.1(a)),co-poly-p-phenylene/3,4’-oxydipheny- fiber in Europe. The para-aramids are the fibers
lene terephthalamide (Fig. lO.l(b)) and used in high performance applicationsand thus
poly-p-phenylene-benzimidazole-terephthala- will be emphasized in this chapter.
mide (Fig. lO.l(c)). In meta-aramids, on the
other hand, the chain-extending bonds are in
10.2.2 MANUFACTURE
the meta-position on the aromatic ring, as in
poly-m-phenyleneisophthalamide (MPIA) (Fig. Historically, meta-aramid fibers were the first
10.1(d)). Commercially available para-aramids to be produced, with DuPont’s Nomex fiber

0
II
-0 .C
\
H

k-(=&IA \
H

H 1 -0;-
-0
0
I1
C
0
H
I
N
\
1

HI
0-
-0
0 H H
I1 I I
C

0
I1
C
\
I
N-
H d+-
0
Fig. 10.1 Structural formulae of (a) the para-aramid poly-p-phenylene terephthalamide (PPTA), (b) the
para-aramid co-poly-p-phenylene/3,4’-oxydiphenyleneterephthalamide, (c) the para-aramid poly-p-
phenylene-benzimidazole-terephthalamide(PBIA), and (d) the meta-aramid poly-m-phenylene isophthal-
amide (MPIA).
204 Organicfibers

being introduced in the 1960s. The first para- 10.2.3 STRUCTURE

aramids were synthesized in 1965 by S.L.
The excellent properties of para-aramids result
Kwolek of DuPont (Kwolek, 1971; Kwolek,
from both chemistry and physical microstruc-
1972; Kwolek, 1974).Forming these into usable
tures. In both meta- and para-aramids, the
fibers is very difficult because para-aramids
aromatic rings in the backbone chain produce
show no melting point and are soluble in a
high thermal resistance. In addition, in para-
limited number of solvents.
aramids the orientation of the chain-extending
The problem of spinning the polymer into
bonds produces a polymer which is an
fibers was solved for PPTA following the dis-
extended-chain rigid rod. Spinning produces a
covery that the polymer would dissolve in
fiber made up of extended-chain crystallites
strong acids to form a liquid crystalline solu-
which are almost completely aligned parallel
tion. Undiluted sulfuric acid is the solvent
to the draw direction and to each other. The
usually used. Blades (1973, 1974) devised a
crystallites have a very high length-to-diame-
special manufacturing process - known as
ter ratio and extensive interconnection of
continuous dry jet wet spinning - for forming
molecules between crystallites. Thus, an
the liquid crystalline solution into filaments.
unbroken ’infinite’ filament can be formed.
The polymer solution is extruded through
Within the crystallite the chains are bonded
spinnerets at elevated temperature through an
to one another by hydrogen bonds, as shown
air layer into a coagulating water bath. The
in Fig. 10.2. Although these bonds are not
cold water bath also contains a base to neu-
nearly as strong as the covalent bonds which
tralize and remove the retained acid.
occur within the molecules, hundreds or even
Continuous dry jet wet spinning is the man-
thousands of such bonds form between adja-
ufacturing technique used for most
cent para-aramid molecules. Since the
para-aramid fibers. Teijin’s Technora fiber,
molecules are rigid, the only way to separate
however, is produced by wet spinning fol-
them in tension is to break all of the hydrogen
lowed by drawing (Hongu and Phillips, 1990).
bonds at once. This requires a large force and

0
I
H
H
H

-N
I
0
II
0
A&=(-*
H
I \

-C H
\ llc - e \
0

0
-0
H

Fig. 10.2 Schematic showing hydrogen bonding between PPTA molecules in the crystallite.
 Aramid fibers 205

is the reason para-aramid fibers are exception- mechanical, thermal, physical and other proper-
ally strong in axial tension. However, since the ties. This anisotropy may produce design
bonds can be broken easily one at a time, the limitations, but can also be used to advantage.
fibers are quite susceptible to damage by
bending, buckling or transverse loading.
Physical and thermal properties
In meta-aramids, on the other hand, a
crooked chain results. Since even in pure ten- Table 10.1 compares the physical and thermal
sion the chain-extending bonds can flex and properties of some representative aramid
rotate, meta-aramids are much less rigid than fibers.
para-aramids and not as strong. However, Due to their highly aromatic and ordered
because the chains are more flexible, meta- structure, aramids have very high thermal
aramids are easier to manufacture than resistance for organic materials. They do not
para-aramids and are less expensive. melt prior to decomposition,in spite of the fact
that they are technically classified as thermo-
plastics. This is because melting of the
10.2.4 PROPERTIES
crystalline phase, like rupturing the fiber in
Aramid fibers offer some significant advan- tension, would require that all of the hydrogen
tages over other fibers, but also have their bonds between two molecules be severed at
drawbacks and limitations. Both advantages once. Nonetheless, because of decomposition,
and limitations will be described more fully in their temperature resistance is not equal to
the sections on properties and in the sections that of inorganic fibers. Thermogravimetric
on design considerations and applications. analysis of Kevlar fibers shows that weight
Both DuPont’s Kevlar family of fibers and loss begins at above 350°C (660°F)in air (Penn
Akzo‘s Twaron fibers are based upon PPTA and Larsen, 1979; Yang, 1992), with complete
(Fig. lO.l(a)). Teijin’s Technora fiber and the decomposition occurring at between 427 and
para-aramid marketed by Hoechst AG in 482°C (800 and 900°F) (DuPont, 1992a).
Europe, on the other hand, are a para-aramid Exposure to elevated temperature will
copolymer, co-poly-p-phenylene/3,4’-oxy- degrade the properties of aramid fibers. Figure
diphenylene terephthalamide (Fig. lO.l(b)).It is 10.3 shows the strength retention of Kevlar 29
likely that Kaiser VIAM’s SVM fibers are poly- and Technora fibers as a function of time and
p-phenylene-benzimidazole-terephthalamide temperature. This change in properties occurs
(PBIA), (Fig. lO.l(c)) rather than PPTA as a result of slow oxidation. For this reason,
(Gerzeski, 1989). Kaiser VIAM’s Armos fiber the long-term use temperature of para-aramid
may be PBIA or PPTA. Both DuPont’s Nomex fibers is typically limited to about 150-175°C
and Teijin’s Teijinconex fibers are based upon (300-350°F).
MPIA (Fig. lO.l(d)).These chemical and struc- In the transverse direction para-aramids are
tural differences produce different properties like most other materials in that they expand
for the fibers. In addition, differences in spin- with increasing temperature. However, in the
ning conditions and, most importantly, longitudinal direction the fibers actually con-
post-spinning heat treatments are used to alter tract somewhat as temperature increases. The
properties further. For example, by changing negative thermal expansion coefficient of
processing conditions, Kevlar fibers can be para-aramids can be used to advantage to
produced with elastic moduli ranging from 63 design composites with tailored or zero ther-
to 143 GPa (9 to 21 Msi) and elongations at mal expansion coefficient.
break from 1.5 to 4.4%. Aramids are flame resistant but can be
Because of the anisotropy of their microstruc- ignited. While pulp or dust of Kevlar may con-
ture, para-aramid fibers have very anisotropic tinue to smolder once ignited, fabrics do not
206 Organicfibers

Table 10.1 Physical and thermal properties of representative aramid fibers

Fiber Kevlar 49 Twaron HM Technora Nomex Teijinconex

Type para-aramid para-aramid para-aramid meta-aramid meta-aramid
copolymer
Reference for data DuPont Akzo Teijin DuPont Teijin
1992a 1990,1991 1989,1993 1981,1993g 1991
Density 1.44 1.45 1.39 1.38 1.38
g cm-3 (lb in-?) (0.0520) (0.0524) (0.0502) (0.0499) (0.0499)
Melting temperature -538°C" >5OO0C - >371"C
(1000°F) (>932"F) (>700"F)
Decomposition 427482°C 500°C 500°C 371°C 400430°C
temperature in air (800-900°F) (930°F) (930°F) (700°F) (750-805°F)
Long-term use 149-177°C -
temperature in air (300-350°F)
Longitudinal linear -4.9 -3.5 -6.2 +15 +20
thermal expansion (-2.7) (-1.95) (-3.4) (+8.3) (+11)
coefficientb
10-6/ "C
OF)

Transverse linear +66"

thermal expansion (+37)
coefficientb:
/"C ( / O F )
Specific heatb 1.42 1.42 1.09 1.21 1.05
kJ/kg K (BTU/lb OF) (0.34) (0.339) (0.26) (0.29) (0.25)
Longitudinal thermal
conductivityb 4.11' 4.0 0.13 0.13
W/m K (2.38) (2.3) (22) (22)
BTU/h ft OF)
Transverse thermal
conductivityb 4.82' 5.0
W/m K (2.79) (2.9)
BTU/h ft OF)
Equilibrium 3.5% 3.5% 2.0% 4.5% 5.0-5.5%
moisture contentb
Typical filament 12 or 15 12 12 max: 15-17 -10 to 15 X 45
diameter (0.48 or 0.59) (0.48) (0.48) (0.6-0.7) (-0.4 to 0.6 X 1.1)
pm in)
Typical filament round round round oval to oval to
shape dogbone dogbone

* Data from Yang, 1992.

Varies with temperature; room temperature values are given.
Data from Chiao and Chiao, 1982.
 Arumidfibers 207

rL I I I I

100

.
be 80

-
C
0
+
C
2w 60
L11

fm
-
e
I= 40
iz
- Technorag
20 -

0' I I I I L

0.1 1 10 100 1000

Time, h

Fig. 10.3 Strength retention of Kevlar 29 and Technora fibers following elevated temperature exposure
(DuPont, 1992a; Teijin, 1989).

continue to burn when the flame source is
removed (DuPont, 1992a). The lower thermal
conductivity of aramids compared to inor-
ganic fibers can improve the fire resistance of
their composites, since aramids do not readily
conduct heat into the more volatile matrix.
Mechanical properties
Composite materials are most commonly used
because of their superior strength and/or stiff-
ness at a given weight as compared to
conventional structural materials. Figure 10.4
compares the specific strengths and specific
stiffnesses of various reinforcing fibers. (The
strengths and stiffness in Fig. 10.4 are expressed
in units of grams per denier (gpd). This is a tex-
tile term often used for organic fibers which
measures specific strength and/or stiffness. This
term is further explained in the appendix to this
chapter.) As can be seen, aramid fibers perfonn
very well. In fact, until the emergence of high
strength intermediate modulus carbon fibers
and the commercialization of polyethylene
fibers in the mid-l980s, aramid fiber composites
had the highest specific strengths of all compos-
ite materials. Although composites from newer
fibers have taken over that position, aramids
still offer outstanding combinations of proper-
ties, such as high specific strength, toughness,
creep resistance and moderate cost, for specific
applications.
Table 10.2 compares the mechanical proper-
ties in axial tension of several commercially
available aramid fibers.
Aramid fibers have some definite limita-
tions. They are weak in bending and show
obvious damage if subjected to kinking or
buckling. As a result, they are also weak in com-
pression (where microbuckling is inevitable)
and in transverse tension (wherebond-by-bond
breakage of hydrogen bonds is likely). In addi-
tion, even though the para-aramid chain is
quite polar in nature, almost all of the polar
groups are fully involved in hydrogen bonding
to other aramid molecules. As a result, para-
aramid fibers do not form strong bonds with
other materials such as composite matrices,
208 Organicfibers

Table 10.2 Axial tensile mechanical properties of representative aramid fibers

Fiber Reference Spec$c Initial tensile Tensile strength, Elongation at

gravity modulus, GPa (Msi) MPa ( h i ) break, %
Bare" Epoxy- Bare" Epoxy- Bare"
impregnatedb impregnatedb
Kevlar DuPont, 1993h 1.44 71.8 2920 - 3.6
Type 956, (10.4) (424)
1500 denier
Kevlar 29 DuPont, 1992a, 1.44 70.5 83.0 2920 3600 3.6
Type 964, DuPont, 19938 (10.2) (12.0) (424) (525)
1500 denier
Kevlar 49 DuPont, 1992a, 1.44 112.4 124.0 3000
Type 965, DuPont, 1993g (16.3) (18.0) (435)
1140 denier
Kevlar 68 DuPont, 1993g 1.44 99.13 3050 - 2.9
Type 9898, (14.4) (442)
1420 denier
Kevlar 119 DuPont, 1990 - 54.6 3050 - 4.4
1500 denier (7.9) (442)
Kevlar 129 DuPont, 1993i 1.44 96.0 3380 - 3.3
denier (13.9) (490)
unspecified
Kevlar 149 DuPont, 19938 1.47 142.7 2340 - 1.5
Type 965A, (20.7) (339)
1140 denier
Kevlar HT DuPont, 19938 1.44 99.1 3370 - 3.3
Type 964C, (14.4) (489)
1000 denier
Kevlar KM2 DuPont, 1992d - 63.4 3280 - 4.0
850 denier (9.2) (476)
Twaron Akzo, 1991 1.44 70 2800 3500 3.6
(10.2) (406) (508)
Twaron Perkins, 1993 1.44 88 3230 - 3.3
Type 2000, (12.8) (468)
930 denier
'microfilament'
Twaron HM Akzo, 1991 1.45 103 3500 2.5
(14.9) (508)
Armos Kaiser VIAM, - 147 - 3.2
58.8 tex 1993a' (21.4)
SVM Kaiser VIAM, 1.43 123
58.8(300) 1993g' (17.8)
X17-1000 Gerzeski, 1989
Continued on next page
 Aramid fibers 209

Table 10.2 Continued

Fiber Reference Specific Initial tensile Tensile strength, Elongation at

gravity modulus, GPa (Msij MPa (ksij break, %
Bare" Epoxy- Bare" Epoxy- Bare"
impregnatedb impregnatedb
~~ ~

Technora Teijin, 1989 1.39 73 - 3440 - 4.6

(10.6) (498)
Nomex DuPont, 1993g 1.38 11.6 - 596 - 28.0
Type 430, (1.68) (86.6)
1200 denier
Teijinconex Teijin, 1991 1.38 7.9-9.7 - 610-670 - 3545
(1.1-1.4) - (88-97)
Teijinconex Teijin, 1991 1.38 11.6-12.2 - 730-850 - 20-30
HT (1.7-1.8) (110-120)

a Data for DuPont fibers taken from conditioned yarns tested according to ASTM Standard D885.
Modulus data for Akzo fibers from testing according to ASTM Standard D885M. Test technique
unspecified for Akzo fiber strengths and elongations and for all data from Kaiser VIAM and Teijin fibers.
Data for DuPont fibers taken from epoxy-impregnated strands tested according to ASTM Standard
D2343. Data for Akzo fibers from testing according to impregnated strand test method DIN 65356, part
2. Test technique unspecified for Kaiser VIAM fibers.
Preliminary data.
50 . . . . I .. I . I . . . I l l l l l l . . . . l l . . I I I I . . I . I . .

40 - PED HM -
Armos
0
Carbon TlOOOG 0
'pectra 'Oo0
Dyneema SKBO Carbon
30 - Technora Tekmilon
0
'spectra 900
. Vectran HS
0 Kevlar 49
. Twaron O O S ~0 Carbon T-300
. .waron HM
2o - S-Glass
0 Kevlar 149 0 Carbon T-50

. PE (H.C.) Boron
E-Glass

. Steel
Carbon P-100
1
2 10 Organicfibers

further aggravating the poor transverse, bending
and compressive properties of the fiber itself.
The basic chemical structure differences
between the aramid fibers produce many of
the mechanical property differences seen in
Table 10.2. The ether (-0-) linkages in the
backbone of the Technora copolymer fiber pro-
duce a lower modulus than that of Kevlar and
Twaron PPTA-based fibers. On the other hand,
the additional cyclic ring in the SVM PBIA-
based fibers produces a higher basic modulus.
However, heat treatment and other fabrication
steps can also alter mechanical properties sig-
nificantly, as is seen in the property differences
between the various Kevlar fibers.
The mechanical properties of aramid com-
posites are illustrated in the data of Table 10.3.
For this filament-wound composite the longi-
tudinal compressive strength was about
one-eighth that in longitudinal tension, the in-
plane shear strength was one-seventy-fifthand
the transverse tensile strength over two hun-
dred times smaller. While the relative values of
properties may change for composites made
from other aramid fibers and/or other matrices
and/or prepared using other fabrication
processes, the general trend is valid: aramid
fiber composites have poor off-axis properties.
In axial tension, both aramid fibers and
their composites are linear to failure. In spite
of this fact, the same microstructural charac-
teristics which lead to the weakness of aramid
fibers in buckling also make them very tough.
During failure, the widespread bending, buck-
ling and other internal damage to the fibers
absorbs a great deal of energy. Similarly, the
strength of aramid fibers is not very strain rate
sensitive: an increase in strain rate of more
than four orders of magnitude only decreases
the tensile strength by about 15%. (Abbott et
al., 1975) This property alone provides design
advantages over all inorganic and many other
organic fibers.
The mechanical properties of aramid fibers
decrease with increasing temperature. Figure
10.5 shows the fiber elastic modulus as a func-
tion of temperature for several organic fibers.
At 177°C (350°F) the modulus of para-aramid
fibers is about 80% of that at room tempera-
ture. Figure 10.6 compares the fiber tensile

Table 10.3 Mechanical properties of a filament-wound composite of 60 vol YO aramid fiber in a room-tem-
perature curable epoxy matrix (Clements and Moore, 1977)
Fiber: DuPonf’s Kevlar 49, Type 968, 1420 denier
Matrix: 100 parts Dow Chemical DER 332 (diglycidyl ether of bisphenol-A epoxy) and 45 parts Jefferson
Chemical reffamine T-403 polyether triamine
Cure: 1 day at room tnnperuture, postcure 16 h ut 85°C (185°F)
Elastic constants:
Longitudinal Young’s modulus E,,, GPa (Msi) 81.8 f 1.5” (11.9 k 0.22)
Transverse Young’s modulus E,,, GPa (Msi) 5.10 k 0.10 (0.74 & 0.014)
Shear modulus G,,, GPa (Msi) 1.82 k 0.09 (0.26 f 0.013)
Major Poisson’s ratio vl, 0.310 k 0.035
Minor Poisson‘s ration u,, 0.0193 f 0.0014
Ultimates: Tension Compression In-plane shear
Longitudinal strength, MPa (ksi) 1850 f 50 (268 f 7.3) 235 f 3 (34.1 k 0.4) -
Longitudinal ultimate strain, Yo 2.23 f 0.06 0.48 5 0.3 -
Transverse strength, MPa (ksi) 7.9 k 1.1(1.15 f 0.15) 53 f 3 (7.7 f 0.4) -
Transverse ultimate strain, Yo 0.161 f 0.023 1.41 f 0.12 -
Shear stress at 0.2%, offset, MPa (ksi) - - 24.2 f 2.4 (3.51 k 0.35)
Shear strain at 0.2% offset, Yo - - 1.55 k 0.16
-
a Limits are 95% confidence limits. Each value is the result of five or more tests.
 Aramidfibers 211

si s
- 5
25 -

1992a; Teijin, 1989).

3500 -1 a - 1 8 - m q
500

:
Techno ra

- 400
2500 1 Kevlar

.-
n=
;:0003
8
g 2000
300 Y"
f
0, m
1500 - c
t? - 200 ?!
3i Polyester
looo;,
Nylon - 100
500

0 , ,: 0

Fig. 10.6 Tensile strength as a function of temperature for two para-aramid fibers and for two polymer
fibers and steel (DuPont, 1993h; Teijin, 1989).
212 Organicfibers

strength as a function of temperature for sev- wet transverse tensile and in-plane shear
eral organic fibers. For Kevlar fiber the strengths were only about half of the 52% r.h.
strength at 177°C (350°F) is about 80% of that values. The data in boiling water illustrate that
at room temperature, while for Technora the the drops in strength due to the presence of
strength is about 70% of the room temperature moisture alone were almost as severe as those
value. On the other hand, at cryogenic tem- due to the combined presence of moisture and
peratures modulus increases slightly and elevated temperature. This relative loss in
strength is not degraded. properties is less for the Technora para-aramid
The presence of moisture also reduces the co-polymer fiber. Care must be exercised when
mechanical properties of aramid fibers and using aramid composites in high moisture
their composites. The effect upon longitudinal applications.
tensile properties is relatively small, but the Both para-aramid co-polymers and homo-
loss is pronounced for off-axis properties. polymers exhibit very little creep. In general,
Table 10.4 illustrates this loss for Kevlar 49 creep strain increases with increasing tempera-
fiber in a room-temperature curable epoxy. ture, increasing stress and decreasing fiber
The longitudinal tensile strength in water at modulus. Like all high performance fibers,
room temperature was 88% of that for com- under long term loading, para- aramids are
posites equilibrated at room temperature and subject to stress rupture, i.e. failure of the fiber
52% relative humidity (r.h.). The wet longitu- under sustained loading with little or no
dinal compressive strength, on the other hand, accompanying creep. Figure 10.7 compares the
was only 75% of the 52% r.h. value, while the stress rupture performance of Kevlar 49 to that

Table 10.4 The effect of environments on the mechanical properties of a filament-wound composite of 50
vol Yo of an aramid fiber in a room-temperature curable epoxy matrix (Wu, 1980)
Fiber: DuPont's Kevlar 49, 4560 denier
Matrix: 100 parts Dow Chemical DER 332 (diglycidyl ether of bisphenol-A epoxy) and 45 parts Jefierson
Chemical Jeffamine T-403 polyether triamine
Cure: Infrared heating, postcure 2 h at 100°C (212°F)
Strength, MPa (ksi)
23"C, dry 23°C' 52% r.k. 23"C, water 1OO"C, water
________
Longitudinal 1370 f 6 2 " 1340 f 112 1190 f 62 1150 f 1 2 4
tension (199 f 9) (194 f 16) (173 f 9) (167 f 18)
Longitudinal 188 f 1 2 169 f 20 126 f 22 107 f 2 1
compression (27.3 f 1.7) (24.5 f 2.9) (18.3 f 3.2) (15.5 f 3.0)
Transverse 7.6 f 1.6 74 f 1.2 3.9 f 0.7 3.6 f 0.2
tension (1.10 f 0.23) (1.07 k 0.17) (0.57 f 0.10) (0.52 f 0.03)
Transverse 31.3 f 3 . 2 29 f 4.0 22.5 f 3 . 2 22.1 f 23.6
compression (4.54 kO.46) (4.21 f 0.58) (3.26 f 0.46) (3.20 f 3.42)
In-plane shear 27 f 3 . 0 26.5 f 1.6 13.8 f 2.2 13.6 f 2.5
(3.92 f 0.44) (3.84 f 0.23) (2.00 f 0.32) (1.97 f 0.36)
Hygrothermal Properties
Equilibrium moisture - 4.1 7.8 8.9
concentration, Yo
~

Limits are 95% confidence limits. Each strength is the average of five tests.
 Aramid fibers 213

0
+, 100
!
.I4
2 90 Kevlafl 49
1
W
o 80
d

a
. 70
a
u
," 60
a
a
0 50
.rl
rl

2a 40

10-2 10-1 1 io io2 103 104 105

Lifetime, h

Fig. 10.7 Stress-rupture behavior of epoxy-impregnated Kevlar 49 fibers compared to that of epoxy-
impregnated S-glass fibers (Chiao,Chiao and Sherry, 1976).

of Sglass. Para-aramids perform well under
these conditions, but the phenomenon of stress
rupture must be considered in any design
where long term loading is anticipated.
Strength retention cannot be used to estimate
the remaining life of aramid fibers or compos-
ites under long term load (Chiao, Sherry and
Chiao, 1976),so estimates of long term behavior
must be derived from actual data, or acceler-
ated testing methods (Chiao and Chiao, 1982).
Para-aramid fibers and their composites per-
form very well in fatigue. For aramids,
tension-tension fatigue generally is not of sig-
nificant concern in applications where an
adequate static safety factor has been used
(Yang, 1992). Aramid composites have been
found to be superior to glass fiber composites in
both tensile-tensile and flexural fatigue load-
ing. For the same lifetime (cycles to failure),
Kevlar 49/epoxy composites can operate at a
significantly larger percentage of their static
strength than can glass-reinforced composites
(DuPont, 1986). Para-aramids also can be
expected to perform better than carbon fibers in
fatigue (Teijin, 1989; Yang, 1992). Technora
para-aramid co-polymer is found to have even
better fatigue resistance than the para-aramid
homopolymer fibers (Teijin, 1989).
Chemical and environmental properties
PPTA fibers are quite stable chemically; their
resistance to neutral chemicals is usually very
high. They are, however, subject to attack by
acids and bases, especially by strong acids.
Because the spin process used for Teijin's
Technora para-aramid co-polymer produces a
very pure polymer, the chemical and environ-
mental resistance of Technora is superior to
that of the PPTA fibers. Table 10.5 reports the
resistance of Kevlar and Technora fibers to
various chemicals. Technora has better acid
and alkali resistance than PPTA and its steam
resistance is also superior.
214 Organicfibers

Table 10.5 Stability of para-aramid fibers in various chemicals

Concentration, Temperature, Time, Effect on breaking strength"

Chemical Yo "C ( O F ) hr None Slight Moderate Appreciable Degraded
Acids
Acetic 40 21 (70) 1000 Kb
40 95-99 (203-210) 100 Tb K
Formic 90 21 (70) 100 K
90 95-99 (203-210) 100 T K
Hydrochloric 20 20 (68) 100 T
10 71 (160) 10 K
Nitric 10 20-21 (68-70) 100 T K
Phosphoric 10 20-21 (68-70) 100 K,T
10 21 (70) 1000 K
10 99 (210) 100 K
Sulfuric 10 99 (210) 10 K
20 95 (203) 100 T
40 95 (203) 100 T
Alkalis
Ammonium hydroxide 28 21 (70) 1000 K
Sodium hydroxide 10 21 (70) 1000 K
10 95-99 (203-210) 100 T K
Portland cement saturated 95 (203) 100 T
saturated 180 (356) 15 T
Organic solvents
Acetone 100 boil 100 K
Benzene 100 20 (68) 784 T
100 21 (70) 1000 K
Carbon tetrachloride 100 boil 100 K
Ethylene chloride 100 20 (68) 1000 T
Ethylene glycol/water 50/50 99 (210) 1000 K
Ethylene glycol 100 95 (203) 300 T
Gasoline 100 20 (68) 784 T
Gasoline-leaded 100 21 (70) 1000 K
Methyl alcohol 100 21 (70) 1000 K,T
N-Methyl pyrrolidone 100 95 (203) 100 T
Other
Sodium chloride 3 21 (70) 1000 K
10 99 (210) 100 K
10 121 (250) 100 K
Sea water 100 95 (203) 1000 T
Sea water (New Jersey) 100 - 1 yr K
Steam 100 120 (248) 400 T
100 150 (302) 48 K
100 150 (302) 100 T
100 200 (392) 100 T
Water, tap 100 99 (210) 100 K
a None, 0-10% strength loss; slight, 11-20% strength loss; moderate, 2140% strength loss; appreciable,
41430% strength loss; degraded, 81-100% strength loss.
K is for Kevlar aramid fiber (DuPont 1989,1993h);T is for Technora aramid fiber (Teijin, 1989).

Para-aramids are strong ultraviolet (W)
absorbers. Upon exposure, the yellow or gold
fibers turn first orange and then brown, due to
degradation. The degradation occurs only in
the presence of oxygen and is not enhanced by
either moisture or atmospheric contaminants
(DuPont, 1992a). Extended exposure may
cause a loss of mechanical properties. Bare
1667 dtex (1500 denier) Kevlar 29 was found to
have 71% strength retention after 1 month of
outdoor exposure in Wilmington, DE and 43%
after 4 months (Yang, 1992).In both processing
and applications, para-aramids must be pro-
tected from W exposure, such as by painting
or coating. However, since para-aramids are
self-screening, UV protection may also be
effected simply by dense packing of the fiber
itself, with or without a matrix. Thus, bare
12.7mm (0.5 in) 3-strand Kevlar 49 rope was
found to have 90% strength retention after 6
months outdoors in Florida and 69% strength
retention after 24 months (DuPont, 1986).
Unlike inorganic fibers, aramid fibers absorb
water. For some aramid fibers the equilibrium
moisture content (see appendix on page 241 for
defirution) is quite high (5% for SVM, 7% for
Kevlar, Kevlar 29 and Twaron), moderate for
others (3.5% for Kevlar 49 and Twaron HM)
and reasonably low for some (2% for Armos
and Technora and about 1% for Kevlar 149)
(Akzo, 1991; Kaiser VIAM, 1993a; Teijin, 1989;
Yang, 1992). The equilibrium moisture content
is directly proportional to the relative humidity,
rising for Kevlar 49 to 6.2% at 96% r.h. (DuPont,
1992a). Absorbed moisture has only a small
effect upon the tensile properties of the fibers,
but a significant effect upon the transverse ten-
sile, compressive, shear and flexural properties
of the composite. The gain of moisture is com-
pletely reversible and once removed produces
no permanent property changes.
Electrical and optical properties
Aramid fibers are electrical insulators. The
process used to make the Technora fiber, how-
ever, leaves it with fewer ionic impurities than
Aramid fibers 215
in the para-aramid homopolymers and thus
improved electrical properties. Technora fiber
has a resistivity of 5 x lo’* Q/cm (Teijin, 1989).
The dielectric constant of PPTA is 3.85 (Allied,
1989).
The refractive index of Kevlar 49 fiber is 2.0
parallel to the fiber axis and 1.6 perpendicular
(DuPont, 1986).Aramid fibers are opaque and
are yellow to gold in color.
10.2.5 TREATMENTS
Unlike inorganic fibers, few surface treatments
are used on aramid fibers to promote matrix
adhesion. One reason is the futility of increas-
ing the matrix bonding to the surface of a fiber
which readily fails by defibrillation. Most dra-
matic improvements in fiber/matrix bonding
give only modest improvements in off-axis
strengths since they simply move the locus of
failure from the surface to the interior of the fil-
ament. In other cases, longitudinal tensile
strengths are adversely affected by otherwise
successful surface treatments. Not all attempts
at designing surface treatments have been
unsuccessful, but for the most part the surface
treatment used on commercial fibers is mini-
mal compared to that used for inorganic fibers.
Finishes - lubricants which aid in subse-
quent processing steps - are applied to aramid
fibers for some applications. Available finishes
are designed for such purposes as lubrication
during weaving operations, improving abra-
sion resistance for cable applications or better
performance in rubber goods. If the fiber is to
be used in a high performance composite,
however, the user will usually wish to avoid or
remove any finish before impregnating the
fiber with a matrix.
Commercial aramid fibers may also be
twisted. Twist may be quite useful in some
applications and a small amount of twist will
increase the strength of bare yarn or cord.
[This optimum twist for Kevlar fibers occurs at
a twist multiplier of 1.1.At about this value,
the strength of bare yarn is the highest and the
modulus is only slightly decreased from the
2 16 Organic fibers
untwisted level (DuPont, 1992b).] Twist will
make the fiber easier to handle, make subse-
quent weaving or braiding operations easier
and will improve the abrasion resistance of the
fiber. It is also required for rope and cable
applications. However, once the fiber is used
in composite matrix fiber, twist is not desir-
able. This is because twist interferes with full
impregnation of the fiber with resin and with
stress transfer between adjacent fiber bundles.
It also increases stress concentrations, particu-
larly at higher twist levels. For this reason,
most of the aramid fiber manufacturers supply
most or all of their fibers untwisted or with
minimal twist.
10.2.6 FORMS AND AVAILABILITY
Table 10.6 lists most of the commercial types of
para-aramid fibers. Some of these fibers are
readily available in a variety of fiber deniers,
package sizes, finishes and so forth, while oth-
ers are available only in limited quantities for
specific applications. Due to constant changes
in market conditions and other factors, the
user is advised to check with the fiber manu-
facturer concerning current availabilities. The
mechanical properties of fibers with different
deniers and/or finishes and other treatments
will vary somewhat from each other and from
the nominal values given in Table 10.2.
In addition to the yarns, tows and rovings
listed in Table 10.6, DuPont’s Kevlar fibers are
also available as staple (short fibers), floc (pre-
cision cut fibers of very short lengths) pulp
(very short and high fibrillated fibers) and in
specialty compounded forms (DuPont, 1992a,
1993h).A variety of fabrics are also produced.
In addition, DuPont produces a colored fiber,
Kevlar 100, in sage green, yellow, black and
royal blue (Yang, 1992).Both Teijin’s Technora
and Akzo’s Twaron fibers are available as sta-
ple and chopped fiber (very short lengths) and
in a variety of fabrics (Teijin, 1989;Akzo, 1991).
Technora is also marketed in black as well as
natural color. Kaiser VIAM‘s Armos and SVM
fibers are also expected to be offered as tape,
staple, pulp and in various fabrics.
While the meta-aramid fibers are not usu-
ally used as fiber reinforcements in
composites, they are used extensively as rein-
forcements for honeycomb sandwich core
materials. The use of such materials along
with composite face sheet panels has greatly
extended the overall usage of composite mate-
rials, particularly in the aerospace industry.
Information about the availability and
package sizes of the fibers shown in Table 10.6,
about other products and about special formu-
lations can be obtained from Table 10.7. At the
time of this publication, Kaiser VIAM’s Armos
and SVM fibers are just being imported from
Russia. For this reason, information on the
fibers and their availability is limited in this
chapter, but should be readily available later
from the contact given in Table 10.7.
Pricing
Para-aramid fibers are currently priced from
about $20 per pound for the larger denier fibers
to about $60 per pound for most of the small
denier, higher modulus fibers. (However, some
of the very fine denier specialty fibers from
some manufacturers cost hundreds of dollars
per pound.) Prices can vary significantly for
similar fibers of different deniers or from dif-
ferent manufacturers and thus price quotes
should always be obtained before any decision
is made upon use of a specific fiber.
10.2.7 DESIGN CONSIDERATIONS
In the 1970s and early 1980s aramids began to
replace carbon and glass fibers in many appli-
cations. However, the development of high
strength intermediate modulus carbon fibers in
the mid-1980s and the commercialization of
tough, high strength polyethylene fibers
reversed this trend. Today aramid fibers are
used mainly in applications where they offer a
unique combination of properties, such as high
specific strength combined with toughness and
creep resistance.
 Aramidfibers 217

Table 10.6 Availability of commercial para-aramid fibers"

Product Count Filament Comments/typical applications

~ _ _ _ _ _ _ _ _
(reference)
number/ diameter
dtex (den) yarn pm ( 1 C 3 i n )
Kevlarb (DuPont, 1993g; Yang, 1992)
Type 950 1110 (1000) 666 12 (0.48) Finish: tire reinforcement
1670 (1500) 1000 12 (0.48)
2500 (2250) 1000 15 (0.59)
3330 (3000) 1333 15 (0.59)
Type956 800 (720) 490 12 (0.48) Mechanical rubber goods: hoses, belts, etc.
1110 (1000) 666 12 (0.48)
1670 (1500) 1000 12 (0.48)
2500 (2250) 1000 15 (0.59)
3330 (3000) 1333 15 (0.59)
Kevlar 29 (DuPont, 1992b,1993a, 1993b, 1993f, 19938)
Type 960 1670 (1500) 1000 12 (0.48) Cordage finish: high lubricity for improved
3330 (3000) 1333 15 (0.59) abrasion resistance; ropes and cables
17 OOO(15 000) 100OOR' 12 (0.48)
Type 961 1110 (1000) 666 12 (0.48) Textile finish; ropes and cables
1670 (1500) 1000 12 (0.48)
3330 (3000) 1333 15 (0.59)
5000 (4500) 3000 12 (0.48)
17 OOO(15 000) lOOOOR 12 (0.48)
Type 962 1670 (1500) 1000 12 (0.48) No finish; ropes and cables
3330 (3000) 1333 15 (0.59)
Type 963 3330 (3000) 1333 15 (0.59) Textile finish; non-apparel ballistic armor
Type964 215 (200) 134 12 (0.48) Textile finish; ballistics and apparel,
430 (400) 267 12 (0.48) ignition cables
1110 (1000) 666 12 (0.48)
1670 (1500) 1000 12 (0.48)
Kevlar 49 (DuPont, 1992b, 1993c-g)
Type 965 61 (55) 25 15 (0.59) Textile finish; woven reinforcement in
215 (195) 134 12 (0.48) aerospace composites, ballistic armor, and
420 (380) 267 12 (0.48) printed circuit boards
1270 (1140) 768 12 (0.48)
1580 (1420) 1000 12 (0.48)
2400 (2160) 1000 15 (0.59)
Type968 215 (195) 134 12 (0.48) No finish; marine composites, fiber optic
420 (380) 267 12 (0.48) cable reinforcement, ropes, filament-wound
1270 (1140) 768 12 (0.48) composites
1580 (1420) 1000 12 (0.48)
2400 (2160) 1000 15 (0.59)
3160 (2840) 1333 15 (0.59)
4800 (4320) 2000R 15 (0.59)
5070 (4560) 3200R 12 (0.48)
7900 (7100) 5000R 12 (0.48)
Continued on next page
218 Organicfibers

Table 10.6 Continued

Product Count Filament Commenfs/fypicalapplications

(reference)
number/ diameter
dtex (den) yarn pm ( 1 P i n )
~ _ _
Type 978 1580 (1420) 1000 12 (0.48) Cordage finish: high lubricity for improved
2400 (2160) 1000 15 (0.59) abrasion resistance; ropes and cables
5070 (4560) 3200R 12 (0.48)
Type 989 1580 (1420) 1000 12 (0.48) Textile finish; fiber optic cable
2400 (2160) 1000 15 (0.59) reinforcement
3160 (2840) 1333 15 (0.59)
4800 (4320) 2000R 15 (0.59)
6300 (5680) 2666R 15 (0.59)
7900 (7100) 5000R 12 (0.48)
9500 (8520) 4000R 15 (0.59)
Kevlar 68 (DuPont, 1992b, 1992c, 19938)
Type9568 215 (195) 90 12 (0.48) High performance mechanical rubber goods
1580 (1420) 1000 12 (0.48)
Type9898 420 (380) 267 12 (0.48) Textile finish; fiber optic cable
1580 (1420) 1000 12 (0.48) reinforcement
2400 (2160) 1000 15 (0.59)
3160 (2840) 1333 15 (0.59)
4800 (4320) 2000 15 (0.59)
7900 (7100) 5000R 12 (0.48)
Kevlar 129 (DuPont, 1990, 1993h)
Type 956E 1670 (1500) 1000 12 (0.48) Power transmission belts, high-performance
tires, high fatigue applications
Kevlar 129 (DuPont, 1992c, 1993h, 1993i)
Type 956C 1110 (1000) 666 12 (0.48) Mechanical rubber goods
Type964C 830 (750) 500 12 (0.48) Personal body armor
930 (840) 6OOL 12 (0.48)
1110 (1000) 666 12 (0.48)
1580 (1420) 1000 12 (0.48)
Kevlar 249 (DuPont, 1992c, 19938)
Type965A 420 (380) 267 12 (0.48) Woven reinforcement in aerospace composites,
1270 (1140) 768 12 (0.48) hard ballistic armor, printed circuit
1580 (1420) 1000 12 (0.48) boards
Type 968A 1270 (1140) 768 12 (0.48) No finish; marine composites, fiber optic
1580 (1420) 1000 12 (0.48) cable reinforcements, ropes, filament-wound
4730 (4260) 3000R 12 (0.48) composites
7890 (7100) 5000R 12 (0.48)
Kevlar HT (DuPont, 19938)
Type 964C 1110 (1000) 666 12 (0.48) Advanced ballistic protection
Kevlar K M 2 (DuPont, 1992d)
945 (850) 560 12 (0.48) Ballistic protection: helmets, composite armor

Continued on next page

 Ararnidfibers 219

Table 10.6 Continued

Product Count Filameizf Comments/typical applications

(reference)
number/ diameter
dtex (den) yarn Fnz ( l C 3 i n )
Twarond (Akzo, 1990,1991; DeCos, 1993)
Type 1000 420 (380) 250 12 (0.48) Standard finish; multipurpose
840 (760) 500 12 (0.48)
1100 (990) 750 10.5 (0.41)
1260 (1130) 750 12 (0.48)
1680 (1510) 1000 12 (0.48)
2520 (2270) 1500R 12 (0.48)
3360 (3020) 2000R 12 (0.48)
Type1001 420' (380) 250 12 (0.48) Adhesive-activated finish; tires,
840 (760) 500 12 (0.48) mechanical rubber goods, composites
1100' (990) 750 10.5 (0.41)
1260 (1130) 750 12 (0.48)
1680 (1510) 1000 12 (0.48)
3360 (3020) 2000R 12 (0.48)
Type 1010 1680 (1510) 1000 12 (0.48) Very low finish level; composites
3360 (3020) 2000R 12 (0.48)
Type 1020 1680 (1510) 1000 12 (0.48) Special finish for increased abrasion
resistance; cables, ropes, nets
Type 1030 17 OOO(15 300) 5000R 12 (0.48) PTFE + silicone oil impregnated; braided packings
Type 1031 14 OOO'(12 600) 5000R 12 (0.48) PTFE + silicone oil impregnated; braided packings
Type1040 420 (380) 250 12 (0.48) Tangled yarn; multipurpose
840 (760) 500 12 (0.48)
1100' (990) 750 10.5 (0.41)
1260 (1130) 750 12 (0.48)
1680 (1510) 1000 12 (0.48)
Type 1041 1260' (1130) 750 12 (0.48) Adhesive-activated finish; fabrics
1680' (1510) 1000 12 (0.48)
Type2000 930 (840) 1000 6.6 (0.26) Standard finish; high tenacity for
1110 (1000) 1000 8 (0.31) ballistic applications. 930 dtex
1680 (1510) 1000 12 (0.48) fiber is 'microfilament'.
Twaron HM (Akzo, 1991)
Type 1055 1210 (1090) 750 11.5 (0.45) Standard finish; multipurpose
1610 (1450) 1000 11.5 (0.45)
2420 (2180) 1500R 11.5 (0.45)
3220 (2900) 2000R 11.5 (0.45)
4830 (4350) 3000R 11.5 (0.45)
6440 (5800) 4000R 11.5 (0.45)
8050 (7245) 5000R 11.5 (0.45)
Type 1056 1210 (1090) 750 11.5 (0.45) Very low finish level; composites
1610 (1450) 1000 11.5 (0.45)
2420 (2180) 1500R 11.5 (0.45)
6440 (5800) 4000R 11.5 (0.45)
8050 (7245) 5000R 11.5 (0.45) Continued on next page
220 Organicfibers

Table 10.6 Continued

Product Count Filament Comments/typical applications

-
(reference)
number/ diameter
dtex (den) yarn pm (1Win)
Twaron IM (Akzo, 1991)
Type 1111 420' (380) 250 12 (0.48) Easily removed finish; fiber optic cable
1260 (1130) 750 12 (0.48) reinforcements, ballistics, composites
1680 (1510) 1000 12 (0.48)
2520 (2270) 1500R 12 (0.48)
Armos (Kaiser VIAM, 1993a)
588 (530) - - - Twisted 48 t/m; multipurpose
SVM(Kaiser VIAM, 1993b-j)
63 (57) - - - Type A1 lubricating finish
143 (130) - - - Lubricating finish on 'acidic' fiber
294 (265) - - - Lubricating finish on 'neutral' fiber
294 (265) - - - Lubricating finish on 'acidic' fiber
294 (265) - - - Type A1 lubricating finish on 'acidic' fiber
588 (530) - - - Two different heat treatments available
588 (530) - - - Type A1 lubricating finish on 'acidic' fiber
Technoru' (Teijin, 1989; Mahn 1993)
T-200 1110 (1000) 666 12 (0.48) Rubber reinforcement
1670 (1500) 1000 12 (0.48)
T-202 440 (400) 1667 12 (0.48) Rubber reinforcement, pre-activated type
1670 (1500) 1000 12 (0.48)
T-220 1110 (1000) 666 12 (0.48) Rope, cable, and cord
1670 (1500) 1000 12 (0.48)
T-221 1110 (1000) 666 12 (0.48) Rope, cable, and cord
1670 (1500) 1000 12 (0.48)
T-230 1670 (1500) 1000 12 (0.48) Fiber-reinforced plastics, rope
T-240 60 (55) 36 12 (0.48) Woven and knitted fabrics, fiber-reinforced
110 (100) 67 12 (0.48) plastics
220 (200) 133 12 (0.48)
440 (400) 267 12 (0.48)
1110 (1000) 666 12 (0.48)
T-241 1670 (1500) 1000 12 (0.48) Woven and knitted fabrics, fiber-reinforced
8330 (7500) 5000R 12 (0.48) plastics
T-360 608 (55) 36 12 (0.48) 'Spunnized' yarn (made up of long but not
220 (200) 67 12 (0.48) continuous filaments) for protective
440 (400) 133 12 (0.48) clothing and other fabric applications
1110 (1000) 267 12 (0.48)
1670 (1500) 1000 12 (0.48)
T-370 220 (200) 133 12 (0.48) High tenacity 'spunnized' yarn for
440 (400) 267 12 (0.48) reinforcement of rubber, etc.
For footnotes see next page
 Aramid fibers 221

Table 10.7 Sources of information o n commercial aramid fibers

Product Information source

Armos and SVM Kaiser VIAM; 880 Doolittle Drive, San Leandro, CA 94577, USA
fibers

Kevlar fibers DuPont Fibers; P.O. Box 80705, Wilmington, DE 19880-0705, USA, (800)
4-KEVLAR
Technora fibers Teijin Limited, 11, 1-chome, Minamihonmachi, Chuo-ku, Osaka 541, Japan
Teijin America Inc; 10 East 50th Street, New York, NY 10022, USA
Twaron fibers Akzo, Aramide Maatschappij v.o.f., P.O. Box 9300,6800 SB A r h e m ,
Westervoortsedijk 73, The Netherlands
Akzo Fibers Inc., 801-F Blacklawn Rd., Conyers, GA 30207, USA

The outstanding toughness of aramids is
often the reason they are used over cheaper,
stiffer or even stronger fibers. Unlike glass and
carbon composites, aramid composites loaded in
compression, flexure or shear fail in a non-brittle
manner, with significant work being required to
fail the composite. Their fatigue resistance is also
excellent. If other concerns such as cost or stiff-
ness preclude the use of aramid composites,
aramids are often used as a hybrid with another
fiber to improve the toughness of the composite.
The poor off-axis and compressive proper-
ties of aramid fibers must be considered in any
design. However, because of their high strength
in axial tension and their toughness, aramid
fibers are often outstanding in applications
such as pressure vessels where the loading is
almost totally in longitudinal tension.
Aramid fibers absorb moisture. Where
either the physical swelling of the fiber or the
amount of moisture absorbed is of significant
concern, one of the lower absorption aramids,
such as Kevlar 149, Armos, or Technora should
be considered.
Aramids are strong UV absorbers and dete-
riorate when exposed to ultraviolet light.
Protective coatings or the self-screening ability
of the fiber should be used to avoid deterio-
ration.
Aramid fibers are opaque and thus the pen-
etration of resin into the fiber bundles cannot
be determined visually for a aramid compos-
ite as it can for those made with glass fibers.
In fabric applications the weave used is
important to the resulting properties. The
same is true for sandwich construction. In
these cases, the fiber, fabric, or honeycomb
supplier can provide design assistance.
The choice of resin system for use with
aramid fibers is an important one. Epoxy resins
give better translation of fiber properties than
do polyesters, producing better shear strength
and flexural properties, but lower impact resis-
tance. Vinyl ester resins give both good shear
strength and impact resistance. Thermoplastic
matrices are also used, particularly in chopped
fiber composites, because of their improved
impact resistance over thermosets. However,

Footnotes for Table 10.6

a All availabilities are subject to market conditions and should be verified with the manufacturer.
All Kevlar fibers are supplied untwisted.
E The ' R indicates that this fiber is a 'roving,' meaning in this case that it is composed of more than one 'end' of yam.

Twaron fibers are normally supplied untwisted. In some circumstances twist may be supplied on special request.
e Under development.
' Technora fibers are supplied with twist as requested. Finishes are supplied as requested or as is appropriate to the
application.For special applications,Technora fibers can be supplied in larger than 12 pm filament diameters.
These fibers, and others 'spun' yarns (composed of discontinuous filaments) are normally measured by '(English)
cotton count' (ECC) rather than dtex or denier, where ECC = 5315/denier.
222 Organicfibers

for thermoplastics the penetration of the resinMany of these are not as structural composites.
into the fiber bundle and the quality of the For example, aramids are used in many rope
fiber-matrix bond is almost always of concern. and cable applications. In mooring ropes to
Because aramids are very tough fibers, they secure oil tankers and to anchor off-shore oil
are somewhat difficult to cut and their com- platforms, the lighter weight compared to
posites can be difficult to machine. Special steel makes the aramid ropes much easier to
handle. In addition, they do not corrode, are
shears and other tools are available for cutting
aramids and many successful machining tech- easier to maintain and have an extension
niques have been developed. The fiber under load which is far superior to both steel
manufacturers are an excellent source of infor-and other organic fibers.
mation in this area. Aramids are widely used to reinforce
As with all high performance fibers, aramidsmechanical rubber goods. The largest volume
should be handled with care before and during of such usage is in pneumatic tires, where
processing. Rough handling will damage any aramids are lighter than steel and offer higher
high performance fiber. In addition, because ofstrength and modulus than other organic
their sensitivity to ultraviolet light, aramidsfibers. Significant usage is also seen in belts
should be protected from such exposure. The and hoses. The excellent fatigue and creep
fibers also should not be exposed to excessive resistance of aramids are important factors in
their usage in these applications. Corrosion
moisture prior to processing. If the fiber is to be
twisted, braided, or woven, it is preferable toresistance and electrical resistivity may also be
condition the fiber for one to two days at roomimportant. Aramids are also used in athletic
temperature and intermediate moisture content shoes and in rubberized sheet materials as
prior to processing (DuPont, 1993h). However, used in aircraft evacuation slides and life rafts.
if the fiber is to be resin-impregnated and In some cases, non-composite applications
processed directly into a composite, so long ashave led to composite uses. For example,
fiber handling is careful, superior properties aramids have long been used in soft body
may be attained by drying the fiber prior to armor, where the fibers absorb and disperse
processing. Tlus is because of improved bond- bullet impact energy to other fibers in the fab-
ing of resin to the filament surfaces. ric weave. This application has now seen a
Aramid fibers present minimal safety or derivative usage in rigid composite ballistic
environmental concerns. In lifelong animal armor, composite helmets and composite spa11
inhalation studies with Kevlar fibers, no liners. In these applications the toughness, RF
health effects were observed at any workplace transparency and fire and corrosion resistance
levels. Nonetheless, as with any textile fiber,of aramid fibers were significant factors in
inhalation of fibrous particles should be their selection.
avoided. Extensive animal and human skin In spite of significantly higher fiber costs
patch tests with Kevlar fibers have shown no than glass, aramids are used in canoes, kayaks,
racing shells and small boats where maximiz-
sensitivity and little irritation, and rat feeding
studies have shown oral toxicity to be very ing strength and minimizing weight are
low. Combustion by-products are similar to important. Aramids offer weight savings for
wool. Aramid yarns are also essentially inert superior speed and better handling and/or
in the environment (DuPont, 1993h). improved range and fuel economy. Toughness
and overall durability and vibrational damp-
ing are also superior with aramids. The
10.2.8 APPLICATIONS
superior properties of aramids allow boats to
Aramid fibers are used in numerous applica- be built at an overall cost only 10-15% higher
tions, some of which are listed in Table 10.6. than with glass fibers and with superior perfor-
 Extended h i i i polyefhylcviefibers 223

mance (DuPont, 1983). These same properties properties but they also have limitations that
have led to the use of aramids in skis. must be considered in design.
Their high strength-to-weight ratio com- Commercially available high strength, h g h
bined with outstanding toughness has led to modulus polyethylene fibers include Spectrakh'
numerous applications of aramids in aero- fibers from Allied-Signal Corporation,
space. In both civilian and military aircraft, the DyneemaO SK60 from Dyneema Vof, Tekmilon"
toughness of aramids - and resulting resis- from Mitsui Petrochemicals and a new, as yet
tance to damage from impacts ranging from unnamed, fiber from Hoechst Celanese.
bird strikes to shrapnel - insures their contin-
ued usage. Engine nacelles and the tail cone on
10.3.2 MANUFACTURE
the McDonnell Douglas DC-9-80 are made
from Kevlar composites and approximately The traditional method of producing fibers
10% of the empty airframe weight of De from polyethylene is to spin them from a poly-
Havilland Aircraft's DASH-8 turboprop com- mer melt. This technique yields fibers
muter aircraft is Kevlar composite. Aramid composed of folded-chain crystalline regions
composites are also widely used in rotorcraft with non-crystalline regions interspersed. With
and other vertical lift aircraft. extraordinary means, the modulus of the
absolute best of such fibers can be brought to
about 80 GPa (11.5Msi). It was long recognized,
10.2.9 CONCLUSIONS
however, that if polyethylene could somehow
Although composites of other fibers have now be produced with extended chain crystallinity,
supplanted aramid composites as having the a very high modulus fiber would result. [The
highest specific strengths, aramids still offer theoretical modulus for polyethylene is
combinations of properties not available with 320 GPa (46 Msi) (Adams and Eby, 1987).]
any other fiber. For example, aramids offer Following earlier work by Pennings, in the
high specific strength, toughness and creep late 1970s Smith and Lemstra of DSM (The
resistance, combined with moderate cost. Netherlands) developed a process with com-
However, the applications of aramid compos- mercial potential which yielded a highly
ites continue to be limited by their poor oriented extended-chain polyethylene fiber
compressive and off-axis properties and in (Hongu and Phillips, 1990).At the same time,
some applications, their tendency to absorb both Toyobo Inc. of Japan and Allied Chemical
water. Nonetheless, aramids will continue to Company in the USA were working on a sim-
be the fiber of choice where properties such as ilar approach. DSM, however, was the first to
outstanding impact resistance combined with patent the process and both Toyobo and Allied
creep resistance are critical. judged it impossible to circumvent the basic
patent filed by DSM. Thus, both companies
entered into technical association with DSM to
10.3 EXTENDED CHAIN POLYETHYLENE
produce polyethylene fibers. Toyobo Inc.
FIBERS
linked with DSM to form the joint venture -
Dyneema Vof - to produce and market the
10.3.1 OVERVIEW
new fiber. In the USA, Allied-Signal is licensed
High performance polyethylene fibers, with from DSM/Stamicarbon to produce and mar-
outstanding strength-to-weight and stiffness- ket a similar fiber.
to-weight performance, show promise in The process which is used to produce most
various specialized applications. While such commercial high strength, high modulus poly-
fibers are not as widely known as aramid and ethylene fibers is called gel spinning, the name
carbon fibers, they possess many superior derived from the gel-like appearance of the
224 Organicfibers

as-spun and quenched fibers. Ultra-high mol-

ecular weight linear polyethylene is dissolved
in a volatile solvent to form a dilute isotropic
solution that is then spun through a spinneret
and quenched in cold water to form a gel pre-
cursor fiber. Following solvent extraction, this
fiber is then hot-drawn to a very high draw
ratio (= 30), yielding a very highly oriented,
highly crystalline, lightweight fiber
(Dyneema, 1987; Jaffe, 1989; Ward and
McIntyre, 1986; Yang, 1992).
Another approach to producing a high
strength polyethylene fiber is melt extrusion
followed by multiple stage drawing of a much
lower molecular weight polyethylene. The
modulus of an experimental fiber of this type,
220 GPa (32 Msi), is the highest ever achieved
for polyethylene (Adams and Eby, 1987). The
new polyethylene fiber from Hoechst Celanese
is the only commercial version of such a fiber.
This fiber has only about 50% of the strength
and 75% of the modulus of gel spun fibers. In
this case, the expense of dealing with a volatile
and potentially toxic solvent is avoided, low-
ering the overall price of the fiber significantly.
Fig. 10.8 Schematic illustrating the difference
between (a) conventional polyethylene fibers and
10.3.3 STRUCTURE (b) gel-spun extended chain fibers.
Figure 10.8 illustrates the difference between
conventional polyethylene fibers and gel-spun hydrogen bonds nor strong covalent bonds
or melt-extruded and drawn extended-chain between them. They are, in fact, held together
fibers. Figure 10.8(a)is a schematic of a con- by weak dispersion-type van der Waals bonds
ventional melt-drawn polyethylene fiber. The which have a distinct effect upon properties.
fiber consists of folded chain crystallites,
mostly oriented in the draw direction, which
10.3.4 PROPERTIES
are joined to one another by tie molecules and
have between them interspersed non-crys- Polyethylene fibers offer a unique combina-
talline material. Figure 10.8(b)is a schematic of tion of properties: low specific gravity, high
a gel-spun and hot-drawn extended-chain specific modulus, high specific strength, high
polyethylene fiber. Such fibers show minimal energy to break, high abrasion resistance,
chain folding, high crystallinity and a very excellent chemical resistance, good ultraviolet
high degree of axial orientation (>95%). resistance and low moisture absorption. They
Since these fibers are based on polyethyl- have outstanding anti-ballistic and vibrational
ene, they have a density of only two-thirds damping characteristics, as well as a low
that of aramid fibers and about one-half that of dielectric constant. However there are trade-
carbon fibers. However, the polyethylene crys- offs involved in the use of polyethylene fibers.
tallites have neither relatively strong They are limited to fairly low use temperatures,
 Extended chain polyethylene fibers 225

they produce composites with poor off-axis treated Spectra 900 fiber in an epoxy matrix
and compressive properties and have poor was found to be -9 x lO"/OC (-5 x 104/OF) in
creep resistance. the axial direction and 100 x lO"/"C (56 x
As with aramid fibers, the anisotropy of 104/"F) in the transverse direction. The axial
their microstructure gives polyethylene fibers thermal expansion coefficient of a similar com-
anisotropic mechanical, thermal and physical posite of Spectra 1000 fiber was -10 x lO"/"C
properties which can be used to advantage in (-5.6 x 10"/OF) and the transverse coefficient
some applications. was 105 x lO"/OC (58 x 10"/"F) (Allied, 1989).
Polyethylene fibers are the only high perfor-
mance fibers with a specific gravity of less than
Physical and thermal properties
1 and thus are the only fibers that float. Their
Polyethylene fibers have a relatively low melt- density is about two-thirds that of aramid
ing point [147"C (297"F)I and thus a low use fibers and about half that of carbon fibers.
temperature. In general, polyethylene fibers Polyethylene fibers will burn slowly if ignited,
are limited to use below 100°C (212°F). They decomposing into carbon dioxide and water.
will, however, tolerate brief exposure (30 min The filament diameters of commercial poly-
or less) at temperatures near the melting point ethylene fibers are relatively large, typically
without major property loss (Dyneema, 1987; 23-38 pm (0.91-1.50 x in), although the
Weedon and Tam, 1986). diameter of Mitsui's Tekmilon monofilament
As would be expected from the lower melt- fibers can be as large as 121 pm (4.76 x in).
ing temperature, the properties of polyethylene The filament cross-section is typically irregu-
fibers are much more sensitive to temperature lar and somewhat elliptical.
than are aramids. Like aramid fibers,
polyethylene fibers contract with temperature
Mechanical properties
in the axial direction, while expanding in the
transverse direction. The thermal expansion Gel-spun polyethylene fibers offer some
coefficient of a composite of 60 vol% plasma- tremendous advantages over other fibers. As

Table 10.8 Axial tensile mechanical properties of representative high performance polyethylene fibers

Fiber Reference Fiber type Spec@ Tensile Tensile Elongation

gravity modulus, strength, at break, %
GPa (Msi) MPa (ksi)
-
Dyneema Dyneema, 1987 gel-spun 0.97 87 2620 -

SK60 (12.7) (380)

Hoechst Hoechst melt- 0.96 55 1300 4
Celanese fiber Celanese, 1993 extruded (8.0) (189)
Spectra 900 Allied, 1993 gel-spun 0.97 86-103 2080-2400 3.6-3.7
(12.5-14.9) (300-350)
Spectra 1000 Allied, 1993 gel-spun 0.97 128-171 2740-3000 2.8-3.1
(18.6-24.8) (397435)
Tekmilon Mitsui, 1989 gel-spun 0.96 59-98 1470-3430 4-6
monofilament (8.6-14.2) (213498)
Tekmilon Mitsui, 1989 gel-spun 0.96 88.3 2450 3
multifilament (12.8) (356)
226 Organicfibers

can be seen in Fig. 10.4, these fibers offer very
high specific stiffnesses and specific strengths,
equivalent or superior to all of the aramid
fibers and to most of the carbon fibers. This
superior performance is offered at a lower
price than that of competitive fibers.
Table 10.8 compares the mechanical proper-
ties of representative commercially available
polyethylene fibers.
Like aramid fibers and for similar reasons,
polyethylene fibers have poor compressive
and off-axis properties. Since the fiber is held
together internally by only very weak van der
Waals bonds, the transverse strength of the
fiber is even worse than that for the aramids.
In addition, the inertness of the polyethylene
fiber means that the untreated fiber bonds
very poorly to a matrix. Although gas plasma
surface treatment can improve the interfacial
bond strength significantly, polyethylene fiber
composites will still have poor off-axis proper-
ties.
Table 10.9 gives mechanical properties for
Spectra fiber composites, including those
made from plasma-treated fibers.
In spite their weak transverse strength, but
because of the non-stick nature of polyethylene
and thus its low coefficient of friction, polyeth-
ylene fibers perform much better than aramids
in abrasion resistance and polyethylene fabrics
are much less easily damaged than are those of
aramid fibers. The abrasion resistance of poly-
ethylene fibers can be up to ten times that of
aramids (Dyneema, 1987)and can be improved

Table 10.9 Mechanical properties of Spectra polyethylene fiber composites” (Allied, 1989)

Matrix: Bisphenol A based epoxy

__ - ~

Spectra 900 Spectra 900 P T ~ Spectra 1000 Spectra 100 PT

-
Axial Tensile Properties:
Volume percent fiber 58 50 53 54
Modulus, GPa (Msi) 27 f 1 24 f 1 50 50 f 3
(4.0 f 0.1) (3.5 f 0.1) (7.3) (7.2 f 0.5)
Strength, MPa (ksi) 552 zk 90 676 f 103 1034 c 228 889 f 55
(80 f 13) *
(98 15) (150 f 33) (129 f 8)
Elongation, % - 3.6 f 0.2 - 2.1 i-0.4
Axial Compressive Properties:
Volume percent fiber 70 70 55 65
Modulus, GPa (Msi) 32 f 5 40 k 5 19c6 54 f 3
(4.7 k 0.7) (5.8 + 0.7) (2.7 f 0.9) (7.8 f 0.4)
Strength, MPa (ksi) 52 k 2 59 + 1 72 f 3 69 f 1
(7.5 f 0.3) (8.6 c 0.2) (10.5 f 0.4) (10.0 f 0.2)
Elongation, YO - - 3.8 k 0.5 3.8 f 0.2
Flexural Properties:
Volume percent fiber 58 54 54 53
Modulus, GPa (Msi) 22 k 1 30f1 23 zk 1 38 f 3
(3.2 f 0.2) (4.3 f 0.2) (3.3 k 0.2) (5.5 f 0.5)
Strength, MPa (ksi) 145 f 7 200 f 7 159 +. 7 214 f 7
(21 k 1) (29 f 1) (23 f 1) (31 k 1)
Short Beam Shear Properties:
Volume percent fiber 58 54 54 53
Strength, MPa (ksi) 8.3 f 0.7 28.3 f 0.7 9.0 c 0.7 21 e 3
(1.2 f 0.1) (4.1 f 0.1) (1.3 f 0.1) (3.1 f 0.4)
a Numbers of specimens tested and criteria for limits not specified.
PT indicates a fiber with gas plasma surface treatment.
 Extended chain polyethylene fibers 227

even further by the use of lubricants.
Because of their high strength, polyethylene
fibers exhibit very high energy to break. On a
per-weight basis, the impact energy absorp-
tion of polyethylene composites is superior to
that of all other fiber composites.
Polyethylene fibers are more affected by
temperature than are higher melting point
fibers. The loss in modulus as function of tem-
perature is shown in Fig. 10.9 for Tekmilon
multifilament fiber and Spectra fibers. Fig. 10.10
shows the loss in strength as a function of tem-
perature for Tekmilon multifilament, Spectra
900 and Spectra 1000 fibers. Because of their
very high specific strength at room tempera-
ture, however, polyethylene fibers still
outperform most other fibers to about 100°C
(212°F).
Room temperature strength retention of
polyethylene fibers following annealing at
temperatures of up to 125°C (260°F) is excel-
lent, while modulus loss following such
exposure is 20-30%. The loss in both modulus
and strength are reduced if annealing is per-
formed under tensile loading.
Unlike aramid fibers and their composites,
polyethylene fibers and composites show very
little or no loss of properties, axial or off-axis,
when exposed to moisture.
Creep resistance of extended-chain polyeth-
ylene is of concern. Because of its low melting
temperature, the resistance of the fiber to creep,
even at room temperature, is less than ideal.
This is significant, since the creep of carbon,
glass and aramid fibers is minimal. Spectra
1000 is a 'stabilized' version of the fiber, which
shows better creep resistance than the Spectra
900 fiber. Figure 10.11 shows the creep
response of the two Spectra fibers at room, ele-
vated and low temperatures. At low load levels
at room temperature and/or at low tempera-
tures the creep encountered is not severe,
especially for the Spectra 1000 fiber, but at
higher loads or temperatures the creep is much

r L 1 . 8 8 I , I I I I , , I S *

- - 15
100

0 75 - .-ul
a
c) - 10 =
ul i
-33 -3
50 - U
0
z I

- 5
25 -

0 ~ ~ . l l ~ l . ~ ' ~ ~ ~ 0 ~ l ~ ~ ~ ~ I * l l l l

Fig. 10.9 Modulus as a function of temperature for Spectra 900, Spectra 1000, and Tekmilon multifilament
polyethylene fibers (Prevorsek, 1989; Mitsui, 1989).
228 Organicfibers

Temperature, OF

50 100 150 200 250 300

500

3000 -
- 400
2500 -
0 .-
- 300 -$
% 2000 1
f f0,
VI C
5 1500 1 - 200 3;
e
i7l
1000 -
- 100
500 -

0
0 25 50 75 100 125 150
Temperature, OC

Fig. 10.10 Strength as a function of temperature for Spectra 900, Spectra 1000, and Tekmilon multifilament
polyethylene fibers (Allied, 1991e; Mitsui, 1989).

- Spectra 900

.___-- ------RT, 10% Load

0 ~ ~
0 10 20 30 40 50 60 70 80 90 100

time, h
<a)

Fig. 10.11 Creep of Spectra extended chain polyethylene fibers (a) at room temperature and 10% of static
ultimate and at room temperature and 30% of static ultimate.
 Extended chain polyethylene fibers 229

6:
.-C
e
G 1
t - Spectra 900
Spectra 1000
.___

0 25 50 75 100 125 150 175

time, h
(a)

time, h
<C)

Fig. 10.11 (Continued) Creep of Spectra extended chain polyethylene fibers (b) at 5°C (41°F)and 20% of
static ultimate, and (c) at 70°C (160°F)and 275 MPa (40 ksi), which is 18% of static ultimate for Spectra 900
and 11%of static ultimate for Spectra 1000 (Allied, 1991a, 1991b, 1991c, 1991d).
230 Organic fibers

more significant. The creep of polyethylene
fibers does not preclude their use in applica-
tions such as sailcloth or structural
reinforcement, but does require that the creep
demands of an application be carefully evalu-
ated. Because of their relatively poor creep
resistance, polyethylene fibers are often
hybridized with other, more creep resistant
fibers in applications where prolonged loading
is anticipated.
The fatigue resistance of polyethylene fibers
is excellent. In one test of loading and unload-
ing of ropes, polyethylene fiber ropes
withstood approximately eight times the cycles
before break as aramid fiber ropes (Weedon and
Tam, 2986). T ~ indicates
E a superiority in ten-
sile fatigue even to aramid fibers, which are
known for their excellent fatigue resistance.
Chemical and environmental properties
Polyethylene is inert. It is stable in almost all
organic solvents and in a variety of other chem-
icals. It is also biologically inert. It is the best of
all high modulus fibers in an alkaline environ-
ment (Jaffe, 1989). It shows superior chemical
resistance to PPTA in hydrochloric, nitric and
sulfuric acid (Dyneema, 1987).Table 10.10 com-
pares the chemical resistance of Spectra
polyethylene fiber to that of aramid fiber.
Polyethylene fibers also show good resis-
tance to UV exposure. After 100 hours UV
exposure in a fadeometer, Dyneema SK60
retained 70% of its original strength and after
1500 hours, retained 25% strength. This latter
exposure is equivalent to about 2 years of out-
door exposure (Dyneema, 1987).
Polyethylene fibers are hydrophobic and
thus absorb very little moisture. The moisture
regain of polyethylene fibers is less than 1%.
Their weatherability is excellent: after 600
hours exposure in a Weatherometer, Tekmilon
fiber retained 80% of its strength and 90% of its
modulus. Following similar exposure, an
aramid fiber had only 40% strength retention
(Mitsui, 1989).Because of their excellent chem-
ical and moisture resistance, articles made
with polyethylene fibers can be cleaned in
soap and water.

Table 10.10 Comparison of strength retention after chemical immersion for polyethylene and aramid
fibers (Allied, 1989)

Strength retention, YO
Spectra Aramid
6 months 2 years 6 months 2 years
Chemical (4380 h) (17 500 h) (4380 h) (17 500 h)
Sea water 100 100 100 98
Hydraulic fluid 100 100 100 87
Kerosene 100 100 100 97
GasoIine 100 100 93 a

Toluene 100 100 72

Glacial acetic acid 100 100 82
1M hydrochloric acid 100 100 40
5M sodium hydroxide 100 100 42
Ammonium hydroxide (29%) 100 100 70
Perchloroethylene 100 100 75
10"/0detergent solution 100 100 91
Chlorine bleach 91 73 0
Too weak to test
 Extended chain polyethylene fibers 231

Electrical and optical properties bonding of the fiber to matrices. Through

1992, Allied-Signal marketed plasma-treated
Polyethylene fibers are electrically non-con-
Spectra fibers. However, polyethylene surface
ductive. The dielectric constant of Spectra
treatments are available after fiber purchase
fiber is 2.2, with a loss tangent of 2 x lo4
from specialty companies. The fiber manufac-
(Allied, 1993).This compares to dielectric con-
turers can suggest sources of these services.
stants for aramid fibers of 3.85, quartz fibers of
The inertness and high abrasion resistance
3.78 and E-glass fiber of 6.31 (Allied, 1989).
of polyethylene fibers means that little or no
They are white in color and are transparent to
finish is required. This is fortuitous since adhe-
X-rays, radar and sonar.
sion to polyethylene is so difficult that finishes
generally will not stay on the fibers. All Spectra
fibers are supplied with ’low percent process
10.3.5 TREATMENTS
finishes’ whose purpose is simply to aid in
Because of their chemical inertness, polyethyl- holding the filaments together in the bundle.
ene fibers bond poorly to matrices, with Like aramid fibers, polyethylene fibers may
consequent negative effects upon the mechan- be twisted, particularly for applications such as
ical properties of their composites. Surface marine cables. For bare fiber, twist initially
treatment by acid etch, plasma etch or corona increases the strength, although it decreases
discharge can significantly improve the the modulus of the fiber. For Spectra fiber, the

Table 10.11 Availability of commercial polyethylene fibers

Product Count Fihmen t Cornmen t s

(reference)
number/ diameter
dtex (den) yarn pm (IO”in)
Dyneema SK60 444 (400)
(Dyneema, 1987) 888 (800)
1780 (1600)
Hoechst Celanese fiber 100 (90)b
(Adams, 1993) 200 (180)
Spectra 900 722 (650) 60 38 (1.50) All Spectra fibers are supplied
(Allied, 1990, 1993) 1333 (1200) 120 38 (1.50) untwisted and with only sufficient
5333 (4800) 480 38 (1.50) finish to hold the fiber bundle
together
Spectra 1000 239 (215) 60 23 (0.91)
(Allied, 1990, 1993) 417 (375) 60 30 (1.18)
722 (650) 120 28 (1.10)
1444 (1300) 240 28 (1.10)
Tekmilon (Mitsui, 1989)
Monofilament 5.6 (5) 1 27 (1.06)
22.2 (20) 1 54 (2.13)
111 (100) 1 121 (4.76)
Multifilament 555 (500) 50 =38 ( ~ 1 . 5 )
1110 (1000) 100 =38 (~1.5)
a All availabilities are subject to market conditions and should be verified with the manufacturer.
This fiber is newly commercially available. It will be supplied in multiples of 100 dtex.
232 Organicfibers

strength of the bare fiber is optimized at a twist Pricing

multiplier of 3, but at this value there is also
Spectra fibers are currently priced from about
about a 20% loss in modulus. As with aramids,
$15/lb for larger denier fibers to about $45/lb
however, twist is not desirable in fibers used in
for the small denier fibers. Dyneema fibers are
composites. Polyethylene fiber manufacturers
not marketed in the USA. Because of the strong
provide most of their fibers untwisted.
yen, at the time of writing Tekmilon fibers are
significantly more expensive than Spectra
10.3.6 FORMS AND AVAILABILITY fibers in the USA. The new melt-extruded
polyethylene fiber from Hoechst Celanese is
Table 10.11 lists the availability of most of the
designed to offer good properties at a lower
commercial high performance polyethylene
cost than the gel spun fibers. It costs 15-50%
fibers. In most cases, each denier of fiber is
less than the comparable Spectra fibers.
available in only one package size and weight.
The mechanical properties of different deniers
may vary somewhat from the nominal values 10.3.7 DESIGN CONSIDERATIONS
given in Table 10.9.
Like aramid fibers, polyethylene fibers are
In addition to the fiber forms listed in Table
mainly used in applications where they offer
10.11, Dyneema SK60 is available in various
a unique combination of properties. This
fabrics. Spectra fibers are also available as
property combination includes outstanding
chopped fiber in lengths from 6 to 20 rnm (0.25
specific strengths and stiffnesses, high
to 0.8 in) and in fabrics of various weaves.
toughness, outstanding abrasion resistance
Tekmilon is available as monofilament, multi-
and very low density.
filament and tape.
In any design, the relatively low melting
Information about the availability of the
point and low use temperature of polyethylene
fibers shown in Table 10.11; information about
fibers as well as the relatively poor creep
other products and about special formulations
resistance must be considered. The creep resis-
can be obtained from the sources given in
tance is improved in a fiber such as
Table 10.12.

Table 10.12 Sources of information on commercial polyethylene fibers

Product Information source

Dyneema fibers Dyneema Vof, Dr. Nolenslaan 119A, PO Box 599,6130 AN Sittard, The
Netherlands
Dyneema Japan Ltd., 2-8, Dojima Hama 2-chome, Kita-ku, Osaka 530,
Japan
Hoechst Celanese’s Hoechst Celanese Corporation, PO Box 32414, Charlotte, NC 28232-2414, USA
high performance
polyethylene fiber
Spectra fibers Allied Fibers, Allied-Signal Inc., High Performance Fibers Technical
Center, PO Box 31, Petersburg, VA 23804, USA
Tekmilon fibers Mitsui Petrochemical Industries Ltd., Advanced Materials and Products
Department, Kasumigaseki Bldg., 2-5, Kasumigaseki 3-chome, Chiyoda-
ku, Tokyo 100, Japan
Mitsui Petrochemicals (America), Ltd., 1000 Louisiana, Suite 5690,
Houston,
TX 77002, USA

Allied-Signal’s Spectra 1000, which has signifi-
cantly improved creep resistance compared to
Spectra 900. Polyethylene fibers are often
hybridized with other more creep-resistant
fibers in applications where prolonged loading
is anticipated. Without hybridization polyeth-
ylene fibers must be limited to applications
where long term, high load level, or elevated
temperature loading is not anticipated, or
where creep is otherwise not of concern.
As with aramids, the poor off-axis and com-
pressive properties of polyethylene fiber
composites may also be concern. This is not a
problem, of course, in applications where the
loading is mainly in axial tension.
The X-ray and radar transparency of the
fiber can present significant design advan-
tages. The UV resistance of the fiber is very
good and thus does not present a design prob-
lem in most applications.
Because of its chemical inertness, polyethyl-
ene fibers are almost impossible to dye,
although color can be added during the fiber
spinning process. As with aramids, polyethyl-
ene fibers are optically opaque, so resin
penetration within a composite cannot be
determined visually.
Polyethylene fibers can be used with a vari-
ety of resins, including polyurethanes,
epoxies, vinyl esters, polyesters and thermo-
plastics, so long as the composite can be
processed below 120°C (250°F).Polyesters are
economical, vinylester resin systems provide
outstanding impact properties and epoxies
give better translation of structural properties.
The preferred thermosetting matrix cure tem-
perature is 93-104°C (200-220°F) (Allied,
1990). The fiber manufacturers can be very
helpful in choosing an appropriate resin sys-
tem for an application.
As with aramids, polyethylene fiber com-
posites are relatively hard to machine and
producing a smooth final machined surface
requires special techniques. Machining tech-
niques developed for aramid composites can
be used successfully, as can hot knife or hot
wire cutting (Allied, 1989).
Extended chain polyethylene fibers 233
Polyethylene fibers can be damaged by
rough handling and should be handled with
care before and during processing. They pre-
sent minimal safety or environmental concerns
and most are biocompatible, offering another
potential design advantage.
10.3.8 APPLICATIONS
Most of the current applications of polyethyl-
ene fibers are not in structural composites.
One of the main uses is in ropes and cables,
particularly in marine and off-shore applica-
tions. The fibers are used because of their high
strength, outstanding abrasion resistance (up
to ten times that of aramids), low density
(since they float), good UV stability, resistance
to seawater and high durability. The fibers are
also used as marine sewing threads.
In another major application, UV- and
water-resistance are again important. Both
Spectra and Dyneema fabrics are used, typi-
cally with a film coating, in sails. Unlike
aramids, polyethylene sail can be folded and
repacked numerous times without damage.
This latter quality also led to the selection of
Spectra fabric for the anchor balloon of the
Hilton Earthwinds round-the-world balloon
flight project and to their usage in lightweight,
durable backpacks.
Polyethylene fabrics are used as filter
cloths, where the excellent chemical resistance
is a tremendous advantage. Spectra fabric has
been used in oil containment and recovery
systems following the Persian Gulf war. The
fabric is treated so that water passes through it
but oils and other floating pollution do not.
Because of their excellent biocompatibility,
polyethylene fibers are used as sutures and as
artificial ligaments. They are also used in sur-
gical gloves, because of their excellent cut
resistance, biocompatibility and low absorp-
tion of fluids. While the poor temperature
resistance rules out the use of polyethylene
fibers in thermal protection, they are used in
industrial protective clothing and in ballistic
protection and impact shields, with or without
234 Organic fibers
a matrix. Allied makes a special non-woven
polyethylene fabric called Spectra Shield@,
which has alternating unidirectional layers
held together by a polymer matrix and gives
outstanding performance in such applications.
As composites, polyethylene fibers and fab-
rics are used in boat hulls, water skis,
sailboards, canoes and kayaks. They have
been explored for sporting goods ranging
from archery bows to ski poles. In all these
examples the excellent impact resistance they
impart to their composites is another signifi-
cant advantage. In applications such as skis
and tennis rackets, as well as speaker cones,
the excellent vibrational damping capability is
also an advantage. However, in spite of this
superior performance, the much higher cost of
polyethylene compared to glass has limited
the usage in boat hulls and sporting goods to
high end applications such as racing competi-
tions where performance and/or safety are
more important than cost. In some cases, how-
ever, the addition of polyethylene fiber
actually lowers the overall cost of the product.
One such application is in wrapping ice
hockey sticks with Spectra fiber to improve
their durability. In this case, the additional cost
to wrap the stick is more than offset by the
longer life achieved.
Polyethylene fibers are also used to rein-
force rubbers and elastomers. In many of
these applications, their excellent vibrational
damping characteristics are important.
However, the temperature sensitivity limits
the usage in tires to off-road vehicles
(Dyneema, 1987). Because of their X-ray,
radar and sonar transparency and low dielec-
tric constant, they have significant potential
in applications such as radomes, sonar domes
and X-ray tables.
As mentioned before, polyethylene can be
hybridized with other fibers to provide signif-
icant improvements in impact resistance.
Current hybrid applications range from bike
frames to impact shields.
CONCLUSIONS
For many applications extended-chain poly-
ethylene fibers are superior to all other fibers,
particularly when properties such as tough-
ness, dielectric constant, and/or hydrolytic
stability are of concern. However, because of
their relatively low melting temperature, poly-
ethylene fibers must be limited to moderate
temperatures and to applications where the
creep response is acceptable.
For sail-cloth, marine rope, pressure vessels
and other applications where the service tem-
perature is not a governing factor,
polyethylene fibers can be expected to make
serious inroads into or even dominate their
respective industries. However, they cannot
supplant aramid, carbon, or glass fibers in
applications where elevated service tempera-
ture or creep resistance are critical.
10.4 OTHER ORGANIC FIBERS
10.4.1 AROMATIC POLYESTER FIBERS
Aromatic polyester fibers are prepared by
spinning from a liquid crystalline melt fol-
lowed by heat treatment to form high strength,
high modulus fibers. While many such fibers
have been synthesized since the late 1970s, the
only fiber commercially available in the USA
today is Vectran@fiber from Hoechst Celanese
Inc. The general structural formula of this fiber
is shown in Fig. 10.12.
Vectran was developed in the 1970s in
response to tire customers who wanted equiva-
lent performance to aramid fibers but at a lower
p:
Y
Fig. 10.12 General structural formula of Vectran.
aromatic polyester fiber.
 Other organic fibers 235

cost. Hoechst Celanese was successful in pro-
viding a fiber with the desired performance,
but unfortunately the resulting cost was even
hgher than the aramids. Shortly thereafter,
Hoechst Celanese stopped marketing Vectran
fiber and marketed Vectran resin instead.
Vectran resin quickly became the material of
choice in the electronics and computer indus-
tries for small, very close tolerance connectors,
plugs and other components. Based upon this
success, in 1989 Hoechst Celanese reintroduced
Vectran as a fiber product. Since the fiber is
more expensive, by 1.5to 3 times, than aramids,
the marketing focus is on areas where aramids
do not meet the performance requirements
(Adams and Farrow, 1993a).
Vectran is a polyester-polyarylate fiber.
Unlike the aramids, Vectran melts at high tem-
perature. It is melt spun on conventional
polyester spinning equipment and the as-spun
fibers are then heat treated in a sequence of
steps (Adams and Farrow, 1993b).It is the only
commercially available melt-spun liquid crys-
talline polymer fiber (Hoechst Celanese, 1990).
Properties
Vectran HS offers a unique combination of
properties: high strength, no creep, low mois-
ture absorption, negative coefficient of
thermal expansion, good property retention
over a broad temperature range and excellent
chemical resistance.
The density of Vectran HS is 1.41 g ~ m - ~
(0.0509 lbs in") (Hoechst Celanese, 1990). It
melts at 330°C (636°F). Like aramid fibers,
Vectran HS has a negative axial coefficient of
thermal expansion. From 20°C (68°F) to 145°C
(293°F) its longitudinal linear thermal expan-
sion coefficient is 4 . 8 x lo4 /"C ( - 2 . 7 ~
/OF). The coefficient increases to -14.6 x 10"
/"C (-8.1 x lo4 / O F ) from 145°C (293°F) to
200°C (392°F) and to -26.7 x lo4 /"C (-14.8 x
/ O F ) from 200°C (392°F) to 290°C (554°F)
(Beers and Ramirez, 1990).It has good temper-
ature resistance, although not as good as
aramid fibers since it melts at high tempera-
ture. Its shrinkage in hot air at 177°C (350°F)or
in boiling water is less than 0.5%.
Vectran HS fiber is outstanding in its
mechanical properties. Its axial mechanical
properties are summarized in Table 10.13.
Vectran displays no creep when tested for 2760
h at 50% of its ultimate tensile strength. This
behavior is significantly better than both
aramid and polyethylene fibers. Vectran also
has excellent vibrational damping characteris-
tics, better than aramids. Vectran HS has
superior abrasion resistance to Kevlar 29,
although not as good as polyethylene fibers. In
flexural fatigue, Vectran HS braid exhibited a
10% reduction in strength after one million

Table 10.13 Axial tensile mechanical properties of representative non-aramid, non-polyethylene organic
fibers

Fiber Reference Specific Tensile Tensile Elongation

gravity modulus strength, at break, %
GPa (Msi) MPa (ksi)
Vectran HS Hoechst Celanese, 1.41 64.8 2840 3.3
1990 (9.4) (412)
Adams and Farrow, 1.41 62-86 2500-3100 2.2-2.5
1993a (9.0-1 2.5) (363450)
PBO (Dow) Burk, 1993 1.56 152 5650 3.5
(22) (820)
PBO, high Burk, 1993 1.56 276 5520 1.5
modulus (Dow) (40) (800)
236 Organicfibers

cycles (and maintained this strength level to
five million cycles), while a Kevlar 29 braid
showed a 30% strength reduction under the
same conditions (Beers and Ramirez, 1990).
Vectran absorbs very little water, having a
moisture regain of less than 0.1%. It is
hydrolytically stable. It has excellent chemical
resistance being resistant to organic solvents,
to acids at less than 90% concentration and to
bases at less than 30% concentration (Hoechst
Celanese, 1990).
Vectran's dielectric constant is 3.3at 1 kHz
(Hoechst Celanese, 1990).
Like aramid and polyethylene fibers,
Vectran is difficult to cut and its composites are
difficult to machine. Typical aramid composite
machining techniques can be used successfully.
Forms, availability and treatments
Vectran is produced in the USA by Hoechst
Celanese Corporation and in Japan by the
Kuraray Corporation under license from
Hoechst Celanese. It is available as Vectran
HS, a high strength reinforcement fiber,
Vectran M, a high performance matrix fiber,
and as engineered, commingled combinations
of Vectran HS with Vectran M and S-2 Glass
fiber with Vectran M.
Vectran HS fiber is available in dtex (deniers)
of 222 (200),833 (750), 1000 (900)and 1667
(1500).These fibers are composed of 40,150,180
and 300 filaments respectively, with the fila-
ments being 23 pm (0.91x 10" in) in diameter.
Vectran HS fibers are offered with or without a
standard textile finish to assist in processing
and/or to provide (dramatically improved)
abrasion resistance. Commingled Vectran HS or
M fibers have no finish. (In the commingled S-2
glasslvectran M products, the glass fibers are
producer-sized.) (Hoechst Celanese, 1990).
More information on Vectran can be
obtained from the source listed in Table 10.14.
Applications
As with aramid and polyethylene fibers, ropes
and cables are an important usage. Marine
cables, fish nets, towing ropes, cargo tie
downs, slings, sails, bicycle brake cables and
optical fiber reinforcement all have been made
from Vectran HS. Olympic target archers use
bow strings from Vectran HS having a propri-
etary abrasion resistant finish. The result is
increased arrow speed with no creep of the
string. At the last America's Cup yacht races,
Vectran HS was used in at least six yachts,
either in sails or in marine cables. Vectran sails
stretch far less than either aramid or polyeth-
ylene and they have four to six times the life of
aramid sails (Adams and Farrow, 1993a).
Safety materials and protective garments
have also been made of Vectran in industries
ranging from meat packing to metal working.
In these applications, Vectran is superior to
aramids, which have poor resistance to bleach,
and to polyethylene fibers, which are sensitive
to the high temperatures used in drying laun-
dered garments.
Vectran composites have been used in aero-
space applications and in recreation and
leisure applications such as canoes, golf clubs,
baseball bats, hockey sticks, tennis rackets,
bicycles, skis, ping pong paddles, paragliders
and stereo speaker cones. Vectran properties of
importance in these applications include the
low moisture absorption, the excellent damp-
ing characteristics, high stiffness, lack of creep

Table 10.14 Sources of information on non-aramid, non-polyethylene organic fibers

Product Itzj?ormation source

Vectran fibers Hoechst Celanese Corporation, P.O. Box 32414, Charlotte, NC 28232-2414, USA
PBI fibers Hoechst Celanese Corporation, P.O. Box 32414, Charlotte, NC 28232-2414, USA
PBO fibers The Dow Chemical Company, Midland, MI 48674, USA

and good flexural fatigue properties. Vectran
is used where the cost of the fiber is secondary
to its performance (Adams and Farrow,
1993a).
Hybrid tennis rackets have been made by
Prince Manufacturing Company and Dunlop.
Vectran HS is combined with carbon fiber to
give greater speed and power with vibration
characteristics as good as wood. Jennifer
Capriatti played with a Vectran racquet at
Wimbledon in 1992.
Other actual or potential uses include
antenna guy wires, chemical resistant pack-
ings and gaskets, heat and creep resistant
belting, medical and surgical equipment, pres-
sure vessels, printed circuit board substrates
and aerial tow ropes.
10.4.2 AROMATIC HETEROCYCLIC POLYMER
FIBERS
Two aromatic heterocyclic polymer fibers are
currently available or in development in the
United States. These are PBI fiber from
Hoechst Celanese and PBO fiber from Dow
Chemical Company.
PBI fiber
PBI fiber is produced from a high performance
polybenzimidazole. Chemically it is poly-2,2'-
rn-phenylene-5,5'-benzimidazole,with the
structural formula shown in Fig. 10.13. The
fiber was commercialized by Hoechst Celanese
Fig. 10.13 Structural formula of poly-2,2'-rn-pheny- stretched to improve its orientation and prop-
lene-5,5'- benzimidazole (PBI) (Yang, 1992).
Other organic fibers 237
Fig. 10.14 Structural formula of poly-p-phenylene
benzobisoxazole (PBO) (Yang, 1992).
in 1983. It has excellent chemical and solvent
resistance and does not burn. It is, however,
more expensive than the aramids and has an
intrinsically high moisture absorption. It is
used mainly in woven form in fireblocking lay-
ers, including aircraft seat cushions and
fire-fighting overgear. It was also used in
chemical warfare suits in Operation Desert
Storm. In order to reduce cost, PBI is also used
in blends with aramids for thermal protective
apparel. PBI has potential applications as a
fiber reinforcement in composites, but cur-
rently its only composites application is as a
matrix resin or as a matrix-precursor for car-
bon-carbon composites (Yang, 1992; Conrad,
1993). More information on PBI can be
obtained from the source given in Table 10.14.
PBO fiber
PBO fiber is a polybenzoxazole, specifically
poly-p-phenylene benzobisoxazole, with the
structural formula shown in Fig. 10.14. PBO
fiber resulted from a US Air Force program
aimed at developing high strength fibers for
advanced composites. In the late 1980s, Dow
Chemical purchased worldwide rights to the
polymer. Dow has now constructed pilot plant
facilities for monomer, polymer and fiber and
the fiber is available for evaluation in pre-pro-
duction quantities (Burk, 1993).
As with aramids, PBO fibers are spun from
a liquid crystalline solution using dry-jet wet
spinning. This is, however, a more difficult
process than for aramids. The fiber is then heat
erties (Wolfe, 1990).
238 Organic fibers
PBO is one of the most thermally and
thermo-oxidatively stable organic polymers
known. No weight loss was observed for PBO
held at 316°C (600°F) (Wolfe, 1990)and weight
loss of only O.O6%/h was observed at 370°C
(700°F) (Burk, 1993). Its decomposition tem-
perature is 600°C (1110°F) (Burk, 1993).
Exposed to flame, PBO chars, but does not
support combustion. (Wolfe, 1990) Dow's PBO
fiber has a longitudinal coefficient of thermal
expansion of -6 x 104/OC (-3.3 x lO"/"F)
(Burk, 1993).
PBO fiber has a significantly higher tensile
strength and modulus than any other known
organic fiber. PBO fibers have been produced
with tensile moduli of as high as 470 GPa
(68 Msi). Dow's current pre-production fibers
do not achieve these high levels, but do
nonetheless have excellent axial mechanical
properties, as shown in Table 10.13. However,
like all other high performance organic fibers,
PBO fibers are quite weak in compression,
with a fiber compressive strength comparable
to that of aramids (Burk, 1993).They also bond
poorly to epoxy matrices, so their off-axis
properties are also poor (Wolfe, 1990). For
these reasons, as with other organic fiber com-
posites, PBO composites are limited to
applications where structural loading is
mainly in axial tension.
Moisture regain for Dow's PBO is 2.0% for
the standard fiber and less than 0.570 for the
high modulus version. The moisture resis-
tance is significantly better than aramids
(Burk, 1993).PBO is highly resistant to hydrol-
ysis, acid chemical attack, bases, solvents,
electron bombardment and laser radiation. Its
UV stability is outstanding (Wolfe, 1990).
Dow's PBO fiber has a lower and more stable
dielectric constant than that of aramids, 3.0 at
100 kHz (Burk, 1993).
The price for commercial PBO will be vol-
ume dependent, but will be higher than that
for aramids. PBO fiber will be used where
aramids and other fibers do not meet the per-
formance needs, particularly for strength,
modulus and flammability. Potential applica-
tions include composites loaded in tension,
such as pressure vessels, missile cases and ten-
sile beams. PBO fiber composites may also be
used in non-load-bearing applications where
high temperature exposure or harsh chemical
environments are anticipated, such as rocket
insulation systems and brake and transmis-
sion systems. The high strength could also
lower the weight of composites used in space-
craft and in recreation and sporting goods.
PBO also has significant potential application
to ballistics, where, as a fabric or composite, it
performs equally well at half the weight of an
aramid. PBO composites could provide out-
standing containment systems for high speed
rotors and turbines where high temperature
exposure is of concern. The fibers also have
potential for bomb containment systems, for
fire resistant and cut resistant apparel and fire
blocks, as well as ropes and cables (Burk,
1993).
More information on PBO can be obtained
from the source given in Table 10.14.
10.5 CONCLUSIONS
While high performance organic fibers are not
competitive with inorganic fibers in all of their
properties, they offer certain properties and
combinations of properties that are unavail-
able with inorganic fibers. All suffer from
certain limitations, such as poor off-axis and
compression properties and/or temperature
limitations. However, if these limitations are
properly considered, high performance
organic fibers can make possible designs that
can be achieved in no other way.
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Allied. 1991b. Creep at 30% load (room tempera-
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Allied. 1991c. High temperature creep. LB005.6/91.
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Chiao, T.T., Chiao, C.C. and Sherry, R.J. 1976.
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Chiao, C.C. and Chiao, T.T. 1982. Aramid fibers and
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George Lubin, pp. 272-317. New York: Van
Nostrand Reinhold.
Clements, L.L. and Moore, R.L. 1977. Composite
Properties of an Aramid Fiber in a Room-
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Quarterly 9: 6-12.
Conrad, D. 1993. Private communication. 7-19-93.
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DeCos, L. 1993. Private communication. 9-27-93.
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DuPont. 1981. Properties of Nomex aramid filament
yarns. Bulletin NX-17. December 1981.
Wilmington, DE: E.I. DuPont de Nemours & Co.
Inc.
DuPont. 1983. Kevlar aramid, the fiber of choice in
boat hull reinforcement. E-46814. 10/83.
Wilmington, DE: E.I. DuPont de Nemours & Co.
Inc.
DuPont. 1986. Data manual for Kevlar 49 aramid.
May 1986. Wilmington, DE: E.I. DuPont de
Nemours & Co., Inc.
DuPont. 1989 (received). Kevlar aramid, the uncom-
mon material for uncommon solutions.
H-05500-1. Undated. Wilmington, DE: DuPont,
Fibers Department.
DuPont. 1990. Presenting Kevlar 119 aramid fiber,
for longer service life in demanding applica-
tions, 5/90. Wilmington, DE: DuPont Fibers
Department.
DuPont. 1992a. Kevlar aramid fiber technical guide.
12/92. Wilmington, DE: DuPont Fibers, Kevlar
Products.
DuPont. 199213. Kevlar aramid, properties and uses
of Kevlar 29 aramid, Kevlar 49 aramid, Kevlar
68 aramid in fiber optic and electromechanical
cables. Information bulletin K- 506C, revised
November 1992. H-37390. Wilmington, DE:
DuPont Fibers Department.
DuPont. 1992c. Internal price list, Kevlar yarn,
11/23/92. Wilmington, DE: DuPont.
DuPont. 1992d (received). Kevlar aramid KM2, pre-
liminary information bulletin, H-35645.
Undated. Wilmington, DE: DuPont Fibers,
Kevlar Products.
DuPont. 1993a. Prices for Kevlar 29 yarns used in
textile processing. Price list effective 1/4/93.
240 Organic fibers
Wilmington, DE: DuPont.
DuPont. 199313. Prices for Kevlar 29 yarns used in
ropes and cables. Price list effective 1/4/93.
Wilmington, DE: DuPont.
DuPont. 1993c. Prices for Kevlar 49 yarns used in
textile processing. Price list effective 1/4/93.
Wilmington, DE: DuPont.
DuPont. 1993d. Prices for Kevlar 49 yams used in
fiber optics. Price list effective 1/4/93.
Wilmington, DE: DuPont.
DuPont. 1993e. Prices for Kevlar 49 yarns used in
ropes and cables. Price list effective 1/4/93.
Wilmington, DE: DuPont.
DuPont. 1993f. Rope and cordage products. H-
37399. 2/93. Wilmington, DE: DuPont Fibers
Department. DuPont.
DuPont. 1993g. Properties of DuPont industrial fil-
ament yarns, DuPont nylon, Cordura nylon,
Dacron polyester, Nomex aramid, Teflon fluoro-
carbon, Kevlar aramid. Technical Information,
Multifiber Bulletin X-273, April 1993. A-90240.
Wilmington, DE: DuPont, Fibers Department.
DuPont.
DuPont. 199317. Properties and processing of
DuPont Kevlar Aramid Yarn for Mechanical
Rubber Goods. Technical Information, Kevlar
Bulletin K-10, June 1993. Wilmington, DE:
DuPont Fibers Department.
DuPont. 1993i (received). The second generation of
ballistic protection, new Kevlar 129. H-13653.
Undated. Wilmington, DE: DuPont.
Dyneema. 1987. Dyneema SK60, high
strength/high modulus fiber, properties and
applications. Sittard, The Netherlands:
Dyneema Vof.
Gerzeski, Roger H. 1989.Vniivlon/polyamidobenz-
imidazole - USSR’s aramid fiber forming
polymer. In Reference Book for Composites
Technology, Vol. 1, ed. Stuart M. Lee, pp.
271-325. Lancaster, PA: Technomic Publishing
Company.
Hoechst Celanese. 1990. Vectran liquid crystalline
polymer fiber. Charlotte, NC: Hoechst Celanese
Corporation.
Hoechst Celanese. 1993 (received). Typical proper-
ties of high modulus polyethylene. Charlotte,
NC: Hoechst Celanese Corporation.
Hongu, Tatsuya and Phillips, Glyn 0. 1990. New
Fibers,. London: Ellis Honvood Ltd.
Jaffe, M. 1989. High-modulus high-strength organic
fibers. In Concise Encyclopedia of Composite
Materials, ed. Anthony Kelly, pp. 129-134.
Oxford : Pergamon Press.
Kaiser VIAM. 1993a. Certificate, synthetic aramid
filament, 58.8 tex. San Leandro, CA: Kaiser
VIAM.
Kaiser VIAM. 1993b. Certificate, fiber SVM 6.3(40)-
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Kaiser VIAM. 1993c. Certificate, fiber SVM 14.3-A1
‘acidic.’ San Leandro, CA: Kaiser VIAM.
Kaiser VIAM. 1993d. Certificate, fiber SVM
29.4(200)-Al ’ N (neutral). San Leandro, CA:
Kaiser VIAM.
Kaiser VIAM. 1993e. Certificate, fiber SVM-K 29.4
’acidic.’San Leandro, CA: Kaiser VIAM.
Kaiser VIAM. 1993f. Certificate, fiber SVM 29.4-A1
’acidic.’San Leandro, CA: Kaiser VIAM.
Kaiser VIAM. 1993g. Certificate, fiber TOW SVM
58.8(300)X17- 1000; VTV heat treatment. San
Leandro, CA: Kaiser VIAM.
Kaiser VIAM. 1993h. Certificate, fiber TOW SVM
58.8(300)X17- 1000; TOSN heat treatment. San
Leandro, CA: Kaiser VIAM.
Kaiser VIAM. 1993i. Certificate, fiber SVM 58.8
’acidic.’ San Leandro, CA: Kaiser VIAM.
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Al. San Leandro, CA: Kaiser VIAM.
Kwolek, S.L. 1971. U.S. Patent 3 600 360.
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munication. 9-27-93. New York: Teijin America,
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Tekmilon. 7/89. Tokoyo, Japan: Mitsui
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 Appendix 241

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as the weight in grams of 1000 meters of the
material. A related term is decitex (dtex),0.1
tex, which is often used in order to be com-
parable to the US quantity 'denier.'
Equilibrium moisture content: moisture
absorbed by a fiber after it has been dried at
50°C (122°F)for 2 h and then equilibrated at
20°C (68°F)and 55% relative humidity
Strength retention: percent of room tempera-
ture strength retained following exposure
to the conditions indicated
Tenacity: the ultimate failure strength of a fiber
per unit original area per unit weight. The
most commonly used units are 'grams per
denier' (gpd) and 'newtons per tex'
(N/ tex).

10.6 APPENDIX Conversion factors

DEFINITIONS AND CONVERSION FACTORS Fiber size:

1 tex = 9 denier = 10" kg/m
Definitions Twist:
1 tpi (turns per inch) = 39.37 t/m (turns per
Denier: Term in common usage in the fiber meter)
industry in the USA to describe the fineness Twist multiplier = [t/m (dtex)'/*]/3000= [tpi
of a fiber or fiber bundle. The denier is (denier)'/'/ 731
defined as the weight in grams of 9000 Modulus, stress, strength, and tenacity:
meters of the material. This is also known as 1kgf / mm2 = 9.806550 MPa
the 'count'. Its inverse measure is the 1 ksi = 6.894757 MPa
'yield', expressed in yards per pound or 1cN/tex = 0.01 N/tex = 10 pf MPa = 1.45 pf ksi
meters per kilogram. where pf is the specific gravity of the fiber
Tex: Term in common usage in the fiber indus- 1 gpd = 8.826 cN/tex = 88.26 pf MPa = 12.8 pf
try outside the USA to describe the fineness ksi
of a fiber or fiber bundle. The tex is defined
PARTICULATE FILLERS
Harry s. Kat2
11.1 INTRODUCTION
The preceding chapters of this handbook dis-
cussed fiber reinforcements. Fibers play an
important role as the outstanding means for
obtaining great increases in the strength and
modulus of the matrix material. The focus of
attention on fiber reinforcements has usually
blinded potential end users of composite
materials to the many beneficial uses of non-
fibrous, or particulate, fillers. However,
industrial experts are now becoming more
aware of these benefits and there will
undoubtedly be increased particulate filler
usage in future polymers, ceramics and met-
als. Particulate fillers can provide improved
materials, as compared with the unfilled
matrix and can also be synergistic with a fiber
reinforcement to further improve the system
performance.
A fiber may be described as a particle with
a length-to-diameter ratio of greater than 10 to
1. A particulate filler may be described as a
non fibrous solid that fits the definition given
in the Compilation of ASTM Standard
Definitions, ‘a solid compounding material,
usually in finely divided form, which may be
added in relatively high proportions to a poly-
mer for technical or economic reasons.’ This
chapter will not include additives such as
antioxidants or internal mold release agents,
which serve important compounding func-
tions, but are used at low levels, usually below
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
11
2 wt.% in the composite material. The only
exception is the inclusion of a brief discussion
of coupling agents, which serve an important
function in achieving optimum physical prop-
erties in particulate filler composites.
There are many good reasons for using par-
ticulate fillers in plastic, metal or ceramic
matrices, in addition to the obvious usual
reduction in cost of the final product. In the
case of plastics, the addition of fillers provides
a reduction of shrinkage during the cure of a
thermoset polymer system or the injection
molding of a thermoplastic resin. This reduced
shrinkage results in important benefits such as
avoidance of the warpage or cracking that
may occur, especially in the case of large
molded parts. Also, the thermal conductivities
of mineral fillers are usually in the order of ten
times greater than the thermal conductivity of
polymers. Therefore, the filled polymer has a
much greater thermal conductivity than the
unfilled resin. This provides an important
advantage in processes such as injection mold-
ing, where the cycle time is often determined
by the time to cool the part in the mold. The
faster cooling rate of the filled plastic will pro-
vide cost savings due to the faster cycle time.
Another advantage of the higher thermal con-
ductivity is the faster dissipation of localized
hot spots, which could cause thermal decom-
position of a polymer or failure of a sensitive
electronic component adjacent to the plastic.
There are many types of particulate fillers1.
They may be classified as mineral, natural or
synthetic, inorganic or organic. The mineral
fillers include calcium carbonate, clay,
 Corninon particulate fillers 243

feldspar, nepheline syenite, talc, alumina tri- 11.2.1 CALCIUM CARBONATE

hydrate, natural silicas and mica.
Calcium carbonate is one of the lowest cost
The importance of particulate fillers is read-
particulate fillers. Price varies depending on
ily apparent:
the grade and quantity purchased. During
’In 1993, about 4.9 billion pounds of fillers and 1994, the listed price for good quality standard
extenders, which included minerals, synthetic uncoated grades ranged from about $80 to
and organic based materials, were used by the $200 per ton. Special grades, such as precipi-
US plastics industry. The estimated value of tated and coated can cost over 25 cents per
these materials was $1.2 billion. Minerals rep- pound. Calcium carbonate is non-toxic, non-
resent the majority of these products. The irritating, odorless and is white in color with a
annual growth rate of synthetic fillers was esti- low refractive index. It is nonabrasive and is
mated at 7%.12 the standard material for Mohs’ 3 rating on the
Mohs’ hardness scale. There is an abundant
Manufactured fillers include products such
supply of this mineral filler and it is commer-
as glass beads, metal powders and synthetic
cially available in a wide range of particle
silicas.
sizes. It exhibits a low oil absorption rating
There are many particulate organic fillers
and is readily dispersed at high loadings in
such as wood flour, carbon black, various
liquid systems. As is the case with other par-
starches, ground rice hulls, peanut shell and
ticulate fillers, its use reduces shrinkage
reclaimed rubber.
during molding and curing. Because of this
Low density particulate fillers are available
characteristic, it is a usual filler in low shrink
and these include perlite and hollow micros-
reinforced polyester sheet molding com-
pheres of glass, ceramic, or organic polymers
pounds. Even with high loadings, it provides
such as phenolic and polyvinylidene chloride.
relatively low stiffness to the composite. It is
Specific particulate fillers can give a com-
stable up to 800°C.
posite material special characteristics such as
electrical conductivity, biodegradability, ther-
mochromic, photochromic, low surface 11.2.2 FELDSPAR AND NEPHELINE
friction or magnetic properties. Feldspar and nepheline are similar minerals
and serve the same purposes. These are anhy-
drous, alkali, aluminosilicates having excellent
11.2 COMMON PARTICULATE FILLERS
chemical resistance and are offered in coarse to
There are many commercial particulate fillers medium particle sizes. Because the index of
and the end user must take into consideration refraction of this mineral is equivalent to
many facts before deciding whether to use a polyvinyl chloride and other polymers, its use
particulate filler and which material will be best can result in retention of transparency or
for the application. The following paragraphs translucency in most polymers. Thus, less
present some information as a starting point for color pigment may be required to obtain a
possible selection of one of these materials for a given intensity. These mineral particulates
specific end use. Most of these descriptions are usually provide ease of wetting and are read-
condensationsof the more complete details that ily dispersed and de-aired. They cause little to
can be found in The Handbook of Fillers for no effect on promoters, accelerators, or addi-
I’lastics’. It should be noted that the descrip- tives that are used in liquid polymer systems.
tions are mainly aimed at the use of these Because of the low oil absorption values,
materials in a polymer matrix, but some of high loadings of these minerals can be added
these particulate fillers may have similar uses in to liquid polymer systems without running
metal or ceramic matrix composites. into the problem of excessively high viscosity.
244 Particulatefillers
Feldspar and nepheline syenite are not con-
sidered to be a health hazard or toxic and these
minerals have been recommended as suitable
for use in composites that contact food.
Feldspar is obtained from white granite by
quarrying the rock and crushing it. Nepheline
is the mineral derived from syenite rock and is
referred to as nepheline syenite. High-grade
deposits consisting of millions of tons are
mined and processed northeast of Toronto,
Canada.
11.2.3 KAOLIN (CLAY)
Kaolin is the common term for the mineral
kaolinite, a hydrous aluminosilicate mineral,
one of a number of minerals called clays. It is
available in two primary grades: the natural
hydrous form and a calcined, anhydrous form.
The larger average particle sizes consist of
mixtures of blocky and platy particles. The
finer fractions are almost entirely thin plates.
Clay is a rock term applying to soft, earthy
ores which are plastic when mixed with water.
The hydrous forms are non-abrasive, chemi-
cal resisting and have relatively high surface
area, which results in high viscosities in liquid
polymer systems. They disperse readily in most
plastics, especially with the aid of dispersants
or surfactants. In reinforced and thermoset
plastics, they control flow properties to provide
more uniform composite properties.
Calcined kaolin is considerably harder and
provides improved electrical properties in ther-
mosets and thermoplastics. Many surface-
treated types of each grade are available to pro-
vide outstanding water resistance, electrical
properties and reinforcement, in a variety of
systems.
11.2.4 SILICA
There are over 20 distinct phases of silica and
each is chemically SiO,. A number of them are
useful as fillers in plastics. These different
phases offer advantages and disadvantages,
for example a synthetic colloidal form, or
amorphous phase, of silica has very high sur-
face area. When added to liquid systems, this
type of product can provide a thixotropic
effect and reinforcing properties in cured rub-
bers or polymers. Flocculated varieties of the
colloidal form give flatting characteristics and
composite properties different from the partic-
ulate colloidal phase. The synthetic forms are
so fine in particle size that they offer little in the
way of hardness in the finished composites.
Natural silica products, as in the case of the
low quartz phase, come from quartzite and
tripolitic forms, which are generally termed
natural, microcrystalline quartz. These are
usually less expensive than the synthetic, col-
loidal forms. They offer excellent electrical
insulation, good mechanical properties and
lower surface area, hence better rheological
flow. Drawbacks are increased wear of pro-
cessing equipment and the lack of reinforcing
properties.
Fused silica is manufactured by subjecting
high purity quartzite to temperatures in excess
of 2200°C (4000°F).Finely divided fused silica
has a very low coefficient of thermal expan-
sion. This is desirable in composites subjected
to wide variations in temperatures.
Silica surfaces can be modified to offer
organofunctionality,hydrophobicity and non-
functionality. commercial activity in surface
modification is limited now, but the future will
surely see more functional particulate silica
materials with the interface tailored to specific
end uses.
11.2.5 ANTIMONY OXIDE
Antimony oxide is an opaque white mineral
powder which has been used as a pigment
because of its good color and high hiding
power. It is no longer competitive with more
economical white pigments and its high cost
and density makes it unattractive as an ordinary
filler or extender. The major use now is as a
flame retarder.
Synergism between antimony oxide and
halogens accounts for the widespread use of
 Common particulate fillers 245

antimony oxide in plastics. Antimony oxide is mal conductivity to a polymer composite. In

added at 1-15 wt.% and affects physical prop- each application, the grade and manufacturer
erties in the same way as other fine particle must be carefully selected in order to obtain
size minerals. The halogen compound has a optimum performance.
greater effect on plastic properties because There are a wide variety of commercial car-
larger quantities are added. The halogen com- bon black products. Differences include
pound is a plasticizer, which lowers modulus particle size and particle size distribution, spe-
and strength. An additive system must be cific surface area, surface structure, amount of
selected for the fabrication method to be used agglomeration, moisture content and minor
and for flammability and physical require- contaminants, such as metals, sulfur, oxygen
ments of the specific application. and hydrogen. These differences originate
from the fact that various hydrocarbon raw
materials and production methods are used to
11.2.6 ALUMINA TRIHYDRATE
produce different grades of products, which
Alumina trihydrate (Gibbsite)is a refined min- include furnace, thermal, acetylene, lampblack
eral which offers a bonus of flame retardance and channel blacks. Carbon blacks exhibit pH
and smoke suppression in most plastics appli- of 2-9 when slurried in water.
cations. It is available in different grades, which Many polymers are susceptible to pho-
contain various amounts of minor impurities todegradation upon exposure to sunlight or
and range in particle size from coarse materials, UV radiation. An effective method for reduc-
almost entirely +325 mesh, to very fine prod- ing or eliminating this effect is by adding
ucts less than 1 Fm in mean particle diameter. about 3 wt.% of an appropriate carbon black to
Alumina trihydrate is non-toxic and rela- the polymer.
tively inert chemically. In electrical There are a number of specific grades of car-
applications, it provides the benefit of arc and bon black, especially acetylene blacks or
track resistance. Since its surface has a low furnace-produced carbons, that are very effec-
sorptive capacity, trihydrate has low resin tive in providing high electrical conductivity
demand in liquid polyester, epoxy and acrylic in a polymer composites. High electrical con-
systems. Because it undergoes thermal decom- ductivity can also be obtained by use of the
position, it is not suitable for processing at many different grades of graphite flakes and
temperatures above about 200°C (428°F). The powders that are commercially available.
endothermic evolution of water at the decom-
position temperature is the basis for the fire
11.2.8 MICA
retardant property of this particulate filler.
Mica is a generic term for a family of potas-
sium alumininosilicate minerals, which
11.2.7 CARBON BLACK AND GRAPHITE
include muscovite, phlogopite, biotite and flu-
Particulate carbon is available commercially in orphlogopite. The exact composition of these
many forms and from many suppliers. The minerals can vary from mine to mine. In all
filler known as carbon black is usually cases, the mineral is readily ground and split
obtained by the pyrolysis of hydrocarbon into thin flexible sheets or flakes. Mica flake
gases or oils. Its largest end use is for filling fillers have had a high growth rate as a plastics
and reinforcement of rubber polymers in filler because they can provide a much greater
products such as automotive tires. However, it increase of matrix modulus than most other
also finds widespread applications as a filler mineral fillers. This improvement is further
and coloring agent in plastics, inks, paints and optimized when the mica surface is treated
paper. It can also provide electrical and ther- with appropriate coupling agent^.^
246 Particulate fillers

11.2.9 TALC ture initiation of failure of a polymer matrix

composite.
The talc of major interest to plastics users is a
There are many types of solid microspheri-
finely ground product consisting of thin
cal fillers, including glass, ceramics and
platelets and is white in color. Due to the platy
plastics. Commercial 'A' glass spheres are
nature of this form of talc, it is considered to be
available in a range of diameters, usually from
a reinforcing filler in many plastic applica-
30-750 pm. Incorporating these products into
tions. Its low cost qualifies it as an extender
a resin matrix may result in poor bonding
while its platiness qualifies it as a reinforcing
between the resin and the sphere. For opti-
filler. White, platy, fine, ground talcs are avail-
mum composite properties, a surface
able from a number of different suppliers.
treatment that is specifically tailored for the
Composites with platy talc exhibit higher
resin should be applied to the sphere. Various
stiffness and creep resistance at ambient and
surface treated products are commercially
elevated temperatures, when compared with
available.
equivalent composites filled with a particulate
There are many types of hollow micro-
filler such as calcium carbonate. For example:
spherical fillers. These include glass, ceramics,
polypropylene filled with a 40% loading of
polvinylidene chloride and phenolic plastic.
talc, the flexural modulus or stiffness triples
These fillers can be used to prepare polymer
from about 1380 MPa (200 000 psi) for the
composites with low densities and relatively
unfilled polypropylene to about 4140 MPa
high compressive strengths.
(600 000 psi) for the talc-filled equivalent. A
40"/0 loading of calcium carbonate only
increases the modulus to about 2760 MPa 11.3 METHODS OF PRODUCTION
(400 000 psi).
There are many different methods for produc-
High loadings of talc are usually accompa-
tion of particulate fillers. As indicated above,
nied by a reduction of the impact strength of
the mineral fillers are simply produced by min-
the polymer matrix composite. However, this
ing, grinding and then removing undesirable
can be minimized through proper selection of
components/contaminants and separation
the particle size and size distribution, surface
into various size fractions.
treatments on the talc and resin formulation.
In many cases, the end user has a choice
between the natural mineral filler and a syn-
thetic product that can provide superior
11.2.10 MICROSPHERES
performance for specific applications. Calcium
There are two main reasons why microsphere carbonate is the most widely used filler or exten-
fillers are an excellent choice for many appli- der pigment in the plastics industry. For many
cations. The spherical shape provides the applications, the filler is manufactured by
lowest possible surface to volume ratio, which merely crushing the mineral, followed by pul-
limits the area of resin adsorption. This per- verizing and air classification into the desired
mits a relatively high loading of the spheres in particle size. However, a precipitated calcium
a fluid matrix without the resultant high vis- carbonate is usually specified where purity, uni-
cosity that would occur if the same volume of form small particle size and superior whiteness
equivalent size non-spherical particulate were is required. The two types of calcium carbonate
added. Second, the spherical shape provides a have their advantages and disadvantages.
uniform stress distribution on its surface, in Different manufacturing methods will pro-
contrast to the sharp edges of most other par- duce different size distributions of the
ticulates. Sharp edges create a localized high particulate fillers and size distribution is an
stress concentration, which can lead to prema- important factor to evaluate in the choice of a

filler. Manufacturers of particulate fillers pre-
sent this type of data as graphs (Fig. 11.1).
Each of the four calcium carbonate fillers,
Atomite, duramite, Snowflake P.E. and
Supermite, has quite different particle size dis-
tributions even though they are all produced
by a wet grinding process. The mean particle
size of these products is 3, 11,5.5 and 1 in the
order cited above and the oil absorption val-
ues, by the rubout method, are 15,8,9 and 19.
Note that the mean particle size of Snowflake
P.E. is one half that of Duramite, whereas the
oil absorption number is about the same. The
relatively flat particle size distribution curve
of Snowflake P.E. gives it good packing char-
acteristics so that it provides high loading
levels with low viscosity in liquid resins.
Therefore, it is a good choice for a wide variety
of polyester compounding methods, such as
bulk molding compounds, sheet molding
compounds, transfer molding compounds,
pultrusion and spray up applications.
100 -
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
I I I I I
50" 20
Equivalent Spherical Diameter pm
Fig. 11.1 Size distributions of calcium carbonate fillers (a) Duramite, (b) Snowflake P.E., (c) Atomite,
(d) Supermite. (Courtesy of ECC International, Atlanta, GA.)
Methods of production 247
Precipitated CaCO, is produced by heating
CaCO, to form CO, and CaO. The latter prod-
uct is reacted with water to form calcium
hydroxide, which is then recombined with the
CO, to produce CaCO,. Median particle sizes
are usually 0.2-2.0 pm. This material is avail-
able in high purity grades for USP, FDA and
food contact applications. A disadvantage is
that the cost is higher than the ground mineral
products.
Fumed silica is prepared by the hydrolysis
of silicon tetrachloride in a flame of hydrogen
and oxygen at a temperature of 1000°C or
higher. While still molten, the primary small
particles of silica fuse into secondary particles
called aggregates. Particle size and surface
area of the resultant fumed silica are con-
trolled by varying the ratio of the reactants.
After passing through a coagulation and cool-
ing zone, the silica particles are separated from
the HC1-containing combustion gases by
means of cyclones or filters. The residual HC1
248 Particulatefillers

is removed by treating the silica with moist hot shape from the previous two materials. This
air. emphasizes that the choice of a particulate
Microsphere fillers are produced by a num- filler should not be made on the basis of the
ber of different methods. These include the fire generic type, but must be made after evalua-
polishing of ground particles, atomization of tion of different grades that are available from
molten materials and calcining of crushed par-
ticles. There are a number of patents on
methods for production of glass micros-
phere~"~. Fly ash microspheres are
commercially available. These are obtained by
beneficiation of the waste fly ash product that
is generated in large quantities by the many
utility companies that burn powdered coal.

11.4 TYPES OF PARTICULATE FILLERS

11.4.1 CHARACTERIZATION BY SHAPE I

4
The shape of a particulate filler is an important Fig. 11.2 Montana talc. (Courtesy of Speciality
consideration in the selection of the optimum Minerals Inc.)
filler for a specific end use.

Microspheres
As described above, spheres have many
advantages over irregularly shaped particu-
lates when used as fillers in a polymer matrix.
Therefore, when particulate fillers are being
considered for use in a composite material, the
selection process should include the evalua-
tion of microsphere fillers

Flakes Fig. 11.3 Italian talc. (Courtesy of Speciality

Minerals Inc.)
Flake or platelike (lamellar) particulates can
provide important benefits for composite
materials. In coatings, this shape of filler can
lead to a highly loaded composite that is a
good permeation barrier, since any penetrant
must go through a tortuous path within this I
material. Polymer composites, with flake rein-
forcements, can exhibit planar isotropy and
higher modulus than composites with an
equivalent loading of an irregular shaped par-
ticulate filler. The crystal form of talc may be
platelike or flakes as in Montana talc (Fig. 11.2)
and Italian talc (Fig. 11.3).In contrast, the New Fig. 11.4 New York talc. (Courtesy of Speciality
York talc (Fig. 11.4) is quite different in particle Minerals Inc.)
 Types of particulatefillers 249

various sources and companies. There can be 11.4.2 CHARACTERIZATION BY FUNCTION

dramatic differences in compounding charac-
In addition to the categories or classifications
teristics and in critical properties, such as
discussed above, particulate fillers may be
strength Or modulus~based On the
characterized by the function they serve.
specific grade of a particulate filler, how it has
been processed and whether or not there is a
surface treatment. In addition to talc, other Fire retardants
flake Or Platy Some ‘lays An important type of particulate filler is the
and graphite.
solid fire retardants discussed above. The use
Mica flakes have been discussed above’ A
of these fillers will continue to increase as a
high performance type of this material is the
means for reducing the loss of life and prop-
high ratio grades. The ratio Of erty due to fires in hotels and aircraft.
flakes is defined as the ratio of the flake aver-
age diameter to the thickness. The higher
aspect ratio flakes are more effective than low Lightweight fillers
aspect ratio flakes in the transfer of stress from
Particulate fillers can reduce the specific grav-
the relatively weak polymer matrix to the
ity of the composite material. Among the
stronger flake reinforcement. Optimizing the
particulates for this category are perlite and
properties of mica filled polymer composites
the many types of hollow microspherical
has involved a number of developments,
fillers discussed above. Perlite is an excellent
including surface treatment with coupling
low density filler, derived from a natural min-
agents, improvements in flake separations and
eral, which is mined, ground, expanded by a
orientations and reduction of flake damage
heat process and screened to various size frac-
during processing. The impact strength of tions. It is a multicellular material, which has
these composites is often poor, but improve- the advantage that if some of the outer wall is
ments have been obtained by combinations of broken, the remaining closed cell structure
mica flakes with high strength short fibers and prevents penetration by a liquid resin. Perlite
by use of polymer impact modifiers.
is a low cost filler, especially when evaluated
The predominant filler for manufacture of
in terms of cost per unit volume.
conductive polymer composites and inks is sil-
ver flake.
High density fillers
Irregular shaped particulates Particulate fillers may be used to increasing
the specific gravity of a polymer composite.
Most commercial fillers may be considered as Appropriate fillers in this category are barium
irregular in shape, even though the basic crys- sulfate, nickel and lead powders.
tal structure may be a square or block type
lattice. As mentioned above, mineral particu-
late fillers that are obtained by simple High hardness fillers
grinding and classifying into various size frac- High hardness fillers such as alumina and
tions are essentially irregular shaped crystalline silica may be used to increase
particulate fillers. These fillers, such as crys- hardness and provide abrasion resistance for
talline silica or ground quartzite, have sharp polymer matrix composites.
edges or points that result in high stresses
within a polymer composite and can lead to
initiation of premature failure of the structure.
250 Particulate fillers

High thermal conductivity fillers 11.4.3 CHARACTERIZATION BY SURFACE

PROPERTIES
Beryllium oxide powder has been used in
polymer matrices because it provides high The surface characteristics of a particulate
thermal conductivity and c xcellent electrical filler are important in determining the final
resistivity. However, this powder is highly properties of the composite. Surface treat-
toxic and this has severely limited its usage. ments are well established as a means for
Alternate choices for this end use have improving the processing characteristics dur-
included magnesium oxide and aluminum ing the addition of particulate fillers into
oxide fillers. As noted above, mineral fillers liquid resins and for improving the physical
have much higher thermal conductivity than properties and retention of the composite’s
polymers, so most of these fillers will provide properties upon aging. Therefore, even though
a polymer matrix composite with much higher this chapter does not deal with additives, their
thermal conductivity than the polymer matrix. importance in achieving optimum physical
properties in particulate filler composites,
merits brief discussion.
Electrically conductive particulate fillers
In composites technology, the term cou-
Electrically conductive particulate fillers such pling agents has been used to designate
as silver flake, nickel powder and graphite chemicals that are used to treat the surface of
particulates can be used to provide polymer fillers and reinforcements in order to obtain
matrix coatings and composites with static optimum physical properties and for long-
discharge characteristics and electrical con- term retention of physical properties.
ductivity. Coupling agents are chemical molecules with
dual functionality, wherein one part of the
molecule will adhere to one surface, e.g. filler
Magnetic particulate fillers
or reinforcement, while another part of the
Ferrite or ceramic magnetic powders are used molecule provides a bond to the matrix mate-
as fillers in polymers to produce bonded mag- rial. Thus, a bonded bridge is formed between
nets. The loading of these powders ranges two different materials.
from 85-90 wt.%. Plastic magnets are available Coupling agents can provide benefits as
in either a flexible or rigid form. processing aids for polymer matrix compos-
ites. Dramatic reductions in viscosity can
occur in some highly filled liquid polymers
Low friction particulate fillers
when a relatively small quantity of an appro-
Particulate fillers such as Teflon@powder, priate coupling agent is added to the
molybdenum disulfide and graphite have formulation.
been added to plastics in order to obtain low
friction composites. Typical end uses have
Silanes
been oil-free bearings and molded plastics
inserts for sliding drawers or windows. Silanes are currently the predominant cou-
pling agents or surface treatments for
particulate fillers. Many commercial fillers are
available with various silane treatments and
each silane is designed for optimum use in a
specific type of polymer.R

Titanates and zirconates
Titanates and zirconates produced by
Kenrich Petrochemicals Inc., Bayonne, New
Jersey, have received much attention in recent
years and show promise of affording some
remarkable improvements in processing
characteristics and final properties of many
composites systems. These coupling agents
are analogous to the silanes. Each product has
organic functionality and an inorganic back-
bone, so that one end can interact with the
matrix resin and the inorganic component will
have an affinity for the filler or reinforcement
surface.
Miscellaneous coupling agents
There have been many polymer additives and
modified polymers that have been used to
improve the properties of particulate filled
polymer composite^.^
Polypropylene has been grafted with
acrylic acid and this modified polypropylene
has provided improved bonding to mica and
talc in polypropylene composites. Copolymers
of styrene and maleic anhydride have been
shown to have improved mechanical proper-
ties in filled thermoplastics compared to a
polystyrene matrix. Dupont produces a line of
fluorosurfactants, with the trade name Zonyl,
that have been recommended for use as a
polymer additive to improve wetting and
bonding with fillers.
11.5 REPRESENTATIVE PROPERTIES OF
PARTICULATE FILLERS
11.5.1 PROPERTIES OF PARTICULATE FILLERS
In considering the use of particulate fillers all
factors should be evaluated including chemi-
cal and physical properties, surface
characteristics, particle size and size distribu-
tion. Among physical properties are specific
gravity, bulk density, specific heat, coefficient
of linear expansion, index of refraction and
Mohs' hardness value. These properties can
Representative properties of particulate fillers 251
vary widely for the many different types and
grades of particulate fillers.
11.5.2 OIL ABSORPTION NUMBER
The oil absorption number is an important
characteristic of a particulate filler. An analo-
gous situation exists in the paint and coatings
industry, where two ASTM specificationshave
been used to determine the oil absorption of
pigments. The objectives of these tests are 'to
obtain information about the vehicle demand
of the pigment when it is used in a pigment
paste.' In ASTM D1483, linseed oil is added in
drops to the gently stirred pigment. The
amount of oil required to form a paste is used
to calculate an oil absorption value. In ASTM
D281, linseed oil is added dropwise to a small
quantity of pigment, while rubbing vigorously
with a spatula. The end point occurs upon
obtaining a 'stiff, putty-like paste, that does
not break or separate.' ASTM D281 refine-
ments, which can involve the use of
appropriate liquids other than linseed oil,
have been described for determination of oil
absorption or packing fractions of fi1lers.l" In
most applications, it is desirable to choose
fillers with low oil absorption values, since
these fillers will cause the minimum increase
in viscosity of the matrix material.
11.5.3 HARDNESS
The particulate fillers that are commercially
available have a wide hardness range. They
are usually rated by use of qualitative scale in
which the hardness of a mineral was deter-
mined by its ability to scratch or be scratched
by another mineral. The scale was set up by a
mineralogist, Friedrich Mohs. In the Mohs' rat-
ings, the standard hardness minerals are: talc, 1;
gypsum, 2; calcite, 3; fluorite, 4; apatite, 5;
feldspar, 6; quartz, 7; topaz, 8; alumina, 9 and
diamond, 10. The hardness can be important
in the choice of a particulate filler. In the case
of a polymer matrix cast part that must be post
machined, it will usually be advantageous to
252 Particulatefillers
choose a soft filler such as talc or calcium car-
bonate, since an alumina filler may result in
severe abrasion of standard machining tools.
Also, in the extrusion or injection molding of
polymer composites, a quartz or alumina filler
may cause severe abrasion of processing
equipment or molds.
11.5.4 TOXICITY CONCERNS
Extremely fine particle size fillers can present
a health hazard and should be handled with
special precautions. During recent years, fillers
with a high content of fine crystalline silica
have been withdrawn from the market as a
result of concern as a suspected carcinogen.
Other particulates with well known health haz-
ards are asbestos and beryllium oxide powders.
In general, most particulate fillers do not repre-
sent a significant hazard when handled by use
of standard industrial safety procedures.
11.6 DESIGN CONSIDERATIONS IN THE USE
OF FILLERS
11.6.1 PACKING CONCEPTS
An understanding of packing concepts is
important for optimum physical properties in
most particulate filler composites. It is easy to
visualize this concept in its simplest form, from
the following considerations. When solid
spheres of any uniform size are placed in a con-
tainer, the spheres will occupy 62.5%) of the
container volume and the interstitial void con-
tent will represent 27.5% of the volume. If much
smaller spheres, with a size that permits them
to fit within the interstitial space of the larger
spheres, are now placed into the container, it is
obvious that the interstitial void volume will be
reduced. By appropriate choices of the sizes of
the large and small spheres, a void volume of
only 15% can easily be achieved with this
bimodal packing. The difference between 27.5%
voids and 15% voids can be extremely impor-
tant in compounding with liquid polymers or
resins, since the high void content requires a
much higher ratio of resin/filler to fill the voids
before the system becomes sufficiently fluid for
most processing or molding procedures. Many
applications will benefit from the use of a par-
ticulate filler and the proper packing of the
filler, filler blends or filler and fiber combina-
tions will be useful to optimize the physical
properties of the composite.'l
11.6.2 SHRINKAGE OF PARTICULATE FILLED
PLASTICS
An important advantage provided by the use
of particulate fillers is the reduction in the
shrinkage of polymers, so that less warpage is
obtained in large molded plastic parts.
However, designers of molds for unfilled plas-
tics must be careful to modify the design for
use with particulate filled plastics. The lower
shrinkage can result in parts that are out of tol-
erance, when mating structures are involved.
Also, there may be problems in efficient
removal of parts from a mold.
11.6.3 ORIENTATION OF FLAKE FILLERS
The design of molds for flake filled polymer
composites must include the flow orientation
of the flakes. This can result in directional
strength problems unless injection gate shapes
and locations are properly designed. Another
consideration for injection molding of these
polymer composites is that flow conditions
often result in the formation of knit lines,
which may have much lower strength than the
base material.
11.6.4 FILLER ADDITION REDUCES
ELONGATION OF POLYMERS
The elongation at failure of a polymer will be
greatly reduced when compounded with a
particulate filler. This can lead to a significant
reduction of toughness or impact resistance.
This factor must be evaluated before making a
final choice in the use of particulate fillers and
loading levels.

11.7 TYPICAL END USES FOR PARTICULATE
FILLERS
The traditional source for particulate filled
plastics has been from plastics compounders.
There are many custom compounders with
appropriate equipment such as Banbury mix-
ers and twin screw extruders that are used to
obtain a uniform blend of the filler and matrix.
Various filled polymer compounds, usually in
the form of small pellets that have been
chopped from extruded rods, are available
from these compounders. In addition, large
resin producers have introduced filled grades
of their compounds. Among the many prod-
ucts that are commercially available are Nylon
and PBT resins filled with talc or mica from
GAF; Nylon filled with kaolin from Hoecht-
Celanese, Dupont (Minlon), or Monsanto
(Vydyne); and GE’s Valox 700, which is a PBT
resin filled with mica. GE’s Valox HV7000
series resins are PBT composites that are
highly loaded with mineral filler. Grade 7075
has 68 wt.% filler.
Most commercial particulate filled plastics
have had a maximum filler loading of about
40 wt.% because the physical properties have
usually fallen dramatically when this level of
filler has been exceeded. However, as the art
and science of compounding progresses, it
may be anticipated that future composites will
effectively use much higher average loadings
of mineral fillers. This trend is apparent from
the high loading of minerals in GE’s HV7000
series mentioned above. Synthetic marble,
which is used to fabricate bathroom sinks, is
usually formulated by use of polyester resins
that have been highly loaded with calcium
References 253
carbide fillers. Flexible and rigid plastic mag-
nets contain about 90 wt.% loading of ferrite
powder. These magnets are used in many
automotive and appliance applications, such
as door seals and refrigerator gaskets.
Mica-reinforced polypropylene has been
used in many automotive applications, such as
fan shrouds, seat backs, glove compartment
moldings and inner fender linings.
Among the many end products that are
made by use of particulate filled composites
are electronic components, toys, marine com-
ponents, grinding wheels, display items, tools,
housewares and cameras.
REFERENCES
1. Katz, Harry, S., and Milewski, John V., Handbook
of Fillers for Plastics, New York: Van Nostrand
Rheinhold (now Chapman & Hall), 1987.
2. Fillers and Extenders f o r Plastics, Norwalk, CT
Business Communications Co., 1995.
3. Canova, L.A., Effect of surface treatments in
mica-filled polypropylene, Plastics Compounds,
1990, July/August, 3843.
4. Davis, et d.,US Patent 2 460 977,1949.
5 . Searight, et d., US Patent 3 138 444, 1964.
6. Bland, et d., US Patent 3 150 947, 1964.
7. Schmidt, et d.,US Patent 3 190 737,1965.
8. Plueddeman, E.P., Silane Coupling Agents, New
York Plenum Press, 1982.
9. Skeist, I., Handbook of Adhesives, New York: Van
Nostrand Reinhold, 1989.
10. Ferrigno, T.H. in Handbook of Fillers for Plastics,
New York: Van Nostrand Reinhold (now
Chapman & Hall), 1987, pp. 17,19-20.
11. Milewski, J.V. and Katz, Harry S., Handbook of
Reinforcements for Plastics, New York: Van
Nostrand Reinhold (now Chapman & Hall),
1987, pp. 14-33.
SANDWICH CONSTRUCTION 12
Andrew C. Marshall

12.1 INTRODUCTION 1. a pair of thin, strong facings;

2. a thick, lightweight core to separate the fac-
This chapter covers a unique form of com-
ings and carry loads from one facing to the
posites known as ’structural sandwich
other; and
construction’.
3. an attachment which is capable of transmit-
A structural sandwich consists of three ele-
ting shear and axial loads to and from the
ments, as shown in Fig. 12.1:
core.
I This chapter provides a general background
and a brief summary of the various materials
in common use; the design steps used to cal-
culate loads; some design details for solving
load point, edging and attachment problems;
and a few tables, charts and graphs containing
useful information for the designer. An
attempt is also made throughout the chapter
to provide suggestions and perspectives to
help a new user of sandwich structures tech-
nology to avoid some of the errors of his
predecessors.
Structural sandwich construction is one of
the first forms of composite structures to have
attained broad acceptance and usage. Virtually
all commercial airliners and helicopters and
Fig. 12.1 The elements of a sandwich structure are nearly all military air and space vehicles make
as follows: (a) two rigid, thin, high strength facings; extensive usage of sandwich construction. In
(b) one thick, low density core; and (c) an adhesive recent years, most commercial space vehicles
attachment which forces the core and facings to act
as a continuous structure.The facings of a sandwich have also adopted this technology for many
panel act similarly to the flanges of an I-beam, components. The effectiveness of sandwich
resisting the bending loads and increasing the construction is shown in Fig. 12.2.
bending stiffness of the structure by spreading the In addition to air and space vehicles, the sys-
facings apart. However, unlike the I-beam’s web, tem is commonly used in the manufacture of
the core gives continuous support to the flanges or cargo containers, relocatable shelters and air-
facings. field surfacing, navy ship interiors, small boats
and yachts, duplicate die models and produc-
Handbook of Composites. Edited by S.T. Peters. Published tion parts in the automobile and recreational
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7

Fig. 12.2 A striking example of how conversion to sandwich stiffens a structure without materially increas-
ing its weight. This example uses 1.6 mm (0.063 in) thick aluminum facings and 1/4-5052 37 kg/m7 (2.3
lb/fPj aluminum core.
vehicle industry, snow skis, display cases, resi-
dential construction materials, interior
partitions, doors, cabinets and a great many
other everyday items.
Although the employment of sandwich
design to produce lightweight or special pur-
pose load-carrying members is thought to
have originated as early as 1820, routine com-
mercial use of the idea did not occur until
about 110 years later. What started this sudden
acceptance was the successful commercial pro-
duction of structural adhesives, starting in
both UK and USA in the 1920s and 1930s.
This early production began with the use of
casein glue and later urea-formaldehyde and
phenolics, with wood facings and cores. The
search for better adhesives subsequently
resulted in the development of the rubber-
phenolics and the vinyl-phenolics, which were
suitable for use with metals. Commercial
adhesives such as ’Cycleweld,’ (from Chrysler
Motors), ’Plycosite,’ (from US Plywood) and
’Redux’ (from Bonded Structures, in Duxford,
UK) adhered well to both wood and metals
and possessed rather high and predictable
strength.
The result was the beginning of a revolution
in bonding technology. Many further develop-
ments followed in only a few years. They
included improved cleaning methods for
metal skins; low weight, high strength/stiff-
ness honeycomb core materials; ‘B’ staged
tape adhesives which could be stored for long
times; glass fabrics and collimated tapes
preimpregnated with accurately measured
Fncing material 255
amounts of ’B’ staged resins; high strength
resins; tough, high peel adhesives requiring
lower cure temperatures and pressures; as
well as the discovery of the resistance of sand-
wich to sonic fatigue.
12.2 FACING MATERIAL
The primary function of the face sheets in a
sandwich structure is to provide the required
bending and in-plane shear stiffness and to
carry the edgewise and bending loads, as well
as the in-plane shear loading. In the aerospace
field, facings most commonly chosen are resin
impregnated fiberglass cloth or a laminate of
unidirectional fibers (commonly called
’prepreg’), graphite prepreg, 2024 or 7075 alu-
minum alloy, titanium alloy, or any of several
stainless steel or refractory metal alloys. Even
the most economical of these products repre-
sents a substantial cost and customary practice
is to choose among them very carefully on a
value engineering, or lowest lifetime cost,
basis.
12.2.1 SUITABILITY OF MATERIALS
When choosing facing materials (as well as the
core, adhesive, or other materials) for an appli-
cation, it is wise to examine the less obvious
properties of the material, such as toughness
or brittleness, mode of fracture, durability and
weatherability, compatibility with rivets and
bolts and other such attributes which may
directly affect the usability or success of the
256 Sandwich construction
end product, even though not directly
involved in stress analysis or weight savings.
An understanding of these requirements has
resulted in a switch from aluminum to fiber-
glass skins and from fiberglass to aramid
(Nomex, from DuPont) cores for most aircraft
cabin interior panels.
12.3 CORE MATERIALS
The primary function of a core in sandwich
structures is that of stabilizing the facings and
carrying most of the shear loads through the
thickness. In order to perform this job effi-
ciently, the core must be as rigid and as light as
possible and must deliver uniformly pre-
dictable properties in the environment (such
as high humidity) in which the finished part is
to perform.
12.3.1 TYPES OF CORE MATERIALS
Wood
Several different materials are used exten-
sively as sandwich cores. The oldest of these is
wood, which continues to be used in many
applications as a core for such common appli-
cations as doors, partitions and many other
’builder’s supply’ items. It is also used in the
majority of snow skis, either flat-grain or end-
grain, although a few of the higher
performance skis employ honeycomb, foam,
or reinforced plastic cores. End-grain balsa has
broad acceptance in boat hulls up to lengths of
15.2m (50 ft) or more and is still used for
replacement flooring for many older and a few
new aircraft.
The traditional advantage of the low cost of
wood has been progressively eroded with the
passage of time and many users report diffi-
culty in supply, even at prices higher than foam
and sometimes approaching that of honey-
comb. Even so, the ease of use and excellent
durability of the end product has led to sub-
stantially increased usage, particularly of the
carefully selected grades of end-grain balsa, in
applications such as boat hulls, large tanks and
airborne pallets and containers. This broaden-
ing usage is also prompted by its excellent
compressive strength and modulus properties
when compared to all but the aramid paper
honeycombs, which are much more expensive.
Complete information can be obtained from
the leading producer of these materials,
BaltekI3,or Balsa Ecuador Lumber Company.
Foam
The use of foam as a structural core has been
and is now, extensive. Recent developments in
the technology of foam injection have sharply
increased the use of these materials. The most
novel of these is use of a cold-cavity die, in
which the foam is injection molded in a single
production step. A careful adjustment of the
mixing and curing reaction of the foam,
together with the heat-sink effect of the mold
results in a part with facings which are simply
an un-foamed, higher density form of the
same polymer which constitutes the foamed
core. The high productivity and modest cost of
this scheme have resulted in many applica-
tions in the automotive and industrial fields.
Another fast-growing form of the material is
in cores for fiberglass snow skis and tennis
rackets, in which an assembly of facings and
close-out details is placed in a closed cavity
mold and foam injected to form both the core
and the adhesive attachment to the pre-cured
glass fiber skins and various edge details. The
saving in labor over conventional assembly
methods has resulted in rapid acceptance of
the process and the construction of many new
factories.
Foams can also provide special properties
such as insulation or radar transparency, when
used with appropriate facing materials.
The very low cost polystyrene foams are
used primarily in non-sandwich applications,
their role in structural parts for refrigerated
vehicles and buildings having been largely
taken over by the urethanes. The single major

exception to this statement lies in the extensive
use of polystyrene foams as cores in several
thousand amateur-built composite aircraft.
This application was pioneered by Burt Rutan,
in his ’moldless construction’, used in his
series of high performance small aircraft and
the many similar designs offered by others in
subsequent years.
The polyvinyl chloride (PVC) foams, which
made an impact on the transport aircraft
industry as flooring cores, have been largely
replaced by the more efficient high density
aramid honeycombs.
The foam-in-place system of producing
sandwich structures has been used for more
than 35 years, because of its simple concept.
However, users of this system have always
had difficulty with the continuing problem of
producing uniform properties from one mix to
the next and in achieving uniformly high core
and bond strengths to the metal or pre-cured
glass fiber skins. The use of systematic incom-
ing inspection, automatic mixing and
dispensing equipment and, in the case of criti-
cal airframe parts, test coupons, produced
integrally with the basic part, have all helped
to keep the problems under control.
It will be noted that Table 12.1 does not list
the shear strength of many of the various
Roll
HOBE Block HOBE Slice
Expanded Panel
Expansion Process of Honeycomb Manufacture
Corrugated Sheet
Roll Corrugating Rolls
Corrugation Process of
Honeycomb Manufacture
Cove materials 257
foams, even though this value is needed for
sandwich panel design. This property, even
where listed, cannot be considered to be a reli-
able value. The actual value for an application
at hand must be determined for the actual
materials and conditions of use in order to be
considered reliable. When a value for shear
strength is not available, it may be roughly
estimated to be about 0.7 times the compres-
sive strength shown. Even the compressive
strength cannot be considered to be reliable,
however, as many differing methods of mea-
suring this value are commonly used and each
results in a substantially different value
reported.
12.3.2 HONEYCOMB
Honeycomb types in common usage include
products made from uncoated and resin-
impregnated kraft paper, various aluminum
alloys, aramid paper and glass or carbon fiber
reinforced plastic in a number of cloth weaves
and resin systems. Honeycombs based on tita-
nium, stainless steel and many others are used
in lesser quantities. Most honeycomb cores are
constructed by adhesively bonding strips of
thin material together, as shown in Fig. 12.3.
In the case of aramid paper honeycomb, the
c T r
+
I
Corrugated Block
Fig. 12.3 Most honeycomb is
produced by the expansion
process. Actual cell shape
produced by either method
may vary greatly.
258 Sandwich construction

Table 12.1 Properties of several foam materials used as cores*

TYP Compressive
Tensile strength Maximum
strength at 10% deflection service
Density (ASTM 01623) (ASTM 01621) temperature
lb/ft3 kg/m3 psi MPa psi MPa "F "C
ABS
(acrylonitrile
bu tadiene-styrene)
Injection molding
type pellets 40-56 641-897 20004000 13.8-27.6 2300-3700 15.8-25.5 176-180 80-82
Cellulois acetate
Boards and rods
(rigid, closed
cell foam) 6.0-8.0 96-128 170 1.2 125 0.86 350 177
Epoxies
Rigid closed cell, 5.0 80 51 0.35 90 0.62 350 177
precast blocks, 10.0 160 180 1.2 260 1.8 350 177
slabs, sheet 20.0 320 650 4.5 1080 7.4 350 177
Phenolics
Foam-in-phase 'X-1% 5-24 3-17 0.021-0.12 2-15 0.014-0.10
liquid resin 2-5 32-80 20-54 0.1384.372 22-85 0.15-0.58 Continuous
7-10 112-160 80-130 0.552-0.896 158-300 1.09-2.07 service at 145
300
Polypropylene
Pellets 50 801 5500 37.9 7500 51.7 270 132
Polypropylene" 35.0 561 1600 11.03 2100 14.4
Polyurethaneb 1.3-3.0 2148 15-96 0.104.65 15-60 0.10-0.41 180-250 82-121
4-8 64-128 90-290 0.62-1.99 70-275 0.48-1.90 200-250 93-131
9-12 144192 230450 1.58-3.10 290-550 1.99-3.79 250-275 121-135
13-18 208-288 475-700 3.284.83 650-1100 4.48-7.58 250-300 121-149
19-25 30p400 775-1300 5.34-8.96 1200-2000 8.27-13.8 250-300 121-149
Skinned molded
(rigid)
Skin 25-65 400-1041 100-2700 0.68-18.6 40-3000 0.28-20.7 150-250 66-121
Core 3-30 48481 15-1500 15-1500 150-250 66-121
Polyvinyl chloride
Rigid closed cell 3 48 1000 6.90 95 0.65
andup andup
boards and billets 6 96 200 1.38
* Where shear strength and modulus properties are not shown, use a figure of 0.7 times the compressive strength shown
as a first approximation for design feasibility consideration. Always test actual material used for true value of shear
strength and modulus.
a High density, foam, molded, parts and shapes, with solid, integral skin.

Rigid (closed cell) molded parts; boards, blocks, slabs; pipe covering; one-shot, two- and three-package systems for
foam-in-place;for spray, pour, or froth-pour techniques.
 Core materials 259

Table 12.1 Continued

Type Thermal
conductivity Shear Shear
strength modulus
BTU in
h-'Pf2 Wm-' K-I psi MPa psi MPa
~ _ _
ABS
(acrylonitrile
butadiene-styrene)
Injection molding
type pellets 0.58-2.1 0.08-0.30
Cellulose acetate
Boards and rods
(rigid, closed
cell foam) 0.31 0.04
Epoxies
Rigid closed cell, 0.26 0.04
precast blocks, 0.28 0.04
slabs, sheet 0.32 0.05
Phenolics
Foam-in-phase 0.2 1-0.28 0.03-0.04
liquid resin 0.20-0.22 0.03-0.04
0.24-0.28 0.03-0.04
Polypropylene
Pellets 1.05 0.15
Polypropylene" 4.2 0.61
Polyurethaneb 0.11-0.21 0.2-0.4 20 0.14 226 1.56
0.15-0.29 0.02-0.04 90 0.62 1500 10.3
0.19-0.35 0.03-0.05 180 1.24 4500 31.0
0.26-0.40 0.04-0.06
0.34-0.52 0.05-0.07 450 3.1 15000 103.5
Skinned molded
(rigid)
Skin 0.12-0.80 0.02-0.12
Core 0.21-0.55 20-500 225-15 000
Polyvinyl chloride
Rigid closed cell 2.0 at 70 65 0.45 1200 8.3
boards and billets 120 0.83 2200 15.2
* Where shear strength and modulus properties are not shown, use a figure of 0.7 times the compressive strength shown
as a first approximation for design feasibility consideration. Always test actual material used for true value of shear
strength and modulus.
a High density, foam, molded, parts and shapes, with solid, integral skin.
Rigid (closed cell) molded parts; boards, blocks, slabs; pipe covering; one-shot, two- and three-package systems for
foam-in-place; for spray, pour, or froth-pour techniques.
260 Sandwich construction

inherent toughness and abuse resistance of the enced by the properties of the materials from
material makes cores of 1 6 4 8 k g / m 3 (1-3 which they are manufactured. Some of these
lb/ft3) an excellent choice for aircraft cabin differences are obvious in the thermal conduc-
interior walls and ceilings, even with glass fab- tivity information shown in Fig. 12.4 and Fig.
ric-reinforced skins as low as 0.254 mm (0.010 12.5. However, several significant properties
in) in thickness. of honeycomb cores are peculiar to the materi-
Physical and mechanical properties of the als and should be separately noted.
honeycomb core materials are strongly influ-

Thermal Resistance - Aluminum Honeycomb

.028
N

E13021
W
P-=x
&j.014
w
0)
U
007

(4 0
25(1 0) 5 0 (20) 76(30 lO(40)
Core Thickness- cm (in )

Fig. 12.4 Thermal conductivity Thermal Resistance-Non Metallic Honevcomb

70 4
through sandwich panels can be
isolated into the contribution of cu
each component: facings, core $13 53 3
W
and adhesive. The resistances (or 9
reciprocal of conductivity) can 2 35 2
simply be added - including the e
PI
effect of boundary layer condi- U
18 1
tions. The thermal properties of
typical facing materials may be
found in many handbooks.
1 3 (05) 25(10) 3 8(1 5) 5 0 (20 )
Thermal resistance values for Core Thickness- cm (in )
typical core to facing adhesives
are typically 0.03 for film adhe-
sives with a scrim cloth support Effect of Mean TemDerature
and 0.01 for unsupported adhe-
sives. These graphs give the
resistance for aluminum and
non-metallic honeycomb at a
mean temperature of 23.9"C
(75°F). Note that for non-metallic
honeycomb, it has been found
that the cell size is more critical
than core density. The reverse is
true with aluminum honeycomb.
To correct for mean temperature, -1 29 -17.8 93 204
divide the resistance at 23.9"C
(75°F) by coefficient Q.
 Core materials 261

1.2 , I I I I I I I I
1.1

1.o
Y
a .9
8
4:
Y
.e
.7
5
F .6
8 .5
0
0 .4
I 1 I I I
I
I I

Fig. 12.5 Measured core shear strength will vary

1 125 L E KRAFT PAPER,
PHENOLIC RESIN,
1
depending upon the test method, core thickness, & " I N C H XEXAGON CELLS
3003 - H I 9 ALUMINUM
skin thickness and many other factors. The above
curves may be used only for preliminary correction
factors. Physical tests of the final design must be (bl 0
I' I
I
00024 -INCH FOIL
;':INCH

2
I
HEXAGON' C E L L S

3
I I
4
used to confirm actual values obtained, as the CORE THICKNESS (INCHES J

curves shown above are only approximate.

Density
All mechanical properties increase with higher
density, as shown in Fig. 12.6.
Cell shape
All honeycombs are anisotropic and the result-
ing directional properties should be adapted to
the loads anticipated. Figure 12.7shows typical
differences in shear strength for the L and W
directions. In addition, some cell shapes allow
easy forming or curving at a small loss in
strength/weight ratio. This attribute can be of
great importance in manufacturing curved
parts of appreciable thickness.

Fig. 12.6(a) Typical stabilized

compressive strengths.
262 Sandwich construction
0 20 40 60 80 100 120
Density
Fig. 12.7 Plate shear test values may be signifi-
cantly different from test results obtained from
testing beams. Values shown above are typical for
5052 aluminum honeycomb.
Cell shape variations
Cell shape variations may be either furnished
to specification by the core manufacturer, or, in
certain materials such as aluminum, shapes
may be intentionally or inadvertently altered
by the core user. It should be noted that the
under- or over-expansion of the core changes
its cell shape and density. The over-expanded
version of Fig. 12.8(c) changes directional
properties such that the L direction becomes
slightly the weaker of the two major axes.
1 PCF
I L Fig. 12.6(b) Typical 'L' shear
140 160kglm'
strengths.
C D
E F
G H
Fig. 12.8 A few of the many cell configurations in
common usage. 8, G and H are only produced by
the corrugating method. F is a cell configuration
nearly always used in the manufacture of welded
metal honeycomb. C is flexible in one axis, while G
and H are flexible in both axes. A, C and D are
expanded from identical unexpanded slices, A
being normal expansion, C fully over-expanded
and D 50% expanded. B is a reinforced corrugated
core, with an extra layer of uncorrugated web mate-
rial placed between each layer of corrugated web
material. Reinforcing layers may be added in dis-
crete locations or patterns and may be of the same
or different web material or thickness.
 Core materials 263

Since the drop in the L direction strength can

amount to as much as 30%, such changes in
cell shape must not be allowed to occur by
error.

Cell size
Although cell size tends to be a secondary
variable for most mechanical properties of
core materials, it is primary in fixing the
strength level of the core-to-face attachment
(or, more accurately, in fixing the required
lower limit on core-to-panel adhesive weight)
and in determining stress levels at which
intracell buckling or face dimpling of facings
occurs.

Thickness v :
The shear and compressive properties noted
Fig. 12.9 Plate shear test for honeycomb shear
for a 'pecific 'Ore type can Only be strength and modulus 1.27 cm (0.50 in) thick steel
when test methods are 'Pecified and plates are oven-cleaned and may be reused many
controlled and the correct thickness of core is times.
tested. Failure to allow for the effect of thick-
ness can affect observed values by a factor of 4
or more, as noted in Fig. 12.5. It should be
emphasized that the correction factor shown
may be considerably different, depending on
skin material and thickness, as well as the
exact test method used.

Specimen geometry and test method

Like thickness, these must be specified and
carefully controlled in order to obtain compa-
rability -with test values obtained by others.
Shear strength values obtained using plate Fig. l2*l0 Short beam shear test for
core. Note the ample bearing area provided at each
shear test methods of Fig. 12.9 are quite nor-
load and support point to preclude core crushing
mally up to 25% below those obtained when prior to ,-hear failure.
using the flexure method shown in Fig. 12.10.
Both methods are accepted and used and any
lack of understanding of the differences can
Paper honeycomb
lead to monumental, if nonsensical, problems.
It will be noted that the tables of mechanical Paper honeycomb is the first predecessor of all
properties for various honeycombs, Tables the types of honeycomb, having been pro-
12.4-12.12, specify the shear test method used duced for some 2000 years. Early forms were
in producing the data shown. not used as structural cores, but were
264 Sandwich constructiotz
Core materials 265
266 Sandwich construction
m
n
. -
 Core materials 267
x x x x
0000
\ \ \ \
yE z2 z2 z2 z2 a,
6 3
L
268 Sandwich construction
employed as decoration - and are still fre-
quently seen today as seasonal decorations in
department stores in the form of expanded
bells, spheres and so forth.
Current materials used as sandwich cores
are different, in that much stronger kraft paper
is employed and 11-35% phenolic resin is fre-
quently used to improve mechanical
properties, as well as moisture and fungus
resistance. Many variations are available in
cell sizes of 10,13 and 19 mm (%, X and % in) or
even larger sizes. The higher strength versions
are only produced in the smaller cell size, with
the 10mm (% in) cell available as a water-
migration resistant grade meeting military
specification MIL-H-2104Q.
Most applications are found in non-aircraft
uses, where cost saving is the one primary
objective. Usage is growing rapidly in recre-
ational vehicles; for doors, walls and
partitions; for factory produced kitchen cabi-
nets; in packaged patio room additions for
homes; in curtain wall panels; and in bearing
walls for commercial building.
Aluminum honeycomb
This family of materials has been in produc-
tion and growing since about 1947.Aluminum
honeycomb now includes four alloys, at least
five cell shapes and many foil gauges to pro-
vide a range of densities. The alloys generally
available are:
0 3003-H19, the lowest strength of the group,
usually used for non-aircraft applications;
0 5052-H39, the most often used aircraft
grade, available with a corrosion resistant
surface treatment. Mechanical properties
are listed in Table 12.2;
0 5056-H39, the strongest of the regular air-
craft grades, available with a corrosion
resistant surface treatment;
0 2024-T3 or T81, the most heat-resistant alloy
and slightly stronger in some properties
than 5056-H39. Available with a corrosion
resistant surface treatment.
Some of the above alloys are also available as
corrugated, corrugated and reinforced, over-
expanded and flexible cell configurations.
Some have also been produced in a specially
tailored geometry to make all the cell axes lie
on a true radius of a cylinder, a sphere, or
other unique configurations. These same alloy
foils can also be wound as a corrugated spiral
to form a cylinder or tube for very light energy
absorption applications.
The aluminum honeycomb cores remain
the most used, as well as the most versatile of
the various core materials obtainable and are
often found to possess the most favorable per-
formance/cost ratio available. Expanded
aluminum cores commercially available
ranges from a low of about 32 kg/m3 (2 lb/ft3)
to a high of 192kg/m3 (12.0Ib/ft").
Corrugated aluminum cores, however, start at
under 128kg/m3 (81b/ft3) and can be pur-
chased up to 880 kg/m3 (55 lb/ft3). At
densities below 128 kg/m3 (8 lb/ft3) corru-
gated core suffers a serious penalty in shear
properties when compared to expanded core.
Glass fiber-reinforced plastic honeycomb
This family of materials is most commonly
used in electrically sensitive parts, such as
radomes and antennae, or where a heat resis-
tant resin and low thermal conductivity make
it a natural choice. It has also seen distin-
guished service as a matrix for retaining
non-structural ablative materials, such as soft
silicone rubbers or syntactic rigid epoxy
foams, which otherwise could not have been
used effectively as ablative heat shields on the
Gemini and Apollo re-entry vehicles.
Only high temperature phenolic and poly-
imide cores are generally produced. They are
commonly available in cell sizes of 5, 6.3 and
10 mm (K, X and X in) with a 3 mm (% in) cell
available in a bias weave glass reinforcement.
Densities range from 32 to 192 kg/m" (2 to 12
lb/ft3). Mechanical properties of several com-
mercially available glass fiber-reinforced cores
are shown in Tables 12.3-12.6.
 Core materials 269

Table 12.4(a) Properties of glass-reinforced phenolic honeycomb (bias weave reinforcement)*

Conipressiue Plate shear

-~_____. ~~- -.--_____ -. ~

Bare Stabilized 'L' Direction 'W' Direction

Honeycomb
~

__
designation Strength, Strength, Modulus, Strength, Modulus, Strength, Modulus,
material - cell - density__ psi psi ksi psi ksi psi ksi
typical typical typical typical typical typical typical
HFT - 1/8 - 3.0 300p 350p 22p 185p 17P 95P 7P
HFT - 1 / 8 - 4.0 390p 575p 45p 300p 32P 150p 12p
HFT - 1 / 8 - 5.5 52533 960p 67p 425p 42P 225p 17p
HFT - 1/8 - 8.0 1450p 1625p 1OOp 575p 48P 340p 25p
HFT - 3/16 - 1.8 75P 120p 14p 105p 13P 5% 4P
HFT - 3/16 - 2.0 loop 170p 17p 115p 15P 6OP 5P
HFT - 3/16 - 3.0 27513 375p 32p 200p 24P loop 9P
HFT - 3/16 - 4.0 435p 550p 45p 275p 3% 140p 12p
HFT/OX - 3/16 - 6.0 lOOOp 11OOp 67p 290p 13P 335p 30p
* Test data obtained at 0.500 in thickness. Honeycomb is normally not tested for bare compressive strength.

Table 12.4(b) Properties of glass-reinforced phenolic honeycomb (bias weave reinforcement)*(metric)

Compressive Plate shear

~ _~-
_ _____

Bare Stabilized 'L' Direction 'W' Direction

Honeycomb
designation Strength, Strength, Modulus, Strength, Modulus, Strength, Modulus,
material - cell - density kPa kPa MPa kPa MPa kPa MPa
typical typical typical typical typical typical typical
HFT - 1 / 8 - 3.0 2068p 2413p 151p 1275p 117p 655p 48P
HFT-1/8-4.0 2688p 396413 310p 206813 220p 1034p 82P
HFT - 1 / 8 - 5.5 3619p 6618p 461p 2930p 289p 1551p 117p
HFT - 1 / 8 - 8.0 9997p 11203p 689p 3964p 331p 2344 172p
HFT - 3/16 - 1.8 517p 827p 97P 724p 89P 344p 27P
HFT - 3/16 - 2.0 689p 1172p 117p 792p 103p 413p 34P
HFT - 3/16 - 3.0 1896p 2585p 220p 1378p 165p 68913 6%
HFT - 3/16 - 4.0 2999p 3792p 310p 1896p 206p 965p 82P
HFT/OX - 3/16 - 6.0 6894p 7584p 461p 1999p 89P 2309p 206p
* Test data obtained at 12.70 mm thickness. Honeycomb is normally not tested for bare compressive strength.

Aramid paper honeycomb

This is an especially tough and damage resis-
tant product, based on a completely synthetic,
calendered 'Nomex' paper material produced
by DuPont. The core is expanded very much
like aluminum or glass fabric honeycomb and
then dip-coated with phenolic or other suit-
able resin system. The mechanical properties
of the material as a structural core are some-
what lower than aluminum, especially in
modulus, but it possesses a unique ability to
survive overloads in local areas without per-
manent damage. This translates into abuse
resistance when applied to very light interior
aircraft panels or flooring and gives the mate-
rial a competitive edge even at the higher cost
it represents. The base material is relatively
incombustible and the small amounts present
270 Sandwich construction

Table 12.5 HFT glass-reinforced phenolic honeycomb (Fibertruss bias weave)*

~~

Compressive Plate shear __-

_ ~ _ _ _ _ _ _ . ~~~~ _ ~ ~ _ _ _ -
~

Bare Stabilized 'L' _Direction 'W' Direction-~

Honeycomb ~ ~ _ _ ~~ _
drsignation, Strength, Strength, Modulus, Strength, Modulus, Strength, Modulus,
materid - cell - densitu mi asi ksi psi ks i psi ksi
typical typical typical typical typical typical typical
HFT - 1/8 - 3.0 250p 360y 21P 185p 16P 96P 6.4~
HFT - 1/8 - 4.0 460p 530p 45P 310p 25P 150p 9.5p
HFT - 1/8- 5.5 850p 9501) 65P 460p 34P 240p 13.5p
HFT - 1/8 - 8.0 1600p 1750p 95P 600p 43P 340p 20.0p
HFT - 3/16 - 2.0 90P 140p 17P 118p 15p 55P 4.3p
HFT - 3/16 - 3.0 250p 320p 32P 170p 20P 90P 6.5~
HFT - 3/16 - 4.0 460p 530p 45P 310p 25P 150p 9.5p
IIFT/OX - 3/16 - 6.0 l000p 1100p 67P 290p 13P 335p 30.0~
* Test data obtained at 0.500 in thickness. p = preliminary properties

in typical panels result in low volumes of
smoke and gases given off in fire tests. Typical
applications make use of these properties very
effectively.As a consequence, they have grown
to a commercial volume nearly as large as that
of aluminum, for use in aircraft structures.
Uses outside the aerospace industry are lim-
ited due to the high cost of the material, but
despite this it has seen some application in
boat hulls up to 10.2 m (40 ft) in length, as well
as in skis, racing shells and several other prod-
ucts.
Aramid core is normally produced in cell
sizes of 3, 5, 6.5 and 10 mm (%, 36,X and % in),
in densities of 24-192 kg/m3 (1.5-12 lb/ft").
Densities higher than 64 kg/m3 (4 lb/ft3) are
almost entirely used for aircraft flooring.
Mechanical properties of some of these core
materials are shown in Table 12.6.
Carbon fiber honeycomb
Reinforced plastic honeycomb has for many
years employed glass fabric reinforcement,b u t
only rarely employed other fibers. In the past
few years, however, both Kevlar and carbon
fiber have become much more common as
reinforcing fibers for honeycomb. Carbon
fibers only now are beginning to be used in
space vehicles. In addition to this small usage,
however, carbon fiber honeycomb is now used
as the structural core for nacelle assemblies in
the Boeing Model 777 transport aircraft. The
constant pressure for lighter structures in such
designs has led to the use of carbon fiber fac-
ings, which have a potential corrosion
problem when used with aluminum cores.
This concern for corrosion problems has sub-
sequently led to the adoption of a new class of
carbon fiber honeycomb materials for this air-
craft and will possibly lead to further use in
other future designs.
Two types of carbon fiber cores are now
being produced. One is for purely structural
applications, while the other has a require-
ment for heat transfer through the thickness of
the panel. The former type uses only the usual
pan based carbon fibers, while the latter
employs pitch based carbon fibers, which
duplicate the heat transfer properties of the
aluminum core which it replaces. Although
neither of these materials is as yet in large vol-
ume production, the economic impact is
substantial, since these honeycombs are
markedly higher in price than the aluminum
or Nomex cores they replace.
Little data is yet available on these new
cores, but it is likely they will see substantial

use and public scrutiny in the next several
years.
Kevlar honeycomb
This honeycomb has been in use for a number
of years as a core for space vehicle antenna
reflectors. The purpose of the Kevlar honey-
comb is to allow transmission of radio signals
through the panel, while at the same time the
Kevlar facing acts as a partial reflecting antenna
for a different wavelength of a different signal.
Kevlar honeycomb, based on one of several
fabrics woven from Kevlar yarn, is usually
produced in cell sizes of 6.3-9.5 mm (%-% in) .
Usual densities available range from 16 to
64 kg/m3 (14 Ib/ft3).
Kevlar paper honeycomb
In addition to Kevlar honeycomb made from
woven fabric, DuPont has recently introduced
a new honeycomb, based on a Nomex-like
paper, which is entirely composed of fibers
derived from Kevlar. This material has rather
surprising mechanical and physical proper-
ties, with strengths well above both glass and
Nomex honeycombs and dielectric properties
somewhat superior to Nomex. This material is
trade named 'Kortex' and is available in the
usual range of cell sizes and densities.
Because the material is somewhat more
expensive than Nomex, no large scale replace-
ment of Nomex honeycomb appears likely,
although many special purpose applications
have been developed in both air and space
craft.
12.4 ADHESIVE MATERIALS
Adhesives, as they apply to sandwich struc-
tures, constitute a somewhat different family
of materials than those required to bond an
open cellular core to a stiff and continuous fac-
ing. Although these differences are less
important with some of the newer modified
epoxy materials, they remain basic and must
Adhesive materials 271
be understood by the designer and fabricator
in order for the otherwise inevitable problems
to be avoided. Some factors which merit atten-
tion are discussed below.
12.4.1 PRODUCTS GIVEN OFF DURING CURE
Some adhesive types, such as phenolic, give
off a vapor as a product of the curing reaction
and the presence of these secondary materials
can lead to several problems:
0 internal pressure, resulting in little or no
bond in some areas, or 'blisters';
0 core splitting, as the gas forces its way
through the core to a lower pressure area;
0 core movement, sometimes several inches,
resulting in an unusable cured part;
0 subsequent corrosion of core or skins by the
chemical action of the vapor or its residual
condensate.
12.4.2 BONDING PRESSURE
Adhesives such as the phenolics and some
others actually require more than atmospheric
pressure in order to prevent excessive poros-
ity. Certain forms may be suitable for solid
cores like balsa, but cannot be used at all in
open cores such as honeycomb or large cell
foams. Also, most core materials will not alone
withstand compressive bonding loads exceed-
ing a few atmospheres and consequently
cannot be used with any adhesive system
requiring higher pressures.
12.4.3 FILLET FORMING
In order to achieve a good attachment to an
open cell core, such as honeycomb, the adhe-
sive must have a unique combination of
surface tension, surface wetting and controlled
flow during early stages of cure. Controlled
flow prevents the adhesive from flowing
down the cell wall and leaving a low strength
top skin attachment and an overweight bot-
tom skin attachment.
272 Sandwich construction
Loloo
m m m
OOLo
m a m
+ e m
 Adhesive matevials 273
m o o
d N N
o m 0
d m N
m a -
s;
2.N
-..
6
u
u
m
274 Sandwich construction

12.4.4 ADAPTABILITY
The requirements noted above must all be met
while also meeting all the requirements of a
skin-to-skin to skin-to-doubler attachment. In
the case of contoured parts, the adhesive must
also be a good 'gap-filler ' without appreciable
strength penalty, since tolerance control of
details is much more difficult to achieve on
contoured than on flat panels and a greater
degree of latitude for misfit must usually be
allowed.

12.4.5 BOND LINE CONTROL

This is a need which exists because of misfitting
details and is approximately the opposite of
adaptability. It is the capability of the adhesive
to resist being squeezed out from between fay-
ing surfaces when excessive pressure is applied
to a local area of the part during cure. Many
adhesives are formulated to achieve good core
filleting and are subsequently given controlled
flow by adding an open weave cloth or fibrous
web, cast within a thicker film of adhesive. This
'scrim cloth' then prevents the faying surfaces
from squeezing out all the adhesive, which
would result in an area of low bond strength.
12.4.6 TOUGHNESS
The word 'toughness' has many meanings in
the world of adhesives. Usually, it refers to the
resistance shown by the adhesive to permit-
ting bond line cracks to grow under impact
loading. In the area of sandwich core-to-facing
bonds, it refers to the resistance shown by the
adhesive toward loads which act to separate
the facings from the core under either static or
dynamic conditions. It has been found from
experience that greater toughness in the bond
line usually equates to greater durability and
thus to longer service life.
Many types of tests have been devised to
measure toughness, but the most common one
used for sandwich structures is the climbing
drum peel test (Fig. 12.11). This test has the
Fig. 12.11 Climbing drum peel test for adequacy of
skin adhesion. The difference in diameter of the
cylinders to which the straps are attached and the
cylinder to which the skin is attached causes the
drum to rotate clockwise when tension is applied
by the universal testing machine. This arrangement
allows duplication of test results from one shop to
another.
virtue of being easily duplicated, as well as
possessing an obvious relationship to the
toughness whose value is sought. Values of
peel strength will vary considerably, depend-
inn upon:
toughness of the adhesive;
amount of adhesive used;
density of the core;
cell size of the core;
direction of the peel (with or across the rib-
bon direction);
0 adequacy of the surface preparation;
0 degradation of the adherend surface subse-
quent to bonding.
Because these variables can lead to widely dif-
fering peel strengths for the very same
adhesive, all of them must be properly under-
stood and controlled if the peel test is to be
used and its value compared to other test
results.

The peel test is used to control quality
throughout the sandwich industry. Values
obtained, provided the adhesive weight and
core material are in balance, will give indica-
tions of tooling or cure problems and of
adherend surface preparation problems. It is
particularly useful for this when an environ-
mental exposure involving both elevated
temperature and high humidity is interposed
between manufacture and test. It is also adapt-
able to use with nearly any skin material,
except that it becomes impractical with very
thick or very stiff skins.
It can be readily seen that a number of points
of difference separate the sandwich adhesives
from other structural adhesives. Fortunately for
the sandwich user, many adhesives are avail-
able which satisfactorily meet both sets of
requirements. me types available, along with
some salient features, are as follows.
12.4.7 PHENOLICS BLENDED WITH VINYLS,
RUBBERS OR EPOXY
All of these families of adhesives give off at
least some water during cure and are therefore
used only where their high strength, durabil-
ity or high temperature mechanical properties
are essential. Since the out-gassing cure prod-
ucts usually require venting or perforating the
core material and a number of non-out-
gassing, high temperature adhesives have
become available, their use as sandwich adhe-
sives has sharply declined in recent years.
12.4.8 EPOXIES MODIFIED WITH NYLON OR
OTHER POLYAMIDE POLYMERS
These adhesives were the first to have excel-
lent filleting and controlled flow along with
both high strength and high toughness,
although they are somewhat moisture sensi-
tive. Some versions are provided as one side of
a two-sided tape adhesive, in which the other
side is a rubber or vinyl-phenolic, to provide
both excellent peel and durability at the skin
side with excellent peel at the core side.
Adhesive materials 275
12.4.9 NITRILE RUBBER MODIFIED EPOXIES
These make up a broad group of more recent
materials which provide much of the flow and
toughness shown by the nylon-epoxies, along
with the durability and weather resistance of
the vinyl-phenolics. They are the most com-
mon of the 'toughened' thermosetting
adhesives and are usually limited to about
149°C (300°F) service temperature. Some of
these materials routinely achieve shear
strengths of 34500 kPa (5000psi) and most
can be cured over a wide range of tempera-
tures and pressures.
12.4.10 URETHANES
Urethane based adhesives are used in
commercial structures. Both moisture-cured
and two-part systems are available.
12.4.11 OTHER POLYIMIDES,
THERMOPLASTICS AND HIGHLY
SPECIALIZED ADHESIVES
These are used in a number of applications
ranging up to about 371°C (700°F)service tem-
perature, but do not represent either a very
large group of materials or a large volume of
usage. In addition to categorizing the available
adhesives by chemical type, they can be
grouped by the form in which they are avail-
able. Generally these are as follows.
Light liquids, heavy liquids, thixotropic
liquids, pastes, putties, or syntactic foams
Only a few are used as a core-to-facebond, but
many such materials are used in sandwich
construction to splice pieces of core to each
other in order to provide high strength edges,
areas, or surfaces, or to carry shear loads from
fittings, inserts, or end ribs. Most of the mate-
rials so used are epoxies, modified epoxies,
epoxy polyamides or epoxy polyimides.
Curing temperatures vary from as low as
4.4"C (40°F) for some two-part systems up to
276 Sandwich construction
216°C (420°F) for some of the materials
intended for service at elevated temperatures.
Supported films
Films or tapes having a carrier of light glass
fiber, cotton, nylon, or polyester fabric, or
spunbonded synthetic fiber are provided
either dry or with slight to moderate ’tack’ or
stickiness, so that the parts of the assembly
stay in place as they are being assembled.
Unsupported films, containing only the
adhesive
The very low weight films are nearly always
furnished without a carrier, as the weight of
the carrier itself becomes quite appreciable in
very light sandwich structures. They are often
hard to handle and sometimes have bond line
control problems.
Reticulating films
These are intended for use at very low
weights, with the adhesive being melted by
hot air after placing on the core, so that it
draws back to the cell edge and provides
material to form the largest possible fillet
without wasting any on the inside facing sur-
face in the middle of the cell.
Cell-edge adhesive
This is a material pre-placed on the cell edge
by the honeycomb manufacturer to provide
the same results as those produced with retic-
ulating films.
Self-adhesive skins
These skins are usually structural fabrics of
glass, graphite, quartz, or aluminum coated
glass fibers, pre-impregnated with a resin,
which is then cured so that the fiber-filled
resin becomes both the face structure and the
attaching material.
All the above forms of adhesive are in cur-
rent use at substantial volume and most are
available from many sources.
12.5 DESIGNING A SANDWICH
The usual objective of a sandwich design is to
save weight or to increase stiffness or to use
less of an expensive skin material, or perhaps
all three. Sometimes other objectives, such as
reducing tooling or manufacturing costs,
achieving aerodynamic smoothness, reducing
reflected noise, or increasing durability under
exposure to acoustic energy, are also involved.
The designer’s problems sift down to rela-
tively few, such as getting the loads in, getting
the loads out and attaching small or large
load-carrying members, under constraints of
deflection, contour, weight and cost.
Understand the fabrication sequence and meth-
ods. The cost of a sandwich structure is
fundamentally fixed at the design stage and
a considerable difference in cost can result
from alternate solutions to the design prob-
lem. Both of the edge close-out details
shown in Fig. 12.12 perform essentially the
same job at the same weight. Placing the
legs of the channel facing outward instead
of inward saves the cost of two relief cuts
into the core and the very difficult step of
sliding the edge of the core and adhesive
into the channel. Another alternative at
even lower cost for either fixed or simply
supported edges is shown in Figs.
12.13-12.16.
Use the right core. Several densities of core
can be used in a single panel, each appro-
priate to the load carried in the area and
adhesively bonded to its neighbor, as
shown in Fig. 12.17. In many cases, how-
ever, the weight saved in lower density
areas of core is added back in the form of
core splice adhesive weight. Core splices,
such as those shown in Fig. 12.18(b)or (c),
have been used to produce ablative matrix
structures for large re-entry heat shields,
 Designing a sandwich 277

1 (

GOOD
POOR
~ .. .

Fig. 12.12 The square edge close-out shown here using a channel may result in a neat, clean edge, but
requires machining both the top and bottom of the core and squeezing adhesive and core into the channel
during assembly. The alternative shown on the left would be much better.

Densified Core 2

Fig. 12.13 Densified core edge treatment.

DENSIFIED CORE '

HIGH -S TR€NG TH INSERT' EDGE CELLS FILLED'

ME TAL CHANNEL ' FACINGS FORMED '

HIGH-STRENGTH INSERT,

ME TAL CHANNEL ' CRUSHED AND BONDED

HIGH - S TRENGTH INSER T\ r RE/NFORCEMENT

''2
METAL
F O RMEO RING ---.
Fig. 12.14 Several common edge treatments.
278 Sandwich construction

Strong. Special extru-

Strong. Uses standard
sion. Seals can be
angle. Pop rivets to
incorporated.
locate and apply pres-
sure during bonding.

Very strong. Special

extrusion. Difficult to
apply adhesive uniformly
and assemble
Very strong with inside
Low strength. Very low tie-bar. Can include
cost. Inside facing and external seal or gasket.
core scarfed then bent.
Fill corner with epoxy or
foam to stiffen.

Fig. 12.15 Several suggestions for corner designs, edge close-outs and splices.

Ex trurion,
f Weldd

b
\
Locking Bar

Fig. 12.17 Typical core splice using a foam-tape

adhesive. Foaming of the tape adhesive permits a
less-than-perfect fit of core details, but requires that
the core be precisely fixed in position during the
Fig. 12.16 Additional joints and corner treatments. cure to avoid a step in the surface at the splice line.
 Designing a sandwich 279

ACROSS RIBBON 1Wl DIRECTION IN RIBBON /LI DIMCTION

C
Fig. 12.18 Joint A may be formed by simply crushing one piece of glass fabric honeycomb into the adjoin-
ing section. This method will work to some extent with some aluminum honeycombs, but not with most
other core materials. Joints B and C require a perfect match of cell shape and cell pitch and are very diffi-
cult to produce on any realistic and cost-effective basis.

but become prohibitively expensive to pro-
duce for splices more than a few inches
long.
Do not hesitate to use several joining methods
in the same part. Fittings to be included in a
bonded sandwich may be produced from
weldments, forgings or riveted assemblies,
or may themselves be bonded assemblies.
Available adhesives permit secondary
bonding to be performed at temperatures
from 16°C (60°F) up to 177°C (350°F) with-
out degrading the integrity of the
previously bonded sub-assemblies.
Use bolts and rivets for carrying loads (not for
soothing fears). Where space is not available
for progressive doublers or wide-area
bonded overlaps to carry high loads, the
addition of rivets or bolts is sometimes the
only solution. Their use, however, often
results in lower (sometimes dramatically
lower) fatigue life of the structure, in addi-
tion t o increased weight. The use of
'chicken rivets', added for the sole purpose
of appearance, is to be particularly avoided,
since they often defeat much of the advan-
tage which would otherwise result from use
of the bonded structure.
5. Use doublers where needed, instead of a heavier
facing over the entire part. The use of doublers,
although adding labor cost in assembly,
often improves the part quality. Where
skins are formed of glass or graphite
prepreg, the problem is even simpler, since
extra plies can be added to carry extra loads
exactly where and as needed.
6. Use external doublers rather than infernal dou-
blers wherever possible. The use of internal
doublers usually means that a relief cut
must be made in the thickness dimension of
the core to prevent bridging and a conse-
quent unbonded area where the doubler
ends. Figure 12.19 shows a panel where the
loads which can be carried are the same at
each end of the panel. The design detail on
the left end can cost substantially more to
manufacture than that on the right end.
Figure 12.20 shows the same panel with
both ends produced at low cost, while still
achieving an unbroken outer skin line on
one side. In the case of some skin materials,
such as 0.25mm (0.010in) aluminum, or
most weights of pre-impregnated glass or
graphite cloth, it is feasible to use thin dou-
blers without a relief cut in the core, since
280 Sandwich construction
Fig. 12.19 Internal and external doubler treatment.
I
Fig. 12.20 Low cost doubler treatment.
Fig. 12.21 Doublers at a skin splice.
the gap caused by bridging is small enough
to be within the capacity of the adhesive to
fill. Sometimes an extra layer of adhesive
film is added to help. An example of a dou-
ble skin splice using this method is shown
in Fig. 12.21.
1
12.6 STRUCTURAL ANALYSIS FOR SPECIFIC
CASES
The following notations are used in sandwich
design formulas.* This chapter’s formulas are
only for honeycomb beams and columns
which have the same facings on each side of
the core.
 Structural analysis for specific cases 281

E t h2 12.6.1 DESIGN REQUIREMENTS

D = flexural stiffness; D = JL-
2% Sandwich structures should be designed to
Ec = modulus of elasticity of the honey- meet the basic structural criteria listed below,
comb, Pa (psi) when these criteria pertain to the type of load-
E, = modulus of elasticity of facing material, ing under consideration.
Pa (psi) 1. The facings should be thick enough to with-
Gc = shear modulus of rigidity of the hon- stand the tensile, compressive and shear
eycomb, Pa (psi) stresses induced by the design load.
Kb = bending deflection constant 2. The core should have sufficient strength to
Ks = shear deflection constant withstand the shear stresses induced by the
L = beam span length or column height, design loads.
mm (in) 3. The core should be thick enough and have
b = beam width, mm (in) sufficient shear modulus to prevent overall
M = maximum moment, kg/m width (Ib/ buckling of the sandwich under load.
in width) 4. Compressive modulus of the core and the
P = load, kg (lb) compressive strength of the facings should
Pcr= column critical load, kg/m (lb/in) be sufficient to prevent wrinkling of the
P = column facing yield load, kg/m (lb/in) faces under the design load.
9 = maximum shear force, kg/m width 5. The core cells should be small enough to
(Ib/ in width) prevent intracell dimpling of the facings
d = sandwich total thickness, mm (in) under design load.
h = distance between facing centroids, mm 6. The core should have sufficient compres-
(in); h = tc + t, sive strength to resist crushing by design
s = core cell size, mm (in) loads acting normal to the panel facings or
tc = core thickness, mm (in) by compressive stresses induced through
t, = facing thickness, mm (in) flexure.
w = uniform beam load, Pa (psi)
A = maximum beam deflection, mm (in)
,I6 = 1- Poisson’s ratio of the facing material 12.6.2 MODES OF FAILURE
squared = 1- p 2 Typical modes of failure are shown in Fig.
p = facing material’s Poisson’s ratio 12.22.
of = maximum facing stress, Pa (psi)
uy= yield stress of facing material, Pa (psi)
zc< = maximum core compressive stress, Pa 12.6.3 DESIGN STEPS
(psi) 1. Define Zoads. For multi-point loadings, use
zcs= maximum core shear stress, Pa (psi) the formulas in Roark’s Formulas for Stress
and Strain.16
2. Define beam type. The values of Fig. 12.23
The need to be able to accurately calculate the provide the simple starting point for these
exact performance for many forms of sand- calculations. Some care in using the fixed
wich structures had led to the development of end type of support is needed, as in actual
a substantial body of literature on the subject. practice total fixity is not realized and the
This chapter will cover in detail only the com- resulting deflection is greater than that cal-
monly used analyses and will provide culated.
reference sources for a number of others. 3. Determine deflection limitations. For most
applications, the allowable deflection of the
282 Sandwich construction

Facing failure
Initial failure may occur in either
compression or tension face. caused Of =
M
t, hb
~

by insufficient panel thickness, facing I

thickness, or facing strength. Tensile failure

in facing

Transverse shear failure V

= -
Caused by insufficient core strength hb
or panel thickness.

Local crushing of core

Caused by low core compression
strength u = -P
‘ A

General buckling
Caused by insufficient panel
thickness or insufficient core rigidity.

Shear crimping
Sometimes occurs following, and
as a consequence of, general buckling.
Caused by low core shear modulus, PCr= tcGc
or low adhesive shear strength.

Face wrinkling Adhesive bond

Facing buckles as a ’plate on an

elastic foundation‘. It may buckle 1/2
inward or outward, depending on
relative strengths of core in Core comDression EftC
compression and adhesive in
flatwise tension.

Intracell buckling (dimpling)

Applicable to cellular cores only. Faces buckle into
core cell
Occurs with every thin facings and
large core cells. This effect may cause
failure by propergating across
adjacent cells thus inducing face
wrinkling.

Fig. 12.22 Modes of failure in sandwich structures. Sandwich structures must be designed to resist these
modes of failure. Failures may occur which combine more than one of the modes shown.
 Structural analysis for specific cases 283

Maximum Shear
shear deflection
Beam type
force constant
V

I Simple s t m
. .o r t Uniform load 1
1- I f E
8
5
__
384
1
-
8

1 Both ends fixed Uniform load I

I I
I
Simple support

A
IP
Center load
P
-
2
E
4
“ I +
192

1 Both ends fixed Center load 1 1

1
- 1
-
192 4

I I I
Cantilever Uniform load
P = ql

lrrrrrrr

1 Cantilever Triangular load 1 I

I I I

1 One end simply

. _ supported
..
one end fixed Uniform load
PL
8
I

Fig. 12.23 Loaded beam chart, where P = total load (per unit width), L = span, 0,= facing stress, t, = skin
= core stress, compressive,A = (1 -/,L)~facing prop-
thickness, h = centroid distance, zcs= core stress, shear, tcc
erty, E , = modulus of elasticity of facings, Gc = modulus of elasticity of core in shear, Ism,= moment of inertia,
sandwich, s = cell size, Ec = modulus of elasticity of core in compressions, F S = factor of safety, T = total
sandwich thickness (note that P must be determined for a beam unit width). If deflections are critical,
actual deflections should be verified by tests.
284 Sandwich construction

structure is usually limited to L/360. In the shear component should be calculated

some cases, greater deflections may be
used, or, as in the case of snow skis, very
much greater deflections may be a normal 9. Face wrinkling and intracell dimpling. With
part of the function of the structure.
4. Select skin material. Skin considerations
include the weight target, possible abuse
and local (denting) loads, corrosion or dec-
orative constraints and costs. Select 10. Other considerations. Often, honeycomb
standard thicknesses and make the initial
calculation as outlined below. The facing
thickness directly affects both the skin stress
and the deflection.
5. Calculate first approximation. After the first
sandwich thickness, h, is determined,
another selection of t, or E , may be made to
arrive at more desirable or practical values
of h. Most sandwich structures in ordinary
and the core selection may be influenced by
the shear modulus needed.
thin skins, a local failure of the skin in buck-
ling may be encountered. A check on the
afcrit
will determine whether this may be a
design consideration.
panels are supported on more than two
sides. If the ratio of length to width is
greater than 3: 1, the calculations using the
shorter span and designing as a unit beam
are quite adequate. The formulas in Roark16
are useful where the shear deflection may
be ignored, using the following formulas.
t,h2b bt3
-
'sandw,ich
-~
2 '. I solid =-- 12
,

usage are in the thickness range of

1.5-150 mm (0.06-6.00in). So, for plate calculations:
6. Select skin thickness. Keep in mind that mate-
Isolid= 6t,h2
rials such as fiberglass cloth and aluminum
are available in specific, standard thick- Use of these formulas for deflections may give
nesses. After the skin thickness for lower values than actually experienced, since
deflection is selected, it should be checked the shear deflection may be important. Table
for stress. The formula for 6, is used and a 88 of RoarkI6 gives some approximate multi-
factor of safety determined. pliers to use for plates when supported as
7 Select core. Calculate the core shear stress, sc*. noted.
Note that the core strength is not the same in
the L and W directions. Refine the selection,
12.6.4 SIMPLE FORMULAS
including considerations of material compat-
ibility, cell sizes and types. Determine the Bending stress in facings:
corrections needed to account for the effects
M
of thickness on strength, as shown in Fig. a, =
,
~

12.5. Check the factor of safety using the cal- th

culated stress and the corrected allowable where M is determined by Fig. 12.23.
stress. Other considerationsinclude crushing
Core shear stress:
and compression strengths, modulus in
shear, weight and costs. For rolling wheel = -V
loadings, the crushing strength and the skin cs h
thickness are often the most important con-
where V is from Fig. 12.23.
siderations.
8. Check def7ection. For many applications, the Deflection:
calculation of the expected deflection may ~~1x32 K~PL
omit the shear deflection portion. With a A=- +-
very small deflection limitation, with a very E, t,h2 hGc
thick sandwich, or with a very short span,
 Structural analysis for specific cases 285

( K , and K, from Fig. 12.23). material is to be woven roving, polyester and

core to be KI'-3/8-60(25).
For most beams, the second term is relatively
small, but should be checked if deflection is
critical or span is short. Load, P': P' = 120/144 = 0.833 psi

Moment of inertia, sandwich: Span, L: L = 8 x 12 = 96 in

t,h2b
I,, = ~ Kb, Ks, M, V from Fig. 12.23:
2
Face dimpling: Kb = 0.013, K, = 0.125, M = 8, V= 2.

-[I
2E, t,
ufcnt. = 1 ,
Skin, t,: Try t = 0.090 in

Face wrinkling: A, E , for fiberglass use:

E,tc
A = 0.98, E , = 1.85 x lo6.
Calculate h:
Factor of safety:
K,P'L~~P
Allowable or typical stress A=
FS = tPE,
calculated stress
-
-
0.013 x 0.833 x 964x 2 x O.98ll2
12.6.5 SAMPLE PROBLEM: ANALYSIS OF FLAT
0.090 x 96/270 x 1.85 x lo6
RECTANGULAR SANDWICH BEAMS h = 5.518 (round out to 5.5 = panel total thick-
ness, h = 5.41)
Design a flat roof panel for a bus stop. Use a
Try thicker skin t, = 0.150
snow load of 120 lb/ft2. Use a simple panel
with a simply supported span of 0.203 m (8 ft).
h = 0.013 x 0.833 x 96*x 2 x O.98ll2
Deflection is to be limited to L/270 and the fac- 0.150 x 96/270 x 1.85 x lo6
tor of safety is to be greater than 2.0. Skin
= 4.274
Use 4.00 overall thickness, h = 3.850. Since
either construction is practical check out the
skin and core stresses:
P'L2 - 0.833 ~ 9 6 = ~ 1971 psi
Uf = ~

t$Mc 0.090 x 5.41 x 8

Uf =
0.833 962 = 1662 psi
0.150 x 3.85 x 8
te that the skin stresses are quite close;
therefore, the factors of safety would be simi-
lar.
38 000
Fig. 12.24 Schematic diagram of a flat sandwich FS = = 19;FS = 38000 = 23
panel. 1971 1662
~ ~
286 Sandwich construcfion

For core: 12.6.6 ANALYSIS OF FLAT RECTANGULAR

SANDWICH COLUMNS: COLUMN DESIGN
- P'L - 0.833 x 96 = 739 psi EXAMPLE
'rs - 5.41 x 2
or, /
L=Bfi
t
(20.32 cm)
0'833 96 = 10.38 psi
3.85 x 2 +P
Note that the core stresses are quite low and
there is not much difference in the stresses for
the two thicknesses chosen. For KP-3/8-60(25),
W shear strength = 60 psi. From Fig.12.5: thick-
ness factor = 0.42, W shear modulus = 5800. Facings:
Tempered hardboard, = 3600 psi
W, shear, corrected = 60 x 0.42 = 25 psi
p = 0.99
FS = 25/ 10.4 = 2.4.
E , = 0.65 x lo6 psi
The use of KP-3/8-60(25) with a factor of
safety of 2.4 could be marginal, which may Core:
vary from lot to lot of material. The other
properties, compression strength and density Urethane foam, 6 lb/ft3, tc = 3 in
are acceptable. Note that if the core is oriented From Table 12.1:
to utilize the L shear properties, KP-1/2-80(11),
with rCs= 70 x 0.42 = 29.4 might be satisfactory. Lcs = 90 psi
Calculate deflection: L r - c = 170 psi
KbP'L42 KSP'L2
For 5.50 T,A = ~ + ~
Gr = 1500 psi
t,h2E, G'h
Check facing yielding:
-~0.013 x
- 0.833 x 964x 2
0.090 x 5.412x 1.85 x lo6 Pp = 2t,oY= 2(0.25)(3600)= 1800 lb/in

+ - 0.125 x 0.833 x 962 Check general buckling:

5800 x 5.41 E , t,h2
Pcr = X'D (where D =
= 0.377 + 0.032 = 0.0409 in r l n2D
L'+ ~

Note that the added shear deformation is only t,G'

9% of the total deflection.
0.013 x 0.833 x 96j x 2 D = 0.65 x lo6 x (0.25)(3.25)'
For 4.00 T, A = 2(0.99)
0.150 x 3.852x 1.85 x lo6
= 866 872 lb-in/in of width
+ 0.125 x 0.833 x 96:
5800 x 3.85 n2(866872)
PPV=
= 0.447 + 0.042 = 0.489 in ~ ~ ( 8 872)
66
(96)2 + 3.0(1500)
 Manufacturing sandwich stsuctuses 287

= 112 lb/in or 1352 lb/ft temperature (both pressure and temperature

in the precise amounts, at the precise time
Check shear crimping:
required for cure of the adhesive being used);
PCr= tcGc= (3.00)(1500) and the provision for tooling and fixtures to
hold the assembly in the desired shape and
= 3214 l b in/in of width keep all the details in their proper positions
during cure. Many different ways of providing
Check dimpling and wrinkling: these conditions are currently used, from vac-
Since facings are relatively thick and continu- uum bags or simple presses to autoclaves and
ously supported by foam core, dimpling or unit tools, where volume and complexity can
wrinkling will probably not occur. justify them. Most of the equipment is similar
to equipment used in producing bonded struc-
12.6.7 DESIGN CONDITIONS tures or reinforced plastic parts where no
sandwich structure is involved. However,
In-depth treatments for the design conditions bonding of sandwich structures is nearly
listed in Table 12.7 can be found in MIL- always performed at lower pressures than is
HDBK-23I, available from the US Government the bonding of structures which do not have a
Printing Office. low density core and tooling is sometimes
lower in cost as a result. Aside from the need
for lower maximum pressure, there is little
12.7 MANUFACTURING SANDWICH
noticeable difference between a sandwich
STRUCTURES
bonding facility and one which only handles
The manufacture of sandwich structures non-sandwich bonding.
requires three conditions to be met: the appli- A few suggestions can be offered to aid in
cation of pressure; the application of living with the problems of sandwich bonding.

Table 12.7

Subject MIL-HDBK-23 *
CHAPTER
~~
_ _ ~ ~~~ ~~~

Wrinkling of sandwich facings under edgewise load

Dimpling of sandwich facings under edgewise load
Design of flat, rectangular sandwich panels under edgewise compression load
Design of flat, rectangular sandwich panels under edgewise shear load
Design of flat, rectangular sandwich panels under edgewise bending moment 7
Design of flat, rectangular sandwich panels under combined loads 8
Design of flat sandwich panels under uniformly distributed normal load 9
Design of sandwich cylinders under external radial pressure 10
Design of sandwich cylinders under torsion 11
Design of sandwich cylinders under axial compression or bending 12
Design of sandwich cylinders under combined loads 13
Design of sandwich strips under torsion load 19
Design of flat circular sandwich panels loaded at an insert 20
* M1L-HDBK-23 is revised from time to time, with new chapters sometimes added and older material updated. A check
with the Plastics Technical Evaluation Center, US Army Armament Research and Development Command, Dover, New
Jersey, USA, can verify that you are in possession of the most recent revision.
288 Sandzuick construction
1. Make sure the core is properly sized to fit
the space it is intended to occupy. If it has
been stretched a little, to make the distance
from one edge member to the opposite one,
it will probably shrink back as the cure
cycles starts, leaving mysterious voids next
to an edge member. If it is undersize in
thickness at an edge, the adjoining edge
member or fitting will hold the facing away
from the core and result in an unbonded
area.
2. If a honeycomb core is being used, remem-
ber that the adhesive between the core and
the faces will end up much thinner than the
same adhesive between the edges or solid
inserts and the facings. For this reason, it is
common to require the core to be as much
as 0.25 mm ( 0.010 in) thicker than adjoining
solid parts in the same assembly.
3. The elevated temperatures which most
core-to-facing adhesives require for curing
are often inaccurately measured. A good
point to remember is that only the adhesive
being cured can give you the cure tempera-
ture you are trying to measure. Some shops
insert thermocouples directly into the bond
line to determine temperature and then
leave the thermocouple permanently in the
part after cure is completed.
4. Most adhesives flow at an early point in the
cure cycle. At this time, the bond lines will
change in thickness by substantial amounts.
The tooling employed to establish the shape
of the part and hold details in place must
also allow the details to move into their
final cured position. Simple examples are a
hot platen press, in which the platens close
on the sandwich as the bond lines grow
thinner, or an autoclave, in which a flexible
bag follows the details as the adhesive
flows, continuously transmitting the auto-
clave pressure to the shrinking assembly.
Keep in mind that most adhesives are very
weak and crack-prone as they go through
the gel point.
5. Inserts or heavy members being cured as a
part of a very light assembly will heat up
much more slowly, resulting in warpage
problems upon cool-down. Warpage on
very light parts can also be caused by one
side cooling down too fast as a result of
having one side removed from the still-hot
tooling, while the other side continues to
stay at the temperature of the tool. Also one
side, next to the bag may be heating faster
or to a higher temperature than the oppo-
site face, which is in contact with a massive
and still cold tool. Slower heat-up rates or
better heat distribution in the tool design
will help prevent these problems.
6. Be sure to provide a route for the escape of
trapped air and gases from a totally enclosed
part while it is being cured. This is particu-
larly important in parts which are vacuum
bagged to a female tool and cured in an auto-
clave. A coarse cloth 'breather' should be
enclosed inside the bag to prevent the bag
from sealing off portions of the assembly as
pressure is being applied. Critical or expen-
sive assemblies should have several vacuum
lines attached at different points of the bag,
with each monitored separately by a pres-
sure recorder.
7. Caul plates should be carefully matched to
the job they are expected to perform. These
tooling aids are often used to cover the top
of an assembly containing several different
pieces of core, inserts, edges, etc., so that a
thin skin will not push each detail to the
minimum bond line thickness and result in
an uneven outer surface. When the caul
plate is moderately stiffer than the top skin,
the bonding pressure is transmitted more to
the thicker inserts and less to the under-
sized inserts, allowing all of the details to
'float' in the adhesive before cure, resulting
in optimum relative placement of all the
internal details in the sandwich. If the caul
plate is extremely stiff or thick, this effect is
changed to one of simply bridging over the
most oversized details and the danger of
producing voids or unbonded areas over
the thinner details is substantially
increased. Generally, the caul plate should
 Manufact uring sandwich structures 289

not be more than two or three times the

thickness of the sandwich facing material.
CA
Where thicker caul plates are used, the
t
dimensional control over the size of detail
parts in the assembly must be correspond-
ingly better. The advantage of using such a
thick caul plate derives from the ability to
make both sides of a sandwich part have
the smooth appearance usually associated
only with the 'tool side'.
8. Make sure that core, pre-cured or rigid
-
.-

edges, inserts, skins and other relatively

unyielding details assembled in the lay-up
have close enough dimensional control to
allow adhesives or resins to achieve the tar-
get strengths. In simple bonded assemblies,
a tolerance of + 0.1 mm (+ 0.005 in) is neces- Fig. 12.25 Honeycomb carving bits employing a
sary, while assemblies having multiple slitting saw 0.254 mm (0.010 in) thick x 12.5 teeth
layers of prepreg or many layers of thin per cm (32 teeth per in), 50.8 mm (2 in) in diameter
at the cutting edge. Turning at 12 000 to 30 000 rpm,
metal doublers can sometimes be success- these tools leave a smooth, burr-free surface on
fully produced with much less demanding nearly any core material. The coarse teeth on the
dimensional control. tool in the foreground are for the purpose of break-
ing up and removing the excessive amounts of core
in cut depths of 5.08-50.8 mm (0.2-2.0 in).
12.7.1 CORE SHAPING
When core materials must be cut, trimmed,
carved, or shaped, many special purpose tools
are available. Sawing is the most common
machining method, using either conventional
blade tooth patterns, or, for some trimming
operations, a special 'honeycomb band', in
which the blade appears to be running back-
ward, with the teeth sharpened on the back
side, so that each tooth acts as a slicing knife
blade. A different type of saw is also used as a
mandrel-mounted router bit. Such tools,
shown in Fig. 12.25, are very common where
sculpturing of honeycomb or foam is to be
accomplished. Router speeds vary from
1000-30 000 rpm for blade diameters of
1.8-10cm (0.754 in). Roll forming can be
accomplished on metal cores, as shown in Fig. Fig- 12-26Metal honeycomb may be roll-formed
12.26, while non-metal cores must usually be using Ordinary The surface usuallY must
be protected during the operation by inclusion of a
heat formed' In either forming can be loose sheet of thin sheet metal between the core and
much easier if an inherently formable cell con- the outer forming rolls. The tool being used is a
figuration, such as that shown in Fig. 12.8 'Farham Roll', co-ody used in sheet metal
view H, is used. shops.
290 Sandwich construction
Fig. 12.27 Nose radome core assembly, assembled
by edge-bonding together several post-formed sec-
tions of glass fabric-phenolic honeycomb. Nomex
core may also be formed in this manner.
I
Fig. 12.28 Effect of roll-forming on aluminum hon-
eycomb. The core on the left has been roll-formed in
sheet metal forming rolls, while the piece on the
right has not been pre-formed at all. Note the anti-
clastic, or ‘saddle shape’, which the unformed piece
assumes when forced to a cylindrical form.
REFERENCES
1. MIL-HDBK-23, US Government Printing Office,
Washington, DC*.
2. MIL-HDBK-17, US Government Printing Office,
Washington, DC.
3. MIL-HDBK-5, US Government Printing Office,
Washington, DC.
4. MIL-A-132, US Government Printing Office,
Washington, DC.
5. MIL-A-25463, US Government Printing Office,
Washington, DC.
6. MIL-STD-401, US Government Printing Office,
Washington, DC.
7. Adhesive Bonded Aerosvace Structures Standard
Repair Handbook, US’ Government Printing
Office, Washington, DC,
8, Hexcel Corporation, TSB-120.
9. Hexcel Corporation, TSB-123.
10. Hexcel Corporation, TSB-124.
11. Alcore, TR-il2.
12. American Cyanamid, Handbook of Adhesives.
13. Baltek Corporation, Baltek Catalog.
14. Plantema, Frederic J., Sandwich Construction,
John Wiley & Sons, New York. 1966.
15. American Plywood Association, Plywood Design
Specifica tion.
16. Roark, R.J., Formulas for Stress and Strain,
McGraw-Hill, New York, NY., 5th edn, 1975.
17. Timoshenko, S., Woinowsky-Krieger, S., Theoy
ofPlates and Shells, McGraw-Hill, New York, NY.
2nd edn, 1959.
*Publicationsof the US Government may be updated
and revised from time to time. Be sure you have the
most recent edition. This can be checked by con-
tacting the Plastics Technical Evaluation Center, US
Army Armament Research and Development
Command, Dover, New Jersey. The publication
MIL-HDBK-23 was abandoned some years ago.
However, because the information it contained con-
tinues to be needed by designers of spacecraft
structures, the entire publication will in future be
included within MIL-HDBK-17.
METAL MATRIX COMPOSITES
V. I. Kostikov and V. S. Kilin
13.1 INTRODUCTION
Industrially developed countries are sucess-
fully producing materials and shapes based
on metal matrix reinforced with carbon fibers
(MMC). Metal matrix, ceramic and carbon
composites reinforced with both discrete and
continuous reinforcements have been
described’-6. The present chapter will
describe the results of investigations of the
properties and preparation of aluminum/car-
bon composites
MMC production deals with the solution of
specific problems which involve the formation
of useful structural components, with the
attainment of their potential properties. The
first problem is to fill the interfiber space of the
carbon fibrous framework with matrix metal or
alloy. Several molding methods are available.
Optimization of the materials and the
processes for obtaining usable MMC may fur-
ther the use of MMCs in industry. When the
MMC is reinforced with high molecular and
high strength fibers the composite may be very
brittle and can have thermal dynamic incom-
patibility with many metals used as matrices.
MMC production technology is compli-
cated and requires satisfaction of the following
conditions, of which the most significant are as
follows:
1. maintaining the reinforcing fibers’ strength;
2. ensuring a strong bond of fibers with matri-
ces and between the matrix layers;
Handbook of Composites. Edited by S.T. Peters. Published
in 1998by Chapman & Hall, London. ISBN 0 412 54020 7
13
3. providing the correct fiber length, greater
than the critical length;
4. even distribution of fibers in the matrix;
5. orientation of fibers in the direction of the
applied load;
6. achieving the required shape and dimen-
sions of the MMC;
7. obtaining a MMC strength reasonably near
to theoretical.
Contemporary processes for obtaining an alu-
minum/carbon MMC can be divided into
three main types: solid stage, liquid stage, and
solution sedimentation. In the solid stage, the
greatest effort has been spent in obtaining the
MMC by hot extrusion. In this case, a foil, used
as a matrix, is interspersed with carbon fibers
to form a preform. The preform can then be
subjected to optimum pressure, time and tem-
perature in air, vacuum or inert gas medium.
Considering metal bonding in the liquid stage,
chemical bonds predominate; rarely are there
mechanical bonds and there are no physical
bonds7. Strong chemical bonds are possible
because the atoms (or surface) of one sub-
stance come close enough to the surface of the
other (1.5-3 A) to enter the zone of the surface
atoms’ field-of-forces effectivity.
When MMCs are produced by solid stage
methods (diffusion welding, rolling, extru-
sion), it is practically impossible to provide
full convergence of fiber and matrix surface
due to uneven surface contours. Only applica-
tion of extreme external forces makes the
convergence possibleH.This pressure increase
leads to brittle fiber breakage. Also, some
292 Metal inafvix cotnposites

fibers inside the bundle may not be bonded takes place only after the surface catalysis by
with the matrix because of a shadow effect. treatment in an oxidizing medium, sensitizing
Due to the small diameters of carbon fibers and activation of the carbon fibers prior to
and the short distances between them in the proper metallization. The method is complex
tow (about several microns), poor bonding of because of the requirement for a strong, thin,
matrix to the uncoated fibers located deep in well-adhering bond to the carbon fibers with-
the bundle prevents development of their out compromising their mechanical or
potential strength. Also, during the produc- physical properties. A typical treatment of car-
tion of composite material, MMCs based on bon fibers in an oxidizing medium of 65%
metals such as Al, Mg, Ni, Ti, Cu, etc. and rein- solution of nitrous acid for 5 min does not lead
forced with carbon fibers, the components to fiber strength loss. Ions and radical groups
show high reactivity affecting composite per- that have affinity for metal are attached to the
formance. Protective coatings (silicon, degraded surface of the carbon fibers.
titanium, zirconium carbides, and nitrides) on When silicon carbide is used as a barrier
the carbon fibers can prevent these undesir- layer, an oxidizing treatment of the carbon
able effects9J". fibers is not necessary because the barrier
Many MMCs can be made by soaking the coating itself is a good adhesive layer with a
reinforcing fibers in the molten metal matrix. rough surface structure which bonds to fibers
The problems can be solved by application of and nickel coating. In this case, preliminary
a thin, strongly-bonded metal film that allows treatment for all types of carbon fiber tows
the melted matrix material to completely wet and tapes includes only sensitizing with stan-
the fiber. There are several ways to apply these nous chloride solution at 80°C for 10 min and
coatings: stretching fibers through the melt; activation of palladium chloride at 80°C for 5
spraying the molten matrix metal; depositing min. During the sensitizing process,
a metal film from the gaseous phase. However, hydrolized Sn2+ions which have high absorp-
application of a coating at constant thickness tion properties are strongly attracted to the
on the carbon fibers in tows is not always fea- carbon fiber surface. During activation, palla-
sible because of fiber mutual screening. Fiber dium chloride is reduced to metal by the
coating by a chemical method may be more ionic tin bonds formed at sensitization.
effective. Washing of fibers with water follows. The
activated fiber surface is then dried at
60-70°C for 15-20 min.
13.2 CARBON FIBER COATING METHODS
Nickel coatings are applied from a solution
Chemical methods are used to deposit thin of nickel chloride, 50 g 1-l, sodium hypophos-
coatings and improve wetting on filaments in phite, 20 g I-l, ammonium chloride, and 50 g 1-',
carbon tows and tapes . Because of low depo- trisodium citrate at 80°C at pH 8-9. A lustrous
sition rates, chemical methods cannot be used nickel coating is obtained which varies in
for deposition of thick layers of matrix. There thckness from 0.05-2pm at holding time of
are two widely-used methods of deposition. 0 . 1 4 min. An estimate of coating continuity,
and indirect data on coating adhesion to car-
bon fiber by means of a scanning electron
13.2.1 CHEMICAL PRECIPITATION
microscopy, has shown that the coatings are
(ELECTROLESS DEPOSITION)
applied evenly and that the nickel penetrates
Chemical deposition of nickel and copper on the microrecesses of the fiber surface, fully
carbon tows and tapes with various textile replicating it and filling the grooves and irreg-
structures is based on the reduction of metal ularities. In carbon tows every individual fiber
ions from a water solution. Nickel deposition is coated with nickel.

The textile structure of a braided fabric
-
becomes more complicated. Coating thickness
discontinuities may be considerable because
of reduced clearances between fibers in zones
difficult to access and stagnation and poor
solution exchange take place. In these zones,
the solution is fully depleted, while in other
zones, the nickel plating may continue. The
addition of 0.01 g1-1 lead sulfide to the soh-
tion slows the process of electroless nickel
plating and eases the conditions of the forma-
tion of uniform coating thickness. Reducing
the number of individual fibers in carbon tows
to 100 and the number of ends in tows also
help to provide better uniformity of coating
thickness. When 300-fiber, 6 pm equivalent
diameter, twisted tows of bean shaped cross
section were coated, the coating thickness on
the fibers was uneven and varied from
0.2-0.6 pm up to 0.5-1.0 pm at nickel gain in
weight from 0.5 to 1.0 g. (Editor's note: Carbon
fiber tows are not generally twisted and are all
single end in the USA and other countries.)
The thickness of nickel coatings, used for
subsequent impregnation of carbon tows and
tapes with aluminum melts, is usually about
0.5-1.0 pm. The nickel coating obtained by
chemical deposition from solutions does not
diminish the fiber strength.
The chemical deposition of copper is
accomplished at 20°C in alkaline solution that
contains sodium sulphate, formalin, caustic
soda, potassium sodium tartrate, and diethyl
sodium carbonate. At a holding time of 3-6
min, the coating thickness reaches 0.1-0.4 pm.
Before application of copper coatings, the
fibers are subjected to the same preliminary
treatment as the nickel coating.
The more rapid electrolytic method of
deposition should be a more efficient tech-
nique to obtain thick nickel or copper coatings.
However, the electrolytic method may be used
only for building up of the coating layer on
previously electrolessly coated carbon fibers.
Otherwise, the fiber tows will be coated with a
crusty layer from the outside.
Carbon fiber coating methods 293
13.2.2 THERMAL DECOMPOSITION OF
CARBONYLS
Coatings of refractory metals applied to car-
bon tows and tapes by thermal decomposition
of volatile carbonyls in the gaseous phase have
the following advantages: low temperature of
decomposition of carbonyls of some commer-
cially important metals (Cr, Mo, W, Rhs etc.);
high reaction velocity; uniformity of coating
thickness on each individual carbon fiber; ease
of adjustment of structures and properties of
coatings as a result of change of the deposition
conditions.
The thermal decomposition of the metal
carbony is carried out as follows:
Me(CO)n= Me + nCO
In addition to the main reaction, side processes
that cause the presence of admixtures of metal
carbides in the coating can take place. As the
temperature is increased, the possibility of
obtaining pure metal layers without admix-
tures of free and fixed carbon occurs11. To
obtain pure metals with a minimum content of
admixtures, the process should be run at the
highest possible temperature and sufficiently
high vacuum. Some characteristics of coatings
by precipitation from the gaseous phase are
shown in Table 13.1. The type of substrate
heating is usually determined by temperature
requirements, and may be performed by con-
duction, induction, radio frequency or
infra-red radiation.
During the vapor phase of carbonyl decom-
position there are a number of subsequent
processes: vaporization (sublimation) of car-
bonyls, heat transfer, chemical process in the
gaseous phase and substrate, adsorption-des-
orption on the substrate, formation of nuclei
and growth of coating crystals12.Successively
changing the carbonyl vapor feed velocity
(growth of the coating layer from 0.3 to 6-8 pm
h-l) and the temperature of substrate heating
from 300 to 900°C can result in denser coatings,
which will act as barriers excluding direct inter-
action of the matrix and the fiber, with a more
294 Metal matrix composites

Table 13.1 Conditions for production of metal coat- At the initial deposition stages, thin smooth
ings by thermal decomposition of carbonyls from films reproducing the fiber surface are formed.
the gas phase At this point, one of the most important factors
is the selection of an optimal coating thickness.
Metal Heating
This depends substantially on intended use of
coat ing temperature, "C
- _ _ ~ ~ the material. Extremely thin coatings may be
of carbonyl of base entirely soluble in the matrix and incapable of
~.... ~~~~~~ ~~

cu 20 250400 preventing counterdiffusion of the reacting

Au 20 120-150 components and thus may fail to ensure the
V 20 70-100 barrier effect. Thicker coatings reduce the car-
Cr 40 350-700 bon fibers tensile strength, as shown below.
Mo 50 450-700
The estimated strength of carbon fibers
W 70 450-700
Mn 70 110-300 coated with silicon, titanium and zirconium
Te 20 60-70 carbides as a function of the corresponding ele-
Re 70 400-600 ment content is shown in Figs. 13.1 and 13.2.
Fe 25 100-350 The element content is assumed to be equiva-
Ni 20 100-250 lent to the carbide coating thickness, provided
CO 20 180-220 the coating is uniform. The strength change of
co 20 180-200
carbon fibers with a silicon carbide coating
Ru 20 200-300
Pt 100 500-600 derived from the substrate carbon is of particu-
Pt 20 210-220 lar interest [see Fig 13.1, coating deposition
reaction (l)].The strength of carbon fibers (ini-
tial strength 2000 MPa and thickness 25 nm) at
first increases at a coating thickness of 2-5 nm.
porous upper layer, providing the capillary
effect for wetting and improving the fiber
impregnation.

13.3 APPLICATION OF COATING IN GAS

PHASE

A conventional method for the effective pro-

tection of carbon fibers to avoid reaction with
metals is chemical vapor deposition (CVD) or
refractory coatings.
For example, when carbon fiber materials in
the form of VMN grade tow and a carbon tape
'Kulon' are used as a substrate for the coat-
ings, the coating is deposited from an
appropriate gas mixture by one of the follow-
0 2 4 6 8 10
ing reactions:
Si Content, Wt. 0;o
(1) MeCl,+ C -+ MeC +2C1,
(2) MeC1, + CH, -+ MeC + 4HC1 Fig. 13.1 Variation in strength of CF silicon carbide
(3) 2MeC1, + N, + 4H, -+ 2MeN + 8HC1 coating relative to thickness and composition of
steam-and-gas mixture: (1) deposition reaction:
The coating thickness is controlled by the SiC1, + CH, + Sic + 4HC1; (2) 3 deposition reac-
deposition time. tion: SiC1, + C -+ Sic + 2C1,.
 Application of coating in gas phase 295

Fig. 13.2 Relation between tensile strength of titanium carbide and zirconium carbide coated CF and coat-
ing thickness.

This increase may be a result of healing of fiber

surface defects. Then the strength of carbon "E
E
fibers sharply decreases with increasing coat- >
y" 50
ing thickness. In the case of carbides obtained
by the reaction scheme (2), the carbon fiber
r;w
f
strength is stabilized at a certain level when a ??
5 30
definite thickness of the coating is attained. L%
Sa,
The Young's modulus of carbon fibers with cn
a barrier is a structurally less sensitive factor; it -n
0 4 8 12 16
changes quite insignificantly and is usually Si, Zr, Wt. %
somewhat higher than that of the fiber, irre-
spective of the initial coating thickness and "E
E
type. The shear strength of the carbon fiber 40
Y
surface increases, apparently by surface defect
&-
healing and the strong bonds between the car- w
f
bon fibers and the coating (Fig. 13.3)based on ??
8 20
the results of torsion testing. L%
To determine the barrier properties, the a
S
0)
compatibility of carbon fibers having a refrac- 0
tory coating with a metal matrix (AI, Ni) was 0 2 4 6 8
Ti,Wt. %
investigated by an internal friction method9,12
using suitable microcomposites in the form of Fig. 13.3 Relation between torsional strength of
carbon fibers with a double coating. The nickel coated CF and coating thickness.
296 Metal matrix composites

coating was deposited on the carbon fiber sur- not subject to noticeable structural changes
face by CVD from an aqueous nickel salt connected with interactions of the carbon
solution, and samples of the aluminum matrix fibers with nickel or the coatings. For carbon
microcomposite were cut from plates obtained fibers with and without silicon carbide or zir-
by vacuum hot molding or vacuum aluminum conium nitride coatings, the maximum
sputtering. Internal friction is the logarithmic internal friction background is observed at
decrement divided by x: 600°C which indicates the structural changes
to the carbon fibers. X-ray analysis showed the
presence of nickel carbide. For the same car-
(13.1)
bon fibers having no contact with nickel, the
curve was similar to a curve for internal fric-
where A, and A,+I are the amplitudes of the tion change for fibers with titanium and
first and the nth vibration. zirconium carbide coatings.
Compatibility of carbon fiber and barrier The advantages of carbide coatings over
coatings based on silicon, titanium, and zirco- nitride with thicknesses less than 300 nm were
nium carbides, and titanium and zirconium shown when studying the compatibility of the
nitrides with nickel additions (coating thick- coated carbon fibers with an aluminum matrix
ness 50-100nm at up to 1200°C) is shown in (Fig. 13.5).
Fig. 13.4. It can be seen that up to 11OO"C, the Direct investigations confirming the barrier
internal friction background is negligible in coating efficiency have been conducted with
the case of titanium and zirconium carbides. the systems C-TIC-AI, C-Sic-Ni-A1,
This means that in the absence of pronounced C-Sic-Si-A1. The effect of carbide coatings on
maximum and minimum, the carbon fibers are the carbon fibers-aluminum interaction was

280
1

ZrC
Tic

0 200 400 600 800 1000 1200 200 400 600 800
Temperature, "C Temperature, "C

Fig. 13.4 Relation between internal friction back- Fig. 13.5 Relation between internal friction back-
ground of barrier coated CF and temperature in ground of barrier coated CF and temperature in
contact with nickel. contact with aluminium.
 Application of coating in gas phase 297

investigated with nickel and silicon coatings.
The degree of aluminum-carbon interaction
was estimated in terms of quantity of the
obtained aluminum carbide, using the alu-
minum carbide-water reaction.
The results of determining the aluminum
carbide content on carbon fibers with various
coatings, and their tensile strength after
annealing (the aluminum matrix is etched
away) are shown in Table 13.2.
These results suggest a strong alu-
minum-carbon fiber interaction. The
quantity of aluminum carbide is sharply
increased with annealing temperature and
exposure time. However, a Sic coating with a
thickness of only 28 nm decreases the alu-
minum carbide formation by a factor of 1/5.
Doubling the Sic coating thickness inhibits
the reaction resulting in the aluminum car-
bide formation by an order of magnitude.
Subsequent increases of the coating thickness
affect the aluminum carbide formation at a
lesser degree.
Deposition of nickel and aluminum coat-
ings on a Sic barrier layer substantially affects
the carbon fibers-aluminum interaction. These
coatings, dissolving in the aluminum melt,
ensure impregnation of the carbon fiber tows.
However, in the presence of nickel, the resid-
ual aluminum content on the fibers after
annealing at 720°C is increased. This increase
obviously is associated with a nickel-silicon
carbide interaction that results in opening the
fiber surface.
However, the surface layer increases the Sic
barrier properties. The quantity of aluminum
carbide measured after annealing under the
same conditions is decreased down to the level
which can be obtained for Tic coating. This is
associated with the fact that silicon dissolving
in aluminum saturates it and suppresses the
following reaction:
(4) Sic +A1 + (Sic) +Al,C,
To summarize, based on the estimated
strength of carbon fibers with barrier coatings
and their compatibility with aluminum and

Table 13.2 The effect of coating thickness on the aluminium carbide content in the microcomposite A1-C
and CF strength after annealing

Coating appearance and Temperature, AI& content, rng m-= Tensile

thickness "C strength,,
Time, min.
-~ GPa
5 10 20
Without coating 670 10.5 17.9 35.1
720 22.2 44.8 50.9 1.43 (2.80)
770 28.3 47.0 54.5
Sic, 28 nm 670 2.2 2.8 4.3
720 4.9 5.8 6.5 1.96 (2.90)
770 6.2 10.9 17.7
SIC, 56 nm 670 0.6 0.9 1.1
720 0.8 0.8 1.7 2.34 (2.53)
770 1.0 1.4 2.6
Sic, 97 nm 670 0.5 0.7 1.0
720 0.7 0.8 2.0 2.28 (2.43)
770 0.7 1.4 2.7
Sic, 56 nm + Ni, 200 nm 720 1.2 2.7 3.1
Sic, 69 nm + Si, 230 nm 720 0.4 0.5 0.8
Tic, 53 nm 720 0.3 0.5 0.6
Initial CF (without coating) strength shown in brackets
298 Metal matrix composites
nickel, it can be concluded that titanium and
zirconium carbides are preferred for a nickel
matrix, and that silicon and titanium carbides
are preferred for an aluminum matrix with the
coating thickness of no more than 100 nm.
13.4 TYPES OF COMPOSITE STRUCTURES
Typical cross sections of MMC composite
structures are shown in Fig. 13.6. Many types
of continuous length composite structure can
only be produced by continuous casting. In
some cases, it requires a preliminary applica-
tion of a barrier coating on the fibers by means
of chemical deposition from solution or
vapor-gaseous mixtures. It is convenient to
prepare a unidirectional tape for composite
structures by plasma spraying of matrix alloys
on rows of monofibers or taped fibrous
prepegs. In some cases, use is made of a varia-
tion of a hot extrusion treatment compression
method to obtain a taped foil composite struc-
ture reinforced by one or several rows of fibers
and infiltrated tows, as well as of plasma
sprayed or infiltrated tapes. Sheets and plates
are obtained by rolling in a die and extrusion.
The simplest sections can be produced by
bending of rolled strips, and more complicated
1 2
Fig. 13.6 Typical sections of semifinished items of composite materials; (1)filament with metal coatings
and multifilament braids infilitrated with metals; (2) bars reinforced with braids or filaments; ( 3 ) bands
with single-layer or multi-layer reinforcement; (4) pipes and cylindrical housings with longitudinal rein-
forcement; (5) sections; (6) bands and plates.
shapes, by rolling in dies and extrusion. The
hot extrusion, and consolidating in autoclaves
are used for manufacturing cylindrical cases
and tubes with longitudinal and circumferen-
tial reinforcement.
13.5 CONTINUOUS CASTING
Preformed composite MMC with constant
cross section can be manufactured by contin-
uous casting or drawing of fibers through
melt. The principal advantages of continuous
casting are continuity, reduced time of con-
tact of the fibers with molten metals and
minimum unstable period. This method also
results in a high production system, effi-
ciency and reduced capital investment. The
basic expenditures are for control equipment
since the process only requires a common
melting furnace and a foundry crucible,
molding fixture, a magazine of spools with
fibers and a system for transportation of
fibers and handling products. During opera-
tion the melting furnace must be filled with
argon or evacuated. As a result, the cost of the
MMC produced by continuous casting is
close to the cost of the initial fibers and
matrix.
3 4
@
4

The continuous casting method has a num-
ber of advantages from a metallurgical
standpoint since the composite is prepared
without formation of typical oxide inclusions
which are common in plasma spraying and
hot molding. Most investigators have used
vertical techniques of continuous casting, but
there are versions of horizontal drawing of the
fiber through the melt. Before being sub-
merged into the melt, each fiber is detached
from the other fibers to ensure intimate contact
with the molten metal. Then the fibers pass
through the drawing die that determines the
cross section of the preform. The fibers are
drawn with a rate necessary for solidification
of the matrix to fill up the inner space of the
composite preform. For example, in produc-
tion of cast boron aluminum cable, the
drawing rate could reach 900 m/h, but cannot
exceed 450 m/h due to fiber defects.
The continuous casting process can consist
of two stages: the first stage involves the pro-
duction of the composite preform with a small
cross section, essentially a wire, bar or band; in
the second stage, the previously produced
composite preform is integrated into a more
complicated structure with a larger cross sec-
tion. For example, in the course of production
of a boron-aluminum MMC, the most popular
form of the initial composite structure is a bar
of a circular section, containing 16-19 fibers. In
the second stage, the amount of matrix added
into the MMC can be very small to keep a high
volume fraction of reinforcing fibers in the
final product. The two stage process is used
for the production of such profiles as rods,
angle bars, T-beams, I-beams, and lenses.
The composite resulting from cast lamina
may be obtained in one, two or more steps. To
form profiles, particular attention must be
focused on the first stage since it determines
the basic physicomechanical properties, espe-
cially specific strength. Because of the
organization of the liquid phase process by
stages, the amount of manual labor can be
reduced, the equipment simplified and the
dead time due to fiber breaks shortened. Also,
Infiltration under pressure 299
operations with fibers and the procedure for
testing of fiber volume fraction are shortened.
The production of aluminum carbon fiber
for MMC is complicated due to several fac-
tors associated with the carbon fibers. Their
small diameter (6-10 nm), friability, high
reactability and poor infiltration characteris-
tics with aluminum melts at temperatures
below 1030°C are all contributory factors. The
latter two are most important. The danger of
chemical degradation and reduction of fiber
strength due to graphitization and formation
of carbides increases with greater contact
time of the fiber with the melt and with
higher temperatures.
13.6 INFILTRATION UNDER PRESSURE
lnfiltration of fibrous preforms makes it possi-
ble to obtain intermediate preforms and
composite structures of limited size.
Infiltration is accomplished by various means:
by heating the mold containing the fibers and
matrix material in the form of a foil, powder
or coating on the fibers up to above the melt-
ing temperature of the matrix material with
the subsequent shaping of the mold; by sub-
merging the fibers into the melt or filling
molds with the melt in vacuum, protective
atmosphere or air; by vacuum suction of the
melt; by feeding the melt into the mold under
pressure; and by centrifugal casting. In all
types of infiltration, the common denomina-
tor is the presence of the mold with the fixed
fibers. Because the process is long compared
with continuous casting, the fibers should
have high thermal stability in metal melts.
Experiments on infiltration with uncoated
carbon fibers and with nickel plating by suc-
tion or by filling with melted aluminum or
magnesium in vacuum have been unsuccess-
ful due to the failure of the fiber to be
infiltrated at the melt temperatures without
extensive carbide formation. Common draw-
backs of vacuum infiltration of carbon fibers
with aluminum or magnesium alloys are
incomplete infiltration because of nonuniform
300 Metal matrix composites
penetration of the matrix material into the
interfiber spaces, nonuniform package config-
uration and touching and burning of the
fibers where there is no protective coating.
These drawbacks are especially evident in
infiltration of multifilament braids and bands.
Uneven distribution of fibers results in defects
in the form of isolated groups of filaments not
separated from each other by matrix, thus
serving as stress concentrators. The result is
that with an increase in volume fraction of
carbon fibers to more than 30-35%, which
does not increase the strength of the compos-
ite material but starts to reduce it, due to the
greater number of groups of filaments not
infiltrated with the matrix.
To improve infiltration of the carbon fibers
with aluminum melts with metal coatings
(especially nickel plating), conditions must be
chosen to ensure a high rate of flow and to
considerably shorten the duration of time of
contact of the coating with the melt13.The rela-
tionship between the capillary and excessive
pressure and the infiltration angle and volume
fraction of carbon fiber in the molten alu-
minum matrix on the other, taken at a
temperature range 925-1083"C, shows that the
melt penetrates the braids of the fibers only at
a pressure less than 1.1x lo5 Pa. Experimental
testing shows that, under appropriate pres-
sure, the rate of infiltration of fibers with
aluminum melt with an 1%(mass) titanium
additive moves at 0.5 m/s.
The technology of infiltration of carbon
fibers and fabrics with melts using aluminum
has been advanced with application of exter-
nal pressure. However, the best tensile
strength values of the carbon/aluminum
MMC with V , = 4 0 4 0 % are not in excess of
700-800 MPa, whereas the higher values
(1000-1200 MPa) would be expected from rule
of mixtures.
To eliminate the strength drawback, it is
necessary to determine the nature of barrier
ceramic and process metal coatings which
ensure protection (compared with the nickel
plating) and allow effective infiltration of
braids of carbon fibers with aluminum melts
at lower temperatures and higher pressures. It
has been reported that a two layer coating pro-
duced the best results'l; the first layer of
silicon carbide protects and the second layer of
such transition metals as chromium, molybde-
num, tantalum or tungsten which are properly
infiltrated with aluminum improves infiltra-
tion. They also have a lower affinity for carbon
compared to silicon.
13.7 ROLLING IN VACUUM
Nondeforming process methods, including
ionic and plasma spraying and spontaneous
infiltration make it possible to obtain the high
physical and mechanical properties of car-
bon-aluminum MMC. However, these
methods are characterized by low productiv-
ity and high labor input. The formation of the
structure and properties of carbon aluminum
that has been vacuum rolled within the solidi-
fication range of the matrix aluminum-
magnesium alloy has also been studied.
Rolling of the initial billets of carbon alu-
minum was performed on a vacuum rolling
mill with residual pressure Presid = 6.5 x lo-' Pa.
Powder alloys were used as the matrix, the
carbon band, grade 'Kulon' with two-layer
coating (silicon carbide and free silicon) was
used as reinforcement.The temperature condi-
tions of the rolling were characterized as
follows:
where T is the rolling temperature within the
solidificationrange of the matrix alloy; TIlqand
Tsolare the temperatures of the liquidus and
solidus of the matrix alloy.
The amount of reduction of porosity in the
initial porous billets of carbon aluminum was
determined by considering the maximum
spread and extraction of the part of the matrix
alloy from the billet in compliance with the
following formula:
 Rolling in vacuum 301

= 1- [ m c / p c+ (mm- m'J
(13.5)
/~,1/(1.15 1, bo ho) (13.3) where
where Vf is the volume fraction of fibers in the
mc and mm are the masses of the carbon material;
fibers and matrix alloy in the billet; V;" is the volume fraction of the fibers
p, and p, are the densities of the carbon which are not surrounded with matrix
fibers and matrix alloy; alloy;
1, bo h, are the initial values of the length, VF is the volume fraction of the fibers
width, and thickness of the billets; within the volume of the fibrous material
rdrnis the mass of the matrix metal extruded limited by the contours of the fiber braid.
from the billet in rolling. When the metal completely fills the fiber inter-
Since maximum properties of the composite stices and the fibers are completely well
material can only be reached with a 100% fill- distributed in the matrix K and R are equal to 1.
ing of the interfiber spaces inside the braids of Figures 13.7and 13.8show the relationship
the carbon fibers and the fibers must be evenly between factors K and R and the modes of liq-
distributed within the matrix, the filling (K) uid phase rolling for carbon-aluminum. The
and structural evenness ( R ) factors of the processes of filling up of the interstices and
fibrous material are: the formation of a uniform structure are
highly dependent on the temperature and
Vf - vy
K= (13.4) degree of each reduction in rolling. When
Vf there is a low amount of liquid phase, the

Y
c
c
al
0
L
al
Q

0 0.2 0.4 0.6 0.8 1 .o

Temperature Coefficient, q~
Fig. 13.7 Infusion percentage, K of braids CF MCM AI-C for various rolling modes: (1)& = 1.0 EP; (2) E =
0.75 E ~ (3)
; E = 0.5 E ~ growth
; = 6.65 x lo-' Pa.
302 Metal matrix composites

0 0.2 0.4 0.6 0.8 1.o

Temperature Coefficient, y~

Fig. 13.8 Uniformity, R of structure of MCM A1-C for various rolling modes: (1)E = 1.0 eP; (2) F = 0.75 Ep;
(3) e = 0.5 eo; growth = 6.65 X lo-' Pa.

braids of the carbon fiber are sealed without

CR = N - N R (13.6)
filling up of the interfiber spaces. Thus, ?,bn > N
0.6 due to an avalanche-like decreasing level
of hydrostatic pressure at the deformation
point and efficiency of filling up of the braids
cv = N-NV~
(13.7)
N
is reduced. The latter is associated with phys-
ical changes in the billet during deformation where:
from the solid body with limited inclusions of
the solid phase. Increasing the rate of rolling CR is the relative number of the kinked
and increasing the number of the steps to the fibers;
same total reduction improves the conditions Cv is the number of the broken fibers;
for forming a uniform structure in carbon N is the number of the fibers in the specimen;
aluminum, and the factors K and R approach NR is the number of the fibers that have lost
unity. their original cross-sectional shape
The highest quality composite must be (kinked);
sealed. During rolling, within the solidifica- Nv is the number of broken fibers.
tion range of the matrix alloy, the number of During these experiments, it was found that
shrinkage pores obtained in the composite the probability of fibers breaking during solid
requires seal rolling of the matrix in the solid phase rolling can be reduced by increasing
phase. However, the probability of breakage number of steps before sealing.
and kinking of fragile carbon fibers also When these process requirements are satis-
increases. The degree of breakage and kinking fied by rolling under vacuum, carbon
of fibers has been estimated using relative fac- aluminum composite with the following
tors during microstructural research of the structural characteristics can be obtained:
rolling specimens: fiber braids are filled to 95-97'/0; structural

uniformity is 78-94%; and the number of
defective fibers is 4-10%. High quality rolled
carbon aluminum is most dependent on the
percentage of defective fibers. In a 45% Vf
composite, the properties in the direction of
reinforcement are as follows: tensile strength,
825 MPa; bending strength, 1300 MPa; and
the modulus of elasticity is 200GPa. A two
layer protective coating on the carbon fiber,
with a small amount of aluminum carbide
(- 0.1./0), retains the transverse strength of the
reinforced composite (a, = 55 MPa).
Application of a protective chromium coating
on the carbon aluminum by condensation ion
bombardment also increases its resistance to
corrosion.
However, carbon aluminum is somewhat
unsatisfactory in economic terms because of its
inherent problems with soldering, welding and
mechanical connection with other materials.
These drawbacks can be eliminated by
using combined composites of the following
systems: boron-aluminum - carbon-ah-
minum (high compressive strength, good
resistance to erosion); titanium - carbon-alu-
minum, dispersively reinforced aluminum
(filling agent: Sic, A1,CJ carbon-aluminum
(high hardness, transverse strength).
There are specific criteria for production of
such composites using the method of rolling
along the fibers. It is advisable to use some of
these criteria to optimize the manufacturing
process15. The basic requirements for carbon-
aluminum are: sealing of the porous billets
during extrusion; 100% filling of the interfiber
spaces with matrix alloy; provide for compati-
bility; and prevent component oxidation.
Research considering the influence of
rolling manufacturing parameters on meeting
criteria requirements makes it easier to select
an optimum technology for production of car-
bon aluminum. The main feature of this
technology is that rolling is performed over
10-12 steps at a temperature corresponding to
the median value of the solidification range of
the matrix alloy (- 40-50 vol. YOof the liquid
phase). After solid phase additional sealing,
Rolling in vacuum 303
the rolling must be accomplished at a vacuum
of 6.65 x lo-' Pa, and compacting of the initial
powder-like billets of the carbon aluminum
must be performed with rigid, plastically
undeformed casings.
However, this technology is unsuitable for
production of combined composites. For
example, during production of Ti-A1-C by this
technique, intimate contact of the layers of
titanium with carbon-aluminum is not real-
ized; whereas, during rolling of fibrous
material A1-B-C, an intensive interaction of
the boron fibers with the molten aluminum
takes place. Thus, in the production of com-
bined composites, the criterion requirements
are necessary with at least an additional
requirement for intimate connection of the
separate hybrid components. To produce a
diverse combination, such as MCM AIB-MCM
A1-C, the number of requirements doubles.
However, research shows the requirements
can be met by non-traditional manufacturing
approaches.
The combination Ti-A1-C is an example of
the product of such an approach. The bimetal
titanium-aluminum composite can be success-
fully produced by rolling at temperatures of up
to 500°C (932"F), with high degrees of defor-
mation. The requirement for preservation of
fiber continuity and the elimination of the car-
bon-aluminum reaction decreases the
probability of formation of an intimate connec-
tion between titanium and aluminum layers
during production of the combined composite.
Also, during compaction of carbon-aluminum
within the solidification range of the matrix
alloy, the probability of formation of friable
intermetallic layers between titanium and alu-
minum is very high. Thus, the application of
liquid phase methods (infiltration, soldering,
and rolling above the alloy solidus tempera-
ture) makes it possible to obtain a high quality
combined composite. For the combined com-
posite, the following manufacturing methods
were used. The pack billet consisted of layers
of the matrix alloy, titanium foil, and carbon
bands and was heated to a temperature
304 Metal matrix composites
exceeding the liquidus temperature in the vac-
uum chamber of the rolling mill. Preferred
evaporation of magnesium from the aluminum
alloy with subsequent deposition on the con-
tact surface of titanium, as well as
simultaneous infiltration of the carbon bands
took place. After treatment, the billet was
cooled down to the carbon-aluminum com-
pacting temperature and was vacuum rolled.
Deposition of the protective magnesium coat
does not form chemical compounds with tita-
nium. The infiltration of the carbon framework
with subsequent welding-soldering of tita-
nium with matrix alloy during rolling ensures
that bonding bridges are formed during the
liquid phase high temperature contact of com-
ponents at the moment the infiltration is
completed.
Plate and layer reinforced carbon aluminum
with high resistance to corrosion, with trans-
verse strength exceeding that of the aluminum
by 1.5-2.0 times, has been obtained by this tech-
nology. m s composite can also be successfully
attached to titanium structures by soldering or
welding. The strength of the titanium to matrix
alloy bond is higher than the strength of the
bond between the carbon fibers and the matrix
(attempts to peel the titanium result in fracture
between the aluminum and the carbon).
To obtain the combined composite A 1 - K ,
the following ground rules have been estab-
lished: compacting of plasma porous
semifinished boron aluminum items should be
performed in the solid phase at temperatures
exceeding 560°C (1040"F)15; and carbon-alu-
minum should be compacted in the middle of
the solidification range of the matrix alloy. An
alloy of A1 with 10% Mg with a solidus temper-
ature of 510°C (950°F)was used as a matrix for
carbon-aluminum, but a higher temperature
alloy was used as a matrix in the boron-alu-
minum. The assembled pack billets of
boron-aluminum and carbon-aluminum uni-
directional lamina were rolled at a temperature
of 540-550°C (1004-1022°F) for 9-10 steps (the
compacting mode for carbon-aluminum). With
tlus procedure, filling of the interfiber space in
the braids of the carbon fibers, as well as the
infiltration of the porous monolayer of boron
aluminum with molten melt, but without direct
contact with the boron fiber, takes place. After
cooling below the solidus point of the carbon-
aluminum additional reverse rolling results in
preferred sealing of the boron-aluminum.
Analysis of the microstructure and mechan-
ical properties of the obtained material shows
proper weldability and filling of separate
monolayers, with a minimum number of the
broken fibers. This combined composite
shows better mechanical properties than car-
bon-aluminum. Thus, for a one step filling
technique, the combined composite has
10-15% greater tensile strength than the car-
bon- aluminum composite and the transverse
strength was increased by a factor of 2 (20% B).
Combined fibrous dispersively-reinforced
composites AIM-Sic and Al-C-Al,C, have
been obtained by careful selection of the matrix
alloy or by using an alternative manufacturing
processes. For these composites, adherence to
the criterion requirements is relatively simple.
It is possible to produce sealed monobands
from the dispersively reinforced composites
(AI-Sic, Al-C-AI,C,) with subsequent com-
pacting of the composite using the techniques
developed for compacting carbon-aluminum.
Data developed on compatibility of carbon
fibers with barrier (protective) coatings and
aluminum and nickel matrixes, as well as data
on strength as a function of a barrier coating
thicknesses, have facilitated the development
of a number of MMCs.
Properties for some of these MMCs are pre-
sented in Table 13.3. These materials were
made with 'Kulon' carbon fibers with Russian
production barrier coatings. Data on these
fibrous materials both coated and uncoated
are shown in Table 13.4. Figures 13.9 and 13.10
show articles made of aluminum-carbon and
nickel-carbon composites. Although MMC
properties are excellent, higher strength car-
bon fibers will permit further increases of both
specific and absolute strength of the newly
created MMC.
 Rolling in vacuum 305

Table 13.3 Some properties of carbon reinforced metal-matrix composites

Property Matrix
AL-9 AMG-6 Ni cu
__
Filler Kulon Kulon VMN-4 VMN-4
Tensile strength M,,, GPa 2.5 2.5 2.0 1.5
Elastic modulus, min, GPa 40.0 40.0 25.0 23.0
Coating Tic Sic Ti(Zr)C -

Metal-matrix composite

Density, p, kg m-3 2000-2300 2200-2300 5200-5400 5200-5500

Tensile strength, MPa
at 20°C 900-1000 700-900 450-500 400-500
at 400°C 800-900 - - -

at 800°C - - 400-500 -
Bending strength, MPa 900-1050 800-1100 700-900 600-700
Compressive strength, MPa 800-1000 500-700 -
Elastic modulus, E, GPa 270-300 240-270 140-180 120-170
Specific modulus, 135 109 26 23
E/p, m2s-* x lo6

Table 13.4 Some properties of carbon fibers without coating and with barrier coating

Properties VMN4 VMN4SiC VMN4TiC Kulon-Sic

Density, g cm” 1.72 1.72 1.72 1.91
lb in-3 0.062 0.062 0.062 0.069
Filament diameter, pm 6.5 6.5 6.5 6.5
Elongation at break, YO 1.10 1.10 1.10 1.10
Carbon content, wt. YO 298 295 295 294
Coating w/c Sic Tic Sic
Coating thickness, nm - 60-80 50-80 60-80
Specific surface area, m2g-’ 51.0 50.5 50.5 10.5
Longitudinal CTE X 10“ 2.25 (1.2) 2.25 (1.2) 2.25 (1.2) 2.25 (1.2)
at 21°C (70°F)
Tensile strength, MPa (psi) 22000 22300 22300 22500
(290 000) (334 000) (334 000) (363 000)
Tensile modulus, GPa (psi) 2230 2230 2230 2400
(33 x 106) (33 x 106) (33 x 106) (57 x 106)
Typical Strand Properties:
Threads/strand 24 24 24 24
Filaments/ thread 300 300 300 300
Twist, tpm 100 100 100 100
(tpi) (2.54) (2.54) (2.54) (2.54)
Twist / strand - - - 2
Filaments/strand 7200 7200 7200 600
306 Metal matrix composites
Fig. 13.9 Various types of shaped articles made of alu-
minocarbon composites material: (1) shell; (2) tube; (3)
gas-turbine blade; (4) T-profile.
REFERENCES
1. Lee, S.M. International Encyclopediu of Composites.
New York: VCH, pp. 187-358.
2. Fridlyander, I.N. Metal Matrix Composites (Soviet
Advanced Composites Technology Series). London,
Chapman & Hall.
3. Metal matrix composites. The next generation
of high-performance materials. Emerging
Technologies, No 20 Technical Insight Inc.,
Englwood/Fort Lee, NE, May 1986, p. 190.
4. Bunsell A., Gorg, M. Les matriaux composites a
matrice metallique an Japon. Industrie
Ceramique. 1988, No 830,642.
5. Zimick D.G., Koik B.M. Design of thermally sta-
ble graphite/aluminum tubular structures for
space applications. SAMPE Q., 1990, 21(2), 11.
6. Strength optimization of C/A1 metal matrix
composites produced from prepregs. Ph.D.
Thesis. Masson J.-J. DTR-FB-92-39, ETN-93-
94871.1992. p. 110.
7. Ivanov, V.S. (ed.). Aluminium and Magnesium
Alloys, Reinforced Firbres. M. Science, 1974, p. 202.
8. Fukuda, Sh., Matsubara, T., Tokao, Yo. A fabri-
cation process for fiber-reinforced composites
by using a wire explosion spraying method.
Carbon fiber reinforced aluminum preform
sheets. Yosha, 1990,27(1),3540.
9. Dergunova V.S. et al. Protective coatings for car-
bon fibrous materials. In: Anticorrosive Coatings.
L. Nauka, 1983. pp. 164-168.
Fig. 13.10 Ring made of the composite
material nickel-carbon fiber.
10. Clement, J.R., Kock, H.J., Wu, K.T., Spenser,
H.G. Interfacial modification in metal matrix
composites by sol-gel process. Muter. Manut
Process, 1990, 5(1), 17-33.
11. Syrkin, V.G. Chemistry and Technology of Carbonyl
Materials. M. Chemistry, 1973, p. 185.
12. Moskalenko, A.G. et al. Kinetics of carbon fiber
and aluminium contact interaction. Mekhanika
Polymerov. 1977, No 4,4243.
13. Varenkov, A.N., Kostikov, V.I. Vliyuanie
cmachivania grafitovykh volokon na ysloviya
izgotovleniya materialov metodom vakuum-
noy propitki. (Influence of wetting graphite
fibers on conditions of manufacturing of com-
posite materials by using vacuum impregnation
method). In Volokriistye i dispersno-uprochnenye
kompozitsionnye materialy (Fibrous and Dispersely-
Reinforced Composite Materials). M. Science, 1976,
pp.25-28.
14. Shorshorov, M. Kh. et al. Methods of improve-
ment of infiltration of carbon fibers with
aluminium. Adhesion Melts Soldering Mater.
1976, No 1,86-89.
15. Shorshorov, M. Kh. et al. Electronic and micro-
scopic researching of carbonyl metal coatings
carbon fibers for reinforcement of composite
materials. Phys. Chem. Metal Treatment. 1976, No
4,141-143.
CERAMIC COMPOSITES 14
M.F. Amateau

14.1 INTRODUCTION The mechanical characteristics of ceramic

Ceramics generally are compounds of metallic composites are profoundly influenced by the
or non-metallic elements and other non-metals mechanisms of strengthening and toughening.
such as oxygen, nitrogen, carbon and boron. Successful design of ceramic composites
requires an understanding of the role of the
Compared to metals these compounds have
higher melting temperatures, higher Young’s constituents, including reinforcement, matrix
moduli and hardness, lower densities and and interphase, on the these mechanisms. In
lower electrical and thermal conductivities. addition to the properties and form of the con-
Engineered ceramics are used in thermal and stituents, the characteristics of the processing
method can also have a major impact on
structural applications requiring high temper-
ature resistance, high hardness and chemical mechanical and physical properties.
inertness. Applications that exploit the ther-
mal structural properties of ceramic 14.2 CONSTITUENTMATERIALS
commonly include cutting tool inserts, wear
14.2.1 REINFORCEMENTS
resistant components, ballistic armor, heat
exchangers, burner tubes, prosthetics, dental Fibers used in ceramic matrix composites fall
implants, heat engine components and ther- into three general categories based on their
mal barrier coatings. The dominating diameter: monofilaments, textile fibers and
characteristics of ceramics that limit these and whiskers. In addition, reinforcements in the
other engineering applications are their lack of form of particulates and platelets are used in
plastic behavior at room temperatures and ceramic composite designs. The strengthening
their low tolerance to flaws, i.e. low fracture role of the reinforcements in ceramic compos-
toughness, that lead to catastrophic failure. ites is significantly different from that in
Reinforcing ceramics with particles, polymer and even metal matrix composites. In
whiskers, platelets, discontinuous fibers and metal and polymer composites the reinforce-
continuous fibers significantly improves their ments contribute directly to the increase of
strength, toughness and apparent ductility. strength and stiffness by carrying a significant
Composite design can also be used to tailor portion of the load. In ceramic composites the
other important properties such as high tem- reinforcements usually increase the strength
perature strength and thermal shock indirectly by increasing toughness of the
resistance, wear resistance and low friction, matrix. The load carrying capabilities of the
thermal and electric conductivity and thermo- reinforcements are of secondary interest at
elastic proper ties. most. This places special importance on the
whiskers as reinforcements for ceramic com-
Handbook of Composites. Edited by S.T. Peters. Published posites.
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
308 Ceramic composites

Whisker reinforcements that can profoundly influence their interfacial

Whiskers are a very fine filamentary form of a
material. They are usually 1 pm or less in
diameter and up to 200 pm in length. They are
nearly perfect single crystals with strength
properties approaching the theoretical
strength of the material. Figure 14.1 is a scan-
ning electron microscope image of silicon
carbide whiskers. As a reinforcement for
ceramic matrix composites it is their size and
aspect ratio that is most significant to their
strengthening effect.
The whiskers that have recently been com-
mercially available are listed in Table 14.1.
Silicon carbide whiskers obtained from differ-
ent sources have unique surface compositions
Fig. 14.1 Scanning electron microscope image of
Sic whiskers.
Table 14.1 Selected properties of commercially available whiskers',
properties and hence effectiveness as a rein-
forcement in a ceramic matrix.
Surface layers of the whiskers can contain
crystalline SiO, or amorphous S i 4 4 (so-
called 'black g1ass')l. Surface compositions can
also be modified by chemical treatments such
as HF washing.
Ceramic textile fiber reinforcements
Although significant improvement of mechan-
ical properties of ceramic materials can be
achieved by whisker reinforcement, truly
mechanically robust and reliable structures can
only be approached with continuous reinforce-
ments. Continuous ceramic fibers of sufficient
strength and optimum stiffness and diameter
are now commercially available. They are
capable of being filament wound, woven or
braided into textile forms. They are composi-
tional variations of three systems: A1,03, S i 4
and Si-N. Table 14.2 lists the composition and
selected properties of fibers that are commer-
cially or near commercially available.
The usefulness of these fibers can be mea-
sured by their high temperature properties and
their ability to be shaped into complex pre-
forms for subsequent infiltration. A convenient
measure of the ability to handle these fibers for
processing is their critical bend radius, p,, i.e.
the smallest radius that the fibers can be bent
before they fracture. A simple beam strength

Whisker Grade Source Diameter Length Young's Coefficient Density

(mm) (mm) modulus of thermal (g cm-j)
(GPa) expansion
(10-6PC)
Sic SC-9 Advanced Composite 0.6 10-80 600 4.5 3.2
Materials Corp.
Sic Tokamax Toaki Carbon 0.3-0.6 50-200 400-700 5 3.2
Company
Sic XPW-2 Huber Company 0.05-1.0 5-100 600 4.5 3.2
Si,N, SNWB UBE Industries 0.05-0.5 5-100 370 2.5 3.2
A1,0, Catapal XW Vista Chemical 4-7 40-100 400 7 4.0
Company
 Constituent materials 309

Table 14.2 Commercially or near commercially available continuous ceramic fibers

Manufac- Designafion Composition Tensile Tensile Density Diameter Critical

turer strength modulus Cg cm-’) (pm) bend
OMPa) (GPa) vadius
(mm)
DuPont FP >99 a-Al,O, >1400 385 3.9 20 2.75
Sumitom0 Altex 85 A1,03, 15 SiO, 1800-2600 210-250 3.2 9-17 0.53
3M Nextel 73 A1,03, 27 SiO, 2000 193 3.03 10-12 0.48
550
3M Nextel 62 A1,0,, 14 B,O,, 15 SiO, 1750 154 2.7 11 0.48
312
3M Nextel 70 A1,0,, 2 B,O,, 28 SiO, 2100 189 3.05 10-12 0.045
440
3M Nextel 70 A1,0,, 2 B,O,, 28 SiO, 2275 224 3.05 10-12 0.049
480
DuPont FP A1,0,, 15-25 ZrO, 2100-2450 385 4.2 20 1.83
166
Nippon Nicalon 50 Si, 31 C, 10 0 2520-3290 182-210 2.55 10-20 0.36
Carbon
Ube Tyranno Si, Ti, C, 0 >2970 >200 2.4 8-10 0.27
Dow MPS 69 Si, 30 C, 1 0 1050-2450 175-210 2.65 10-15 0.83
Coming
Dow MPDZ 47 Si, 30 C, 15 N, 8 0 1750-2450 175-210 2.3 10-15 0.50
Corning
Dow HPZ 59 Si, 10 C, 28 N, 3 0 2100-2450 140-175 2.35 10 0.33
Coming
Tonen Silicon 60 Si, 37 N, 30,0.4 C 2500 300 2.5 10 0.60
nitride

analysis will show that the p,, can be calculated
by multiplying the failure strain of the fiber by
the radius of the fiber. Thus high strength, low
elastic modulus and fine diameters produce the
most robust fibers. The first successful alumina
based textile fiber was DuPont FP fiber. This
fiber has a very high elastic modulus but its low
strain to failure results in very large critical
bend radius which has limited its application. A
modification of the all alumina fiber by adding
partially stabilized zirconia, the DuPont FP 166
fiber, has reduced the critical bend radius by
one third. However, only the silica modified
alumina based fibers such as the 3M Nextel
fibers and the Sumitomo Altex fiber have criti-
cal bend radii of about 0.5 mm.
Numerous studies have been performed on
these fibers to determine their strength and
modulus retention after heat treatment. These
studies are critical to developing proper com-
posite fabrication methods since almost all
processing techniques require high tempera-
ture processing. Both FP and PRD166 fibers
can be heated to 1000°C before any serious
reduction in strength occurs3.The boria modi-
fied alumina-silica (Nextel 312) and mullite
compositions (Nextel 440 and Nextel 480) are
also degraded with high temperature heat
treatments as seen in Fig. 14.24.The high tem-
perature degradation in strengths and elastic
moduli of the boria modified alumina silica
bases fibers are summarized in Table 14.3. The
retention of properties at high temperatures
following the relative degree of crystallinity
among the three grades with Nextel 312 being
the least crystalline and Nextel 480 being the
most crystalline.
Strength and Young’s modulus at tempera-
ture of the Sumitomo alumina silica fibers has
310 Ceramic composites

4 480
-*-(===t-A
1oOO- alr
hydrogen
L. '"r=
vacuum

Fig. 14.2 The effect of heat treatment temperature on the strength of alumina and mullite fibers (440 and
4800)4.

Table 14.3 High temperature degradation of boria modified alumina silica fibers4

Property Benchmark Comparative temperature ("C)

~.
Nextel 3 12 Nextel 440 Nextel 480
Strength after heat treatment 50% of initial
in air >1300 1400 >1400
in hydrogen 1200 1100 1200
in vacuum 1200 1350 1400
Hot strength 50% of initial 1000 1120 1200
Hot elastic modulus 50% of initial 950 1000 1250
Creep rate 10-4/h at 69 MPa 800 1010 1190

been measured by Bunsel15u p to 1200°C. Both
the strength and elastic modulus begin to
degrade at 800°C while above 1000°C the
properties drop significantly.
During the last 20 years there have been
significant advancements in the development
of a silicon carbide based textile fiber for com-
posite reinforcement. All commercially
available fibers in this category contain oxy-
gen but can also contain nitrogen and
titanium. Nicalon fiber manufactured by
Nippon Carbon Company and marketed in
 Constituent materials 311

the USA by Dow Corning Corporation is by Monofilament reinforcements

far the most commercially developed. X-ray
Monofilament Sic and boron fibers are pro-
diffraction analysis indicates that Nicalon
duced by chemical vapor deposition onto a
consists of ultra fine p-Sic particles dispersed
fine substrate filament. For the case of Sic
in a matrix of amorphous SiO, and free car-
fibers the core is 37 pm amorphous carbon fil-
bon6. Nicalon has excellent resistance to
ament, while for boron a 13 pm tungsten wire
thermal degradation in argon and air expo-
has been commonly used. The principal
sure at temperatures to 1000°C for as long as
advantage of monofilament reinforcements
100 h7.The loss of tensile strength for Nicalon
are their ability to tolerate some degree of sur-
by exposure to temperatures to 1400°Cin both
air and a r m n are nrewnted in FiP 14 7 face reaction with the matrix during
fabrication or high temperature service. These
fibers can be infiltrated by a number of pro-
cessing methods including powder sintering,
- 3 - powder hot pressing, plasma spraying and
0" t melt infiltration. These fibers are limited to
9.
b structures with relatively simple shapes such
d as sheet, plates and large diameter cylinders
g 2 - because of their large critical bend radius.
g!
r
n Table 14.4 lists the properties of these fibers.
-
Q,

e l - Table 14.4 Properties of monofilament

f reinforcements
'Original fiber
I I I I I I I I .
Boron SCS-6
0
(4 Manufacturer Textron Textron
Composition B Sic
Tensile strength (MPa) 2.5 4.3
Tensile modulus (GPa) 400 427
Density (g ~ r n - ~ ) 2.5 3
0 0 Diameter (pm) 140 140
Critical bend radius (mm) 11 7

14.2.2 MATRIX MATERIALS

0'O\14000C '0
The selection of matrix materials for ceramic
composites is strongly influenced by thermal
stability and processing considerations. The
properties of matrix materials commonly used
in ceramic composites are shown in Table 14.5.
0 These include oxides, carbides, nitrides,
1 10 1d 1o3
borides and silicides. The first indication of the
Heat treatment time, t (h)
ability of a material to resist high temperature
(b)
service is melting temperature. With the
exception of glass ail these materials have
Fig. 14.3 Loss of strength of NicalonTMafter expo- melting temperatures above 1600°C. As the
sure to (a) argon and @) air at temperature to melting temperature increases the ease of pro-
14OO0C7. cessing decreases.
312 Ceramic composites

Table 14.5 Properties of typical ceramic matrix materials

~~

Materials Young’s Poisson’s Modulus of Fracture Density Thermal Me1t ing

modulus ratio rupture toughness (g expansion point (“C)
(GPn) (MPa) (MPa m”?) (10-6PC)
-. __
LAS 117 0.24 138 2.42 2.61 5.76 -
Pyrex 48 0.20 55 0.08 2.23 3.24 1252
Alp, 345 0.26 483 3.52 3.97 8.64 2050
Mullite 145 0.25 186 2.20 3.30 5.76 1850
ZrO, PS 207 0.23 648 8.46 5.75 7.92 2760
ZrO, FS 207 0.23 248 2.75 5.56 13.5 -
TiO, 283 0.28 83 2.53 4.25 9.36 1849
Si,N, SN 310 0.24 496 5.60 3.18 3.06 1870
Si,N, RB 165 0.24 303 3.41 - - -
Si,N, HP 310 0.24 827 5.60 3.19 3.06 1870
SiOz 76 0.16 - 0.77 2.20 0.54 1610
Sic Sn 331 0.19 386 4.94 3.21 4.32 1980
Sic HP 414 0.19 462 4.94 3.21 4.32 1980
290 - 310 - 2.41 3.06 2350
B4C
TiB, 552 0.20 896 6.92 4.62 8.10 2900
Tic 427 0.19 248 - 4.92 8.46 3140
TaC 283 0.24 200 - 14.50 6.66 3880
Be0 359 0.24 234 - 3.00 5.76 2530
wc 669 0.20 - - 15.80 4.50 2870
103 - 262 3.85 5.21 7.56 2435
Cr $4
Cr& 386 0.20 - - 6.70 9.67 1890
34 - 76 - 1.94 6.66 2982
BNL
76 - 110 - 1.94 0.36 2982
BNII -
NbC 448 0.21 - 7.82 6.66 3499

Mechanical and chemical compatibility of the 14.3 PROCESSING METHODS

matrix with the particular reinforcement ulti-
Processing of ceramic composites can be per-
mately determines whether a useful
formed by solid, liquid, or gas phase
composite can be made. For the case of
processing of the matrix material to achieve
whisker reinforced composites the chemical
infiltration of the matrix around the reinforc-
reactions with matrix are particularly critical
ing phase. The goals in processing ceramic
since even minor reactivity can consume the
composites are to achieve minimum porosity
entire reinforcement. Large differences in the
with a uniform dispersion of the constituents
coefficients of thermal expansion between
and controlled bonding between the reinforc-
reinforcement and matrix can lead to large
ing phase and the matrix.
residual stresses during the fabrication and
ultimately result in serious degradation of
mechanical strength. Small or optimum differ- 14.3.1 POWDER PROCESSING
ences can be beneficial to mechanical Fundamental steps in processing ceramics
properties by placing the weaker constituent
composites from powdered constituents are:
in compression or by inducing crack deflection
between reinforcements. 0 powder selection;
0 powder characterization;
0 agglomerate reduction;
 Processing methods 313

constituent mixing; To minimize voids and interfacial weakness

green body fabrication; and maximize the toughening effect of the
green dressing (machining and gate reinforcing phase, a uniform finely dispersed
removal); mixture must be produced. Arranging the con-
binder removal; stituents to minimize free space between them
consolidation and densification; is referred to as ’packing’. When the con-
final dressing (burr removal); stituents are not effectively packed,
inspection. subsequent densification becomes difficult,
requiring higher pressing temperatures, pres-
The selection of constituent powders is the
sures and duration. Both constituent shape
first step in composite design and considera-
and particle size difference can affect packing.
tion must be given to chemical, mechanical
Optimum packing occurs when the particle
and thermoelastic compatibility between the
size distribution contains 30 vol. % of very
constituents as well as the desired final
small particle and 70 vol. % of large particles’.
mechanical and physical properties of the
If uniform round fibers (or whiskers) are per-
composite. In addition to the obvious problem
fectly aligned in a closed packed array then
of reaction between constituents, other incom-
matrix particles approximately 0.15 times the
patibilities such as large differences in melting
fiber diameter would theoretically fit in the
temperature of matrix and reinforcement can
interstices.
preclude successful processing. Thermal
Most ceramic powders can be comprised of
expansion mismatch between constituents can
a mixture of primary particles and agglomer-
cause premature failure in them or at their
ates. Agglomerates are primary particles
interface.
bonded by surface chemical forces, electrosta-
The rational selection of constituents usu-
tic forces or solid bridging. In order to produce
ally requires knowledge of certain physical
a finely dispersed, homogeneous mixture of
characteristics such as particle size distribu-
matrix and reinforcement successfully, the
tion, shape, specific surface area, bulk density,
agglomerates must be reduced. A typical
electrical charge, impurities, etc. The ultimate
agglomerate (mullite in this case) is shown in
aim of such constituent characterization is to
Fig. 14.5. The agglomerate is 8-9 ym in diame-
predict the final characteristics of the ceramic
ter while the constituent primary particles
composite, as shown schematically in
range from 0.1 to 1.5 pm. To uniformly incor-
Fig. 14.48.
porate 0.5-1 ym diameter whisker or particles,

MILL TIME LUBRICANTS

Fig. 14.4 Use of powder characterization in process control8.

314 Ceramic composites
Fig. 14.5 Typical agglomerate found in mullite powders.
the large agglomerates must be broken down
by mechanical action or chemical treatments if
the agglomeration is due to surface forces. If
the whiskers are robust or some degree of
whisker breakage can be tolerated, both
agglomerate reduction and constituent mixing
can be accomplished simultaneously by ball
milling.
Organic binders are usually mixed with the
particle-whisker mixture for near-net-shape
processing by a variety of cold forming opera-
tions including uniaxial pressing, cold
isostatic pressing, tape casting, extrusion,
compression molding and injection molding.
The ceramic preform after cold consolidation
is referred to as the 'green' form. The part in
the green form can usually be machined with-
out damage. In this state additional
near-net-shape processing can be applied such
as gate removal and machining.
Final consolidation and densification is per-
formed at high temperatures. Three of the
most common methods are sintering, hot (uni-
directional) pressing and hot isostatic
pressing. For low fiber or whisker contents
(5 % or lower) sintering may produce satisfac-
tory results. For complete densification of
even low fiber volume fraction composites,
sintering may impractical due to excessive
temperatures and durations. For high fiber or
whisker volume fractions, hot pressing and
hot isostatic pressing are the only effective
methods for densification. Table 14.6 shows
the effect of hot pressing time and temperature
at 31 MPa pressing pressure on the theoretical
density of Sic whisker-Al,O, composites for
various vol.% whiskers. Theoretical densities
of over 99 vol.9'0 can be achieved in unrein-
forced A1,0, at 15OO0C, in lO%SiC whisker
composites at 1650°C and in 2O%SiC whisker
composite at 1800°C10.
14.3.2 LIQUID PROCESSING
When high temperatures and mechanical
forces are used to consolidate composites from
the powder, the optimum strength properties
can be sacrificed. Reducing processing tem-
perature, time and pressure can minimize
damage to the reinforcements but fully dense
 Processing methods 315

Table 14.6 Effect of processing parameters on the theoretical densities of Sic

whisker-Al,O, composites pressed at 31 MPa pressure'"

Vol. % Pressing temperature Pressing time Density Densify

zuh iskers ("C) (mid (g cnz-?) (% theoreticnl)
0 1500 60 3.95 99.1
10 1500 35 3.78 96.7
10 1650 60 3.89 99.5
20 1500 120 3.68 96.1
20 1650 60 3.72 97.1
20 1725 60 3.78 98.6
20 1800 25 3.81 99.5

or near-fully dense composites cannot gener-
ally be produced. Processing by infiltration
with a molten matrix would be an ideal way of
minimizing mechanical damage and still
achieve fully dense structures. The melting
temperatures of ceramics used as matrices in
composites limits the general use of melt infil-
tration as a viable processing route. However,
by careful tailoring of the matrix and the use of
innovative in situ reaction techniques, melt
infiltration has been successfully utilized to
fabricate ceramic composites.
Glass and glass-ceramic matrices have been
successfully infiltrated in the liquid form into
fiber preforms by 'matrix transfer mold-
ing'".The high temperatures required to
achieve the appropriate fluidity of the matrix
limjts the available fiber-matrix compositions
to only those with low mutual reactivity. Other
matrix materials such as CaSiO,, SrSiO, and
SrO~Al,O;SiO, were infiltrated into Sic pow-
der preforms with and without Sic whiskers
with resulting open porosity of about 1%12.
Recently considerable attention has been
applied to directed melt gas-metal reactions
which produce ceramic matrix composites
directly from the liquid metal13.14. Both metal
oxide matrix and metal nitride matrix com-
posites have been produced by this technique.
Net shape composites can be processed at tem-
peratures of the melting temperature of the
metal. The commercial development of this
processes is called the DIMOXTMprocess of the
Lanxide Corporation. In this process oxidation
or nitridation occurs on the surface of the
molten metal forming a layer of solid ceramic.
The layer thickens as the molten metal wicks
up between the grains of the ceramic. A
schematic representation of the process is
shown in Fig. 14.614.The phenomenon is made

Reinforcement preform

Reinforcement preform
entrapped in solid
reaction product

Fig. 14.6 Directional metal oxidation method for processing ceramic composites4.
316 Ceramic composites

possible by dopants which modify the surface 14.3.3 VAPOR PROCESSING

energy between the phases. For instance, if the
grain boundary energy, yB, is less than twice
the energy of the solid-liquid interface, ysI.and
the surface energy of the solid-liquid inter-
face, ysL is greater than surface energy of the
solid-vapor interface, ysv, thickening of the
oxide (or other reaction compound) layer does
not take place. By reversing the relative values
of the surface energies, (i e, yB > 2ys1. and ysr <
ysv) as illustrated in Fig. 14.7the unstable grain
boundary permits wicking of the liquid metal
through the grain boundaries of the reaction
product phase'-'.
Application of this technology to ceramic
matrix components is achieved by allowing
the reinforcement preform to float above the
liquid metal bath for infiltration of the molten
metal. A growth barrier can surround the rein-
forcement preform to produce practical net or
near net shape component^'^, 16.
The infiltration of the reinforcing phase by a gas
that decomposes to form the solid matrix phase
is generally referred to as 'chemical vapor infil-
tration' (CVI).Various carbides, nitrides, oxides
and boridesI7 as well as unreacted carbon'*
have been deposited on silicon carbide-based
yam fibers (e.g. Nicalon and Tyranno fibers),
oxide based fibers (e.g. Nextel fibers) carbon
yam fibers and Sic whiskers. Silicon carbide is
one of the most commonly applied matrices
using CVI. Methyltrichlorosilane is reacted
with hydrogen on the surface of the fiber to
deposit silicon carbide. A typical reaction for
this process is19.
CH,SiC1, + H, + Sic + 3HC1 +H,
This reaction can take place by conventional
chemical vapor deposition (CVD) at tempera-
tures of 1000-1400°C. Silane-hydrocarbon
(SiH,-C,HJ mixtures can be used to deposit
Sic at temperatures below 500°C by plasma
assisted chemical vapor deposition (PACVD).
Table 14.7 lists some of the more commercially
important matrix materials that can be applied
by conventional CVD. A more complete list of
ceramic materials produced by both conven-
tional CVD and PACVD can be found in
reference (20).

I Molten Metal I Table 14.7 Ceramic materials formed by CVI

processes2'

Matrix Reactant Reaction

ceraTnic gases temperature ("C)
~ ~~~

Tic Tic,-CH,-H, 900-1000

Sic CH,SiCl,-H, 1000-1400
B,C BC1,-CH,-H, 1200-1400
TiN TiC14-N2-H, 900-1000
Si& SiCl,-NH,-H, 1000-1400
I Molten Metal I BN BC1,-NH,-H, 1000-1400
A1N AlCl,-NH,-H, 800-1200
*1,0, AlCl,-CO,-H, 900-1100
SiO, SiH-C0,-H, 200-600
Fig. 14.7 Mechanism of directed metal oxidation TiO, TiC1,-H20 800-1000
growth14.(a) no growth due to stable grain bound- ZrO, ZrC1,-C0,-H2 900-1200
ary; (b) oxide growth mechanism with unstable TiB, TiC1,BC13-H, 800-1000
grain boundary. WB WC1,-BBr,-H, 1400-1600
 Design considerations 317

The main drawbacks for processing com-
posites by CVI are the high processing time
and costs. Since the deposition occurs most
rapidly on the outer surfaces, the internal pas-
sages can be blocked off long before full
densification is complete. It is usually neces-
sary to interrupt the infiltration process to
grind the surfaces in order to reopen the gas
access to the fibers or preform in the center of
the part. Residual porosity of 10-20% with less
than 10% open porosity are typically
obtainedz1.
Two basic methods of CVI are isothermal
processing and forced flow/thermal gradient
processing. In isothermal processing the fiber
preform is heated by radiation from the walls
of the furnace (so called ’hot wall reactor’) or
by inductively heating a carbon mandrel on
which the preform is placed. In both cases the
decomposing gases are allowed to diffuse
through the fiber preform. In the forced
flow/ thermal gradient method the reactant
gases are forced through the fiber preform
retained in a graphite holder with a sharp
thermal gradient maintained by water cooling.
A schematic diagram of the forced flow/ther-
mal gradient method is shown in Fig. 14.8.
14.4 DESIGN CONSIDERATIONS
The approach to designing ceramic matrix is
constrained by the brittle nature for both the
matrix materials and reinforcements used.
Unlike polymer matrix composites and even
metal matrix composites, the rationale for
design of ceramic composites is to impart
toughness in a structure that would have unac-
ceptable toughness as a monolithic ceramic”.
Design methods are unique to the form of the
composite, depending on whether continuous
unidirectional reinforcements, discontinuous
reinforcements or multi-layer, multi-directional
reinforcements are being considered. As a start-
ing point in the design of continuous

Exhaust aas
Heating element

Perforated lid

--- Infiltrated preform

Fibrous preform

Reactant gases
Fig. 14.8 Forced flow thermal gradient method for CVI processingzo.
318 Ceramic composites

unidirectional ceramic composites, the rule-of-strength over the range of reinforcement vol-
mixtures can be used to calculate elastic and ume fractions will depend on the relative
thermoelastic properties of the composite. fracture strain, strength and stiffness of the
Strength properties of the ceramic matrix com- constituents. The relative fiber and matrix
posites are poorly predicted by the stress-strain curves and strength prediction of
a composite consisting of a high stiffness, high
rule-of-mixturessince flaw sensitivity and rein-
forcement-matrix bond strength are not strength fiber in a lower stiffness, low strain to
addressed by these tecluuques. Rule-of-mix- failure matrix is represented in Figs. 14.9(a)
tures properties are less important in and 14.9(b),respectively. There are many such
discontinuously reinforced ceramic composites fiber-matrix combinations that have this rela-
since toughness is strongly controlled by the tive behavior as the examination of Tables 14.2
interfacial properties. and 14.5 will reveal. For instance if Nicalon is
selected as the fiber then the selection of mul-
lite, lithium alumino silicate (LAS) or Pyrex
14.4.1 DESIGN OF CONTINUOUS
glass, for the matrix meets the requirement.
UNIDIRECTIONAL REINFORCEMENT
Selecting Sic monofilament produces this case
COMPOSITES
for almost all matrix materials listed in Table
The Young’s modulus of unidirectional contin- 14.5 with the exception of TiB, and Tic. The
uous fiber ceramic composites Ec is composite strength in such a system should
satisfactorily predicted by rule-of-mixtures: increase at a rate predicted by the linear rule-
of-mixtures based on the strength of the
Ec = E , V , + Em V, matrix and the stress on the fiber at the frac-
ture strain of the matrix, a;. At fiber fractions
where E , and Em are the Young’s moduli of the to V,,,, failure of the matrix constitutes failure
reinforcement and matrix respectively and V , of the composite. The behavior of the compos-
and Vm are the respective volume fractions. ites with fiber fraction below Vcr,thave simple
When there is a high bond strength between linear stress-strain behavior to failure. Above
the fiber and matrix, prediction of composite this fiber fraction the matrix breaks before the

% Strain 0 Vcrit 1
Fiber Fraction
(b)
Fig. 14.9 Strength prediction for high stiffness, high strength fiber and a lower stiffness, low strain to fail-
ure matrix.
 Design considerations 319

fibers. The fibers can retain the broken matrix X', is between the range given by
in place before the fibers break at a higher
load. Composite strength above Vcritdepends
upon the fiber strength. A typical stress-strain
curve for such a system above V,,, is shown where T is the interfacial shear stress and r is
the fiber radius. The value of strain at the end
of this process, E ~ isz3
~ ~ ,

u)
u)
The final linear rising portion is the curve is
0
L
the elastic response of the fiber. Continuous
z fiber breakage and fiber pull-out can produce
the pseudo-ductility of the final portion of the
curve.
There are many potential continuous
V
E
fiber-matrix combinations in which the matrix
Emu max has a higher elastic modulus than the fiber. For
Strain instance, matrix materials such as titanium
diboride, titanium carbide, silicon carbide and
Fig. 14.10 Stress-strain behavior for composite alumina with most of the continuous fibers
with high stiffness, high strength fiber and a lower listed in Table 14.2 would have the relative
stiffness, low strain to failure matrix. stress-strain behavior shown in Fig. 14.11(a).
The strength of predictions of such systems is
schematically in Fig. 14.10. The elastic portion shown schematically in Fig. 14.11@).In this
of the curve is followed by a serrated, constant case the predicted strength of the composite
stress portion induced by a matrix failure would decrease with increasing fiber fraction
process. During this process the matrix contin- until a minimum fiber fraction, V,, is reached.
ues to crack until the spacing between cracks, This behavior is similar in appearance to the

sf"

(D
8
b
v)

Of

(b) Fiber Fraction

Fig. 14.11 Strength prediction for a high strength fiber and a higher stiffness, low strain to failure matrix.
320 Ceramic composites

case of a high modulus, low failure strain fiber transverse elastic moduli E, and E,, respec-
in a lower modulus, high failure strain matrix tively, composites with aligned short fibers can
as is typical of many metal matrix composites. be made by using the Halpin-Tsai relation?
However the cause of the minimum behavior
is quite different. Below Vmh failure of the
matrix still constitutes composite failure
where the rule-of-mixtures strength is com-
posed of the matrix ultimate strength, omuand
the stress on the fiber at the matrix failure
strain, a;. Unlike the case for the lower modu-
lus matrix, the stress 0; is lower than the a,,
increasing fiber fraction lowers the rule-of-
mixtures strength. Above Vmi,the fracture of
the matrix no longer constitutes composite tL= 2 l / d , and tT = 2
fracture as the fibers alone are able to carry the
The coefficients of thermal expansion in the
load after matrix failure.
longitudinal and transverse directions, a, and
The above description applies to compos-
aT respectively, can be estimated fromz6
ites with a high fiber-matrix bond strength
and neglects the effect of fracture surface a, = (a,E,V,+ amEmVm) / E,
energy. These conditions are not typical in real
composites and the simple rule-of-mixtures aT = (1+ vf) a,V, + (1+ vm)amVm- aLvLT
predictions must be modified to account for
where
these effects. Aveston et aLZ4accounted for the
effect of the fiber-matrix bond strength on the VLT = vf v, + YmVm
matrix failure strain as follows:
6zTE,Vf 1/3 and vf and vm are the Poisson's ratio for fiber
[
E'f = EkVmrEc]
and matrix respectively. These calculations will
usually overestimate the value of these proper-
where r is the fracture specific fracture energy ties because of ineffective bonding between
of the matrix. fiber and matrix and deviation from ideal fiber

14.4.2 DESIGN OF DISCONTINUOUS

REINFORCEMENT COMPOSITES
In polymer and metal matrix composites it is
usually desirable to design the fiber lengths to
exceed the critical length, 1, given by ufr/t to
allow the fiber to carry its full load prior to
fracture. In ceramic composites, fiber breakage
is rarely the design goal. Instead the role of the
fiber is to provide toughness by a combinations
of fiber pull-out, crack deflection and crack
bridging. Nevertheless, the designer may want
to predict the elastic and thermoelastic proper-
ties of the discontinuous reinforcement
composites' An estimate for longitudina1 and Fig. 14.12 Microstructure of 20 vel. yo SiC-Al,O,
composite fabricated by tape casting.
 Design considerations 321

alignment. Figure 14.12 shows the in-plane laminate fracture theories must be employed.
microstructure for a 20 vol% Sic whisker-alu- Examples of material designs that can make
mina composite fabricated by tape casting and use of laminated-composite concepts for
hot pressing. This processing method promotes improved performance are illustrated in Fig.
fiber alignment in the tape cast direction, how- 14.133z.The magnitude of the surface compres-
ever there is still a considerable deviation from sive stress can be calculated from laminate
the predominant fiber directionz7. theory. Figure 14.13(a) shows a laminate
For randomly oriented fibers or whiskers the design intended to produce surface compres-
elastic modulus, E , of the composites can be sive stresses. In this design the layers toward
estimated from the results of the Halpin-Tsai the mid-plane gradually increase in coefficient
method using the empirical relation: of thermal expansion. The outer layers, con-
ET= (3/8)E, + ( 5 / 8 ) E ,

14.4.3 DESIGN OF MULTILAYER, MULTI-

DIRECTIONAL REINFORCEMENT LAMINATES
The concept of a laminated composite is used
effectively in the design of polymer-matrix
composites to achieve the high degree of
strength, elastic and thermoelastic tailoring.
(a) Design with graded composition
Polymer-matrix composites reinforced with
either continuous or discontinuous fibers are
fabricated by stacking layers with specific char-
acteristics and orientations in a predetermined
sequence to achieve desired mechanical or
physical properties. As with polymer compos-
ites, the ceramic composite layer properties
may be calculated using theoretical and semi-
empirical method^^*-^^ from the constituent
I
properties such as the elastic modulus of the
(b) Design with toughening layers
fibers and matrix respectively, E, and Em, the
orientation factor, f, the volume fraction of the Oxidation
resistant layer
fiber, Vf, the fiber aspect ratio, l/d, and the coef-
ficients of thermal expansion for the fibers and Wear
matrix, afand am.By selection of the sequence resistant layer
of layer orientations and compositions, various High
toughness
elastic, thermoelastic, strength, physical and core
chemical characteristics can be produced.
Classical laminate plate the0ry3&~~ can be used
to accurately predict the elastic and thermoelas-
(c) High temperature wear design
tic properties of laminated composites from the
layer properties. The strength properties, on the
other hand, cannot be readily determined by Fig. 14.13 Typical laminate design concepts for
commonly used laminate failure criteria since ceramic matrix composites. (a) with graded compo-
fracture of these laminates is still strongly con- sition; @) with toughening layers; (c) for high
trolled by the presence of flaws. Modified temperature wear.
322 Ceramic composites

taining increasing amounts of low-expansion stresses that are likely in such a construction.
whiskers generate compressive residual Differences in elastic modulus and coeffi-
stresses as a result of the differential contrac- cients of thermal expansion for layers
tion during cooling after the high-temperature containing different volume fractions of rein-
densification process. A major advantage of forcing whiskers can be used to generate
laminated-composite processing is that it pro- favorable residual stress patterns in fabricated
vides the engineering flexibility to use laminates. The thermal stresses o,T,oy' and T~~
innumerable material and property combina- in each layer of the laminate at any position
tions that would be impossible with through the thickness, z, measured from the
traditional methods involving thermal or midplane, caused by the restraint of the neigh-
chemical tempering. This concept also allows boring layer can be determined by Hooke's
the use of non-equilibrium compositions for
greater degree of stress profile variation. For
instance, the depth and magnitude of the
stress gradient can be independently con-
trolled by selection of layer composition and
properties. Maximizing the stress gradient by
the introduction of a high-expansion material
in the interior of the composite would be
impossible by conventional chemical temper-
ing but is quite feasible by lamination.
Strengthening can also be achieved by ren-
dering surface flaws ineffective through the
introduction of a tougher ceramic layer below
the surface (Fig. 14.1303)). This design miti-
gates surface damage in the outer layers by
blunting the cracks when they reach the under-

[:
lying toughened layer. This layer may contain
whiskers, a toughened ceramic, or metallic Alll A'l2 A'
particles. The use of a toughened ceramic layer
as the outer layer would not be as effective
since abrasion or impact could produce flaws
y:'
]= Af12A'22A':6
"16 Af26
{ q%v]
through its entire depth, thus permitting the
crack to propagate through the lower-tough-
ness interior layers with minimum resistance.
In addition to increased strength and tough-
ness, high-temperature corrosion resistance can
be designed into a composite material by using
a corrosion-resistant layer on the exterior sur-
face (Fig. 14.13(c)) and layers tailored for
high-temperature strength in the interior. A
similar concept may be employed for a material
designed as a high-temperature heat exchanger
by grading the interior layers for high thermal
conductivity. Using composite laminate theory,
a materials designer can tailor the grading to
minimize the deleterious residual tensile
 Properties 323

where t, is the thickness of the kth layer, Q, are

the untransformed stiffness coefficients and al
are the coefficients of the thermal expansion in
the principal material directions. The thermal
moments Mx, My and MXyare zero. The resid-
ual stresses, oLand oT,in the longitudinal and
transverse directions respectively are (a) Bridging

For this laminate geometry the residual shear

stress, rLT= 0. (b) Pull-Out
The compressive residual stresses thus
induced in the outer surface of the ceramic
composite raise the fracture strength by that
amounP3.

14.5 PROPERTIES
The principal objective in design of ceramic
composites is to produce enhanced toughness
and mechanical reliability. Various energy (c) Deflection
absorbing mechanisms are produced by the
reinforcement depending on the relative ther-
mal expansion coefficients, relative elastic
moduli and interfacial bond strength between
the reinforcement and matrix. In addition the
size, shape, distribution and volume fraction
of the reinforcement plays a strong role in con-
trolling the effectiveness of the toughening.

14.5.1 MECHANISMS OF STRENGTHENING

The four principal mechanisms of toughening (d) Microcracking
(crack bridging34,35, fiber pull-out, crack
deflection and matrix microcracking) are
shown schematically in Fig. 14.14. More than
one of these mechanisms can be operative at Fig. 14.14 Toughening mechanisms for ceramic
the same time in a ceramic composite but there matrix composites.
324 Ceramic composites

is usually a dominant one depending on the resistance. A quantitative treatment of the

constituent and interfacial properties. effects of crack deviation on toughness have
Bridging, pull-out and deflection are most been provides by Faber and Evans3'.
effective where the fibers are generally aligned In certain composites the conditions can be
normal to the crack surface. favorable to allow the stress field of the prop-
In the crack bridging mechanism (Fig. agating crack to interact with the stress field
14.14(a))the fibers remain intact for some dis- around the reinforcements to produce local
tance behind the crack front, thus restraining matrix cracking around the reinforcement.
the crack opening displacement and reducing Maximum effectiveness of this mechanism
the stress intensity at the crack tip. The energy requires a fine dispersion of many reinforce-
absorbing processes include fiber fracture, ments as illustrated in Fig. 14.14(d). An
fiber-matrix friction and elastic strain energy appropriate mismatch in thermal expansion
of the fiber. Thus, strong fibers, high strain to coefficients between reinforcement and
fracture fibers and strong fiber-matrix bond- matrix provides the local stress field around
ing promote this mechanism. The toughening the reinforcement. An analysis of this mecha-
produced by a uniform closure stress of the nism of toughening has been provided by
bridging fibers has been estimated by Becher H ~ t c h i n s o n ~ ~ .
et a1.35to be Typical fracture in whisker reinforced
ceramic (SiC/Al,O,) shown in Fig. 14.15 has
dKc = (3fU[VfrEcG,/6(1 - v2)EfGi]l12 elements several mechanisms of toughening.
Whisker pull-out and crack defection are evi-
where Gm and Gi, are the strain energy release dent in this example.

"
between the fiber and the matrix. For fibers of
critical length the increment in toughness is
given as (see Reference 36, for example):

AGc = V ,o f u r / 6 ~

Crack deflection mechanism (Fig. 14.14(c))

forces the crack to deviate out of the normal
stress plane as it negotiates around the rein-
forcements. The driving force for this deviation
is the residual stress distribution produced by
the mismatch in thermal expansion between
the fiber and matrix. Reinforcements with
higher coefficients of thermal expansion than
the matrix will cause the matrix to be in com-
pression near the reinforcement. This state will
tend to deflect a crack as it approaches the
vicinity of the reinforcement which is a higher
crack resistant area to a region of lower crack
Fig. 14.15 SEM photograph of fracture path in Sic
whisker-Al,O, composite.
14.5.2 TYPICAL PROPERTIES
The selection of materials for component
design requires accurate and reliable mechani-
cal property data. Because of the large
variations in processing characteristics and
starting material forms, such data are generally
sparse. The mechanical properties most signifi-
 Properties 325

cantly affected by reinforcements in ceramics 91 1

are fracture strength and fracture toughness.
8 -
Vaughn et ~ 1examined
. ~ ~ the effect of processing
temperature and reinforcement for alumina 7-
and Sic whisker/alumina composites. Table
14.8 shows that processing temperature and
remforcement have little effect on elastic modu-
lus, but a significant impact on strength,
fracture toughness and work of fracture. The
noncompliance with the rule of mixtures for
Young’s modulus is evidence of the lack of
bonding and hence load transfer between fiber
and matrix. The toughening of various ceramic
matrix materials with increasing Sic whisker
content is shown in Fig. 14.1635.
A compilation of fracture strength and frac- 0 0.1 0.2 0.3 0.4
ture toughness for Sic whisker (Silar-SC9) Whisker content (Volume fraction)
/A1,0, composites is given in Table 14.92.The Fig. 14.16 Increment in fracture toughness of Sic
fracture strength of the composites for the whisker composites with various matrices35.

Table 14.8 Mechanical properties of polycrystalline A1,0, and Sic whisker /A1,0, matrix composites3’

Alumina Alumina Alumina Composite Composite

(1500°C) (1659°C) (1900°C) (Silar SC-1) (Tateho SCW-1-5)
Young‘s 371 380 375 375 393
modulus (GPa)
Fracture 456k40 385+18 2534 641+34 606+146
strength (MPa)
Fracture 3.3d.2 5.0~0.2 3.7d.1 8.7M.2 4.6d.2
toughness (MPa m1/2)
Work of 10 20 39 67 21
fracture om-’)

Table 14.9 Room temperature strength and fracture toughness of Sic whisker (Silar-SC-9)/A120,
composites (Adapted from Reference 2 )

Whisker content Fracture strength Fracture toughness Xejerence

(Vol. %) (MPa) (MPa mIn)
0 150 4.3 40
253 3.7 39
5 391 3.6 41
475 4.0 42
10 540 4.8 42
15 652 4.6 41
20 675 6.1 42
30 680 8.7 40
641 8.7 39
720 7.0 42
40 640 7.9 42
850 6.2 43
326 Ceramic composites

same whisker content can vary fairly signifi- 8 * I I I I I I I ~ I I

cantly among the different sources while the SiCw-mulIite

fracture toughness is relatively consistent. -
Above 30% whiskers some composites can -
a
exhibit either a strength or fracture toughness z 6-
Y
-
that actually decreases because of the decrease -
in homogeneity of the whisker distribution. E 5- -
The fracture strength and fracture toughness 7 -
for Sic whisker reinforced mullite are shown 2 -
in Figs. 14.17 and 14.18 respectivelp. These
composites were fabricated by tape casting -
and the L-type designation indicates that the
crack propagation direction is normal to the
tape casting direction and the T-type designa- 26 ' Ib ' io ' io
' 40 ' 5'0 '
tion indicates that the crack propagation SIC Whisker Fraction ( ~ 0 1 % )
direction is parallel to the tape casting direc-
tion. Greater strength and toughness are Fig. 14.18 Fracture toughness of Sic whisker-
mullite composites with the crack propagating nor-
achieved for the case of fiber orientation pre- mal (L-type) and parallel (T-type) to the
dominantly normal to the whisker axis
.predominant whisker direction&.
direction. The maximum strength and tough- -
ness for this system is at 40% whiskers. Table 14.10 Room temperature mechanical
The effect of Sic (Silar S-9) whisker content properties of Sic whiskers/Si,N, matrix
on strength and toughness of Si,N, matrix composites45
composites is given in Table 14.1045.For this
material the maximum toughness occurs at Whisker Fracture Fracture
30% wluskers while the strength maximum is content strength toughness
(Vol. Yo) (MPa) (MPa mIn)
1000 I I I I I I I 0 375 4.0
Sicw - mullite 10 395 4.9
20 550 7.0
30 970 6.4

apparently above this fiber content.An alterna-

tive form of Sic whiskers was used to fabricate
Si,N, matrix composites by Shalek et ~ 1 . 4 This
~.
whisker is formed by the Vapor-Liquid-Solid
p r o ~ e s s ~The
~ , effect
~ ~ . of whisker content and
processing temperature on the elastic modulus,
fracture strength and fracture toughness are
shown in Figs. 14.19, 14.20 and 14.21 respec-
2000 I
IJI
III
III
I
IOII 20 30 40 50
Sic Whisker Fraction ( ~ 0 1 % )
tively. There is an apparent critical processing
temperature above 1600°C to achieve maxi-
mum attainable strength and toughness
Fig. 14.17 Fracture strength of Sic whisker-mullite properties in these composites.
composites with the crack propagating normal (L- Continuous fiber ceramic matrix compos-
type) and parallel (T-type) to the predominant ites are more likely to obey the rule of mixtures
whisker directionM. prediction for elastic and strength properties
 Properties 327

especially where minimum fiber damage and

SIC Whisker -hobpressed porosity occurs. The predictable increase in
Si3 N, matrix composite flexural strength for a Nicalon fiber/borosili-
cate glass composite is seen in Fig. 14.2249.

SIC Whisker -hot-pressed

13 Si3 N, matrix composite

300

: Hot-pressed at 1750°C
B : Hot-pressed at 1850°C
A : Hot-pressed at 1600°C

-0 1
..
..
..
..
1 5 10 IS PO 25 30 35 40

Volume Yo S i c whiskers

Fig. 14.19 Elastic modulus of Sic whisker-Si,N4

composites processed at various pressing tempera-
0 : Hot-pressed at 1750OC
ture~~~. :Hot-pressed at 1850°C
4 A : Hot-pressed at 1600°C

. . . . 1 30 5 10 15 20 25 30 35 40

Volume % SIC whiskers

Si, N, matrix composite

Fig. 14.21 Fracture tougness of Sic whisker-Si,N4
composites processed at various pressing tempera-
1750°C tures&.
1850°C .
1600°C

E3m- *
2500 Rule of mixtures prediction
4-4 B
for SiC/Borosilicate class ,',
03
0) " : 8
50 -,p
I
A
A 2 2000 - ,
#
,
m
t m.
A
E ,
5 1500
1500- ,
'9
,x
A
F
5 1000
1000- ,4
/**4

'7
PI I
500-
/
/
,
0

0 5 10 IS 20 25
Volume Yo Sic whiskers
30 35 40
/
O f '
.1
' . '
.2 .3 .4 .5 .6 .7
' ' ' '
.8
'
.9
Fibre volume fraction
Fig. 14.20 Fracture strength of Sic whisker-Si,N4
composites processed at various pressing tempera- Fig. 14.22 Rule of mixtures strength for Sic fiber
tures". (NicalonTM)-borosilicate
glass49.
328 Ceramic composites

14.6 APPLICATIONS Crater Wear

14.6.1 HIGH TEMPERATURE STRUCTURES
The most advanced demonstration of ceramic
matrix composites for high temperature struc-
tures and components has been for Sic CVI
infiltrated carbon and Sic (NicalonTM) fiber.
Extensive application of these composites
have been made by Societe Europeenne de
Propulsion A demonstration two-
stroke 100 cc engine consisting of Sic-Sic pis-
ton, cylinder and cylinder head has run for ten
hours at full load and a speed of 1500 rpm
without lubricant.
A list of fabricated and tested high temper-
ature ceramic composite structures is given in Notch Nose Wear
Table 14.11. These components operated suc-
cessfully under actual- or simulated service
Fig. 14.23 Typical wear pattern in cutting tool
conditions. inserts.

14.6.2 TRIBOLOGICAL COMPONENTS

(CUTTING)
The application of ceramic composites to cut-
ting tool inserts has made a significant impact
on machining of difficult-to-cut metals. The
typical wear pattern in a cutting tool insert is
shown in Fig. 14.23.Uniform wear due to the
rubbing action of the metal work piece pro-
duces the flank and nose wear. Deeper wear
patterns at the depth-of-cut and trailing edge
region of the insert are due to the sharp edges
of the chip. The abrasion of the rake by the
broad face of the chip produces a crater.
Material removal from the rake face can be by
dissolution, adhesion and chemical reaction.
Low chemical reactivity, hot hardness and
wear resistance allows ceramics to minimize
all these forms of wear.
Unreinforced ceramics, while capable of
high cutting speeds, suffer from unpre-
dictable life due to low impact load tolerance

Table 14.11 Typical high temperature applications of ceramic matrix composites

Application Composition Operating Environment Test condition Reference

temperature
("C)
Combustion Sic-Sic 1200 Oxidizing 14 h running 50
chamber
Turbine blade Sic-Sic 1200 Air-kerosene Thermal cycle 400-1200°C 50
Turbine wheel Sic-Sic 1150 Air-kerosene 1 h up to 55 000 rpm 50
Turbine wheel C-Sic 1150 Air-kerosene 70 000 rpm 50
Leading edge C-Sic 1400 Oxidizing Several hours 51
Nozzle C-Sic 1550 Oxidizing Maximum thermal gradient 52
60"C/mm
Radiant Nextel 312-Sic 1150 Air-natural gas 18 month operation 52
burner tube
 Applications 329

or poor thermal shock properties. Reinforcing reinforced alumina and cemented tungsten
ceramics especially by whiskers is an effec- carbide as seen in Fig. 14.2555.
tive technique to defeat these limitations. The
best known example of this application is the
Sic whisker reinforced A1,0, insert. The com-
mercially available composition contains
about 30% whiskers and is designated WG-
300 by Greenleaf Corp., Saegertown, PA, 35 -
USA. 2
The range of machining parameters for the
r 30-
Sic whisker alumina compared to other con- c
S
c
ventional and advances cutting tool materials 'E 25-
>
is shown in Fig. 14.2454.Carbide cutting tools K
.-

are limited to cutting speeds below 100 m/min + 20-

0
while the ceramic cutting tools range from K
._
over 100m/min to 450m/min. The Sic 3 15-
0
whisker reinforced composite can be seen to $
provide the largest range of machining para- - 10-
L

m
c
meters for the machining of nickel based 2 5-
superalloys compared to other advanced cut-
ting materials such as Sialon and Tic 0-
particulate reinforced alumina.
The Sic whisker reinforced alumina (WG-
300) also has significantly greater tool life and Fig. 14.25 Comparison of tool life and metal
allows much greater rates of metal removal removal rates between various cutting tool materi-
for Inconel 718 compared to Tic particulate ais55.

-
0.25
Al,O,-SiC(w)

0.20 C Sialon
a
FE
-
U

2
E 0.15
(I)

0.10

0.05
0
i 100 200 300
Cutting speed (m/min)
400 500

Fig. 14.24 Approximate range of machining parameters allowed by various cutting tool materials%.
330 Ceramic composites

REFERENCES 15. Mecholsky, J.J., Engineering research needs of

advanced ceramics and ceramic-matrix com-
1. Karasek, K.R., Bradley, S.A. Dormer, J.T., Yeh, H. posites, Am Ceram. SOC. Bull., 1989, 68(2),
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cursors, Composites, 1987,18(2), 107-127. Sinnema, S, Practical designing aspects of engi-
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Folsom, C., Velamakanni, B.V., Zok, F.W. and Oxford: Pergamon Press, 1980, p.106.
Evans, A.G., Powder processing of ceramic 24. Aveston, J., Cooper, G. and Kelly, A,, Single and
matrix composites, Mater. Sci. Eng., 1991, A144, multiple fracture, in: The Properties of Composites,
143-152. Guildford: IPC Science and Technology Press,
10. Kragness, E.D., Processing and mechanical 1971, p.15.
behavior of tape cast and laminated silicon car- 25. Halpin, J.C. and Kardos, J.L. The Halpin-Tsai
bide whisker/alumina composites, M.Sc. equations: a review. Polym. Eng. Sci., 1976,16(5),
Thesis, Pennsylvania State University, 1988. 344-352.
11. Prewo, K.M., Brennan, J.J. and Layden, G.K., 26. McCullough, R.L., Wu, C.T., Seferis, J.C. and
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high performance applications, Am. Ceram. SOC. mechanical performance for anisotropic crys-
Bull. 1986,65(2), 305-322. talline polymers. Polym. Eng. Sci. 1976, 16(5),
12. Hillig, W.B., Melt infiltration approach to 371-387.
ceramic matrix composites, 1. Am. Ceram. SOC., 27. Schapery, R.A. Thermal expansion coefficients
1988, 71(2), C9W99. of composite materials based on energy princi-
13. Newkirk, M.S., Lesher, H.O., White, D.R., ples. J. Compos. Mater. 1968, 2(3), 280404.
Kennedy, C.R., Urquart, A.W. and Claar, T.D., 28. Kragness, E.D., Amateau, M.F. and Messing,
Formation of LanxideTMceramic composite G.L., Processing and characterization of lami-
materials, Ceram. Eng. Sci. Proc., 1987, 8,879. nated Sic whisker reinforced A1203, J. Compos.
14. Newkirk, M. S., Urquart, A.W., Zwicker, H.R. Mater., 1991, 25(4), 416432.
and Brevel, E., Formation of LANXIDETM 29. Paul, B., Predictions of elastic constants of mul-
ceramic composite material, J. Mater. Res., 1986, tiphase materials, Trans. Met. SOC.,AIME, pp.
1(1),81-88.

3 6 4 1 (February 1960).
30. Pister, K.S. and Dong, S.B., Elastic bending of
layered plates, 1. Eng. Mech. Din, ASCE, 1-10
(October 1959).
31. Reissner, E. and Stavsky, Y., Bending and
stretching of certain types of heterogeneous
aelotropic plates, J. Appl. Mech., 402408
(September 1961).
32. Amateau, M.F., Properties of laminated ceramic
composites, The 37th Sagamore Army Materials
Research Conf Proc., (ed. D.J. Viechnicki),
Watertown, Mass: Materials Technology
Laboratory, 317-338, October, 1990.
33. Evans, A.G. and Davidge, R.W., A biaxial stress
method for the determination of the strengh of
sections cut from glass containers and the size
of critical Griffith flaws, Glass Tech. 1971, 12(6),
148-154.
34. Evans, A.G. and McMeeking, R.M., On the
toughening of ceramics by strong reinforce-
ments, Acta Met., 1986, 34, 2435-2441.
35. Becher. P, Hsueh, C.-H., Angelini, P. and Tiegs,
T.N., Toughening behavior in whisker-rein-
forced ceramic matrix composites, J. A m . Ceram.
SOC.,1988,71,1050-1061.
36. Warren, R., Fundamental aspects of the proper-
ties of ceramic-matrix composites, in: Ceramic
Matrix Composites (ed by R. Warren), New York:
Chapman and Hall, 1992, p. 82.
37. Faber, K.T and Evans, A.G., Crack deflection
process, Part I and II., Acta Met., 1983, 31,
565-584.
38. Hutchinson, J.W., Crack tip shielding by micro-
cracking in brittle solids, Acta Met., 1987, 35,
1605-1619.
39. Vaughn, W.L., Homeny, J. and Ferber, M.K.,
Mechanical properties of silicon carbide
whisker/alumina oxide matrix composites,
Ceram. Eng. Sci. Proc., 1987, 8(7-8), 848-859.
40. Tiegs, T.N. and Becher, P.F., Sintering of
Al,O,-SiC whisker composites, Bull. A m . Ceram.
SOC.,1987,66,347-352.
41. Porter, J.R., Langej, F.F. and Chokshi, A.H.,
Processing and creep performance of Sic
whisker reinforced A1,0,, Bull. Am. Ceram. SOC.,
1987,66,343-346.
42. Lio, S., Watanabe, M., Matsubara, M. and
Matsuo, Y., Mechanical properties of alu-
mina/silicon carbide whisker composites, J.
Am. Ceram. SOC.,1989,72,1880-1884.
43. Becher, P.F., Tiegs, T.N., Ogle, J.C. and Warwick,
W. H., Toughening of ceramics by whisker rein-
forcement, in: Fracture Mechanics of Ceramics,
References 331
VoI. 7, Composites, Impact, Statistics and High-
Temperature Phenomenon, (ed. R.C. Bradt, D.P.H.
Hasselman, A.G. Evans and F.F. Lange), New
York Plenum Press, 1986, pp. 61-72.
44. Wu, M., Messing, G.L. and Amateau, M.F.,
Laminate processing and properties of oriented
Sic whisker-reinforced composites, Ceramic
Transactions, Vol. 19, 1991, Westerville, OH:
American Ceramic Society, 665476,1991.
45. Bulgan, S.T., Baldoni, J.G. and Huckabee, M.L.,
Si,N4-SiC whisker composites, Bull. Am. Ceram.
SOC.,1987,66,347-352.
46. Shalek, P.D., Petrovic, J. J., Hurley, G.F. and Gac,
ED., Hot-Pressed Sic Whisker/Si,N, Matrix
Composites, A m . Ceram. SOC., 1986, 65(2),
351-356.
47. Milewski, J.V., Gac, ED., Petrovic, J.J. and
Skaggs, S.R., Growth of beta-silicon carbide
whiskers by the VLS process, J. Mater. Sci., 1985,
20,1160-1166.
48. Petrovic, J.J., Milewski, J.V., Rhor, D.L. and Gac,
ED., Tensile mechanical properties of Sic
whiskers, 1.Mater. Sci., 1985,20, 1167-1177.
49. Dawson, D.M., Preston, R.F. and Purser, A.,
Fabrication and materials evaluation of high
performance aligned ceramic fiber-reinforced,
glass-matrix composite, Ceram. Eng. SOC.Proc.,
1987,8,815-821.
50. Heraud, L.P. Spriet, 'High toughness C-SIC and
Sic-Sic composites in heat engines', in Whisker-
and Fiber-Toughened Ceramics, Proceedings of an
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D.E. Clark, D.C. Larsen and J.O. Stiegler),
International Metals Park, OH: ASM, 1988.
51. Melchior, A.B., Pouliquen, M.F., Soler, E.,
Thermostructural composite materials for liq-
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Joint Propulsion Conference, June 29-July 2,
1987, San Diego, CA, American Institute of
Aeronautics and Astronautics, Washington, DC.
52. Suacereau, D. and Beaurain, A., Demonstration
of carbon-silicon carbide Novoltex reinforced
composite nozzle on a LH2-LOx, Engine, Paper
AIAA-90-2180, AIAA/SAE/SME/ASEE, 26rd
Joint Propulsion Conference, July 16-18, 1990,
Orlando FL, American Institute of Aeronautics
and Astronautics, Washington, DC.
53. Richards, R.E., Bodkins, D. W. and Copes, S. J.,
Progress toward a cost effective thin wall RBT,
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332 Ceramic composites
Washington, DC, Government Institute Inc.
Washington DC, 749-756,1988.
54. Billman, E.R., Mehrota, P.K., Shuster, A.F. and
Beegley, C.W., Machining with A1203-Sic
whisker cutting tools, Bull. Am. Ceram. Soc,
1988,67,1016-1019.
55. Rhodes, J.F., Whisker reinforced ceramic com-
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Technology, Materials Technology Center,
Southern Illinois University, Carbondale, IL,
205-219,1988.
CARBON-CARBON COMPOSITES 15
John D. Buckley

15.1 INTRODUCTION n

Carbon-carbon (CC) materials are a generic

class of composites similar to the
graphite/epoxy family of polymer matrix
composites. These materials can be made in a
1-D 2-D
wide variety of forms, from one-dimensional
to n-dimensional, using unidirectional tows,
tapes, or woven cloth (Fig. 15.1). Because of
their multiformity, their mechanical properties
can be readily tailored (Table 15.1). Carbon
materials have high strength and stiffness
potential as well as high thermal and chemical
stability in inert environments. These materi- 3-D n-D
als must, however, be protected with coatings
and/or surface when used in an OXi- Fig. 15.1 Multiformity and general properties of
dizing environment. carbon-fiber and carbon-matrix composites.

The development of CC materials began in

Table 15.1 General properties of carbon-carbon 1958 and was nurtured under the US Air Force
composites space plane program, Dyna-Soar and NASA's
Apollo projects. It was not until the Space
Ultimate tensile >276 MPa >40 000 psi Shuttle Program that CC material systems
strength were intensively researched. The criteria that
Modulus of >69 GPa >lo7 psi led to the selection of CC composites as a ther-
elasticity mal protection system were based on the
Melting point >41OO0C 7412°F following requirements:
Thermal ~11.W
5 m-' K-' 6.64
conductivity h ft "F 1. maintenance of reproducible strength levels
at 1650°C (3002°F);
Linear thermal ~ 1 .x110"OC 6.1 x W7"F
expansion 2. sufficient stiffness to resist flight loads and
large thermal gradients;
Density <2990 kg m-3 186.6 lb/ft3
3. low coefficient of thermal expansion to min-
imize induced thermal stresses;
Handbook of Composites. Edited by S.T. Peters. Published 4. oxidation resistance sufficient to limit
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 strength reduction;
334 Carbon-carbon composites
5. tolerance to impact damage;
6. manufacturing processes within the state of
the art.
Carbon-carbon composites consist of a fibrous
carbon substrate in a carbonaceous matrix.
Although both constituents are the same ele-
ment, this fact does not simplify composite
behavior because the state of each constituent
may range from carbon to graphite.
Crystallographic carbon, namely graphite,
consists of tightly bonded, hexagonal
arranged carbon layers that are held together
by weak van der Waals forces. The single crys-
tal graphite structure is illustrated in Fig. 15.2
(Bokros, 1969). The atoms within the layer
E a
Reference directions
Fig. 15.2 Tightly bonded, hexagonally arranged carbon layers held together by weak van der Waals forces.
I
LC
Fig. 15.3 Comparison of (a) carbon turbostratic structure with (b) 3-D graphite lattice (Bokros, 1969).
plane or basal plane (a-b direction) have a
covalent bond strength of =524 kJ/mol
(Kanter, 1957), while the bonding energy
between basal planes (c direction) is =7 kJ/mol
(Dienes, 1952). The result is a crystal that is
remarkable in its anisotropy, being almost
isotropic within the basal plane but with c
direction properties that differ by orders of
magnitude. On a larger scale, carbon, in addi-
tion to its two well-defined allotropic forms
(diamond and graphite), can take any number
of quasicrystalline forms ranging continu-
ously from turbostratic (amorphous, glassy
carbon) to a highly crystalline graphite (Fig.
15.3) (Bokros, 1969).
:rdo02

The anisotropy of the graphite single crystal
encompasses many structural forms of carbon.
It ranges in the degree of preferred orientation
of the crystallites and influences porosity,
among other variables. A broad range of prop-
erties is the result of this anisotropy. In CC
composites, this range of properties can
extend to both constituents. Coupled with a
variety of processing techniques that can be
used in the fabrication of CC composites, great
flexibility exists in the design of and the resul-
tant properties obtained from CC composites.
The wide range of properties of carbon
materials can be shown when comparing the
tensile modulus of commercially manufac-
tured carbon fibers that range from 27.6 GPa
(4 x 106psi) to 690 GPa (100 x lo6psi). In fabri-
cation, the fibers can be used in either
continuous or discontinuous form. The direc-
tionality of the filaments can be varied ranging
from unidirectional lay-ups to multidirec-
tional weaves. Fiber volume fraction
constitutes another variable. The higher the
volume fraction of a specific high-strength
fiber in a matrix, the greater the strength of the
composite. The matrix can be formed via two
basic approaches: (1) through the carboniza-
tion of an organic solid or liquid, such as a
resin or pitch, or (2) through the chemical
vapor deposition (CVD) of carbon from a
hydrocarbon. A range of carbon structures can
be obtained by either approach. Finally, heat
treatment of the composite material at graphi-
tization temperatures offers additional
variability to the properties that can be
obtained. Typically, there is an optimum
graphitization temperature at which the high-
est strength can be obtained for a given
composite composition of fiber and matrix
(Edie et al., 1986; Stoller et al., 1974).
15.2 CARBON FIBERS
The properties of carbon fibers can vary over a
wide range depending on the organic precur-
sor and processing conditions used. At
present, graphite fibers are produced from
Carbon fibers 335
three precursor materials: rayon, polyacryloni-
trile (PAN)and petroleum pitch. Fibers having
a low modulus (27.6 GPa (4 x 106 psi)) are
formed using a rayon precursor material that
may be chemically pretreated by a sequence of
heating steps. First, the fiber is heated to
>400"C (752°F) to allow cellulose to pyrolyze
(decomposition or chemical change during
thermal conversion of organic materials to car-
bon and graphite). Carbonization (continued
heating of organic material to >lOOO"C (1832°F)
to initiate ordering of the carbon structures
produced by pyrolysis) is completed more
rapidly at >lOOO"C (1832°F).Upon completion
of carbonization, the fiber is graphitized (con-
tinued heating of carbonized organic materials
to the 2000-3000°C (3632-5432°F) range of
produce 100% graphite-ordered crystal struc-
ture) by heating to >2000"C (3632°F);the fiber
is now, for all practical purposes, 100% carbon.
High-modulus carbon fibers from rayon pre-
cursors are obtained by the additional process
of stretching the carbon fibers at the final heat
treatment temperature. Nigh-modulus (344
GPa (50 x 106 psi)), high-strength (2.07 GPa
(300 x lo3 psi)) carbon fibers are typically
made from PAN or, in some cases, mesophase
pitch precursors. These fibers are processed
similarly in a three-stage operation (Fig. 15.4)
(Diefendorf, 1987).The PAN fibers are initially
stretched from 500-1300% and then stabilized
(cross-linked) in an oxygen atmosphere at
200°C (392°F)to 280°C (536°F) under tension.
Carbonization of the fibers is conducted
between 1000°C (1832°F)and 1600°C (2912°F).
Finally, graphitization is accomplished at
>2500"C (4532°F). Mesophase pitch fibers
undergo the same processing procedure as
PAN fibers but do not require an expensive
stretching process during heat treatment to
maintain preferred alignment of crystallites
(Fig. 15.4) (Diefendorf, 1987). Control of fiber
shape has resulted in improved fiber strength
(4.1 GPa, 600000 psi) (Cogburn et al., 1987)
when produced from melt-spun, mesophase
petroleum pitch (Fig. 15.5) (Cogburn et al.,
1987). Round fibers using the same method
336 Carbon-carbon composites

PAN process

Pitch process 1
tCarbonize
z z I I Graphitize
zim

Spool Epoxy sizing Surface treatment

Fig. 15.4 Carbon fiber production using PAN and pitch processes (Diefendorfer, 1987).

Hydraulic piston

Cartridge housing
Heating collar
Melted-pitch precursor
Spinnerette

Melt-spun carbon
Melt-pressure indicator filaments

Wind-up bobbin

Fig. 15.5 Melt spinning apparatus used to produce noncircular carbon fibers (Cogbum et al., 1987).
 Carbonfibers 337

had a strength of 2.1 GPa (300 x lo3 psi) (Edie
et al., 1986).Of the shapes studied, the C-shape
and hollow fibers were found to be superior in
strength to round solid and trilobal cross sec-
tions (Edie et al., 1986; Cogburn et al., 1987).
15.2.1 CARBON FIBERS IN CARBON MATRIX
Addition of a matrix to carbon fiber, either
through the carbonization of an organic pre-
cursor or by the deposition of pyrolytic
carbon, is conducted at 800°C (1472°F) to
1500°C (2732°F).Subsequent heat treatment of
the composite material may involve tempera-
tures to 3000°C (5432°F).
15.2.2 DISCONTINUOUS FIBER COMPOSITES
Fabrication of discontinuous fiber composites
uses short carbon fibers combined with either
a pyrolytic carbon or pyrolyzed organic
matrix. This approach to CC composites gen-
erally does not have true fiber reinforcement
as an objective. Rather, discontinuous fiber
substrates have been used to:
1. increase fabrication capability of large-scale of the felt. Carbon content in the fibers is
structures;
2. achieve a more nearly isotropic material;
3. increase the composite interlaminar tensile
strength;
4. along with continuous filament substrates,
obtain a stronger composite by providing
additional nucleation sites that serve to
reduce composite porosity.
The most widely used starting materials are a
carbonized, rayon felt substrate with a
pyrolytic carbon matrix and short, chopped
fibers in a pitch-based matrix. Felt is produced
through the mechanical carding of viscous
rayon fibers to produce a continuous web of
fibers. The webs are folded one on top of
another to produce a batt. The batts are then
cut, stacked and needled to produce the
required felt. The rayon felt is subjected to a
controlled carbonization cycle in an inert
atmosphere or vacuum; the maximum temper-
ature determines such factors as shrinkage,
weight loss and chemical composition of the
felt. A maximum carbonization temperature of
1200°C (2192°F) is a nominal standard; the
length of the carbonization cycle and rate of
temperature rise are dictated by the thickness
~ 9 8 % .Carbon-arbon composites have also

Fig. 15.6 Models of fiber arrangements for four short-fiber fabrication techniques: (a) flocking lay-up, (b)
pulp molding, (c) isotropic casting, and (d) spray lay-up (Cook, Lambdin and Trent, 1970; Lambdin, Cook
and Marrow, 1969; Lambdin and Cook, 1971).
338 Carbon-carbon composites
been fabricated from short carbon fibers using
isotropic casting, flocking lay-up, spray lay-up
and pulp-molding techniques (Fig. 15.6)
(Cook, Lambdin and Trent, 1970; Lambdin,
Cook and Marrow, 1969; Lambdin and Cook,
1971.).The rationale for using these short fibers
is to reduce composite anisotropy (Lambdin,
Cook and Marrow, 1969).
15.3 CONTINUOUS FIBER COMPOSITES
Continuous filament substrates reflect the
properties of high-strength filaments or
achieve a high degree of preferred orientation
on the macroscale of the matrix. The fabrica-
tion complexity for continuous-filament
substrates is determined by two parameters:
(1)the directionality of the filaments, and (2)
the amount of layer interlocking achieved in
the substrate. Filament winding of unidirec-
tional tapes can be used to achieve a highly
Fig. 15.7 Interlocking approaches of continuous filament substrates: (a) tape wrapped, shingle; (b) filament
wound, helix; and (c) multidimensional.
oriented substrate, usually with no interlock-
ing between layers. Woven fabrics are used to
form a two-dimensional laminate with no
interlocking between layers. Helical filament
winding, which is directional, results in con-
tinuous, adjacent layer interlocking.
Multilayer locking is achieved through com-
plex weaving patterns or yarn placement
resulting in 'multidirectional' substrates (Fig.
15.7).
15.4 CHEMICAL VAPOR DEPOSITION
The CVD of carbon from a hydrocarbon gas
within a substrate is a complex process.
Various techniques have been applied to infil-
trate various fiber substrates including
isothermal thermal gradient (Pierson, 1968),
pressure gradient (Kotlensky and Pappis,
1969) and pressure pulsation (Beatty and
Kipplinger, 1970).The first two have been the
 Carbonized organic composites 339

most extensively used. The isothermal tech-

nique is illustrated in Fig. 15.8. The substrate is
radiantly heated by an inductively heated sus-
ceptor so that the gas and substrate are
maintained at a uniform temperature.
Infiltration is normally accomplished at
1100°C (2012°F) and at reduced pressures
(6 kPa (50 torr)) with the flow rates primarily
determined by the substrate surface area. This
technique produces a crust on the outer sur-
faces of the substrate, thus requiring
machining and multiple infiltration cycles.
In the thermal gradient technique (Fig.
15.9), the part to be infiltrated is supported by
a mandrel that is inductively heated.
Therefore, the hottest portion of the substrate Hydrocarbon 2(-Carrier Original fiber
is the inside surface, which is in direct contact gas gas substrate
with the mandrel. The outer surface of the
low-density substrate is exposed to a cooler
environment and results in a temperature gra- Fig. 15.8 Isothermal chemical vapor deposition to
dient through the substrate thickness. Surface infiltrate fibrous carbon substrate.
crusting is eliminated because the deposition
rate is greater on the heated fibers near the
mandrel, whereas the cooler outer fibers
receive little or no deposit. Under proper infil-
tration conditions, the carbon is first deposited
on the inside surface and, in a continuous
process, progresses radially through the sub-
strate as the densified substrate itself becomes
inductively heated. Infiltration is normally
accomplished at atmospheric pressure with a
mandrel heated to approximately 1100°C
(2012°F) (Theis et al., 1970).

15.5 CARBONIZED ORGANIC COMPOSITES

Carbonized organic composites have fabrica-
tion procedures that are similar to those of
conventional fiber-reinforced, resin-laminat-
ing techniques. The starting material is usually
a prepregged fabric or yarn (a fabric impreg-
nated with a matrix material in a tacky state).
These precursor materials are staged nomi-
nally at approximately 100°C (212°F) to
achieve the desired degree of tack and flow of
the resin. A laminate is then constructed and Fig. 15.9 Thermal gradient chemical vapor deposi-
cured under pressure. Curing temperatures tion.
340 Carbon-carbon composites
AprepreK+ Cut, lay-up,
Fig. 15.10 Fabrication steps involved in manufacture of 2-D carboniarbon part impregnated with
tetraethylorthosilicate (TEOS).
normally range from 125°C (257°F) to 175°C
(347°F) with curing pressures on the order of
2.76 MPa (400 psi). The reinforced resin lami-
nate is then post-cured at 200°C (392°F) to
275°C (527°F).As pyrolysis is initiated, shrink-
ing occurs as the organic phase decomposes.
Simultaneously the release of vapors from
pyrolysis expands the composite material. A
slow release of these volatile by-products is
required to minimize structural damage to the
char. Finally, as higher temperatures are
reached, thermal expansion of the carbon char
itself occurs after pyrolysis is complete. After
the initial carbonization, the material is then
subjected to a series of reimpregnation and
carbonization cycles until the desired density
or the maximum density is achieved. The
reimpregnation process is usually conducted
under vacuum and pressure to aid in maxi-
mizing the pore filling. If graphitization is
desired, the high-temperature heat treatment
may be used after each carbonization step or at
the end of the reimpregnation and recar-
bonization cycles.
3 t o 5 times I cure I
To summarize, a typical manufacturing cycle
of a 2-D CC part is shown in Fig. 15.10.First, a
woven graphite fabric that is preimpregnated
with phenolic resin is laid up as a phenolic-
graphite laminate in a mold and is autoclave
cured. Once cured, the part is pyrolyzed to
form a carbon matrix surrounding the graphte
fibers. The part is then densified by multiple
furfural alcohol reimpregnations and pyrolyza-
tions. The resulting CC part then is ready for
use in inert or vacuum environments. This
process is very time consuming. A single pyrol-
ysis may take >70 h in a low-temperature,
inert-atmosphere furnace.
Although CC materials can withstand tem-
peratures >3000"C (5432°F) in a vacuum or in
an inert atmosphere, they oxidize and sublime
when in an oxygen atmosphere at 600°C
(1112°F). To allow for use of CC parts in an
oxidizing atmosphere, they must be com-
pounded with materials that produce
oxidation-protective coatings through thermo-
chemical reaction with oxygen at >2000"C
(3632°F) (Buckley, 1967) or they must be coated

and sealed to protect them (Strife and Sheehan,
1988). For applications such as the Space
Shuttle CC leading edges and nose caps, sur-
faces are converted to silicon carbide in a
high-temperature diffusion-coating process
(Fig. 15.10). Because of differences in thermal
expansion between the silicon carbide and the
CC part, the coating develops microcracks
when the part is cooled from the coating tem-
perature. To maintain oxidation protection on
space vehicles such as the Space Shuttle, cracks
are impregnated with tetraethylorthosilicate
(TEOS).The TEOS process leaves silica in all of
the microcracks, greatly enhancing the oxida-
tion protection of the CC substrate. Current
improvements being developed for oxidation
protection of the CC Space Shuttle components
are additions of low-temperature glass formers
that enhance the sealing capability of the exist-
ing coating-TEOS system.
15.6 MANUFACTURING
The fabrication process of the Space Shuttle
Orbiter nose cap and wing leading edge com-
ponents (Fig. 15.11) (Curry, Scott and Webster,
1979) is a multi-step process typical of the
technology used to produce CC composites.
The process steps are illustrated in Figs.
15.12-15.16.
Initial material lay-up is similar to conven-
tional practices with fiberglass-reinforced
plastic parts. Square-weave graphite fabric
impregnated with phenolic resin is laid-up in
an epoxy/fiberglass mold cavity shaped to the
desired configuration (Fig. 15.12) (Curry, Scott
and Webster, 1979).Lay-up thickness for these
components varies from 19 plies in the exter-
nal skin and web areas to 38 plies in the
attachment locations. Upon completion of lay-
up, the part is vacuum-bagged and cured in an
autoclave to 150°C (300°F) for 8 h (Fig. 15.12).
The cured part is rough trimmed, X-rayed and
ultrasonically inspected for irregularities fol-
lowing the cure cycle. Post-cure of the
component involves placing the part in a
graphite restraint fixture loading it into the
Manufacturing 341
RCC Seal strips
(22) LH
(22) RH Wing L.E. RCC panels
Nose cap (1)
RCC Seal strip
(1) LH, (1) RH and
(3) Lower
RCC ExDansion seal
(1) LH, (1) RH and
(3) Lower
Fig. 15.11 Leading edge structural subsystem
(Curry, Scott and Webster, 1979).
furnace and submitting it to a 7-day cycle dur-
ing which it is taken to 260°C (500°F) very
slowly to avoid distortion and delamination
(Fig. 15.12).
The next step is initial pyrolysis as shown in
Fig. 15.13 (Curry, Scott and Webster, 1979).
Pyrolysis tooling composed of graphite
restraining fixtures containing the part are
loaded into a steel retort that is packed with
calcined coke. The retort and its contents then
undergo a 70 h pyrolysis cycle at 815°C
(1500°F)converting the phenolic resin to a car-
bon state. During pyrolyzation, the resin forms
a network of interconnected porosity for the
escape of volatile matter. This stage is
extremely critical since, during controlled char-
ring of the cured resin matrix, the parts are
weak and delamination can easily occur if ade-
quate escape paths and time are not ensured.
After this initial pyrolysis cycle, the carbon is
342 Carbon-carbon composites

2250
I
1650

w 1100
0
j
2 540 ,
I

2 485 ;
g%
:
u1 320
I
I

UJ 260 ;
8 200
z r , h
I\
I:
150' n I

MATERIAL CUT & 0 BAG (MYLAR) 0 A UTO C L A V E 0 REMOVE B A G LOAD IN POST CURE
C OLD I LAY.UP 0 APPLYVACUUM CURE 0 ROUGH T R I M RESTRAIN-
STORAGE I CL O TH 0 CHECK FOR DRILLHOLES ING
j PLIES LEAKS 0 X.RAY A N D / O R FIXTURE
I & ULTRASONIC
I DEBULK

Fig. 15.12 Lay-up and cure cycle (Curry, Scott and Webster, 1979).

2205
- 2250

1650

g iioc
540
F 485
5 430
0 370
320
~ 260
a zw
x
C3 150
95
40
-2c

LOAD IN AUTOCLAVE CURE msi CURE j

VACUUM
LO A DI N PYROLYSIS 0 CLEAN I CHAMBER
RETORT INSPECT IMPREG WITH
PACK WITH FURFURYL
GRAPHITE ALCOHOL
CALCINED COKE
IMPREGNATION CYCLE
ITMREE 131 TIMESI

Fig. 15.13 Initial pyrolysis (Curry, Scott and Fig. 15.14 Densification impregnation and cure
Webster, 1979). (Curry, Scott and Webster, 1979).
 Manufacturing 343

designated reinforced carbon-carbon-0

(RCC-0), a state in which the material is 2250
extremely light and porous with a flexure w 1650 ,
J I
I

strength of 21-24 MPa (3000-3500 psi).

P
F
540

15.6.1 DENSIFICATION
5 485
430
370
w 320
a
Densification for these shuttle parts is accom-
plished in three impregnation and pyrolysis
s 260
200
150
95
40
cycles (Fig. 15.14) (Curry, Scott and Webster, -20

1979).Each part is loaded in a vacuum cham-

ber impregnated with furfural alcohol
followed by a 2-hour cure period in the auto-
clave at approximately 150°C (300"F),
followed by a post-cure for 32 h to 200°C
(400°F). This cycle is followed by a 70-hour
815°C (1500°F) pyrolyzation that is shown in
Fig. 15.13.After three impregnation/pyrolyza-
tion cycles, the material is designated RCC-3
with an increased flexure strength of =124
MPa (18000 psi) at room temperature.
15.6.2 COATING
To allow for use of CC composites at elevated
temperatures above 2000°C (3632°F) in an oxi-
dizing atmosphere, it is necessary to apply
protective coatings to structural components.
The oxidation inhibition process consists of
two steps: (1)diffusion coating the CC compo-
nent and (2) applying a sealer to the surface.
The coating process (Fig. 15.15) (Curry, Scott
and Webster, 1979) used in protecting the CC
shuttle components starts with the blending of
the constituent powders: 10% alumina, 30%
silicon and 60% silicon carbide. This mix is
packed around the CC structural component
in a graphite retort and loaded into a vacuum
furnace where it undergoes a 16-hour cycle
that includes drying at 315°C (600°F) and the
coating reaction to 1650°C (=3000"F) in an
argon atmosphere. The powder characteris-
tics, constituents, formulations and the
manner in which the powders are packed
around the part are important factors that gov-
ern the chemical reactions at the high
processing temperatures, the degree of consol-
:
CLEAN COATING
PREPARATION
' CLEAN
INSPECT 1
, -X.RRY INRETORT SURFACE -X.RAY
! -ULTRASONIC COATING - ULTRASONIC
:e FINALTRIMIDRILL - DIMENSIONAL
.1 DIM. INWECT I
Fig. 15.15 Coating cycle (Curry, Scott and Webster,
1979).
idation and sintering of the powders. During
the process, the outer layers of the CC sub-
strate are converted to silicon carbide. The
silicon carbide-coated CC composite part is
removed from the retort, cleaned and
inspected. During cool down from 1650°C
(3000"F), the silicon carbide coating contracts
slightly more than the carbon substrate, caus-
ing crazing (coating fissures). This crazing
together with the inherent material porosity
provides paths for oxygen to reach the carbon
substrate. To obtain increased useful life of this
CC structural component, it is necessary to
add an additional oxidation inhibitor. The
final process used to provide oxidation protec-
tion to this type of CC structure involves
impregnating (Fig. 15.16) (Curry, Scott and
Webster, 1979)this component with TEOS. The
part is covered with a mesh, placed in a vac-
uum bag and the bag is filled with liquid
TEOS. A 5-cycle TEOS impregnation is then
performed with the bagged part. After the fifth
TEOS cycle, the part is removed from the bag
344 Carbon-carbon composites

W
9 320
9 260
5 200
8 150
w 95
W
U 40
8 -20

45 45 45 45 2 .5 IHRS
TO TO TO TO TO HRS
6 o w m 6 a 2%
MIN MIN MIN MIN HRS

.
F I V E CYCLES
EVACUATE
AND
COATED WEIGHT/ COVER INSTALL CONNECT- BACKFILL REMOVE 0 CURE NDE
PART RECORD wlm - VACUUM VACUUMAND WITHTEOS BAG - % HR @ W ' F - X.RAY
PERSPEC VERIFY MESH FITTINGS F I L L LINES MIX CLEAN - 6HR B W F - EDDY
206.741 -SRi -FILL MIXTEOS OVEN CURE PART CURRENT
- PRi TUEES ILIWIDI 225" + 5O'F -ULTRASONIC
COVER A N D FILL I 4 5 6 0 MINI 0 WEIGH/
WITH MESH RESERVOIR FEED TEOS RECORD
VACUUM M I X A5 R E Q D
BAG TO COVER
5 T H CYCLE CURE
U TO 2x H R MlNl
COOL T O 1WoF

Fig. 15.16 TEOS impregnation (Curry, Scott and Webster, 1979).

and oven cured at 315°C (600"F), liberating all labeled Space Shuttle material, is the strength
of the hydrocarbons. This procedure leaves sil- level of the reusable carbon-carbon (RCC)
ica (SiO,) in all of the microcracks and fissuresmaterial used in the Space Shuttle thermal
greatly enhancing the oxidation protection of protection system. Even though this material
the CC structure. is made with low-strength carbon fibers, its
strength efficiency is superior to both superal-
loys -and ceramics at >lOOO°C (1832°F).
15.7 MECHANICAL PROPERTIES
Development of advanced carbon-carbon
The extreme thermomechanical requirements (ACC) composites has produced a material
of the Space Shuttle have been the impetus for that is twice as strong as the CC composite
evaluating properties of low-density CC. The first put on the Space Shuttle. The ACC mate-
use of CC on the nose cap and leading edges of rial is made using woven carbon cloth. When
the Space Shuttle makes it imperative to know unidirectional carbon fiber tapes are interplied
as much as possible about all the characteris- with woven cloth to create a hybrid ACC,
tics of this material. The effect of temperature strength in at least one direction can be
on the ratio of tensile strength to density for increased by >345 MPa (>50 000 psi). Current
several classes of high-temperature materials data on thermomechanical and thermochemi-
is shown in Fig. 15.17. The major advantage of cal properties of some of the advanced CC
CC materials for high-temperature applica- systems show that material composition, oxi-
tions is that they do not lose strength as the dation resistance, processing, joining and fiber
use temperature is increased. This property is architecture are producing noticeable
in contrast to other materials such as superal- improvements in CC materials and structures
loys and ceramics. Figure 15.17 shows three (Curry, Scott and Webster, 1979; Buch, 1984;
levels of CC strength efficiency. The first, Rummler and Sawyer, 1984; Ransone and
 Thermal properties 345

Temperature, OC
0 ,550 1100 1650
I I I **%O
-
High-strengthcarbon-carbon <- 160

800 1600 2400 3200 4000

Temperature, OF

Fig. 15.17 Strength-to-density ratio for several classes of high-temperature materials.

Ohlhorst, 1984; Webb, 1985; Gray and Engle,
1985; Johnson and Finley, 1985; Sawyer and
Moses, 1985; Maahs and Ransone, 1985;
Ohlhorst and Ransone, 1985).
CC components on the Space Shuttle are
required to have adequate strength at design
temperatures to withstand the aerodynamic
loads of flight and to continue to do so for the
operational life of the component. Minimum
mechanical properties are guaranteed through
statistical analysis of a data sampling having
at least 99% probability and 95% confidence.
The primary variables affecting the structural
design allowables are temperature, material
thickness, coating thickness, biaxial stress con-
ditions and substrate mass loss due to
oxidation through the mission life of the com-
ponent (Table 15.2) (Curry, Scott and Webster,
1979).
Figure 15.18 (Curry, Scott and Webster,
1979) illustrates the typical effect of ply thick-
ness on the allowable stress values for tension,
bending, compression and shear used for
design. As fabricated, room temperature mod-
ulus values for the TEOS material are shown
in Fig. 15.19 (Curry, Scott and Webster, 1979).
The effect of temperature on the as-fabricated
tension strength properties is shown in Fig.
15.20 (Curry, Scott and Webster, 1979). As
shown in Figs 15.17 and 15.20, the strength of
CC composite material does not decrease sig-
nificantly with temperature. Typically, above
1425°C (2600°F) there is an increase in
strength.
The effect of substrate mass loss through
oxidation on tensile strength is shown in Fig.
15.21 (Curry, Scott and Webster, 1979). Mass
loss results in a significant reduction in design
allowable stress, emphasizing the value of the
additional oxidation protection provided by
the TEOS treatment.
15.8 THERMAL PROPERTIES
15.8.1 THERMAL OXIDATION
A critical requirement when using CC com-
posites is the ability to withstand numerous
346 Carbon-carbon composites

Table 15.2

Mechanical properties test Non-TEOS TEOS

-. __
as fabricated conditioned as fabricated conditioned
Flexure 201 221 40 24
Tension 196 80 52 34
Compression 170 57 46 28
Shear 192 79 17 17
Comer flexure 20 - 3 3
Interlaminar tension 20 50 5 5
Interlaminar shear 30 19 - -
Coefficient of thermal expansion 10 6 9 6
Impact, etc. 20 10 - -

Simultaneous cycling - - 3 18
Mission cycling
Tension 3 36 - -
Flexure 3 24 - -

Compression 3 27 - -

Total 868 609 175 135

COMPRESSION

NOTE
BREAK
IN
SCALE TENSION 7

IN-PLANE SHEAR

14 I I 1 I 1 I
15 20 25 30 35 40
NUMBER OF PLIES

Fig. 15.18 Design allowables at room temperature as-fabricated (Curry, Scott and Webster, 1979).
 Thermal properties 347

35 r T V P I C A L SECANT HOOVLUS

E
Y
14
t
7.0 1 Gw
3.5 1 1 I 1 1 I 1
I5 10 25 30 35 4a
NUMBER OF PLIES

Fig. 15.19 Design allowables at room temperature as-fabricated (Curry, Scott and Webster, 1979).

thermal and thermomechanical loads during
re-entries of the Space Shuttle into the earth's
atmosphere. Although CC Space Shuttle com-
ponents have an oxidation-inhibiting silicon
carbide coating, they can lose mass over an
extended temperature range without apparent
surface recession. Photomicrographs of CC
specimen surfaces show minute fissures and
thermal microcracks, some of which terminate
at the coating substrate interface. Specimens
exposed to convective and radiant heat trans-
fer tests micrographically have shown the
presence of voids at the coating substrate sur-
face. Tests to characterize the effects of these
flaws were performed over a wide range of
pressures and temperatures in both plasma arc
jets and radiant-heating test facilities. Arc jet
tests on CC specimens ranged in temperature
from 815°C (1500°F) to 1870°C (3400°F) and
atmospheric pressures from 0.01 Pa to 0.10 Pa.
Radiant-test conditions ranged from 420°C
(800°F)to 1425°C (2600°F)and pressures rang-
ing from 0.01 Pa to 1.0 Pa. Mass-loss data for
the CC shuttle specimens exposed to the arc jet
and radiant-heating tests are presented in Figs
15.22 and 15.23. Figure 15.22 (Curry, Scott and
Webster, 1979) shows mass loss at 980°C
(1800°F)and 0.05 Pa as a function of exposure

z0 . ---_______________---------
___- 28 PLY
111 P L V
2
Y

E 35
.
2
0 -
v)
2
w
I-

28 -
m
ss -
2 ur
< 2 1 - I I . I I I I I 1

Fig. 15.20 Design allowables as-fabricated (Curry, Scott and Webster, 1979).
348 Carbon-carbon composites

38 PLY
28 PLY
25 P L Y

1s P L Y

3
c
UJ 1.4

I 1 I 1 J
0 4.9 9.8 14.7 1U.6 24.5
MASS LOSS - kdm’x 1P

Fig. 15.21 Design allowables conditioned (Curry, Scott and Webster, 1979).

P n
z 19.6 -
n 39.0

NONTEOS \ /
/ -
-i
.x
W

- /
d/
/
/
P
9
I 14.7
v)
8/
v)
P,
s N O N TEOS
’ /
/

$ 9.8 - ,
4
I ,

- 9 . 8 W I T1
H TEOS 1
4.9 - d / ,’ &--e---
B
8 \WITH TEOS
I I I I 1
a 2 4 6 8 10 0 2 4 6 8 10
EXPOSURE TIME HOURS EXPOSURE T I M E HOURS

Fig. 15.22 Mass loss comparison plasma arc jet Fig. 15.23 Mass loss comparison radiant environ-
environment (Curry, Scott and Webster, 1979). ment (Curry, Scott and Webster, 1979).

14.5 7
11.1-
'F ai.
B
E
1
8
i'
5'8'
2.9.
-THERMAL
a
f
-0
-28(1
+T
-OTAL
-18
TEMPERATURE "C
Fig. 15.24 Reinforced carbon-carbon thermal properties (Curry, Scott and Webster, 1979).
thermal conductivity is dependent upon the
mass loss experienced by the CC composite,
resulting from subsurface oxidation.
Results of thermal conductivity studies for
shuttle CC composite shuttle materials are
shown in Fig. 15.24 (Curry, Scott and Webster,
1979).To simplify thermal modeling, no differ-
entiation has been made for conductivity
variation resulting from the number of plies in
the substrate. Results for conditioned speci-
mens having a mass loss of 0-5 Pa (0.1 lb/ft2)
suggest that thermal conductivity decreases
with mass loss. Figure 15.24 also shows that
neither specific heat nor emittance was
affected by material or mass loss conditioning.
15.9 APPLICATIONS
An example of the state of the art in CC com-
posite applications is a one-piece, bladed
turbine rotor that, in service, is coated to pre-
vent oxidation. The rotor offers higher
temperature performance without cooling;
low weight and use of low-cost, non-strategic
materials (Miller and Grimes, 1982).Other gas
turbine engine applications using CC compos-
ites include exhaust nozzle flaps and seals,
augmenters, combustors and acoustic panels.
Applications 349
,- SPECIFIC HEAT
THERMAL CONDUCTIVITY
\
PARALLEL TO PLY
CONDUCTIVITY PERPENDICULAR
TO PLY
280
EMISSIVITY
538
818 1094
-
1372 16sO
CC material systems using coatings, TEOS
and additions to the basic CC recipe have
improved the oxidation resistance of products
made of CC composites by an order of magni-
tude. These composites are being used in
products such as the nozzle in the F-100 jet
engine afterburner, turbine wheels operating
at >40 000 rpm, nonwetting crucibles for
molten metals, nose caps and leading edges
for missiles and for the Space Shuttle, wind-
tunnel models and racing car and commercial
disk brakes (Klein, 1986).
Pushing the state of the art in CC compos-
ites is the piston for internal combustion
engines (Miller and Grimes, 1982; Taylor,
1985). The CC piston (Fig. 15.25) would per-
form the same way as any piston in a
reciprocating internal combustion engine
while reducing weight and increasing the
mechanical and thermal efficiencies of the
engine. The CC piston concept features a low
piston-to-cylinder wall clearance; this clear-
ance is so low, in fact, that piston rings and
skirts are unnecessary. These advantages are
made possible by the negligible coefficient of
thermal expansion of this kind of CC (0.54 x
/OF). (Carbon-carbon composites can
have a range of thermal expansion coefficients,
350 Carbon-carbon composites
Fig. 15.25 Carbon+arbon automotive piston.
depending on the processing techniques.) CC
material maintains its strength at elevated
temperatures allowing the piston to operate at
higher temperatures and pressures than those
of a comparable metal piston. The high emit-
tance and low thermal conductivity of the CC
piston should improve the thermal efficiency
of the engine because less heat energy is lost to
the piston and cooling system. The elimination
of rings reduces friction, thus improving
mechanical efficiency.
Besides being lighter than conventional pis-
tons, the CC piston can produce cascading
effects that could reduce the weight of other
reciprocating components such as the crank-
shaft, connecting rods, flywheels and
balances, thus improving specific engine per-
formance (Taylor, 1985).
ACKNOWLEDGEMENTS
The author acknowledges Mr. D.M. Curry of
NASA Johnson Space Center and H.C. Scott
and C.N. Webster of the Vought Corporation
for the data, as referenced, on which a portion
of the present paper is based.
Acknowledgement is also given to Mrs. H.A.
Coombs for her valuable contribution in
assisting in the formatting of this paper.
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Ransone, P.O. and Ohlhorst, C.W., 1984, Interlaminar
Shear and Out-of-Plane Tensile Properties of
Thin 3-D Carbon-Carbon. Metal Matrix, Carbon
and Ceramic Matrix Composites, (ed. John D.
Buckley) NASA CP-2357, pp. 137-148.
Rummler, D.R. and Sawyer, J.W., 1984, Properties
and Potential of Advanced Carbon-Carbon for
Space Structures. Metal Matrix, Carbon and
Ceramic Matrix Composites, (ed. John D. Buckley)
NASA (3-2357, pp. 149-170.
Sawyer, J.W. and Moses, P.L., 1985, Effect of Holes
and Impact Damage on Tensile Strength of Two-
Dimensional Carbon-Carbon Composites.
Metal Matrix, Carbon and Ceramic Matrix
Composites, (ed. John D. Buckley) NASA
(3-2406, pp. 245-260.
Stoller, H.M., Butler, B.L., Theis, J.D. and Lieberman,
M.L., 1974, Carbon Fiber Reinforced-Carbon
Matrix Composites. Composites: A State of the Art,
(eds. J.W. Weeton and E. Scala) Metallurgical
Society of the American Institute of Mining,
Metallurgical and Petroleum Engineers, Inc., pp.
69-136.
Strife, J.R. and Sheehan, J.E., 1988, Ceramic Coatings
for Carbon-Carbon Composites. Ceramic Bulletin
67(2):369-374.
Taylor, A.H., 1985, Carbon-Carbon Pistons for
Internal Combustion Engines. NASA Tech
Briefs 9 (4):156-157.
Theis, J.D., Jr., Taylor, A.J., Rayner, R.M. and Frye,
E.R., 1970, Filament Wound Carbon/Carbon
Heatshield SC-11FW-Y12-7, A Process Histoy.
SC-DR-70425, Sandia Labs.
Webb, R.D., 1985, Oxidation-Resistant
Carbon-Carbon Materials. Metal Matrix, Carbon
and Ceramic Matrix Composites, (ed. John D.
Buckley) NASA CP-2406, pp. 149-162.
HAND LAY-UP AND BAG MOLDING 16
D.R. Sidwell

16.1 INTRODUCTION Table 16.1 Advantages and disadvantages of hand

lay-up structures
This chapter presents practical fabrication and
tooling methods that have been successful for Adva n tages
high performance applications. Increasing per-
Design flexibility
formance requirements limit traditional hand Large and complex items can be produced
(’wet’) lay-up methods. Today’s prepreg resin Minimum equipment investment is necessary
systems allow for longer working life and low Tooling cost is low
cure temperatures. Improvements have made The start-up lead time and cost are minimal
the current prepreg systems the choice for high Design changes are easily effected
performance composite structures. Molded-in inserts and structural reinforcements
Composites are a combination of a high are possible
Sandwich constructions are possible
performance resin matrix and various fiber
Proto-typing and pre-production method for
combinations, which have brought about a molding processes
change in the engineer’s traditional approach Semi-skilled workers are needed, and worker
and allow matrix alloying for specific struc- training is minimal
tural applications. Improved materials,
Disadvantages
analysis and manufacturing methods have let
traditional composite structures reach new The process is labor-intensive
limits of achievement. Table 16.1 presents Only one tooled (molded) surface is obtained
Quality is related to the skill of the operator
some of the advantages and disadvantages of It is a low-volume process
hand lay-up of composite structures. Longer cure times required
Composite structures have been manufac- The waste factor can be high
tured from fiberglass and wood to some of the
most expensive 800 GPa pitch fibers for space
applications. The engineer’s imagination is the a structural part upon which the external paint
only limitation in the fabrication of composite finish is applied. The reverse of this procedure
structures. Large, complex co-cured structures occurs with composite materials fabrication,
are successfully manufactured with all engi- where the formless materials harden and take
neering and manufacturing disciplines the shape of the container into which they are
working as one. applied. The makeup of the resulting laminate
In the fabrication of wood or metal prod- is an elementary engineering material. The
ucts, flat sheet stock is joined together to form physical properties can be changed by varying
the resin and fiber ratio, the type and direction
of reinforcement and the type of resin matrix.
Handbook of Composites. Edited by S.T. Peters. Published Today bag molded (vacuum and pressure)
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 composites provide higher performance and

are competitive with alternate types of con-
structions that result from optimization of
process controls, design refinements and
improved materials. Composite designs and
bag molding processes are interrelated by pro-
duction goals, the desire to control
manufacturing costs and by service or mission
requirements. The responsibilities shared by
fabricators and designers include:
0 reproducibility and knowledge of process-
ing characteristics of candidate materials;
knowledge of requirements for facilities
and tooling including provisions for assem-
bly, inspection and quality control;
0 reduction of total part count;
0 avoiding design as replacement for sheet
metal;
0 selecting the best material for the applica-
tion.
16.2 HISTORY
Composite materials first arrived in the New
World with the early Spanish explorers who
produced adobe bricks for the building trades
from a mix of straw and adobe clay. Modern
day users developed the chopper gun and
fiberglass roving that use low cost inexperi-
enced labor; many fabrications utilize ’wet’
lay-up for making bath tub enclosures and
truck hoods. Early use of carbon fiber compos-
ites was primarily for secondary structure
aerospace applications. In the early 1970s, the
first woven graphite fabric was developed for
aerospace structural applications.
Complex and highly detailed hybrid (unidi-
rectional and woven carbon materials)
structures were developed for an interconti-
nental ballistic missile (ICBM) program. It did
not take long to integrate the woven graphite
prepregs into mainstream production, reducing
labor costs over 70% from that of the previous
unidirectional tape structures. During the
1980s, composite hybrids were developed
using the best of all material forms available.
The hybrid structures utilizing both unidirec-
Histoy 353
tional and woven product forms (fiberglass,
graphite and aramid) were developed for com-
mercial applications; aerospace structures were
the prime users of 100%graphite materials.
The fabrication of a 1979 Ford LTD with a
finished weight of 1138 kg (2504 lb) proved
that graphite could be used as reinforcement
for just about any automotive component
including bumpers, hoods, frames, doors and
drive line. The major drawback to automotive
use of these composites was the processing
cost. During the 1990s, processing times were
reduced to acceptable levels (less than 5 min)
for automotive components, using resin trans-
fer and resin injection molding. Improved
mechanical properties, lower costs and
improved resin systems allowed for greater
inroads for fiber-reinforced plastics in the
automotive industry.
The use of ultra high modulus pitch-based
carbon fiber in modern communication satel-
lites has led to refinement in the art of hand
lay-up and vacuum bag molding. The primary
structural element of some communications
satellites is a central cylinder. A typical cylin-
der is about 180 kg (80 lb) and supporting a
13 000 kg (6000 lb) payload at launch. A typical
cylinder consists of 520GPa (75msi) pitch
fiber skin laminates and aluminum honey-
comb core, the structure is oven co-cured
utilizing a nylon vacuum bag. The require-
ments for ever lighter structures created the
need for ultrathin unidirectional prepregs.
Solar array panels for a modern communi-
cations spacecraft required the use of
0.0004 cm (0.001 in) thick unidirectional
520 GPa (75 msi) graphite prepreg. Solar array
panels, made with three-ply skins bonded to
an ultralight honeycomb core, are manufac-
tured on a regular production basis, utilizing
vacuum bag molding process and oven cure.
An example of what can be involved in a
high visibility composite materials application
was the 1992 America’s Cup Challenge, the
first application of graphite composite materi-
als for the America’s Cup racing yachts. The
example utilized here is the ’Spirit of
354 Hand lay-up and bag molding
Australia’ program entered by the Darling
Harbor Yacht Club, Sydney, NSW, Australia.
(See section 16.7.2.) Design and analysis were
performed by Ian Murray and Associates,
yacht designers; the design parameters were
established by the America’s Cup Rules
Committee. The program objective, deter-
mined in large part by available funding, was
to manufacture one America’s Cup racing
yacht. A program of this magnitude requires a
substantial amount of material. The ’Spirit of
Australia’ was a relatively small program
compared with some of the other syndicates.
Twenty-seven America’s Cup yachts were fab-
ricated, representing eight countries, with a
total investment of over $600000000. The
material combinations utilized in the hull con-
struction of the various entries included
Spectra, aramid, graphite and wood. The over-
all goal was to acheve the specified minimum
laminate density and still retain the required
load carrying capabilities.
Various hybrids of Spectra/graphite,
aramid/graphite and graphite/wood were
utilized to achieve the design results. The pro-
gram for ’Spirit of Australia’ required much
dedication from supporters and suppliers to
make it to the elimination trials with competi-
tors. There were significant other concerns in
addition to the normal decision factors in
selecting composite materials for a program,
such as mechanical properties, tack, resin flow
and gel. These other concerns can have a large
influence on the program outcome and require
planning the materials’ delivery schedule,
testing, packaging, export license, custom for-
malities and shipping method. If the program
is within a few hours flight time, the prepreg is
usually packed with dry ice and shipped on
the next available aircraft. On international
programs, the weight of just the dry ice can
equal the material cost and delivery takes 3 4
days. Scheduling becomes the critical path in
overall planning. In the case of ’Spirit of
Australia’, America’s Cup challenge 1993, air
shipments were a minimum of three days. The
three days were a best effort to get the mater-
ial from the supplier, to the freight forwarder,
airline, customs, importer clearing house and
then delivered to the manufacturing facility.
This effort can go astray; the shipment can be
off-loaded at an intermediate stop or off-
loaded at the incorrect destination. Sea
shipping requires 30 days to get material from
the manufacturer to a sea forwarder, provid-
ing the container is off-loaded as scheduled.
All of these considerations combined with
availability of funds and tight fabrication
schedule play a primary role in design and
fabrication decisions.
16.3 MATERIALS
Fiber reinforced composite materials are now
being used to satisfy the high strength and/or
stiffness-to-weight requirements of aerospace
structures. Fibers of extremely high strength
are incorporated into a relatively weak matrix
that is used to bind the fibers; the combination
results in a light, extremely strong structural
material. Experience and theoretical studies
have shown that fibers will always be stronger
than bulk materials. Some of the properties
that can be improved by combining the con-
stituents into a composite are strength,
stiffness, wear resistance, corrosion resistance,
fatigue life, temperature resistance and electri-
cal and thermal conductivity.
The relationship between resin viscosity and
the cure cycle can be used to obtain maximum
performance in a composite structure. Figure
16.1 shows the relationship between resin vis-
cosity and a stepped autoclave cure cycle. The
curves shown are for a typical 121°C (250°F)
curing epoxy resin system. The viscosity will
vary with a change in heat-up rate and tem-
perature. This information relating the effect of
rate and temperature is available from the
material suppliers. Using this information as a
starting point, a cure cycle can be defined for a
specific composite structure. The cure cycle
production capability becomes increasingly
important as the complexity of the composite
structure increases. To help in planning a
 Materials 355

Apply 689 KPa

(loo PSI)
when Part
Reaches 78OC
Heat at 2°C +3"C, Hold 15 Heat at 2% per Hold 120 Minutes at Down to 75
Per Minute Minutes Minute 120°C "C
Curecycle I 1 II I II I

125

Resin Flow-

.1
0 101 201 301 401 501 60I 200
Time (Minutes)
Resin Flow 1 I
I
I
I
I
I
I
I b
Initial Resin Removal of Maximum Resin Resin Crosslinking and Cool Down
Flow Entrapped Air Resin FIOW Gel
and Resin
Bleed

Fig. 16.1 Typical autoclave stepped cure cycle.

composite structure, the material supplier can spray-up. In contact molding, after a gel coat-
provide information on specific applications, ing is applied to the mold (if required),
processing parameters, material properties, fiberglass chopped mat, cloth or woven roving
test data and fabrication methodology for the is placed into the mold, saturated with resin
material. Because most materials have compet- and brushed or rolled to compact the material
itive products available, one must consider not and remove entrapped air. This process can
only the price and delivery available but also also utilize 'wet' prepregs. The wet composite
local technical support in selecting a supplier. is then vacuum bagged to compact the mater-
There are two basic types of composite ial and remove entrapped air. Spray-up
matrix fiber combinations: chopped-fiber reinforced composites consist of relatively
reinforced composites and continuous-fiber short fibers mixed with a matrix or binder
reinforced composites. The selection of the material resulting in a composite with gener-
proper matrix material for use in a particular ally lower physical properties.
structure is influenced by many factors Continuous fibers in a matrix material result
including weight limitations, environmental in a composite that exhibits higher strength and
resistance and types of loading. stiffness than the chopped-fiber counterparts.
'Wet' lay-up procedures are divided into Fabrication of parts that use continuous-fiber
two main types, contact or open mold and reinforced composites can be achieved by
356 Hand lay-up and bag molding

several techniques such as hand or machine 1. Thermoplastics. Thermoplastics may be

lay-up, filament winding and pulhusion. shaped, remelted and reshaped, much like
Hand lay-up composites are a special case candle wax. Examples of thermoplastics are
of continuous fiber reinforced composites. nylon, polysulfone, polyethylene, polyvinyl
Layers of unidirectional or woven bidirec- chloride and polyarylsulfone.
tional composites are combined to result in a 2. Thermosetting. Thermosets, once shaped and
material exhibiting desirable properties in one set, cannot be remelted and reset (like a
or more directions. Each layer is oriented to cooked egg it cannot be uncooked). When
achieve the maximum utilization of its proper- heated, a thermosetting plastic becomes
ties. Layers of different materials (different increasingly infusible. It undergoes an irre-
fibers in different directions) can be combined versible chemical change called
to further enhance the overall performance of polymerization (a process in whch simple
the laminated composite material. Some of the molecules combine to form more complex
initial considerations that must be considered ones) during curing of the material.
before undertaking the manufacture of a com- Examples of thermosets are polyesters,
posite structure are: epoxies, phenolics, cyanates and poly-
imides.
0 performance goal to be achieved;
0 can the structure be designed to reduce part In advanced composite materials manufac-
count? ture, there are controls to provide a workable
0 do not duplicate a sheet metal design; resin system. The main control points include
0 manufacturability - in-house or outside volatile content to minimize voids and delam-
supplier; inations, tack that controls the handling of the
0 overall cost compared with performance; prepregs, flow to allow removal of excess
0 use only the amount of expensive materials resin and entrapped air and gel that deter-
needed. mines the point at which the resin starts cross
linking.
Many structures can be designed and manu-
factured with fiberglass laminates using
small amounts of graphite, aramid or Spectra, Volatile content controls
hybridized to obtain the additional stiffness
or reduced density. The high performance of Quality control test results do not distinguish
graphite (both PAN and Pitch) is attractive inert from reactive volatiles but are used to
for fishing rods, tennis rackets, golf clubs and establish volatile content values. They provide
racing applications. Special incentives for qualitative evaluations of prepreg advance-
performance can make cost a secondary ment, degree of volatilization of solvents and
objective. amount of degradation due to aging. Volatile
contents measured prior to lay-up are com-
pared to values when the prepreg was first
16.3.1 MATRIX MATERIALS received and may provide indications of
Plastics are used as the matrix material in excessive aging.
most fiber reinforced composites. These
materials are generally of high molecular
Tack controls
weight and intricate molecular complexity.
Their form and properties can be transformed Tack is the adhesion characteristic that is con-
by the techniques of applying heat and/or trolled to facilitate lay-up operations. It is
pressure. In general, plastics can be divided affected by resin and inert volatile content,
into two categories: prepreg advancement and humidity and

temperature of the lay-up room. Sometimes,
tack is increased by increasing resin and
volatile content, less prepreg advancement, or
a slight increase in lay-up room temperature.
At other times, tack can be modified by the
prepreg manufacturer by changes in resin for-
mulations or new additives blended into the
resin. Alterations to the formulations should
not be accepted without prior requalifications
by the user. Often, properties are severely
affected for a cured laminate; therefore, per-
formance and durability must be verified.
Prepregs with excessivelyheavy tack gener-
ally cannot be handled without grossly
disrupting resin distribution and fiber orienta-
tion or causing a roping (fiber bundling) of the
composite laminate. Excessive tack makes it
difficult to achieve reproducibility in compos-
ite structures since undetermined amounts of
resin are always removed when the release
film or backing is separated from the prepreg.
In general, all the disadvantages of wet lay-up
systems are inherent in the excessively tacky
prepregs.
Prepregs with no tack are either excessively
advanced or have exceeded their normal stor-
age life. Such materials cannot attain adequate
cured properties and should be discarded.
Exceptions are silicones and some polyimides
that can only be prepared with no tack. Lay-
ups with these materials are limited to those
occasions where lower mechanical properties
can be tolerated in exchange for improved
heat resistance or electrical properties.
Thermoplastic prepregs typically do not
exhibit much tack.
Most prepregs are staged to attain more
manageable tack. The tack qualities should be
adequate for adhering the prepreg to prepared
molding surfaces or preceding plies for a lay-
up and still light enough to release the backing
film without loss of resin. Provided that cured
laminates will not be adversely affected, tack
qualities can be specified to require the
prepreg to remain adhered to the backing until
a predetermined force is applied to peel it off.
Tack requirements can be modified to suit
Materials 357
individual plant fabrication conditions. Air
conditioning minimizes local temperature and
humidity sensitivities; reducing the tempera-
ture makes heavy tack manageable. Judicious
use of hot air guns can improve dry tack.
Flow controls
Flow measurements indicate resin capabilities
to fuse successive plies in a laminate and bleed
out the void producing gas reaction by-prod-
ucts. Flow is also an indicator of prepreg age
or advancement. It is often desirable to opti-
mize resin content and tack to attain adequate
flow but, in some cases, flow is controlled by
thickening additives in a resin.
Gel times
Gel time is an indicator of the degree of cure of
resin systems. The amount of staging or
advancement limits gel time for prepregs.
Most prepregs are formulated to attain a use-
ful life (out time) of 8 days or more at standard
atmospheric conditions. Out time can be pro-
longed by storage at -18°C (O'F), but each time
the prepreg is brought to equilibrium at room
temperature, the useful life is shortened. Gel
time measurements can be used as quality
control verifications. Criteria based on those
results determine whether to initiate more
costly property testing or to dispose of an
overage prepreg.
Storage
Most advanced composite hand lay-up mate-
rials that are utilized today are
time/temperature critical. Precautions must
be taken in handling, storage and processing.
During the initial processing, where resin is
impregnated onto the reinforcement fiber, the
degrading of the materials starts the moment
the resin is applied to the reinforcement.
However, cases exist where material has been
stored at -18°C (0°F) for as long as 5 years and
was capable of molding a commercially
358 Hand lay-up and bag molding

acceptable laminate. A new generation resin fiberglass fiber

system, the cyanates, tends to be more stable 0 high impact strengths;
than epoxies and outlife has been increased 0 good overall performance;
from 10-14 days to 3 0 4 5 days. Storage at 0 low costs;
-18°C (0°F) has also increased from 6 months 0 available in many forms;
to 1year. 0 higher density.
In planning a project, one should consider
Aramid fiber
the amount of material needed within a given
0 high impact strengths;
period of out time to complete the lay-up and
0 high specific modulus;
cure of a composite component. If one can fab-
0 poor compression strengths;
ricate enough composite parts in a 10 day
0 high costs;
period to utilize a 22 kg (50 lb) roll of mater-
0 difficult to handle.
ial, then that is the size that one should
procure. If not, reduce the size of the roll Spectra fiber
accordingly. By doing this, the material roll 0 very low density;
has to be removed from the freezer only once 0 difficult to handle;
and the recorded out time can be accurately 0 bond interface poor;
maintained. 0 very high impact resistance;
0 high costs.

16.3.2 REINFORCEMENTS
In continuously reinforced composites, the
fibers carry nearly all of the load applied to the
system, with the matrix transferring the load
into the fibers. In chopped fiber reinforced
plastics, the load is distributed between the
fibers and matrix, depending upon the nature
of the constituents,percentages of each and the
orientations of the fibers. Selection of the
proper fiber for a specific application depends
upon the type and magnitude of loading, oper-
ating temperature and cost limitations. The
following are attributes of several applicable
fibers:
PAN-based carbon fiber
0 high strengths;
0 improved strain to failure;
0 workable;
0 available in many forms.
Pitch-based carbon fiber
0 high to ultra high modulus;
0 low strain to failure;
0 high cost;
0 can be difficult to handle.
Carbon fiber reinforced composites
Carbon/graphite fiber is an attractive material
because it has the best balance of material
characteristics to compete with metals. Carbon
fiber is the end product of a series of manufac-
turing processes that begin with the basic PAIV
precursor that is carbonized and graphitized.
It is then collimated, woven or, chopped to
become tape, cloth, or molding compound
when prepreged with an appropriate matrix
material. Carbon composites offer many
advantages over conventional materials.
Major advantages are:
0 high specific strength and stiffness;
0 can be woven into cloth;
0 dimensional stability at temperature;
0 tight product control;
0 ease of manufacturing;
0 high fatigue resistance;
0 extremely complex structures can be fabri-
cated.
While offering significant advantages, carbon
fiber does present the following problems rel-
ative to conventional materials that must be

considered when designing for specific appli-
cations:
low strain to failure compared to most metals;
relatively low impact resistance;
potential for galvanic corrosion;
potential matrix bonding problems;
low interlaminar shear;
high cost;
chemical resistance.
Non-woven and collimated tape
During lay-up with unidirectional tape, there
are several techniques that will help achieve a
cost effective structure. As soon as unidirec-
tional tape has been selected, start preliminary
planning as to ply orientations and develop
basic patterns for the initial fabrication. The
results of this preplanning will be that wastage
will be minimized and better quality can be
built into the finished part,
Using unidirectional tape on contoured sur-
faces presents a number of lay-up problems.
As the tape is placed on the mold surface, the
orientation can change dramatically during its
application. In order to minimize angle
changes, narrow pieces of unidirectional tape
can be used. Scrap material can be used for
local reinforcements and to fill gaps between
pieces of unidirectional tape. Gay filling pieces
up to 3.2mm (1/8 in) wide are generally
acceptable,
Woven fabric
Joints with woven materials can be more of a
challenge than those with unidirectional tape.
On a highly stressed composite structure, the
selvage edge must be removed to minimize
the discontinuities in the lay-up joints. Joints
in succeeding plies must not be adjacent but
staggered by a minimum of 51 mm ( 2 in).
Hybrid materials
Many combinations of composite materials
have been developed over the past 15 years.
Materials 359
Some are better than others; some have appli-
cation only to specific needs of a particular
structure. Some of these are presented to show
the basic selection process that is required in
the initial design phase and the manufactura-
bility of each product form into a successful
composite structure.
All fibers can be obtained in many different
forms: unidirectional tapes, Unidirectional
tows or yarns, woven cloth, chopped and in
hybrid Combinations. The combinations are
unlimited in hybridizing fibers together. The
following list shows some of the hybrid rela-
tionships and Table 16.2 shows some of the
properties of composite material forms.
Carbon/fiberglass
0 high impact strengths;
0 high modulus;
0 high performance;
0 cost effective.
Spectralcarbon
0 improved bond interface;
0 little improvement in overall properties;
0 low density.
Aramid,@ergIms
0 reduced overall costs;
0 limited applications.
Aramid/graphite
0 limited applications;
0 high costs;
0 highly resistant to cracking;
0 better impact resistance.
16.3.3 EXPENDABLE MATERIALS
Supporting materials can contribute to a pro-
gram’s success as much as the composite
structures. If there are problems with the vac-
uum bag, release film, or sealant tape, the final
product quality can be compromised although
the overall unit cost of most of these materials
is low. Specifications to control support mate-
rials have been slow to develop with the
industry. There have been problems with
expendables such as release coating of porous
360 Hand lay-up and bag molding

Table 16.2 Limits of composite material forms

Material Fiber Tensiltf Compressionc Tensile

form modulus properfies properties modulus
GPa MPa MPa GPa
(mi) (ksi) (ksi) (mi)
Fabric
Graphite 8HS 228 586-724 522489 62-83
(33) (85-105) (80-1 00) (9-12)
Graphite 5HS” 228 758-896 758-827 76
(33) (110-1 30) (110-120) (11)
Graphite 5HSb 537 927-1114 240 188
(75) (132-158) (34) (26.7)
E-glass 8HS 72.4 462483 469-510 22.0-26.2
(10.5) (67-70) (72-74) (3.2-3.8)
Kevlar‘ 49 8HS 130.9 510-579 138-1 79 29.6-33.8
(19.0) (74-84) (20-26) (4.34.9)
Unidirectional tape
Graphite 228 1586-1 792 1517-1 724 124-138
(33) (230-260) (220-250) (18-20)
Graphite” 228 1930-2137 1379-1 723 138-152
(33) (280-310) (200-250) (18-20)
Graphite 345 1069-11 72 896-1034 200-228
(50) (155-1 700) (130-150) (29-33)
Graphiteb 520 1760 420 300
(75) (256) (61) (44)
Graphite 720 1760 330 420
(105) (256) (48) (61)
Graphite 780 1760 330 450
(114) (256) (48) (65)
E-glass 72.4 1034-1171 483-620 41-55
(10.5) (150-170) (70-90) (6-8)
S-2 glass 86.8 1241-1379 552-690 48-62
(12.6) (180-200) (80-100) (7-9)
Kevlar‘ 49 130.9 882 - 64.9
-
(19) (128) (9.4)

a High strength >3447 MPa (>500ksi) PAN based graphite fiber

High strength >3630 GPa (>SO0ksi) pitch based graphite fiber
Composite laminate properties

Teflon fabric where there was insufficient coat-
ing material to provide an effective release,
resulting in a bond between the Teflon fabric
and the composite structure and when using a
perforated release film, the perforations were
torn rather than pin pricked, allowing exces-
sive resin bleed.
Specifications would help limit the incon-
sistency of some of these products. If one
encounters a problem utilizing support mate-
rials, contact the supplier who can provide
technical assistance on its products. During
the lay-up of composite structures, care must
be taken to insure that all areas are covered
with a release or separator film. The bleeder
and/or breather will bond nicely to composite
laminates if there is no separator.
 Tooling 361

16.4 TOOLING for steel, include superior durability, ample tol-

Tooling includes materials, equipment, or erance for elevated temperature service and
forms onto which (or into which) the product good thermal conductivity.
is made, assembled, or cast. Tooling issues are Ceramics have favorable characteristics for
a result of a number of interacting require- molds. They have the lowest coefficient of
ments that are considered when selecting the thermal expansion and their thermal conduc-
most cost effective tooling. These require- tivity approaches that of some hardened tool
ments are as follows: steels. However, ceramics are brittle at ambi-
ent temperatures and they must be protected
ability to achieve a uniform heat up rate, from processing and handling hazards. One
taking into account the mass of the tool; way to get protection is to enclose ceramic
allowing sufficient movement of the lami- inserts in a steel case.
nate while achieving pressure and Dual steel molds are candidate tools for
compaction in all regions; reproducing high quality composites.
accommodating resin flow; However, these tools are costly and produc-
facilitating or allowing for removal of cured tion quantities are often not sufficient to
part; amortize tooling costs at competitive prices for
realistic tolerance for tool and laminate; the production items so less costly alternatives
finishing requirements - coarse finish can are desirable.
create lock-on problems; Aluminum molds are less costly. Although
adequate area for applying sealant tape for thermal conduction is better for aluminum
vacuum bagging and test coupons as than for steel, the tools are less durable and the
required; thermal expansion is large. Shallow or flat
provisions for vacuum fittings and han- mold plates are usually limited to cures below
dling of tool. 177°C (350°F). Other metal tools include
Tooling is less expensive for vacuum bag and sprayed or electroformed molds reinforced
autoclave/oven molding than for matched die with cast backings. Alternate types of tooling
can include composite molds usually based on
molding methods. Molds and molding plates
high temperature resistant cast or laminated
are required to withstand curing conditions
epoxy resins.
without distorting or degrading and to toler-
Master forms for laying-up composite tools
ate handling during the fabrication processes.
can also be fabricated using any of the materi-
They are not necessarily resistant to unbal-
als described; a mock-up model of the item
anced pressures. The higher costs of composite
may be used, or plaster masters can be pre-
tooling can be amortized by taking advantage
pared from models. The quality of the plaster
of the improved capabilities to mold complex
masters depends on the strain compatibility
constructions. Composites that may ordinarily
between the plaster and its reinforcements and
require secondary bonding are often more eco-
on the condition of the hardened surface.
nomically co-cured.
Composite tools can be laid-up using fiber
orientations that most closely match the
expansion of the items to be produced.
16.4.1 MOLD PREPARATIONS
Fiberglass and graphite fibers are the principal
Coefficients of thermal expansion for conven- reinforcements. Woven fiber reinforcements
tional tooling materials and composites are are the most economical to use. Mold mainte-
given in Chapter 25. For metals, the coefficient nance is best relegated to specialized
for steel compares most closely with the coeffi- personnel while preparations for the bag
cients for the composites. Other characteristics molding processes are assigned to production
362 Hand lay-up and bag riiolding
personnel. A successful practice is to provide
production personnel with soft tools and sol-
vents that do not degrade the molding
surfaces. If the production tools and solvents
are inadequate for removing debris and clean-
ing, the molds are taken out of service for
maintenance, repair, or replacement. After
they are returned to service, they are solvent-
wiped clean and mold release agents are
applied.
16.4.2 RELEASE AGENTS
Release agents for bag molding composites
include carnauba paste wax, aerosol dis-
pensed compositions that contain carnauba,
fluorocarbon resins, or silicone resins, plastic
films and metal foils. On most occasions, the
wax or resin mold releases do not contaminate
the composite surfaces excessively nor prevent
subsequent secondary bonding or coating
operations. Prior to bonding, the composite
surfaces are cleaned with solvent and lightly
sanded to remove resin gloss. The user should
be aware of national or regional limitations on
solvent usage due to toxicity or ODS (ozone
depleting substances) concerns. Peel plies can
be used to protect clean surfaces for primary
adhesive bonds. Plastic films, metal foils and
sprayed metal coatings also serve as release
agents when they are integrally laminated to
the co-cured composites.
Both the polished wax surfaces and the
sprayed wax coatings are excellent mold
releases for composites cured below 121°C
(250°F). However, the wax degrades and dis-
colors the composites at higher molding
temperatures. Commercial fluorocarbon mold
releases are used for higher cure temperatures.
FEP (fluoroethylene propylene) mold
releases form a continuous film on mold sur-
faces. Although the condition of the release
film is easy to maintain below 177°C (350"F),
the coating degrades at higher temperatures
above this. Fluorine which is noxious, corro-
sive and highly toxic can be released from the
polymer above 177°C (350°F).
PTFE (polytetrafluoroethylene) is stable and
is often contained in mold releases for service in
excess of 260°C (500°F).The mold releases con-
tain suspensions of micropulverized PTFE in a
volatile dispersant. Depositions on mold sur-
faces do not form continuous films, but the
PTFE particles provide excellent dry lubrication
for the release of the cured composite.
Furthermore, the residual particles on the cured
composite surfaces are easily removed with a
solvent-wipe. Since a variety of commercial
mold releases that contain fluorocarbon (or
equivalent)are on the market, it is essential that
manufacturers' recommendations on uses and
limitations be scrupulously followed.
Silicone oils and greases are to be avoided
since they are the most persistent contami-
nants of molded composite surfaces. They
release secondary bonds and coatings from
composite surfaces as effectively as they
release the cured composites from the molds.
Silicone oils and greases migrate and defeat
most removal attempts. They contaminate the
solvent wetted cloths and sand papers so that
instead of removing the silicones, they spread
them. Contaminated surfaces may be salvaged
for painting by sandblasting with virgin grit.
Table 16.3 summarizes the precautions nec-
essary for successful hand lay-up and vacuum
bagging operations
16.4.3 MOLD DESIGN
hlold design is a function of cost and projected
life and/or use. A production mold should be
made carefully from the best materials. Such a
mold will be designed by an experienced
designer who will incorporate the necessary
thicknesses, materials, structural reinforcement
and hardware required for the intended use.
16.4.4 PATTERNS (PLUGS)
A pattern (plug) is a temporary form in the
exact shape, contour and finish of that to be
molded. (If the outer shape of the items
desired the inside contour is used.) Patterns

Table 16.3 Hand lay-up and vacuum bagging precautions
Mold release application
Selection of correct mold release
‘Seasoning’ new tool to insure coverage a
minimum of three coast
Compatibility of resin system and mold release
Repeated applications can cause excessive
buildup
Sealant tape
Ease of use, release from backing
Double or single strip application
Removal after cure
Cheapest when suitable
Flash breaker tape
Check compatibility
Useful for holding prepreg during lay-up and
heat debulks
Separator film
Compatability and will release as intended
Quality control on perforations
Drapability for complex shapes
Elongation (%) (high elongation)
Bleeder
Not all bleeders the same, select for application
Ensure no compaction during cure
Potential seal off during cure
Excessive bleed can saturate bleeder
are made of many materials: wood, plaster,
plaster/metal and other combinations. Almost
any material can be considered as a pattern
material if it holds its shape.
It is assumed that when only one large com-
posite structure is required, such as a 23 m
(75ft) America’s cup yacht hull, the cost of
making a pattern and a mold in order to make
the hull may not be justified. However, the
construction of a pattern that becomes a male
plug can be cost effective for high performance
composite structures. To avoid excessive cost
with this tooling approach, one must remem-
ber that it is the total cost of the end product
not just the cost of the pattern (plug) that must
be considered. A limited use plug for a large
marine hull 14-23 m (45-75 ft) in length would
be made as follows: a simple wood frame to
Tooling 363
Breather
Able to malntain vacuum path
Care not to puncture nylon film
Bagging film
Higher the percent elongation the more
forgiving
Pliability
Defect free
Select for temperature performance
Thermocouples
Through bag/sealant tape, potential vacuum
leaks
Placed on outside of bag - reliability
Vacuum fittings
Caution not to allow resin to fill
0 Source for potential leaks
Removal from bagging film before disposal
0 Integral with tooling
Vacuum lines
Ensure fittings do not leak
Hose has not been crushed
0 Not pinched off
Not filled with resin
the inside contour of the hull is constructed
from stanchions and stringers and covered
with strips of wood, with a laminate of 2 45”,
90” layers. The tooling plug is finished and
covered with mold release.
16.4.5 INTEGRATING INSPECTION AND
MACHINING
A machine tool is for machining. If it isn’t mak-
ing chips, it’s wasting time, so keep non-cutting
time to an absolute minimum. That’s the stan-
dard philosophy most shops try to live by. In
fact, many shops are investing in pallet shuttles,
quick-change fixtures, tooling systems, rapid
transverse fixtures, programming and schedul-
ing systems to keep spindles turning and
cutting tools w o r h g at optimum capacity.
364 Hand lay-up and bag molding

Inspecting the workpieces right on the five- parts. If the workpiece will not fit into the hard
axis mills, has the equipment functioning as gauge, it has out-of-tolerance features and will
both machine tool and coordinate measuring not fit mating parts. The workpiece is rejected.
machine, so that the production of parts and A soft gauge can be used to make similar
producing inspection data become equally either-it-fits-or-it-doesn’t comparisons. Instead
important. Such a radically different plan of placing two physical objects together, two
means that design, numerical control (NC) CAD models are laid one over the other on the
programming, machining and inspection can- graphics screen. The software version of the
not be separate functions.Just as each machine checking fixture is the soft gauge. The soft-
tool would have to serve more than one role, ware version of the workpiece to be inspected
one computerized database would have to is a geometric model constructed from inspec-
share the same information with designers, tion data. Out-of-tolerance conditions will be
programmers, operators and inspectors. This just as conspicuous in this comparison, but
combination allows a shop to machine, inspect analysis is far more complete and much faster.
and analyze any surface without removing the Moreover, a soft gauge is created directly from
work piece from the five-axis machine. This the original design data. Because it is created
system helps produce higher quality tooling on a computer screen instead of in a tool room,
with significant gains in productivity. a soft gauge can be constructed quickly and
A large machine bed will accommodate modified easily. It spares the high cost of
unusually long workpieces and also leave building and validating a hard gauge.
room for smaller workpieces to be clamped on
one end while another workpiece is being
Closed-loop machining
machined at the other end (see Fig. 16.2).
Closed-loop machining begins with electronic
data representing part geometry from the cus-
Soft gauge
tomer. This data describes the outer surface of
A soft gauge can be compared and contrasted the customer’s end product. The CAD system
with a ’hard’ gauge such as a conventional then creates a 3D model of its surface. Once
checking fixture used for inspection and qual- this surface has been established, all manufac-
ity control. If a workpiece drops into the hard turing operations will be derived from and
gauge, it is acceptable and will fit with mating related to it. NC tool paths will be generated

Fig. 16.2 Closed-loop machining - mounting vari- Fig. 16.3 Closed-loop machining - touch probe
ous tools. (Courtesy of Coast Composites, Inc.) inspection tool. (Courtesy of Coast Composites, Inc.)

from it. Using dynamic display of the tool
path, programmers can visually verify the NC
program, check clearances and make sure
gouges are avoided.
The inspection path will be generated from
the same surface geometry. By referencing the
soft gauge, the inspection path will be sure to
include checks of all critical features. The path
of the probe can be visually verified in the
same way as the NC program.
After executing the NC program, the work-
piece can be inspected immediately using the
touch probe in the spindle (see Fig. 16.3). This
inspection can be considered in-process,
because the workpiece is still fixed on the
machine tool and can be remachined without
being moved or refixtured. This approach is
called closed-loop machining.
Results of this inspection routine are auto-
matically used to create a 3D model of the
features checked. By comparing this model to
the soft gauge, any out-of-tolerance conditions
can be identified. It will also show where addi-
tional machining passes will be required.
Final inspection can performed on the
machine tool. These results are compared to
the soft gauge again to verify that the con-
toured surface of the graphite tooling will
produce the intended part. Using this machin-
ing approach for inspection on the machine
tool reduces inspection time by 80%. The
biggest savings come from eliminating work-
piece moves and additional setups and from
streamlined programming of the inspection
routines. By integrating inspection and
machining, overall manufacturing cycle time
can be reduced by 30%.
16.4.6 THERMAL EXPANSION MOLDING
Thermal expansion molding techniques are
utilized for special applications of small com-
plex composite structures and composite
tubing with critical outside surfaces. Figures
16.4(a)and (b) illustrate the methods allowing
the expansion of the silicone rubber to provide
the required pressure for the compacting of
Tooling 365
the composite materials. For complex shapes
with integral stiffeners, each block of silicone
rubber is wrapped on all but one side, the side
in which the tooling rubber is removed (see
Figs 16.4(c) and (d)). In tooling a thermal
expansion molding, it is best to avoid using
rubber on both sides of a laminate as illus-
trated in Fig. 16.4(e)unless straight edges are
not critical. Vacuum bag assist (see Fig. 16.4(f))
provides an alternate method.
The linear thermal coefficient of most sili-
cone rubbers that have been measured fall into
the range of 1-2.1 x This range is consis-
tent over a 23-246°C (75480°F) temperature
range. The rubbers are said to have a linear
expansion of approximately 17 times that of
carbon steel which is why they are used to
mold composites by thermal expansion mold-
ing techniques. Precautions in mixing some
silicone rubber compounds are required if full
potential is to be achieved. During prolonged
storage, the catalyst tends to separate and set-
tle to the bottom of the container. Mixing the
catalyst prior to adding it to the base rubber
will allow correct mixtures and long tool life.
(a) Compression molding
(b) Oven cure critical outer surfaces
Fig. 16.4 Thermal expansion molding. (Continued
on next page.)
366 Hand lay-up and bag molding
(c) Enclosed molding
3 50-75 composite parts before having to be
~~~~
(d)Negative draft molding
r - - - - 1
I 1
(e) Oven/press cure
(f) Vacuum bag assist
Silicone rubber
Steel molds
IICompositelaminate
Fig. 16.4 Continued.
Incorrect mixtures will be light or dark in color
and materials such as Silastic J@ will start to
crumble within a few thermal cycles.
The use of thermal expansion rubber can be
hazardous if not planned well. The tooling
rubber can exert up to 6.9 MPa (1OOOpsi)
during its first few thermal cycles. The tool-
ing rubber requires the minimum of five full
cure heat cycles free standing after the initial
cure in order to stabilize the expansion charac-
teristics. The tooling is capable of producing
replaced.
One other problem with thermal expansion
rubber is with its removal from the composite
structure. Sharp pointed objects will have a
very lasting effect on tool life; once the rubber
is damaged, it will continue to tear, needing
replacement much sooner than usually
required. Silicone rubber is very slow to cool
down and extra time must be allowed because
the rubber is impossible to remove from the
composite part until it has shrunk back to its
original size. Putting the thermal expansion
rubber tooling into a freezer can accelerate the
manufacturing cycle. However, since some of
the tools are heavy, due to steel outer encase-
ments, a 12-15 h cooling down period should
be planned into the manufacturing cycle.
Experimentation is suggested with this mold-
ing method since extreme pressures can be
generated and undesirable results may occur
if the molding method is picked arbitrarily.
16.5 BAG MOLDING PROCESS
Molding methods include vacuum bag, pres-
sure bag, oven and autoclave molding. Bags,
the thin and flexible membranes or silicone
rubber shapes, separate the laid-up construc-
tions from atmospheric pressure during
composite cures. The bagged lay-ups in auto-
claves are usually vented to pressures lower
than those applied to the bag. Consolidations
and densifications of the lay-ups are achieved
by the resulting pressure differentials across
the bag contents. Consolidations are achieved

when the separate plies of prepreg in the lay-
ups and other adherents are bonded together.
Densifications result in reduction of voids and
removal of excess resin. Other results desired
of bag molding methods during cure include
prevention of blistering in the composites,
increased controls of pressure and heat appli-
cation and control of the fiber/resin ratio.
Consolidations and densifications of vac-
uum bag moldings can be achieved by
atmospheric pressure alone as the bagged lay-
ups are evacuated throughout the cure cycles.
The pressure-bagged and autoclaved-cured
composites are pressurized by hot gases. Vents
to the atmosphere or vacuum provide for the
escape of the volatilized reaction by-products
and the entrapped air from the curing com-
posites. If the pressures within the bag are not
reduced from those applied to the bag, the
membrane remains inert and there is no com-
paction. Of the three methods, vacuum bag
molding is least limited as to the size of con-
structions that can be processed. On a few
occasions, 'wet' lay-up vacuum bag molded
composites are room-temperature cured. Most
are thermally cured to produce improved
properties. Thermal cures are best attained in
air circulating ovens/autoclaves, but can also
be achieved in infrared heated and passive
type convection ovens.
Pressure bag molding methods are efficient
for producing both deeply contoured struc-
tures and shallow composites. Sonar domes,
radomes and antenna housings are examples
of deeply contoured composites.Architectural
panels, door panels and aircraft fairings are
examples of shallow composites. Heavy
molds are built to reproduce deeply con-
toured structures. Each specialized mold is
constructed to withstand the elevated temper-
atures and increased pressures required for
the cures.
Shallow items may often be bag molded in
modified compression presses. The lower
press platens contain vents and vacuum lines.
The upper press platens are made hollow to
enclose the mold plates together with the laid
Bag molding process 367
up assemblies. When the presses are closed,
the sealed chambers are pressurized and
heated to attain molding conditions similar to
those of an autoclave. Unlike the specialized
pressure bag molds, the modified presses are
used to cure many different composite con-
structions.
Autoclave and pressure bag molding condi-
tions to 177°C (350°F) and 1379 kPa (200 psi)
are routinely attained. Newer, customized
autoclaves attain cure conditions that exceed
260°C (500°F) and 3447 kPa (500 psi). Fire haz-
ards are greatly increased at elevated
temperatures and pressures. Pressure vessel
fires are minimized by uses of fire retardant
processing materials and inert pressurizing
gas. Fire prevention measures include uses of
silicone rubber, nylon or Tedlar bags. Before
cure cycles are initiated, the pressure vessels
are purged of all enclosed air. After the ther-
mal cure is completed, the pressure vessels
and their contents are cooled to 68°C (150'F)
before the pressure is relieved and the auto-
clave is opened.
16.5.1 EXPENDABLE VACUUM BAGGING
TECHNIQUES
Bleed-out systems are devised to maintain
reduced pressures within the bags' contents.
The bagged lay-up includes the bleed out sys-
tem designed for the composite part. Bagged
lay-ups can be bled in two ways: vertically or
edge bled. The classical differences between
the two can be seen by comparing Figs 16.5
and 16.6. Many of today's resin systems are
mostly 'net resin' and do not require any resin
bleed during cure. This allows for better con-
trol of the resin content of the composite
structures. If a resin bleed sequence is pre-
ferred, the following sequence can be used as
a guide.
0 The surface of the mold is prepared with
the release agent.
0 The composite plies are applied and rubbed
out to remove entrapped air.
368 Hand lay-up and bag molding

ATMOSPHERIC
OR VACUUM
VENT

Fig. 16.5 Vacuum bag edge bleeder - schematic.

CAUL PLATF

RAG

NOTE HEAVY PROTECTION AGAINST BAG PERFORATIONS DUE TO INCREASED

AUTOCLAVE PRESSURES

Fig. 16.6 Vacuum bag vertical bleeder - schematic.


A perforated release film is applied over the
composite laminate and extended approxi-
mately 3.2 mm (1.25 in) beyond all edges.
A predetermined number of bleeder plies
are applied over the release film and
extended to the perimeter of the lay-up.
A perforated release film is applied over the
bleeders and extended 3.2 cm (1.25 in) from
edge.
One or two layers of a non-woven breather
is placed over the lay-up and extended over
the release film.
Sealant tape is applied around the perime-
ter of the bleeder.
The vacuum bag is positioned and sealed.
The contents are evacuated and smoothed
and the bag is checked and sealed against
leaks.
The bagged lay-up is ready to be cured.
In any bagging sequence, the types of release
film, bleeder, breather and bagging materials
used vary from company to company and from
supplier to supplier. Each supplier has typical
data sheets on expendable materials to acheve
the most efficient use of the materials.
f SEALANT TAPE
VACUUM BAG
Fig. 16.7 Vacuum bag bridging (Morena, J., Advanced Composite Moldmaking; New York, Van Nostrand
Reinhold, 1988).
Bag molding process 369
In a typical vacuum bag lay-up, there are
several methods available; some use double
sealant tape side/side, some single and some
one on top of the other. The best system is the
one that works. The side/side method is used
to provide some insurance during cure that
the bag will not shrink, pulling an edge off,
causing loss of vacuum. The over/under
method is used to provide ease of placement
of ears to allow some movement of the vac-
uum bag. No matter which method is chosen,
it is important to remember that vacuum bags
tend to pull down more than expected and
can puncture, if bagging is over a sharp
object. During the application of a vacuum
bag, 'ears' are required to facilitate the uni-
form application of vacuum to the composite
laminate.
Vacuum bag bridging is one of the leading
causes of resin rich and excessive voids in cor-
ners of composite laminates. Figure 16.7
illustrates this common problem. One method
of eliminating bridging of the vacuum bag is
presented in Fig. 16.8by means of 'ears' in the
bag. Another method to help reduce resin rich
LAMINATE BEING FORMED
370 Hand lay-up and bag molding

fSEAMNT TAPE

VACUUM BAG
4- INCH HIGH PLEAT OR FOLD

LAMINATE BEING FORMED

Fig. 16.8 Elimination of vacuum bag bridging (Morena,J., Advanced Composite Moldmaking; New York, Van
Nostrand Reinhold, 1988).

Fig. 16.9 Large vacuum bagged structures. (Courtesy of Richmond Aircraft Products.)
 Bag molding process 371

and excessive voids in corners is the place- 16.5.2 REUSABLE VACUUM BAGGING
ment of an intensifier over the area, usually TECHNIQUES
placed between the separator film and There are material and recurring labor cost
breather. The intensifier can be molded rubber disadvantages to the use of expendable vac-
in the radius desired or some sealant tape to uum bags of plastic films for fabricating
fill the corner. 'Ears' may be required in sev- production composites. Expendable bags, laid
eral sections of a complex part. Experience will up of plastic films and associated sealants, also
determine the height of the ear for a specific incur recurring costs. Expendable bags can be
application; 10 cm (4 in) is a good starting laid up only once because of degradation dur-
point. Some will be smaller and some will be ing handling and the thermal cures.
larger depending upon the complexity of the Use of silicone rubber reusable bags can
component being vacuum bagged. reduce fabrication costs and defective com-
There is essentially no limitation on the size posite parts because of resulting work
of thermoset composite structures. The use of simplification and more positive control of the
the thermoset vacuum-bagged composites bag molding cure conditions. Figure 16.11
(autoclave, oven or integrally heated) will con- illustrates an example of a component being
tinue to provide excellent composite manufactured utilizing a reusable silicone
structures for many years to come. Figures
16.9 and 16.10 illustrate some more complex
uses for expendable vacuum bags.

I I
Fig. 16.11 Disposable vacuum bagging (top);
Fig. 16.10 Complex vacuum bagging. (Courtesy of reusable vacuum bagging (bottom). (Courtesy of
Richmond Aircraft Products.) The Darner Corporation.)
372 Hand lay-up and bag molding

vacuum bag and an expendable vacuum bag. are combined when the product is made. The
There are often difficulties in having the facili- composite designer must consider how the
ties to handle large reusable vacuum bags load bearing fibers are placed and ensure that
weighing several hundred pounds. A cost eval- they stay in the proper position during the fab-
uation must include all aspects of the program. rication.
There are some very large aircraft components
utilizing expendable vacuum bag materials 16.6.1 DESIGN PROCESS
very successfully. The more complex the com-
posite structure becomes, the more effective With some large composite structures, poten-
the reusable vacuum bagging system is. tial problem areas can best be identified using
scale models. Working problem areas on an
individual basis, a major factor in the success
16.6 DESIGN
of a program is the amount of planning that
The fundamental information needed for any can take advantage of the work force experi-
design includes the stresses applied under ence. Successful composite structures are not
storage and use and the strength of the mater- fabricated by one person; they require team
ial used. Assume that the size, shape, quantity work from all disciplines. It is considerably
and rate of production have dictated the use of harder to make a smaller composite structure,
open mold techniques. Then the final thick- than make the full scale article. Procedures
ness, orientation and quantity of reinforcing developed for the scaled article can, however,
fibers are dependent upon the stresses that be easily translated into a full scale structure.
must be resisted, how often and for how long.
It is essential that the designer find out
16.6.2 FIRST ARTICLE FABRICATION
what strength can be built into the laminate.
This sets composite structures apart from The first article, also known as tool proof arti-
other types of materials, since the material is cle, can be used to provide information not
made during fabrication of the product; the only on the tool to manufacture to the correct
percentages and orientation of the reinforce- tolerances but also to produce an acceptable
ment and the types of resins determine the composite structure meeting the design
properties of the final laminate. requirements. In addition, it can be utilized as
During the initial phase of the development a proof of the documentation of quality con-
of a composite structure, there is a need for trol inspection requirements, manufacturing
design, manufacturing engineering, tooling, procedure's verification and allow design
materials and quality control to provide inputs engineering to review overall requirements.
so that the selection processes can be estab-
lished. By coordinating early in a program,
16.6.3 DESIGN DETAILS
one can focus on the real problems of design
and manufacturing. The preplanning phase
Parts with severe contour and thickness
will allow for a program to develop at a more
variations
rapid pace. Confirming materials, manufac-
turing methods, tooling concepts and design It may seem easy to incorporate variations in
requirements early can avoid the extra time contour and thickness into the design of a new
and expense to attempt to make the composite product but in open mold products such vari-
fabrication process successful. ations must be made with caution. The
The design of composite structures, while molding operation requires laying the mater-
essentially similar to conventional design, ial on the mold to follow mold contour. If the
does have the added dimension that materials angles are sharp (90' without radius), the lay-up

will not follow the mold surface and will
develop voids and resin rich areas in the lami-
nate in the vicinity of the angle. For instance,
in inside right angle corners without radius,
(Fig. 16.12(a))the laminate will not pack into
the corner. When there are sharp outside cor-
ners, the laminate (Fig. 16.12(b))will not wrap
tightly over the corner. The solution to such
problems is to design with a generous radius,
preferably 4.75-12.75 mm (0.187-0.500 in)
inside and out. The laminate will then follow
the contour. Abrupt changes in direction are
high stress areas and tend to delaminate and
crack. They should be avoided and moderate
self reinforcing curvatures used.
L I
Fig. 16.12 Corner lay-up techniques (a) radius cor-
ner; (b) no radius corner.
Design 373
Changes in thickness
To change thickness in open mold construc-
tion is to add or remove plies of material. An
abrupt change means that the plies must be
carefully laid up in a precise pattern. An
abrupt change in thickness (Fig. 16.13(a))
results in a stress concentration and should be
avoided as delamination is sure to occur at
such a point. The solution to this problem is
not to have abrupt changes but to gradually
change by stepping back or 'shingling' the lay-
up (Fig. 16.13(b)).
Openings
The best opening is a round hole; the worst, an
opening with sharp, non-rounded corners.
The solution to stresses in an opening is to use
large radii in the corners, to build up thickness
gradually at the sharp corners, or to design a
molded in flange around the opening (Fig.
16.13(c)).
Fig. 16.13 Changes in ply lay-up (a) abrupt
changes; (b) stepped piles; (c) hole reinforcement.
374 Hand lay-up and bag molding

Joints and bonding However, these structures are not generally

highly stressed structures.
Although common practice is to use joints
Large amounts of waste can be expensive
intended for other methods of fastening, struc-
for any program. As a rule, in programs where
tural adhesives require joints of a special
is little or no preplanning, the waste factor can
design. It cannot be stressed too strongly that
be 20-35%. This may be acceptable for low
the practice of using ordinary joints that have
cost materials such as fiberglass but for carbon
been slightly altered can lead to disastrous
prepreg materials costing over US$59OO/kg
results. The type of joint used depends on the
for 827 GPa (120 msi) pitch fiber, the cost for
basic characteristics of the adhesive since
the waste can break an otherwise successful
structural bonds act over an entire area and
composite program. A well-planned approach
not at a single point as rivet fasteners do. A
to the cutting, kitting, lay-up and inspection
joint should therefore be designed to minimize
requirements can reduce the waste factor to
concentrations of stress. There are four basic
10-15%. Large structures tend to have less
types of stress encountered in structural bond-
waste than small components. The carbon
ing: tensile, shear, cleavage and peel.
epoxy central cylinder for a modern commu-
nication satellite has less than 3% material
16.6.4 DESIGN CONSIDERATIONS waste, the majority being for localized rein-
forcements. The America's Cup racing yacht
The initial lay-up starts with the preparation
was fabricated with less than 2% material
of the prepreg ply kits. Individual ply kits will
waste.
reduce the overall labor requirements during -
the ensuing lay-up. Hybridization of materials
can be achieved on a ply-by-ply
- . . - .
basis. Off axis 16.6.5 GENERAL DESIGN PRACTICE
(* 45") ply orientations can be prepared utiliz-
e Attention to ply orientation on strength
ing a woven graphite cloth. Interleaf layers of
controlled laminates can prevent matrix
titanium or fiberglass can distribute high load
and stiffness degradation. The 0" ply orien-
inputs into the laminate.
tation is used to carry the longitudinal
With large composite structures, i.e. racing
loading, the 90" ply orientation the trans-
yachts, the prepreg materials are usually dis-
pensed directly onto the lay-up. One must
*
verse loading and the 45" ply for shear
loading.
allow for 'fresh' prepreg, with maximum tack,
e In order to minimize in-plane shear, place
to be applied to the laminate with minimum
the +45" and -45" plies together; the in-
out time of the material during the fabrication
plane shear is carried by the tension and
phase.
compression in the 45" plies.
One of the first reactions to using hand lay-
To minimize warpage and interlaminar
up fabrication methods for a composite
shear within a laminate, maintain the sym-
structure is: "this will be too labor intensive".
metry about the center line of the laminate.
This can be misconstrued to mean that all
Stress concentrations can be minimized by
composite structures done by the hand lay-up
designing tapered or stepped laminate
are expensive. Complex, integral, stiffened
thickness changes.
composite structures may not only be cost
The placement of specific ply orientations
effective but may not be able to be fabricated
can influence the buckling strength and
by other methods of manufacture.
damage tolerance. The outer ply orienta-
Compression molding, resin transfer mold-
tions influence the laminate bending
ing and sheet molding processes are cost
characteristics more than plies placed at the
effective for specific types of material forms.
neutral axis.

16.7 APPLICATIONS
16.7.1 AEROSPACE
Two aerospace examples that were manufac-
tured utilizing the hand lay-up and vacuum
bagging process were an ICBM equipment
section structure (300 parts) and a central
cylinder (6 parts) for a modern communica-
tion satellite. These two primary composite
structures illustrate that hand lay-up and vac-
uum bag procedures can be effectively utilized
on limited production programs. For greater
production demand or with a less complex
structure other methods (machine lay-up or
filament winding) could have been used.
However, neither alternative process could
achieve the results required with materials
selected.
ICBM equipment structure
The ICBM equipment structure was initially
designed to utilize unidirectional
graphite/epoxy materials because unidirec-
tional materials were available during the
design phase. The development of woven
graphite was undertaken in order to reduce
the manufacturing costs of the program. Initial
prototypes (unidirectional tape) required over
2000 man-hours labor to complete. The first
prototype utilizing woven graphite required
only 900 man-hours, better than 50% reduc-
tion in manufacturing costs. Eventually
production labor requirements were reduced
to less than 200 man-hours.
Satellite central cylinder
The graphite/epoxy central cylinder was a
unique structure from its inception. The pro-
ject was undertaken not just because
composites would be lighter but that the
metallic (beryllium) design required a longer
manufacturing time that was unacceptable.
The materials of choice were a 520 GPa
(75 msi) pitch graphite fiber, epoxy resin and
aluminum honeycomb. During the initial
Applications 375
manufacturing/design reviews, the decision
to fabricate the central cylinder as a one piece
monococque structure was made. One quarter
scale models were made as initial feasibility
trials and the finished cylinder was 108 cm
(42 in) in diameter and 231 cm (91 in) high.
With that initial success, a full size manufac-
turing development cylinder required 1700
man-hours to fabricate. By production unit
five, the fabrication time was reduced to 500
man-hours per cylinder. The final design
incorporated compression molded graphite
inserts for hard mounts and was co-cured as a
one piece structure.
The program set new standards of coopera-
tion between engineering analysis/design,
manufacturing and quality control groups. A
manufacturing plan including all required
inspection points and a detailed fabrication
sequence was prepared. The major problem
during the fabrication was the out time avail-
able with the graphite epoxy resin system.
With only 10 working days available, the kit
preparation, lay-up, compacting cycles and
final cure was on a tight time schedule.
This program used various operational pro-
cedures to achieve success. Tank inserts were
compression molded from chopped
carbon/epoxy material prior to the start of the
laminate schedule on the cylinder. It was
determined early in the development cycle
that the unidirectional tape material handled
better if it was not precut into kits, but pre-
pared just prior to application to the tool. A
combination of heat debulks and pre-bleeding
was utilized to maintain the desired resin con-
tent, until the supplier could prepare an
acceptable net resin unidirectional tape. With
limited facilities to autoclave a large cylinder
with in-house capability, other methods of
manufacture were employed. After the com-
pleted hand lay-up was done, a vacuum
debulk was applied to ensure all air was
removed and the lay-up was compacted. The
cylinder was then wrapped with perforated
shrink tape (to allow for resin/air bleed dur-
ing cure), then breather cloth was applied
376 Hand lay-up and bag molding

prior to final nylon vacuum bag. Studies were Challenge. A typical America’s Cup yacht uti-
conducted on utilizing a silicone rubber vac- lized over 13 006 m2 (140 000 ft’) of ply surface
uum bag, but overall program costs and area of unidirectional graphite tape in the hull
difficulties in handling a large (heavy) bag, and deck structure and 9290 m’ (100 000 ftz)of
pushed the utilization of nylon bagging film ply surface area for a one piece graphite mast
for the final vacuum bag. The part was then structure.
oven cured. Due to the overall size and past experience
with the boat builder, a male wood plug was
fabricated with integral heated wires imbed-
16.7.2 MARINE APPLICATIONS
ded to reduce the heat sink effect during the
The fabrication of an America’s Cup racing final co-cure of a complete hull laminate. As
yacht (Fig. 16.14) presented another set of the maximum temperature allowed was 90°C
requirements. With limited cure temperature, (183”F),wood was a good choice.
resin matrix and control density requirements, The hull laminate was then applied, start-
the challenge was to be able to hand lay-up ing with the inner skin (as on an America’s
and cure a large composite structure to meet Cup racing yacht) then film adhesive and hon-
design requirements. Marine applications had eycomb core was applied. The inner laminate
reached new heights when the new rules went and honeycomb was vacuum bagged and par-
into effect for the 1992 America’s Cup tially cured. The honeycomb core was
smoothed and all joints were filled prior to the
application of the outer skin laminate. The
outer laminate and any local reinforcements
were applied to the core and inner laminate
(Fig. 16.15). The completed hull laminate was
then vacuum bagged and oven cured.
The outside of the hull was essentially com-
plete but had a rough surface. The roughness
was greatly dependent upon the care of work-
ers during the lay-up of the outer laminate
skin. With reasonable precautions, prepreg
material can be placed in such a way that there
are no overlaps and all gaps have been filled
with additional fiber. This effort alone can save
hundreds of man-hours during the final fin-
ishing.
This effort saved over 1200 man-hours com-
pared with a ’wet’ prepreg that did not
produce an acceptable outer surface finish.
The oven cure achieved maximum mechanical
properties required by the design. Laminate

Fig. 16.14 ’Spirit of Australia’. consisted of filling and grinding the surface in

1-
.k&
- ---- -
I
I *
I
t pole and rudder stock utilized variations of
Fig. 16.15 'Spirit of Australia' laminate laydown
(top) 45" ply laminate; (bottom) 0" ply laminate.
two or three stages and culminating with a
final coat of good grade epoxy or urethane
marine paint. This step is often postponed
until the boat is completely assembled and
ready for fitting out. Then, the hull was
inverted and placed in a fitted saddle; the male
plug was removed. Additions of bulkheads,
flooring and interior completed the work.
The manufacture of the carbon/epoxy mast
for the 'Spirit of Australia' presented some
unique challenges. The major program chal-
lenge was how to obtain a mast that would
provide the required performance at affordable
Applications 377
cost. A discussion with design/analysis and
manufacturing concluded that it was possible
to fabricate a one piece mast within the facili-
ties available and technical expertise within
the syndicate. The design of the tooling was
aimed at providing a capability to cure the car-
bon/epoxy resin within the America's Cup
rules. The requirements specified the cure
temperature 120°C (250"F), cure pressure (3
atmospheres), laminate density /modulus of
graphite fiber and overall mast profile. All
these objectives were realized within 100 days,
from start to completion of the first one piece,
35 m (115 ft) in length, America's Cup com-
posite mast. Performance exceeded all
expectations.
Additional masts starting with mast num-
ber 3 were manufactured with the final weight
objective of less than 450 kg (990 lb). Total fab-
rication time for each mast, from the start of
material kit preparation to completion of the
cure, required a maximum of 21 days. The
selected carbon/epoxy resin system was
workable for this limit. The mast, spinnaker
pressure bag molding with integrally heated
fiberglass tooling.
These two tooling approaches allowed for
some of the largest one-piece structures to date
to be fabricated in the commercial marine mar-
ket. Logistics can become a major role player
in the planning required in that not only the
support materials are on hand but that power
is available; materials handling is taken into
account and there is sufficient crew available
to complete the lay-up within the material out
time limits.
As seen in the above examples, the one
major factor for all the programs was the
material out time. With the development of
new resin matrixes, the design of complex
structures can be achieved.
MATCHED METAL COMPRESSION
MOLDING OF POLYMER COMPOSITES
Enarnul Haque and Burr (Bud) L. Leach
17.1 INTRODUCTION
In today’s highly competitive global economy,
the need for materials with the right properties
to meet the demands of design, environment,
durability and economics is growing.
Composite materials, with their high strength
and stiffness-to-weight ratios, have many
advantages and are a desirable engineering
material.
There is no universal definition of compos-
ites. In general, a composite material is a
heterogeneous material system consisting of
two or more physically distinct materials. In a
composite material system, the individual
materials exhibit their unique properties and
the composite as a whole shows properties that
are different from its constituents. In addition
to the constituents’ unique properties, the
properties of composites are also dependent on
the form and structural arrangements of the
constituents and the interaction between the
constituents.
Broadly speaking, composites consist of
two components, a binder or matrix and a
reinforcement. The matrix functions as the
body constituent, serving to bind the rein-
forcement together and giving the composite
its bulk form. The reinforcements are the struc-
tural constituents, providing high strength to
the internal structure of the composite.
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
17
Reinforcement may take the form of fibers,
particles, laminate, flakes and fillers.
Depending upon the type and orientation of
the reinforcement and the manufacturing tech-
nology required to produce them, composites
with various properties and cost can be fabri-
cated. Polymer composites are composites in
which the binder or matrix is a polymeric
material and the reinforcement is usually a
thin fibrous material. Polymer composites can
have either a thermosetting or thermoplastic
matrix. In this chapter we will discuss ther-
mosetting matrix based composites.
Reinforcing fibers may also be of various
kinds, with glass (E-type), carbon, or organic
fibers (e.g. aramid) being the most common.
Glass fibers are the most widely used type of
reinforcement since they offer good strength
and moderately high temperature resistance
(about 260°C) at a cost effective price. Glass
fibers also come in various forms. They can be
continuous filaments, cut or chopped strands,
roving and yarns, or in the form of cloth, mats
or tapes. Thus allows glass fibers to be used in
a variety of applications such as lay-up, fila-
ment winding, matched die-molding, etc.
In this chapter we discuss the matched metal
compression molding of thermoset based poly-
mer composites. Matched metal compression
molding is a molding process in whch the cure
is obtained while the material is restricted
between two mold surfaces and the loading
and closing of the mold causes the material to
conform to the desired configuration. This
 Background 379

process enables large scale production of large 17.2.1 BULK MOLDING COMPOUND (BMC)
surface area parts with contour problems and
tight tolerances. Matched metal compression BMC has been defined as ‘a fiber reinforced
molding employs a ’mold’ or match dies. The thermoset molding compound not requiring
male mold is matched to the female mold so advancement of cure, drying of volatile, or other
that when the dies are closed, a controlled space processing after mixing to make it ready for use
results. A preform charge is placed on the core at the molding press’*. BMC can be molded
and the cavity is pressed against it, applying without reaction byproducts under only enough
direct pressure on the material. The pressure in pressure to flow and compact the material. BMC
this type of molding varies from 1.38 to 6.895 is usually manufactured by combining all the
MPa (200 to 1000 psi) and curing temperatures ingredients in an intensive mixing process.
from 125°C to 160°C (260°Fto 320°F). Recent advances in BMC technology dictate that
both the dry ingredients and wet ingredients be
batch mixed separately and then combined
17.2 BACKGROUND
together in an intensive mixer. The BMC is usu-
Advanced polymer composites are now being ally in a fibrous putty form when it comes out of
applied extensively for all types of applications the mixer and resembles ’sauerkraut’. It is usu-
in the industrial and automotive markets. Table ally compacted and extruded into bars or ’logs’
17.1’ shows the usage of composites in various of simple cross section.
markets during 1991-1993. This section deals The earliest BMCs were probably made
primarily with thermoset polymer composites about 1950, employing a process of impregnat-
used in matched metal compression molding. ing roving strands with blend of resin, filler, etc.
The two most popular reinforced molding com- and chopping them to a length in the wet stage.
pounds used in the plastics industry are Premix Since wetting glass fibers with a resin contain-
or BMC and SMC (also referred to in modified ing much filler is difficult and slow, these
versions as HMC and XMC). Low Pressure premixes had a high glass content. The first
Molding Compounds (LPMC),ZMC and TMC high volume commercial BMC was made with
are also becoming popular. sisal fibers and used in molding automobile

Table 17.1 US Composites shipments: 1991-1993”

Millions of pounds
Markets 1991 1992 1991-1 992 1993 1992-1 993
% change (projected) % change
Aircraft/ aerospace /military 38.7 32.3 -16.5 26.0 -1.95
Appliance/business equipment 135.2 143.2 +5.9 146.7 +2.4
Construction 420.0 483.0 +15.0 522.0 +8.l
Consumer products 148.7 162.2 +9.1 164.1 +1.2
Corrosion-resistant equipment 355.0 332.3 -6.4 336.8 +1.4
Electrical/electronic 231.1 260.0 +12.5 273.0 +5.0
Marine 275.0 304.4 +10.7 317.2 +4.2
Transportation 682.2 750.0 +9.9 810.0 +8.0
Other 73.8 83.4 +13.0 88.0 +5.5
Total 2359.7 2550.8 +8.1 2683.8 +5.2

a Includes reinforced thermoset and thermoplastic resin composites, reinforcements and fillers. Source: SPI Composites
Institute
380 Matched metal compression molding of polymer composites
heater housings. Improvement in the binder
chemistry of glass fibers, development of a
chemical thickening system and thermoplastic
low profile additives help BMC to attain
strength, chemical resistance and to overcome
surface irregularities. Consequently, BMC was
accepted for use in the electrical, chemical and
appliance industries.
Today, BMCs are accepted as high perfor-
mance engineering thermoset molding
compounds and used extensively in the elec-
trical, automotive and consumer goods
industries. BMC is increasingly injection
molded to take advantage of the automation
and reproducibility afforded by the process,
although it is also both transfer molded and
compression molded.
17.2.2 Z MOLDING COMPOUND (ZMC)
ZMC was developed in 1979 in France to
improve BMC performance. BMC suffers
from glass fiber degradation during injection
molding and ZMC was developed to keep
shear forces as low as possible during mold-
in$. A special type of injection molding
machine developed by Billion in France com-
bines the advantages of both a screw machine
and a plunger machine. The ZMC injection
machine uses a screw to homogenize and pre-
cisely measure the shot. The injection is made
like a plunger by the displacement of the
screw and inner barrel inside the main barrel.
In a ZMC, the different components are
mixed in conventional mixers like BMC. The
compound viscosity is usually low and
adapted to injection machine characteristics.
The design of the mold plays a key role in the
processing phase and ZMC parts cannot be
successfully made unless part design and
mold design are combined upfront.
Compared to SMC, ZMC parts have lower
mechanical properties, but higher perfor-
mance when compared to conventional
injection molded BMC.
17.2.3 THICK MOLDING COMPOUND (TMC)
TMC was developed by Takeda Chemical
Industries, Ltd (Osaka, Japan). TMC is suited
to compression, injection and transfer mold-
ing and is usually processed on the same
equipment as SMC and BMC materials. TMC
composites are usually produced up to 51 mm
(2in) thick and glass fiber length can vary
from 6.4 to 50.8 mm (0.25 to 2 in). In TMC,
continuous impregnation and high sheet
weight result in complete wet-out of resins,
fillers and reinforcing fibers. Better wet-out
results in improved mechanical properties
and reduced porosity. TMC is usually used in
business machine housings, appliance com-
ponents and other consumer related
industries.
17.2.4 SHEET MOLDING COMPOUND (SMC)
SMC is a type of fiber reinforced plastic which
primarily consists of a thermosetting resin,
glass fiber reinforcement and filler. Additional
ingredients such as low-profile additives, cure
initiators, thickeners and mold release agents
are used to enhance the performance or pro-
cessing of the material4.
The development of SMC started in the
early 1950s after the finding that the viscosity
of unsaturated polyester resins increases with
the addition of Group IIA metallic oxides,
hydroxides, or carbonates5. The first pub-
lished report on SMC was presented at the
Cleveland Section of the Society of Plastics
Engineers meeting. The report involved work
done in Germany using fiberglass mat
impregnated with a resin mixture containing
magnesium oxide6.At the same time a num-
ber of US patent^^,^ were published on the use
of Group I1 metal oxides, hydroxides, or car-
bonates for use on adhesives. The early
applications of SMC materials were in electri-
cal and industrial goods. During the next two
decades, growth in commercial usage of SMC
followed the evolution of continuously
improving equipment, low profile additive,
 Background 381

catalyst, etc. The automobile industry started 17.2.5 LOW PRESSURE MOLDING COMPOUND
using SMC in the early 1970s for producing (LPMC)
exterior body components, such as hoods or
Low Pressure Molding Compound (LPMC) is
grille opening panels. With the introduction
an SMC type material which can be molded at
of high strength SMCs in the mid-l970s, usage
1.38-2.07 MPa (200 to 300 psi) instead of 5.52
of SMC increased to structural components.
-6.90 MPa (800-1000 psi) required for stan-
SMC is currently used extensively in trans-
dard SMC.
portation, construction (door panels),
LPMC is made by replacing the chemical
appliances (washing machine door, refrigera-
thickening mechanism of alkaline earth
tor housing), furniture (chair, tabletop) and
oxides (Group 11) with a physical thickening
business machines (computer housings). The
mechanism utilizing a crystic polyester. The
transportation industry has the highest level
material is heated to melt the crystic and then
of consumption of SMC. For instance, in the
the other ingredients are added, mixed
North American market alone, the annual rate
together and run through a modified SMC
of consumption exceeds 100 million kg9.
machine maintaining the elevated tempera-
Details of SMC manufacturing are available
ture.
in the literature5.SMC offers many advantages
The thickening occurs as the material cools
which include variety, part consolidation,
to ambient temperature and the compound is
lightweight and dimensional stability.
ready to mold at that time. Cooling rolls speed
With the evolution of flexible backbone
the cooling process and thus the material can
polyester resin systems and development of
be molded right off the SMC machine without
special additives, flexible SMC is becoming
waiting for the 2 4 4 8 h thickening of standard
very popular and is now competing with
SMC. LPMC allows the molder to use lower
thermoplastics for vertical body applications.
tonnage presses to mold larger parts and use
Special applications SMC is also becoming
less steel in building the tools as they do not
popular. With the addition of hollow micros-
have to deal with high pressures and corre-
phere glass bubbles in a standard SMC
sponding forces. The shelf life of LPMC is
formulation, lower density (1.3-1.4) is
much longer than SMC and the physical prop-
obtained for weight reduction. High strength
erties are comparable.
molding compound (HMC) is a SMC contain-
ing 65% chopped glass fiber instead of the
usual 25-35%. HMC uses little or no filler and 17.2.6 CONTINUOUS IMPREGNATED
can be compounded on a standard SMC COMPOUND (CIC)
machine. Directionally reinforced molding
compound (XMC) is a directionally oriented In 1986, continuous impregnated compound
moldable resin-glass fiber sheet containing (CIC) was developed in Germany. This is sim-
65-75% continuous reinforcement. XMC is ilar to TMC. Like TMC, the impregnation is
also usually compounded on standard fila- made between two rolls but the compound is
ment winding equipment and has strength removed by doctor blades and carried by a
five times greater than SMC. Unidirectional screw or plunger to boxes or drums. CIC is
molding compound (UMC) is a system of usually injection molded, but can also be injec-
chopped and continuous fibers produced on tion/compression molded. Properties are
a modified SMC machine. An advantage of comparable to BMC but processing is easier
UMC is that different varieties of fibers can than BMC. Modified CIC is also known as
be used. KMC (Kneaded Molding Compound).
382 Matched metal compression molding of polymer composites

17.3 FORMULATIONS butadiene copolymers. Extensive details of LPA

mechanism are published in the literature9J8J9.
Polymer composites have the unique and dis-
tinct advantage in that their properties can be
tailored to meet different applications by 17.3.3 INITIATORS Ah-D INHIBITORS
designing the formulations. The major compo-
Initiators are used to initiate the curing reac-
nents of polymer composites used in matched
metal compression molding are resin, low pro- tion at elevated temperatures. Composites
are polymerized or crosslinked by a free rad-
file additive, fiber, filler, initiator, inhibitor,
internal mold release agent and other addi- ical mechanism in which the double bond of
the polyester chain reacts with the vinyl
tives (e.g. viscosity reducer, toughness
enhancer, etc.). monomer (usually styrene). This copolymer-
ization reaction provides a three-dimensional
network that converts the viscous liquid resin
17.3.1 RESIN paste into a hard thermoset solid. Initiators
Unsaturated polyesters and vinyl esters are the decompose at elevated temperature and pro-
vide a source of free radicals to initiate the
principal resins used in polymer composites for
compression molding. Epoxies are also used for copolymerization reaction. Peroxyesters and
specialty products which require longer cure peroxyketals are the most common classes of
cycles and higher strength. Phenolics are being peroxides.
used for formulating composites, especially Inhibitors are added in small quantities to
SMC, in applicationswluch require lower flam- prolong shelf life, modify cure rate and mag-
mability, reduced smoke generation and higher nitude of exotherm to prevent cracking of
thermal stability’O. Details of resin chemistry thick molded sections. Inhibitors are also
are available in the literaturel’-l4. Styrene is used to improve resin stability. Two general
commonly used for cross-linking of both poly- classes of inhibitors are commonly used, sub-
ester and vinyl ester resins. Low styrene stituted phenolic derivatives and the
polye~ter’~ is becoming popular due to strin- quaternary ammonium salts (e.g. hydro-
gent EPA requirements on styrene vapors. New quinone, p-benzoquinone, etc). An excellent
resin technology is also being considered for review on initiator and inhibitor chemistry is
compression molding. They include hybrids of available elsewhere y.

unsaturated polyester and urethane16,acryles-

terol resin with polyi~ocyanate’~,etc. 17.3.4 FILLERS
Fillers are used to improve physical properties,
17.3.2 LOW PROFILE ADDITIVES reduce volumetric shrinkage of the resin and to
Low profile additives are thermoplastics that reduce costs. Fillers are typically divided into
are added to the formulation in 2-5% (by functional and non-functional categories.
weight) of the final product or 10-20% (by Examples of functional fillers include alumina
weight) of the organic portion of the formula- trihydrate for flame retardancy, hollow glass
tion to control the shrinkage of the cured bubbles for lower weights, mica and wollas-
composites. Typical thermoplastics include tonite for reinforcement. Non-functional fillers
polyvinyl acetates, poly methyl methacrylate are used for cost reduction and are mineral
and copolymers with other acrylate, vinyl chlo- based. Ground limestone (CaCO,) is the most
ride-vinyl acetate copolymers, polyurethane, common type of filler. An excellent review is
polystyrene, polycaprolactone, cellulose acetate available on filler use in composite^^^^^^
butyrate, saturated polyester and styrene-
 Molding 383

17.3.5 FIBERS 17.3.8 OTHER ADDITIVES

Glass fiber reinforcement is used to achieve Pigments are added to produce color in the
necessary dimensional stability and mechani- molded part. Common pigments include cad-
cal properties. E-glass is the most common mium salts, carbon black, titanium dioxide,
fiber reinforcement for composites. iron oxides, organic dyes and pigments, etc.
Depending on the binder chemistry and Various types of viscosity reducers are used to
amount, glass fibers are classified as hard or lower the viscosity of the paste to increase
soft type. Other types of fibers include carbon, filler loading and glass wet-out. Other addi-
aramid (Kevlar), S-2 glass, etc. Glass loading tives include various elastomeric additives
normally averages 30% by weight in compres- (e.g. Hycar, Kraton, etc.) to increase toughness.
sion molded composites, but can vary from Tables 17.3 to 17.6 show typical formula-
18-65?” by weight. Table 17.2” shows typical tions for BMC, SMC, ZMC and LPMC.
fibers used in polymer composites.
17.4 MOLDING
17.3.6 INTERNAL MOLD RELEASE Matched metal compression molding is one of
Internal mold release agents are added to facil- the oldest manufacturing techniques in the
itate part ejection from the mold. Major types plastics/composites industry. The recent
of release agents include metallic stearates, development of high strength, fast cure,
fatty acids, fatty acid amides and esters and
Table 17.3 BMC formulation
hydrocarbon waxes. Zinc stearate and calcium
stearate are the most widely used internal PHR
mold release agents in SMC and BMC.
Polyester resin 60.0
Low profile additive 40.0
17.3.7 THICKENERS Styrene 5.0
Initiator 1.5
The addition of Group I1 oxides and hydrox- Inhibitor Trace amount
ides to carboxy-terminated unsaturated Mold release 4.0
polyester/vinyl ester resin increases its viscos- Pigment 0.25
Thickening agent 1.0
ity. Magnesium oxide, magnesium hydroxide, Filler 50-200
calcium oxide, calcium hydroxide or combina- Compound
tions of those materials are the most popular Glass fiber 10-25%
thickeners. Paste 75-90%

Table 17.2 Glass fibers used in compositesz1

Fiber Specific Tensile Tensile Tensile Coeficient

gravity strength modulus failure of thermal expansion
(GPa) (GPa) strain (%) (x 1 @6/OC)
E-glass 2.54 3.45 72.4 4.8 5
S2-glass 2.48 4.30 86.9 5.0 2.9
Carbon 1.76-2.15 1.5-5.6 220-690 0.3-1.2 -0.1to -1.2 (longitudinal)
(graphite) 7-12 (radial)
Kevlar 49 1.45 3.62 131 2.8 -2 (longitudinal)
59 (radial)
384 Matched metal compression molding of polymer composites

Table 17.4 SMC formulation physical and mechanical properties can be

obtained in compression molded parts. Figure
PHR 17.1 shows a schematic of a compression
Polyester resin 55.0 molding process.
Low profile additive 40.0 This section addresses the compression
Styrene 5.0 molding of composite parts using SMC. BMC
Initiator 1.5 molding is similar except for the charge prepa-
Inhibitor 250 ppm ration step. The compression molding process
Mold release 4.0
Pigment 1.0 can be divided into four distinct steps.
Thickening agent 2.0
Filler 150-250
Heat and pressure
Compound
Glass fiber (25.4 mm) 25-30%
Paste 70-75%
+
Cavity
Table 17.5 LPMC formulation

PHR
Polyester resin 65.0
Crystic 15.0
Styrene 5.0
Initiator 1.2
Mold release 5.0
Pigment 1.2
Filler 220
Compound 4
Glass fiber 25-30%
I
Paste 70-75% Heat and pressure

Table 17.6 ZMC formulation

Fig. 17.1 Schematic of a compression molding
process.
PHR
Polyester resin 65.0
Low profile additive 40.0
Styrene 5.0
17.4.1 CHARGE PREPARATION AND
Initiator 1.5
Inhibitor 100 ppm PLACEMENT
Mold release 4.0 When the SMC has reached its desired molding
Filler 220
Compound
viscosity, pieces of SMC are cut to pre-specified
Glass fiber size after removing the carrier films. The SMC
Paste is cut using slitters, pizza type or guillotine type
cutters. Several pieces of SMC plied together
form the 'charge'. The charge pattern/ply
SMC/BMC and advancement in press tech- dimensions are chosen so as to cover 20-80% of
nology is making the compression molding the mold surface area. The charge pattern and
process very popular for mass production of placement on the mold determines the quality
composite parts. In comparison with the injec- of the molded parts, since it influences the
tion molding process, in general, better length of flow in the mold, fiber orientation,
 Properties 385

flowline and other surface defects. In order to entire surface. After IMC injection, the press is
reduce cycle time, sometimes the charge is pre- closed and the curing operation is repeated at
heated to a temperature below gel point using or above the SMC molding pressure.
infra-red or dielectric heaters. Sometimes the IMC is injected at high pressure
without mold opening and closing prior to
17.4.2 MOLD CLOSING AND FILLING complete cure of the SMC charge.
After proper placement of the charge in the
core of the mold, the cavity is quickly closed to 17.4.4 PART EJECTION AND POST-CURE
contact the top surface of the charge. The cav-
At the end of the molding cycle, the mold is
ity is then closed at a slower rate, usually 4-12
opened and the part is ejected from the core
mm/s. In most cases the mold is heated to (for
with the use of integral ejector pins and
example) 150°C, which causes the charge vis-
allowed to cool to ambient temperature. Hot
cosity to be reduced. With increasing mold
parts are handled carefully and are usually
pressure as the mold is closed, the charge
placed on a support racks to cool to ambient
flows towards the cavity extremities, forcing
temperature. As the part cools outside the
air out of the cavity. The mold closing speed is
mold, it continues to cure and shrink which
very important as it induces gelation of the top
creates residual stresses due to differential
charge surface if the closing speed is slow or it
cooling at various sections in the part. After
causes trapped air if closing speed is fast. The
the part is placed on support rack, it is
filling stage is usually completed in 0.5-20 s5.
deflashed while still hot and stored in racks for
Vacuum molding is increasingly being used
secondary operations like punching, drilling,
during charge flow to reduce surface porosity
bonding, etc.
and air entrapment in the part. Vacuum level
The compression molding process is com-
is usually in the range of 7-9 x lo4Pa (21-27 in
plex and there are several important variables
Hg). The molding pressure based on projected
that influence molding. Compression molding
part area ranges from 1 to 10MPa (100 to
may also produce a variety of surface and
1200 psi). Higher molding pressure causes
internal defects which can be eliminated by
sink marks, while lower pressure cause scum-
proper material selection, part design and
ming of the mold and porosity.
molding technique. Details of the molding
variables and the source and remedies of
17.4.3 CURING major molding defects are available in the lit-
After filling, the charge remains in the hot erature5,'.
mold for the crosslinking reaction to be com-
pleted. The curing time is usually between 25 s
17.5 PROPERTIES
to 3 min, but depends on several factors,
including resin-initiator-inhibitor reactivity, The properties of a polymer composite can be
part thickness and mold temperature. tailored, within limitations, to meet different
Sometimes in class A or appearance grade applications by designing its formulation. This
parts, in-mold coating (IMC) is used to unique characteristic of polymer composites
enhance the surface of a molded part. The makes definition of detailed properties diffi-
most common method of IMC injection cult. The properties are usually used for
requires opening the mold by a small amount information and guidelines for preliminary
(0.2-0.5 mm) after the curing cycle. IMC is part design, material selection and to under-
usually a coating of polyester or stand the effect of formulation variables on
polyester-urethane hybrid which covers the mechanical properties.
386 Matched metal compression molding of polymer composites
17.5.1 STATIC PROPERTIES
Table 17.7 shows the static and impact proper-
ties of SMC, BMC, ZMC and LPMC. In
general, tensile and flexural properties are
routinely measured and are presented here.
Compressive and shear properties are mea-
sured only for use in special applications. The
static properties of SMC and BMC are highly
dependent on the fiber content, length, type
and orientation. Tensile strength increases sig-
nificantly with increasing fiber content;
however, the tensile modulus is affected only
moderately. Increasing the length of chopped
fiber increases the tensile strength, but has no
effect on the modulus. Glass fiber type (E-glass
or S-glass) has a significant effect on both the
tensile strength and modulus. The resin chem-
istry also influences tensile properties at low
fiber content. In general, flexural and com-
pressive properties follow the same trend as
the tensile properties. Flexural strength is
always higher than tensile strength, though
the modulus may be comparable.
17.5.2 FATIGUE PROPERTIES
The fatigue properties of SMC and BMC are
usually based on tensile cyclic loading of
unnotched specimen. A typical S-N diagram is
shown in Fig. 17.221.In general, the fatigue
strength increases with increasing fiber con-
tent and there is no fatigue limit, unlike low
carbon steel. Details of such testing are pub-
lished elsewherez1,".
Table 17.7 Static and impact properties"
Property Tensile Tensile Flexural
strength modulus strength
(MPa) (GPa) (MPa)
SMC 65-100 9.5-14 130-200
BMC 30-70 8-12 50-150
ZMC 30-70 8.5-12.5 50-150
LPMC 65-100 9.5-14 120-200
a Published industry data
17.5.3 OTHER PROPERTIES
Several other tests are now being performed to
correlate properties with operation conditions.
The dynamic mechanical analyzer (DMA) is
used to measure complex and storage modulus
at various temperatures and frequency ranges.
The effect of environmental conditions on var-
ious properties is tested to simulate end-use
environment. Creep and stress relaxation tests
are also done on SMC/BMC for use in struc-
tural applications. Electrical properties are also
important, permitting BMC to be used in elec-
trical applications. Arc resistance is important
and dielectric strength, dielectric constant, dis-
sipation factor, etc. are also measured.
17.6 APPLICATIONS
Reinforced composites materials offer the max-
imum design versatility and capability of any
material. With the excellent cost/performance
characteristics of reinforced composites, the
variety and quantity of products being pro-
duced with these materials grow annually
around the world. Matched metal molded rein-
forced composites should be considered when
the finished product can be enhanced by one or
more of the following characteristics.
Part consolidation Reinforced composites can
be molded in three dimensions in one opera-
tion. Complex shapes that require multi-piece
assembly using materials, such as wood or
steel, may be molded in one step with the use
of ribs, bosses and varying wall thickness.
Flexural IZOD Specific Coeficient
modulus impact gravity of thermal
(GPa) (unnotched) expansion
(x 1 P P C )
8-14 600-1200 1.3-2.0 8-14
9-1 7 100-700 1.7-2.1 15-20
7-12 200-500 1.8-2.0 11-27
8-14 600-1200 1.8-2.0 7-10
 Applications 387

100 -
R = 0.05

80 -

a"
z
6 60-
-
v)

cn
E
2 40-
.-E
X

r"
20 -

01 I I I I I I I
0.1 1 10 102 103 104 105 106
Number of cycles, N

Fig. 17.2 Typical fatigue !+N diagram for SMC (21) A: at 40°C; 0:at 23°C; Cl:at 93°C. [Reproduced from
Composite Materials Technology: Processes and Properties (ed P.K. Mallick and 5. Newman) by permission of
the publisher.]

Light weight Reinforced composites offer a from most organic chemicals and can be for-
greater strength-to-weight ratio than most mulated to resist acidic and basic solutions.
non-reinforced plastics and many metals.
Electrical resistance Reinforced composites
Dimensional stability Reinforced composites are very poor conductors of electricity. As
can maintain the critical tolerances required of such, they have a lvgh dielectric strength for
the most demanding applications. Composites application in the electrical and electronic
meet the most stringent material stiffness, industriesz3.
dimensional tolerance, weight and cost criteria
Resistance to minor impact Reinforced com-
in many diverse applications.
posite components have an excellent memory
High strength Reinforced composites have characteristic. Instead of yielding or deforming
excellent strength-to-weight properties. By under minor impact as with steel, a reinforced
weight, reinforced composites surpass the ten- composite panel will deflect and spring back to
sile strength of iron, carbon and stainless its original surface form4(Fig. 17.3).
steels. Many glass reinforced compounds
Surface quality Reinforced composites can
equal or exceed the flexural strength and
achieve a variety of surface textures, from very
impact resistance of metals23.
smooth and glossy to a rough texture.
Corrosion resistance Reinforced composites Insignias and alphanumeric characters can be
do not rust or corrode, are resistant to attack molded as raised or indented characters.
388 Matched metal compression molding of polymer composites
Steel
- 0 basic end use function;
/////
Composite
Fig. 17.3 Minor impact.
Molded-in color Color can be added to the
reinforced composite compound, often elimi-
nating the need for a secondary painting
process.
Recycling Most reinforced composites can be
recycled either by regrinding or pyrolysis.
Reground material can be used as filler or rein-
forcing material. Pyrolysis reduces the
composite into its basic components by heat-
ing the material in the absence of oxygen. The
process yields gas, oil and solid by-products
that can be recycled back into composites, or
used in building and agriculture materials 4.
Thousands of products are molded each year
utilizing reinforced composites: aerospace,
automotive parts, sports and recreational
equipment, boats and business machines to
name a few. This wide variety of applications is
indicative of the versatility, capability and cost
effectiveness of reinforced composites.
17.7 DESIGN CONSIDERATIONS
Given the wide range of options provided by
reinforced composites, it is imperative that the
designer accurately establish the functional
and performance requirements of the product
or component. The designer must:
1. establish size and shape limitations based
on:
0 aesthetics and marketing;
0 shipping limitations;
0 weight requirements;
0 strength and stiffness requirements;
0 flexibility requirements or limits;
0 process limitations.
2. establish the structural requirements based
on:
various loads that will be impacted to the
part including weight, pressure and
dynamic loads;
duration of the loads on the part;
temperature variations on the part and
surface;
number of cycles of temperature change;
liquid, moisture and vapor resistance
requirements;
relative significance of strength-to-
weight ratios.
3. establish the non-structural requirements
based on:
0 corrosion, weathering, moisture and
temperature resistance;
0 moisture and vapor penetration for con-
densation protection;
0 fire safety relative to combustibility;
0 flame-spread rate requirements;
0 light transmission (transparency,translu-
cency and opaqueness);
0 surface textures, both aesthetic and func-
tional;
0 surface coatings for protection or aesthet-
ics;
0 thermal insulation;
noise and sound control;
0 dielectric requirements for electrical
insulation24.
With the establishment of the functional and
performance requirements the product design
can be developed.

There are some general design principles
which can assist in the development of struc-
turally efficient configurations for reinforced
composite components.
17.7.1 SHELL AND PLATE CONSTRUCTION
These are the most common configurations of
reinforced composite parts. A reinforced com-
posite component is constructed from layers of
reinforced composite materials molded into
the shape desired creating a geometric 'shell'.
It is good practice to design so that only forces
that place a part in tension or compression are
applied to any component. Compound curve
shapes provide good transmission of uniform
loads into tensile and compressive forces
within a part.
Ribbed configurations are often used to
achieve required strength and stiffness in
structural components (Fig. 17.4).
Corrugated or open ribbed configurations
are used to achieve needed structural depth
while efficiently using materials and fabrica-
tion processes (Fig. 17.5).
17.7.2 DRAFT
Draft is a slight angle introduced relative to the
direction of the opening and closing of the
mold. It is necessary to design the part so that
all side walls, both interior and exterior, have
draft. This enables the part to be removed from
the mold without hanging or rubbing, which
Fig. 17.4 Rib configuration.
Design considerations 389
Circular jf Pitch )t '
Rectangular
Fig. 17.5 Corrugated configuration.
can degrade 'appearance' surfaces (Fig. 17.6).
Minimum draft angle of 1" for the first
76.2 mm (3 in) of depth, 2" for 76.2-101.6 mm
( 3 4 in) of depth, 3" for 101.6-127 mm (4-6 in)
of depth and 1" for every additional 50.8 mm
(2in) thereafter is recommended on all sur-
faces parallel to the mold movement. This
pertains to all part details, such as ribs, bosses,
elevation changes and holes. A draft angle of
1" on standing ribs and bosses will yield a
thickness change of 0.43 mm (0.017 in) per
inch per sidez4.
'Zero draft' may be obtained by designing
the mold in such a way so the draft-free sur-
face lies at an angle to the mold direction. This
will affect the positioning of bosses, ribs and
other details of the part.
390 Matched metal compression molding of polymer composites
Draft angle
(1’ recommended)
mold movement
Fiig. 17.6 Draft.
17.7.3 RADIUS
In mold making, the radius defines the curva-
ture established between two intersecting
surfaces. The more generous the radius, the
better the flow of molding material for a
stronger part (Fig. 17.7).
A minimum radius of 1.59 mm (1/16 in) is
recommended for all radii for both interior
and exterior plane intersections. Radii should
be designed to maintain relatively uniform
part thickness (Fig. 17.8).
Ribs and bosses opposite an appearance
surface should have the radii eliminated to
reduce the likelihood of warpage or ’sink’
(surface depression).
Fig. 17.7 Outside radii.
1Ae” Minimum
Recommended
Radius Determined
‘By Part Thickness
Fig. 17.8 Minimum draft.
17.7.4 NOMINAL THICKNESS
The nominal thickness is the overall design
thickness of most of the part. It is desirable to
establish uniform thickness throughout a part,
to achieve minimum cure time, uniform cool-
ing and minimize warpage and shrinkage
(Fig. 17.9).
Nominal thickness for reinforced compos-
ites is 2.544.57 mm (0.100-0.180 in).
Recommended minimum thickness is 1.53mm
(0.060 in). Recommended maximum thickness
25.4 mm (1.00 in).
By designing hollow ribs, bosses and eleva-
tion changes can achieve intricate part
geometry while maintaining nominal thick-
ness throughout the part.
17.7.5 EDGE STIFFENING
Edge stiffening is a design characteristic
applied to unsupported edges to prevent
warping or bowing. Edge turning is preferable
to edge thickening due to the possibility of
porosity at the edge of part caused by the lack
of molding pressure on the thick area (Fig.
17.10).
 Design considerations 391

Fig.17.9 Nominal thickness. Uniform thickness promotes uniform flow and curing and minimizes the risk
of warpage, distortion and telegraphing at thickness changes through the surface.

17.7.6 RIBS for draft angles. They should be dimensioned

Linear projections 90" from the plane surface
so that their thickness at the juncture of the rib
with its plane surface is between 75 and 90% of
of a part are called ribs. The use of ribs will
nominal (Figs 17.11 and 17.12).
allow the part to meet strength and rigidity
requirements, preventing warpage and bow-
ing in large plane surfaces while reducing the
bulk and mass of a part.
Ribs should be designed to maintain the
nominal thickness and follow the guidelines

4- 0.5"draft

Fig. 17.11 Rib geometry for class 'A' surfaces.

radius
(0.06'')

+1.0" draft
Fig. 17.10 Edge stiffening (a) Preferred edge flange
designs to increase panel stiffness; (b) Thickening Fig. 17.12 Rib geometry for non-appearance
the edge flange may increase cycle times. surfaces.
392 Matched metal compression molding of polymer composites
17.7.7 BOSSES
Projections from a plane surface of a part,
called bosses, provide attachment and support
for related components. They may be solid,
hollow or have molded in inserts. They should
also follow the guidelines for draft angles and
nominal thickness (Fig. 17.13).
Nominal thickness should be
maintainedthroughout part I itself as the surface of the part. Many different
Fig. 17.13 Boss design.
17.7.8 INSERTS
Inserts are objects (usually metal) which are
molded into a part to facilitate repetitive fas-
tening and unfastening of associated parts and
can be provided with male or female threads.
Inserts can provide bearing or bushing sur-
faces, electrical or other mechanical
connections. Inserts should have knurls,
grooves or shoulders to lock them in place and
should be located parallel to the direction of
mold travel.
17.7.9 MOLDED-IN THREADS
It is difficult to mold a thread into reinforced
composites and requires highly sophisticated
and costly molds and molding procedures.
Molded threads should be rounded rather than
sharp. Rounded threads will resist chipping
and cracking and will also facilitate flow of
molding material into all areas of the thread.
Molded threads are usually preferred over
inserts if the threaded hole diameter is over
12.7mrn (0.5 in), unless the thread is to be sub-
jected to continual fastening and unfasteningz4.
17.7.10 MOLDED SURFACES
Surfaces exhibited by the part as it comes from
the mold have not been subject to any post-
molding operation other than the removal of
flash. The surface of the mold will reproduce
textures can be produced on the surface of a
part. High gloss surfaces can be produced by
highly polished molds. Draft is critical when
parts are to be textured on a vertical wall. For
every 0.254 mm (0.001 in) of texture depth,
draft must be increased by 1".
Raised or indented characters can be
molded into the part. The characters should be
rounded and smooth and positioned on the
surfaces parallel to the parting line of the
mold.
17.8 TOOLING
A good set of matched metal chromed steel
tools is required for the optimum conditions
when one is molding reinforced composites.
Anticipated production quantities expected
from the mold or the product end use, or both,
should dictate the choice of steel as shown in
Table 17.B5.
17.8.1 MOLD STRESSES
It is important to consider the stresses created
by the flow of material at typical molding
 Tooling 393

pressures from 4.13 to 8.37 MPa (600 to 1200 forced composite parts should be designed so
psi). Due to unbalanced flow, narrow mold the height of any projecting mold section does
sections that project from the mold surface not exceed two times the width of its base.
could bend or break under such stresses. To Angular sections must not be less than 30°4
ensure sufficient strength in the mold, rein- (Figs 17.14 and 17.15).

Table 17.8 Mold steel selection5

A . Production planning volumes
Type of steel
Planning volumes Core Cavity
5000-20 000 parts/y AISIa-1045 steel AISI-1045 steel
20 000-30 000 parts/y AIS14140 forged steel AIS14140 forged steel
prehardened to Rockwell C prehardened to Rockwell C
of 28-32 of 28-32
Over 30 000 parts/y AIS14140 forged steel P-20 forged steel prehardened
prehardened to Rockwell C to Rockwell C of 28-32
of 28-32
100 000 parts or less AISI-1045 steel AISI-1045 steel
100 000-200 000 parts AIS14140 forged steel AIS14140 forged steel
for mold life prehardened to Rockwell C prehardened to Rockwell C of
of 28-32 28-32
Over 200 000 parts AIS14140 forged steel P-20 forged steel prehardened
during mold life prehardened Rockwell C to Rockwell C of 2&32
of 28-32
B. Product end use
Structural items where AISI-1045 AISI-1045 steel
surface appearance is
not critical, such as
reinforcing panels,
truck front ends, etc.,
where molded surface
quality is of secondary
importance.
High-quality surface AIS14140 P-20 forged steel
appearance decorative
items, such as grille
opening panels, head
lamp surroundings,
quarter wheel opening
covers, etc. where a
high degree of polish
is required on the outer
part of cavity surface.

a American Iron and Steel Institute

394 Matched metal compression molding of polymer composites

Fig. 17.14 Projecting mold section; any projecting Fig. 17.15 Angular mold section: should not be
mold section should not exceed two times the <30°.
width of its base.

17.8.2 SHEARS
All matched metal compression molds use
telescoping shear edges around the perimeter
of the part. The shear of the mold halves is
never in contact but bypass each other as the
mold closes, leaving a thin amount of flash
(0.154-0.254 mm, 0.006-0.01 in). The bypass-
ing feature allows the mold cavity to be fully
filled regardless of small variations in charge
weight.
A minimum of 3" of draft is preferred for
return flanges. A minimum of 1.0 mm (0.04 in)
nominal flat clearance should be provided to
keep the cavity and core halves of the mold
from contacting each other. A surface normal to
die draw should be provided at the edge of the
part. A nominal angular tolerance of QO" and a
1.5 mm radius should be allowed for mold
building and finishing allowances Fig. 17.16).
Knife edge shears are to be avoided as they
create a thin mold section which can bend or
break under molding pressures (Fig. 17.17).
Shear edges should be flame hardened to a
Rockwell C of 55-60.
17.8.3 HEELBLOCKS
Compression molds should have heel blocks
and wear plates suitable to withstand all lat-
eral forces at 12.41 MPa (1800 psi) molding
pressure. The heel blocks should be an integral
part of the mold and flame hardened to a
Rockwell C of 50-55. Bronze wear plates
should be bolted opposite the heel blocks and
have a minimum of 3.18 mm (1/8 in) chamfer
lead in to avoid shearing off the wear plate.

Normal to die
draw +/- 200
Fig. 17.16 Shear edge design; part design requirements to maintain sufficient tool strength at the shear
edges.
Fig. 17.17 Knife-edge shear should be avoided. It
can be eliminated by adding a minimum flange of
5 mm (0.2 in) to the part edge.
17.8.4 GUIDE PINS
Compression molds should have leader or
guide pins, the diameter of such to be a mini-
mum of 2% of the width plus length of the
mold. All guide pins should be the same
height and be a minimum of 6.35 mm (0.25 in)
longer than the highest point of the core. They
should be chamfered for lead in and guide pin
retention should be a minimum of 1.5 times
the pin diameter. One guide pin should be off-
set to prevent misalignment of core and cavity.
Acknowledgements 395
l.0mm (0.04")
min flat
-1I t
+0.15mm (0.006")
flash
17.8.5 MOLD STOPS
Mold stops should be provided to control the
mold's vertical travel. They should be flat and
oil-hardened steel to a Rockwell C of 55-60.
The minimum part thickness can be controlled
by the mold stops.
17.8.6 SURFACE POLISH
The mold surface should be polished to the
degree that is required on the surface of the
part. The final 'stoning' or polishing on verti-
cal walls should be done in draw direction.
ACKNOWLEDGEMENTS
The authors would like to express their grati-
tude to Mr. M. Kilpinen and Mr. E. Kleese of
GenCorp Automotive for their support and
permission to write this manuscript. Thanks
are due to Ms. Marialyce Orr for editing and
proof-reading the manuscript.
396 Matched metal compression molding of polymer composites
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Reinforcements for Plastics. New York: Van
Nostrand Reinhold.
21. Mallick, P.K. 1990. In Composite Materials
Technology: Processes and Properties, (ed. Mallick,
P.K. and Newman, S.) pp. 25-32. New York:
Oxford University Press.
22. Heimbuch, R.A. and Sanders, B.A. 1978. In
Composite Materials in the Automobile Industry.
American Society of Mechanical Engineers :
111-137.
23. Owens-Corning Corp. 1984. Publication 54%
12910. (a) pp. 2; (b) pp. 3.
24. Owens-Corning Corp. 1986. Publication 5-PL-
23920. (a) pp. 5; (b) pp. 16; (c) pp. 22.
TEXTILE PREFORMING 18
Frank K. KO and George W. Du

18.1 INTRODUCTION resulting composite can be tailored. These

Textile preforming is a fiber placement fiber placement methods create textile pre-
method utilizing textile processes prior to the forms which possess a wide spectrum of pore
geometries and pore distribution; a broad
formation of composite structures. Textile pre-
range of structural integrity and fiber volume
forms are the structural backbone of a
fraction; and fiber orientation distribution as
composite analogous to the structural steel
well as a wide selection of formed shape and
framework in a building. Starting with linear
net shape capability.
assemblies of fibers in continuous and/or dis-
As illustrated in Fig. 18.1, textile preforming
crete form, these micro-fibrous structures can
provides a link between raw material systems
be organized into one-, two- or three-dimen-
and the composite product. Depending upon
sional structures by means of twisting,
the textile preforming method used, the range
interlacing, intertwining or interlooping. By
of fiber orientation and fiber volume fraction
proper selection of the geometry of the fibrous
of the preform will vary, subsequently affect-
structures and architecture and the method of
ing matrix infiltration and consolidation as
placement or geometric arrangement of the
well as the translation efficiency of fiber prop-
fibers, the structural performance of the
erties to composite product.

Vacuum Impregnation

Y I..CU Squeeze Casting

K
Vacuum Infiltration
Composite
Design and Product
material system
selection

Liquid Impregnation

Fig. 18.1 The role of preforms in composite processing.

Handbook of Composites. Edited by S.T. Peters. Published

in 1998by Chapman & Hall, London. ISBN 0 412 54020 7
398 Textile preforming
When combined with high performance
fibers, matrices and properly tailored
fiber/matrix interfaces, fiber architecture
promises to expand the design options for the
manufacturing of tough and reliable structural
composites. With an integrated network of
structural cells in two- and three-dimensional
arrangements, textile structures not only pro-
vide a mechanism for structural toughening of
composites but also facilitate the processing of
composites into net or near net shape struc-
tural parts.
Considering the important role which tex-
tile preforms play in the chain of composite
manufacturing processes, there is a worldwide
revival of interest in the technology and sci-
ence of the processing of textile preforms for
composites. The serious interest in the subject
of textile composites can best be illustrated in
the two recent publications on textile compos-
ites, one in English (Chou and KO, 1989) and
the other in Russian (Tarnpolski’i et al., 1987).
These two books have been translated respec-
tively into Russian and English. Special
journal issues have been devoted to the subject
of textile composites as well (for example,
Jouvnal of The Textile Institute, 1990, No. 4,
Textile Institute). This article intends to pro-
vide a quick reference to textile preforming
from the point of view of composite process-
ing science. To facilitate discussion, textile
preforms are classified into linear, planar and
three-dimensional fibrous assemblies. After a
brief introduction of the processing technol-
ogy of textile preforms, discussion will focus
on the processing kinematics of the preforms
and the geometric parameters which control
two of the most important parameters in com-
posite design: fiber volume fraction (V,) and
fiber orientation (0). The role of fiber archtec-
ture in the forming, resin infiltration and the
translation of fiber properties to the composite
is also discussed along with experimental evi-
dence. For readers interested in further
pursuing the technological aspect of the sub-
ject, there are several outstanding general
references on industrial textiles (Kaswell, 1963;
Svedova, 1990). For more specific references
one can examine the book by Goswami et al.
(1977) on yarns (linear fibrous assemblies);
Lord et al. (1973) on weaving; Spencer (1983)
and Raz (1987) on knitting and Krcma (1971)
on nonwovens.
18.1.1 THE ROLE OF TEXTILE PREFORMS
The final goal of manufacturing a composite
structure is to meet design requirements
including performance and cost. How success-
fully the goal can be met depends on the
effective use of the reinforcement material and
the cost of manufacturing a quality product.
Preform fiber architecture plays a key role
in composite manufacturing by facilitating
processing steps including forming and resin
infiltration. The properties of the composite
will also vary depending on the fiber architec-
ture. Fiber orientation (13)and volume fraction
(V,)are key engineering parameters for textile
composite formability, permeability and per-
formance. Accordingly, after reviewing the
experimental evidence of the dynamic interac-
tion of process-structure-performance, this
article will examine textile preforms through a
unit cell based analysis relating the preform
geometric parameters of V, and I3 and their
relationship to textile preform performance.
Formability
The manufacturing of composites often
requires transformation of the fiber reinforce-
ments into various structural shapes through
net shape fabrication or formed shape process-
ing. While 3-D textile preforming is more
suitable for the creation of net structural
shapes, 2-D textile preforms are usually
formed into shapes by molding or stitching.
One of the earlier studies of fabric formability
in composite manufacturing (Potter, 1979)
showed that total available deformation could
be imposed on the fabric uniformly and that
the modes of deformation are important para-
meters for fabric formability. Potter
 In trod uction 399

demonstrated that weft knitted fabrics are sig-

nificantly more conformable than biaxially
woven fabrics because deformation of the
knitted fabric in the axial, transverse and bias
direction are 50%, 50% and 26% respectively,
compared to 0%, 0% and 45% for the woven
fabric.
The same point can also be illustrated in a
comparison of the shear resistance of biaxially
and triaxially woven glass fabrics (Scardino
and KO, 1981). Comparing the strain behavior
of plain woven and triaxial basic fabric of sim-
ilar area density (281.5 compared with
284.8 g/m2), under biaxial loading, it was
found that the shear deformation of the triax-
ial fabrics is considerably more uniform than
that of the biaxial fabrics (Fig. 18.2).As a result
of this comparison, it was found that triaxial
fabric is more adaptable to 3-D draw molding
than biaxial fabrics made from the same yarn.
In quantifying the formability of fabrics,
Dow (1985) suggested that yarn slippage and
low yarn jamming angles are required for
fabric conformability. Accordingly, in fabric
formability modeling, fiber volume fraction ORIENTATION 8 (degrees)
distribution, fiber orientation and fiber inter- (b)
lacing intensity as well as the limit of
Shear strains .10
geometric deformation (all of which are gov- m
erned by the architecture created by specific f 800
textile preforming techniques) must be con- Y

Q)
sidered. g 600
W
z
Permeability - 400
(L
IL

Textile fluid flow permeability is an indication

G
of how easily and uniformly a matrix can be 2
I
200
infiltrated into the fibrous assembly. McCarthy v)

et al. (1991)concluded that the permeability of

'0 20 40 60 80 100
textile preforms is mainly affected by fiber vol-
ORENTATION e (degree)
ume fraction and fiber orientation (Fig. 18.3). (4
In the same figure, it can be noted that, for the
same fiber volume fraction, ordered structures Fig. 18.2 (a) Triaxial and biaxial plain-weave fabric
such as 0/90° woven fabrics have higher per- specimens partially deformed (50% of maximum
force) in ball-burst test at same displacement of ball
meability than disordered structures such as into fabric plane; (b) effect of test direction on the
discrete chopped fibers. shear stiffness of biaxial fabrics at various normal
The dependence of permeability on fiber stresses; (c) effect of test direction on the shear stiff-
volume fraction was also observed by Loos et ness of triaxial fabrics at various normal stresses.
400 Textile preforming
6W-
4 iayers
meability of the preforms, especially for pre-
;DO
forms with high fiber volume fraction. The
Koczeny-Carman equation was found to be
adequate to provide a quantitative relation-
ship between permeability and preform
porosity.
233 -
Properties
Fiber architecture plays an important role in
the translation of fiber properties to the com-
posites as well as controlling the level of
matrix infiltration. The dynamic interaction of
Fig. 18.3 Permeability against fiber volume fraction material (fiber),fiber architecture and compos-
of textile preform.
ite properties are best illustrated by Figs. 18.5
0.1 and 18.6. In Fig. 18.5 (Dow, 1985), the in-plane

0.05 1 tensile and shear properties of carbon/epoxy

composites having a 60%)fiber volume fraction
are compared for unidirectional angle ply
structure, 2-D woven 3-D braided structures.
0.02 -

0.01 ;

0.005 -
N -

9
z
Y
0.002 -
0.001 -
a &,mu
0.0005 &: 4
n
a_oooz

2
0.0001 ~ " ' " ' ' ' I ' " " ' ' '
0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.6C
Porosity, 0
Fig. 18.4 Normalized through-the-thickness per-
meability against porosity for multiaxial warp knit
fabric preforms.

a2. (1991), as shown in Fig. 18.4. In their study Fig. 18.5 Range of values of in-plane Young's mod-
of carbon multiaxial warp knit preforms, it ulus, E.r and shear modulus GXYwith T-300 carbon
was found that the introduction of through fibers in 5200 epoxy at a volume fraction reinforce-
thickness fibers significantlyincreased the per- ment of 0.6.
 Introduction 401

18.1.2 CLASSIFICATION OF TEXTILE

e AUnldirectional PREFORMS
a e Owoven laminates

There is a large family of textile preforming

P
a methods suitable for composite manufactur-
P
ing (KO, 1989).The key criteria for the selection
of textile preforms for structural composites
are (a) the capability for in-plane multiaxial
reinforcement, (b) through thickness reinforce-
00 01 02 03 04 05
ment and (c) the capability for formed shape
Void fraction
and/or net shape manufacturing. Depending
Fig. 18.6 Effect of fiber architecture on the flexural on the processing and end use requirements,
strength of SiC/SiC composites. some or all of these features are required.
On the basis of structural integrity and fiber
It can be seen that with each reinforcement linearity and continuity, fiber architecture can
group, fiber orientation has a significant influ- be classified into four categories: discrete; con-
ence on the overall performance of the tinuous; planar interlaced (2-D); and fully
composite. Within the envelope of in-plane integrated (3-D) structures. In Table 18.1 the
properties of unidirectional reinforcement lies nature of the various levels of fiber architec-
a broad range of properties for 2-D and 3-D ture is summarized (Scardino, 1989).
textile composites. A discrete fiber system such as a whisker or
For very brittle composites such as the fiber mat has no material continuity; the orien-
SiC/SiC composites produced by the chemical tation of the fibers is difficult to control
vapor infiltration (CVI) process, the effect of precisely, although some aligned discrete fiber
fiber architecture on the level of infiltration is systems have recently been introduced. The
quite evident. Comparing the flexural strength structural integrity of the fibrous preform is
of short fiber mat, unidirectional tape, woven derived mainly from inter-fiber friction. The
laminates and 3-D braided reinforced ceramic strength translation efficiency, or the fraction
matrix composites, one can see that a 3-D fiber of fiber strength translated to the non-aligned
architecture produces structures superior to fibrous assembly of the reinforcement system,
others because of the three-dimensional inter- is quite low.
connected network of Sic fibers. The The second category of fiber architecture is
unidirectional composite has the highest vari- the continuous filament, or unidirectional (OO)

ations of void factor and unidirectional system. This architecture has the highest level
strength. It is clear in Fig. 18.6 that the perfor- of fiber continuity and linearity and conse-
mance of composites depends not only on the quently has the highest level of property
volume fraction but also the fiber orientation translation efficiency and is very suitable for
of the preform (KOet aZ., 1988a). filament wound and angle ply tape lay-up

Table 18.1 Fiber architecture for composites

Level Reinforcement Textile Fiber length Fiber Fiber

system construction orientation entanglement
~~~~-
-~ ~~ ~ _ _
I Discrete Chopped fiber Discontinuous Uncontrolled None
I1 Linear Filament yarn Continuous Linear None
I11 Laminar Simple fabric Continuous Planar Planar
IV Integrated Advanced fabric Continuous 3-D 3-D
402 Textile preforming
structures. The drawback of this fiber architec-
ture is its intra- and interlaminar weakness
due to the lack of in-plane and out-of-plane
yarn interlacing.
A third category of fiber reinforcement is
the planar interlaced and interlooped system.
Although the intra-laminar failure problem
associated with the continuous filament sys-
tem is addressed with this fiber architecture,
the interlaminar strength is limited by the
matrix strength due to the lack of through
thickness fiber reinforcement.
The fully integrated system forms the
fourth category of fiber architecture wherein
the fibers are oriented in various in-plane and
out-of-plane directions. With the continuous
filament yarn, a three dimensional network of
yarn bundles is formed in an integral manner.
The most attractive feature of the integrated
structure is the additional reinforcement in the
through-thickness direction which makes the
composite virtually delamination-free.
Another interesting aspect of many of the fully
integrated structures such as 3-D woven, knits
and braids is their ability to assume complex
structural shapes.
Another way of classifying textile preforms
is based on the fabric formation techniques:
through fiber entanglement or yam twisting,
interlacing, interlooping, intertwining or mul-
tiaxial placement. While most textile preforms
are converted from fiber to yarn or yarn to fab-
ric structures, some preforms, such as fiber
felts, are converted directly from fiber to fab-
ric. In Table 18.2, the four basic yarn-to-fabric
formation techniques are compared.
Table 18.2 A comparison of fabric formation techniques
Preforming technology Yarn introduction direction
Weaving Two ( O o / 9 O 0 ) (warp and fill)
Nonwoven Three or more (orthogonal)
Knitting One (0" or 90")
(warp or fill)
Braiding One (machine direction)
While weaving, braiding and knitting can
produce planar or 3-D structures, nonwoven
fabrics can be a 2-D planar system with ran-
dom or organized fiber orientation, as well as
the orthogonal 3-D system. The 2-D and 3-D
fabrics are distinguished by yarn orientation
distribution and the number of yarn diameters
in the thickness direction. A 2-D fabric consists
of two to three yarn diameters in the thickness
direction with fibers oriented in the x-y plane.
A 3-D fabric, consisting of three or more yams
in the thickness direction, is a fibrous network
wherein yarns pass from surface to surface of
the fabric in all three directions.
18.2 YARN PREPARATION FOR TEXTILE
PREFORMING
18.2.1 CLASSIFICATION OF YARNS
In addition to preforming methods and para-
meters, the physical properties of textile
preforms, such as thickness, fabric tightness,
fiber orientation, etc., are also affected by the
characteristics of yarns. Linear fibrous assem-
blies can be composed of filaments of discrete
(staple yarns) or continuous lengths (filament
yarns). Staple yarns are held together by an
appropriate level of twist, whereas filament
yarns may or may not have twist. Larger fila-
ment bundles that have little or no twist are
called rovings; yams are usually smaller than
rovings and some level of twist is generally
added. The majority of high performance
yarns are continuous filament yams having
single or multiple strands.
~ ~~~
Formation technique
Interlacing (by selective insertion of
90" yarns into 0" yarn system)
Mutual fiber placement
Interlooping (by drawing loops of
yams over previous loops)
Intertwining (position displacement)
 Yarn preparation for textile preforming 403

18.2.2 YARN GEOMETRY volume fraction can be shown to equal (Du,

The geometric parameters which describe a lin- Popper and Chou, 1991)
ear fiber assembly include: shape of bundle 3N1(N1- 1) + 1
cross-section, number of fibers in the bundle, Yopen = 1- (18.1)
(2N1- 1)’
dimension and shape of fiber cross-section,
bundle twist level, degree of fiber migration in where N , is the number of rings and its rela-
the radial direction and fraction of interfiber tionship to the number of fibers, N,,
is given by
packing. Usually, the fiber bundles are assumed
to be circular in cross-section, but in reality, the
1
2 +
N, = - {[-41 + -(2Nf
1
3 - I)] (18.2)
fibers or filaments can be packed in to various
shapes. Most of the engineering fibers, such as For large numbers of fibers the fiber volume
glass and carbon, have a circular or near-circu- fraction approaches 0.75.
lar cross-section with a constant diameter. For In squared packed bundles, the fibers are
some ceramic fibers, such as Nextel, the fibers arranged in a square array. For any number of
have an ellipse shape and varying dimensions. circular fibers, if the outer layer is completely
The filament bundles used for composites have filled, the fiber volume fraction can be shown
a small amount of twist, usually less than 4 tpi, to equal the area ratio of a circle to an enclos-
the bundle surface twisting angle is small. ing square:
The geometry of interfiber packing in fiber
x
- = 0.785 (18.3)
bundles has been studied by a number of
Vfsquarr
= 4
researchers primarily for textile applications
(Hearle et al., 1969). Three basic idealized Similar to square packing, the fiber volume
forms of circular fiber packing were identified: fraction of close packed bundle is equal to the
open-packing, in which the fibers are arranged area ratio of a circle to an enclosing hexagon:
in concentric layers (Fig. 18.7(a));square-pack-
ing, in which the fibers are enclosed by a 0.907 (18.4)
square (Fig. 18.7(b)); and close-packing, in
which the fibers are arranged in a hexagonal The level of bundle fiber volume fraction pre-
pattern (Fig. 18.7(c)). dicted by the above models assumed circular,
In open-packed bundles the fiber volume square and hexagonal fiber bundles for open,
fraction, defined as fiber to bundle area ratio, square and close packing, respectively.
has been computed as a function of the num- However, they apply equally well to other
ber of fibers. If the outer ring is completely shapes if the number of fibers is sufficiently
filled and the fibers are circular, the fiber large.

Fig. 18.7 Idealized fiber packings: (a) open packing; (b) square packing; (c) close packing.
404 Textile preforming

(surface helix angle) and the twist level, as

Fig. 18.8 Geometry of twisted yarn.
shown in Fig. 18.3. Clearly, for a given twist
inserted to the fiber bundle, as fiber orienta-
tion angle increases, yarn diameter increases
(as indicated by equation (18.6)) whereas the
fiber volume fraction decreases as can be seen
in Fig. 18.9, which is useful in determining the
twist level of fiber bundles. For example, to
obtain a fiber volume fraction (or fiber packing
fraction) 0.8 and a fiber orientation angle lo",
twist level of 3 tpi should be used for the 12K,
7 pm fiber diameter carbon yarns.

For twisted fiber bundles, the fibers are no

longer aligned along the bundle axis. Instead,
the fibers assume a helix configuration within
the bundle, as shown in Fig. 18.8. The fibers in
different radial layers of the bundle have a dif-
ferent helix angle:
Bi = tan+ [n(D,- d)T] (18.5)
where d is the fiber diameter, T is twist level
and Di is the diameter of the fiber layer. 0 10 20 30 40 50 60 70 80 90
Apparently, fibers at the outer layer have a 9 (")
maximum orientation (helix) angle:
Fig. 18.9 Relationship of fiber volume fraction to
8 = tan-' [n(D- d)T] (18.6) fiber orientation at various twist levels.
where D is the diameter of the bundle.
According to Hearle (1969), yarn diameter is
related to the number of filaments ( n ) in the
yarn and the packing fraction of the fibers ( K ) 18.3 WEAVING
in the following relationship:
18.3.1 PROCESSING TECHNOLOGY
(18.7) Weaving, which is the interlacing of two sets
of yams usually at a right angle to each other,
Viewing a yarn bundle as an individual pre- requires holding one set of yams in parallel
form, its fiber volume fraction is actually equal rows and passing another set over and under
to its fiber packing fraction, i.e. V , = IC. the first set. The set of lengthwise yarns is
Combining equations (18.6) and (18.7), we called warp and the set of crosswise yarns is
have the fill. The simplest two-hamess loom is
-2 sketched in Fig. 18.10 and may be used for
(18.8) making biaxial plain weave fabrics shown in
Fig. 18.11(a).For more complex weaves such
For a 12K carbon yarn with 7 p m fiber diame- as twill and satin as illustrated in Figs 18.11@).
ter, one can establish the relationship between and (c), looms with more than two harnesses
its fiber volume fraction, fiber orientation are required.
 Weaving 405

harnesses are lifted. Fabrics with as many as 17

layers have been successfully woven with this
method.

beam

Shuttle Reed

Fig. 18-10A simple two-harness weaving loom Fig. 18.12 Structural geometry of triaxially woven
(Smith and Block, 1982). fabrics (basic weave).

In a novel departure from standard weaving

methods, triaxial weaving interlaces two warp
yarns and one filling yarn at 60" angles as
p\
shown in Fig. 18.12 (Dow et al., 1970).The tri-
axial fabric has excellent dimensional stability
;B a:
and is currently used almost exclusively for \
industrial products. \
Three-dimensional woven fabrics are pro-
duced principally by the multiple warp
weaving method, long used for the manufac-
turing of double cloth and triple cloths for
bags, webbings and carpets. A typical setup of
a multiwarp weaving loom is shown in Fig.
18.13.The number of layers of yarns in the fab-
rics is governed by a special shedding
mechanism which controls the height that the Fig. 18.13 Setup of a multiwarp weaving loom.

Fig. 18.11 Structural geometry of biaxially woven fabrics: (a) plain weave; (b)twill weave; (c) satin weave.
406 Textile preforming
18.3.2 STRUCTURAL GEOMETRY
Biaxial weaves consist of 0" and 90" yarns
interlaced in various repeating patterns or
topological unit cells. The three basic weave
geometries from which many other patterns
evolve are the plane, satin and twill weave. A
schematic diagram for the various views of
these three basic weaves are shown in Fig.
18.11.These three fabrics are distinguished by
their frequency of yarn interlacing and the lin-
earity of the yarn segments. The plane weave
has the highest frequency of yarn interlacing
whereas the satin weave has the least number
of yarn interlacing, with the twill weave some-
where in between. Accordingly, the plane
weave has a higher level of structural integrity
and greater ductility due to the crimp geome-
try produced by yarn interlacing. On the other
hand, the satin weave has the highest level of
fiber to fabric strength and modulus transla-
tion efficiency due to the low level of yarn
interlacing and yarn linearity. The low level of
yarn integration in satin weave also allows
freedom of yarn mobility which contributes to
higher fiber packing density and consequently
higher level of fiber volume fraction.
Fig. 18.14 Structural
geometry of various
3-D woven fabrics: (a)
solid orthogonal panel;
(b) variable thickness
solid panel; (c) rectan-
gular core structure;
(d) triangular core
structure; (e) angle
interlock.
Triaxial weave has 90+60" yarns oriented in
one plane, resulting in a high level of in-plane
shear resistance (Dow et al., 1970).High levels
of isotropy and dimensional stability can be
achieved with triaxial weave at low fiber vol-
ume fraction. Figure 18.12 shows a schematic
diagram of triaxial weave geometry.
Using the multiwarp weaving method, var-
ious fiber architectures can be produced
including solid orthogonal panels, variable
thickness solid panels and core structures sim-
ulating a box beam, or truss-like structure as
illustrated in Fig. 18.14. Furthermore, by
proper manipulation of the warp yarns, as
exemplified by the angle interlock structure,
the through-thickness yarns can be organized
into a diagonal pattern, as shown in Fig.
18.14(e). One limitation of the multiwarp
weaving method is the difficulty of introduc-
ing yarns in the bias direction as in the triaxial
weaving or circular weaving process.
However, this is now being addressed by a
modification of triaxial weaving techniques
(Dow, 1989).
As illustrated in Fig. 18.15 (Pastore and Cai,
1990a), there are four basic components to a
generalized three-dimensional woven fabric
 Weaving 407

geometry: warp, web, fill and surface weave
yarns. Warp yarns are the system of yarns
which run in the machine direction and have
no crimp. These are also called ’stuffer’yarns
or ’longitudinals’. Because of their very low
crimp, these yarns provide the primary
strength and stiffness in the longitudinal (x)
direction of the material. Web yarns run in the
machine direction and provide the interlacing
necessary for fabric integrity. These yarns con-
tain crimp in the through thickness direction,
providing the z-directional properties of the
system. These yarns are sometimes called
’weavers’. The ‘weave angle’ of the web yarns
(6) refers to the angle of orientation of the web
yarn with respect to the warp direction. Fill
yarns are perpendicular to machine direction
and interlace with the web yarns. These yarns
are sometimes called ’picks’. These yarns also
possess crimp in the through thickness direc-
tion, but this crimp is negligible compared to
that of the warp yams for these fabric systems.
These yarns provide the transverse (y) direc-
tional properties of the composite system.
Surface weave yarns run in the machine direc-
tion and form what is essentially a
two-dimensional weave on the surface of the
fabric. Surface weave yarns are incorporated
into the structure when the web yarns are
insufficient to provide a smooth surface on the
face and back of the cloth. These yarns experi-
ence crimp in the through thickness direction.
When surface weave yarns are employed in
the fabric, there are two yarns for every warp
plane of the fabric. This system of yarns con-
tributes the least to the mechanical properties
of the composite.
18.3.3 DESIGN METHODOLOGY
Figure 18.16 gives the unit cell geometry for
plain biaxial weave, as proposed by Dow and
Ramnath (1987). In their analysis, Dow and
Ramnath assumed circular yarn cross-section,
the same yam diameter and pitch length for
both fill and warp yarns. The expression of the
fiber volume fraction was derived:
I
2-+46
(18.9)
where K is the fiber packing fraction, d is the
yarn diameter, L is the pitch length, T is the
fabric thickness, I is the dimension shown in
Fig. 18.16. The yarn inclination angle to the
fabric plane, 6, is given by:

Surface weaver

Weaver or
web yarn

Pick or
filling yarn
Warp yarn
Fig. 18.15 Schematic illustration
of generalized 3-D woven fabric
projected to the x-z (fabric
length-thickness) plane.
408 Textile preforming

lengths for fill and warp yarns can be analyzed.

Based on the structural geometry shown in
Fig. 18.15, the orientations and volumetric dis-
tributions of all yarns in the 3-D weave can be
calculated also using the unit cell method.
Detailed analysis is given by KO and Du (1992).
__---
V

t .+I I 10
09
08

> 06
05
SCCTION -
.-.
04
03
02
Fig. 18.16 Unit cell geometry of plain weave. 01
00
0 10 20 30 40 50 60 70 80 90
The fabric thickness is very close to two yarn
diameter, i.e. 0()

T=2d (18'11) Fig. 18.17 Relationship of fiber volume fraction to

and approximately: fiber orientation for plain weave.

1 - 1
(18.12) 18.4 KNITTING
d tan8
18.4.1 PROCESSING TECHNOLOGY
Equation (18.9) is then simplified to
Knitting is the interlocking of one or more
yarns through a series of loops (also called
stitches). The lengthwise columns of stitches
corresponding to the warp in woven fabrics
are called wales; the crosswise rows of stitches
Figure 18.17 plots the fiber volume fraction corresponding to the filling are known as
against the yarn inclination angle. It can be courses. Knitted structures can be classified by
seen that as the inclination angle increases, the basic loop formation mechanism into weft
pitch length becomes longer which results in a knits and warp knits. In weft knitting, as
lower fiber volume fraction. The woven fabric shown in Fig. 18.18(a),yam feeding and loop
has the tightest structure at the inclination formation occur at each needle in succession
angle of 60" (when Lld = 3 in equation (18.10)). along the wale direction and all the courses of
In this calculation, the fiber packing fraction K loops are composed of single strands of yam.
is assumed to be 0.8. In warp knitting, there is a simultaneous yarn-
The above analysis is given only for the sim- feeding and loop-forming action occurring at
plest of woven structures. Different weave every needle and all the wales of loops are
patterns, non-circular yarn cross-sectional composed of single strands of yarn as illus-
shape, different yarn dimensions and pitch trated in Fig. 18.18(b).

Fig. 18.18 Yarn feeding and loop formation: (a) weft knitting; (b) warp knitting (Spencer, 1983).
Stitch (loop) formation is similar in both weft
and warp knitting. The formation of the
stitches in a single wale is illustrated in Fig.
18.19. In Step 1, the needle rises through loop
A from its lowest position; in Step 2, yarn slips
under the tip of the needle and onto the stem;
in Step 3, ascending hook catches the new yarn
at the top of its rise and begins to descend; in
Step 4, the new yarn slips under the tip and
into the hook; in Step 5, the needle moves
down until the tip slides under loop A and the
hook pulls the new loop through. After the
completion of five steps, loop B is formed and
the process is repeated. In a knitting operation,
each of the needles is controlled by a cam to
rise and fall in synchronization with the other
needles. Detailed description of the knitting
,Hook
Ti
1 2
Knitting 409
J ’Djrection of knitting
technology can be found in Spencer (1983)and
Raz (1987).
Knitted 3-D fabrics are produced either by
weft or warp knitting. An example of a weft
knit is the near net shape structure knitted
under computer control by the Pressure Foot@
process (Williams, 1978). In a collapsed form
this preform has been used for carbon-carbon
aircraft brakes. While weft knitted structures
have applications in limited areas, multiaxial
warp knit (MWK) 3-D structures are more
promising and have undergone a great deal
more development in recent years. Schematic
of a MWK LIBA system is given in Fig. 18.20,
in which up to six layers of insertion yarns
plus one layer of non-woven can be stitched
together.
3
Fig. 18.19 Stitch for-
mation in knitting
machines (Smith and
Block, 1982).
410 Textile preforming

Fig. 18.20 Multiaxial warp knit with four layers ( O O , 90" and &) of inserted yarns and (a) chain stitch or (b)
tricot stitch.

18.4.2 STRUCTURAL GEOMETRY ture for the incorporation of 0" and/or 90"
insertion yarns.
Knitted fabrics are traditionally identified
The MWK fabric system consists of warp (O"),
with socks, underwear and sweaters. In the
search for methods to reduce composite man- weft (90") and bias (d) yarns held together by
ufacturing costs, textile preforms including a chain or tricot stitch through the thickness of
knitted structures are receiving increased the fabric, as illustrated in Fig. 18.21.
interest in the composite industry. While con- Theoretically, the MWK can be made to as
formability and productivity are obvious many layers of multiaxial yams as needed, but
attributes for knitted preforms, the availability current commercially available machines only
of a broad range of micro- and macrostructural allow four layers (the Mayer system) of 0", 90",
geometries has only recently been recognized. +O and 4 insertion yams, or six layers (the
The non-linearity of knitting loops, severe LIBA system) of 2(90"), 0", 2(+8) and 2 ( 4 )
bending of yams during the knitting process insertion yarns to be stitched together. All lay-
and limited fiber packing density resulting in ers of insertion yarns are placed in perfect
the formation of resin pockets within a knit- order each on top of the other in the knitting
ting loop prevent kmts from being considered process. Each layer shows the uniformity of the
for structural applications. uncrimped parallel yams. The insertion yarns
The development of technology for the usually possess a much higher linear density
directional insertion of linear yarns in weft than the stitch yarns and are therefore the
and warp knits greatly enhances opportunities major load bearing component of the fabric.
for knitted preforms for conformable struc-
tural composites by combining the
18.4.3 DESIGN METHODOLOGY
conformable foundation knit structure with
directional reinforcement. As shown in Fig. Similar to the 2-D woven fabrics, the unit cells
18.20, sewing threads (high twist yams) or for the knitted structures are also different,
very fine yams are used to form a base struc- depending on the knit constructions such as

Fig. 18.21 Multiaxial warp knit LIBA system.
stitch patterns and laid-in insertions. To illus-
trate the use of the unit cell method for
relating fiber volume fraction, yarn orientation
and processing variables, a plain weft knit as
shown in Fig. 18.18(a) is selected as an exam-
ple. The unit cell geometry identified for the
plain weft knit is shown in Fig. 18.22, having a
dimension of x (course width), y (half wale
width) and z (fabric thickness).
Fig. 18.22 Unit cell geometry of plain knitted struc-
ture.
In traditional textile fabric manufacturing,
highly twisted fiber bundles are used. These
materials can maintain a circular shape with a
width-to-thickness aspect ratio of f = 1, as
Knitting 411
illustrated in Fig. 18.23(b).For untwisted fiber
bundles under compression applied during
preforming or composite processing, they
have a ribbon-like cross-section similar to a
race-track with a width-to-thickness aspect
ratio off > 1 as illustrated in Fig. 18.23(a).For
composite applications, untwisted fiber bun-
dles are usually used in knitting, which have
an aspect ratio f slightly larger than 1 at the
off-machine state. To increase the fiber volume
fraction for knitted structures, very high pres-
sure will be required to reduce the knit
thickness. Under the compression status, the
yarn aspect ratio f can increase to as high as 12
for untwisted bundles, provided that there are
no restrictions applied to yarn edges.
(a) f =w/t 1 (b) f =1
Fig. 18.23 Idealized yarn cross-sections: (a) race-
track cross-section with width-to-thickness aspect
ratio f > 1; (b) race-track shape becomes circular
whenf = 1.
412 Textile preforming
In this analysis, the knit thickness is assumed
to be approximately equal to two yarn thick-
ness (t)for computational purposes, i.e.
z = 2t (18.14)
The yarn orientation angle (e), which is the
angle made by the fabric axis (in x direction)
and the yarn path projected to the fabric sur-
face plane ( x - y), is given by:
(18.15)
The fiber volume fraction (V,),which is defined
as the ratio of volume of total fibers to the over-
all composite volume, can be derived as:
Y = 3, y/w = 2 and k = OB), its maximum fiber
(18.16)
1+tan -
where k is the fiber packing fraction within
yarn bundles and a is the shape correction fac-
tor defined as:
(18.17)
The limiting geometry of the knitted structure
due to yarn jamming is governed by:
X
-23 (18.18)
W P
1 2 2 (18.19)
W 10
The processing window of fiber volume frac-
tion for knitted structures within the possible
ranges of key processing parameters, such as
relative course width (x/w), relative half wale
width (y/w) and yarn aspect ratio (f)under
compression is depicted in Fig. 18.24, using the
geometric model developed. In the calculation,
we use the fiber packing fraction k = 0.8, which
is within the range for tightly packed yarn bun-
dles according to experimental observation.
Also, to show the processing window of fiber
volume fraction in highest region, one can
assume yam jamming in the course (x) direc-
tion, i.e. x/w = 3 according to equation (18.18).
As can be seen from Fig. 18.24, the fiber vol-
ume fraction V , decreases with the increase in
relative half wale width in the range of y/w =
2-10. When y/w is beyond 10, the fiber vol-
ume fraction slightly increases and soon
approaches a constant with the increase in rel-
ative half wale width. The wale width cannot
be smaller than 4 yarn widths, or y/w 2 2 as
given by equation (18.19). Knitted yarns have
an aspect ratio f = 1 at free-stress status (as
made off-machine) and the fiber volume frac-
tion for the knitted preform has a minimum
value. Figure 18.24 shows that, for the plain
weft knit at its tightest possible structure (x/w
volume fraction is only about 0.274.
To increase the fiber volume fraction, a com-
pression in the fabric thickness direction is
necessary. The effect of the compression is the
increase in yam aspect ratio (i.e. yams within
the knitted structure become wider in x-y plane
060
020
f = 1 (circular yarn without compressior
LL
0.10
ooo
100 1000
Ylw
Fig. 18-24 Processing window of fiber volume frat-
tion for the plain knitted structure.

but thinner in z direction).As a result, the yarn
coverage over the fabric increases, whereas the
volume of the preform decreases due to the
decrease in fabric thickness. These two factors,
the increased yarn coverage and decreased pre-
form volume, raise the fiber volume fraction to
a much higher level. As shown in Fig. 18.24, at
a maximum aspect ratio f = 12, the fiber vol-
ume fraction can be as high as 0.475.
A series of studies on the technology, struc-
ture and properties of the MWK preforms and
composites have been reported by KO and his
co-workers (1980,1982,1985,1986,198813).In a
recent study, a unit cell based geometric model
of the four-layer MWK structure as shown in
Fig. 18.21was developed by Du and KO (1992).
Based on the experimental observations, the
unit cell geometry of the MWK fabric is iden-
tified and a geometric model is developed
relating the fiber volume fraction and fiber ori-
entation in terms of structural and processing
parameters.
18.5 BRAIDING
18.5.1 PROCESSING TECHNOLOGY
Braiding is an old textile technology, tradition-
ally used for the manufacture of a wide variety
of linear products ranging from cables, electri-
cal insulators and shoelaces to surgical sutures.
Recognizing the high level of conformability
and the damage resistance capability of
braided structures, the composites industry
had found structural applications for braided
composites ranging from rocket launchers to
automotive parts to aircraft structures.
Two-dimensional braided structures are
intertwined fibrous structures capable of form-
ing structures with 0" and & fiber orientation.
Although 2-D braids can be fabricated in tape
form, the majority of braided structures are
fabricated with a tubular geometry. Thickness
is built up by overbraiding previously braided
layers similar to a ply lay-up process. Braiding
can take place vertically orhorizontally, but a
majority of the composite braiders are horizon-
Braiding 413
tal. A schematic of a horizontal braider is
shown in Fig. 18.25.Although braiding is simi-
lar to filament winding in many ways, the
major difference between braiding and fila-
ment winding is that braids are interlaced
structures having as many as 144 or more inter-
lacing per braiding cycle (or pick).
Three-dimensional braiding technology is
an extension of 2-D braiding technology in
which the fabric is constructed by the inter-
twining or orthogonal interlacing of yarns to
form an integral structure through position
displacement. A unique feature of 3-D braids
is their ability to provide through the thickness
reinforcement of composites as well as their
ready adaptability to the fabrication of a wide
range of complex shapes ranging from solid
rods to I-beams to thick-walled rocket nozzles.
Three-dimensional braids have been pro-
duced on traditional Maypole machines for
ropes and packings in solid, circular or square
cross-sections. The yarn carrier movement is
activated in a restricted fashion by horn gears.
A 3-D cylindrical braiding machine of this form
was recently introduced by Albany with some
modification that the yarn carriers do not move
through all the layers (Brookstein, 1991). 3-D
braiding processes without using the horn
gears, including Track and Column (Brown et
al., 1988) and 2-Step (Popper and McConnell,
1987),have been developed since the late 1960s
in the search for multidirectionally reinforced
composites for aerospace applications.
A generalized schematic of a 3-D braiding
process is shown in Fig. 18.26. Axial yarns, if
present in a particular braid, are fed directly
Axial yarns, /Carrier track
Fig. 18.25 Schematic of tubular braider with gantry
system.
414 Textile pyeforrning

,;;urbanism Track and column braiding is the most pop-

ular process in the manufacturing of 3-D
braided preforms. The mechanism of these

-
Forming point
Convergence point
Fig. 18.26 Schematic of a generalized 3-D braider.
into the structure from packages located below
the track plate. Braiding yarns are fed from
bobbins mounted on carriers that move on the
track plate. The pattern produced by the
motion of the braiders relative to each other
and the axial yarns establish the type of braid
being formed, as well as the microstructure.
braiding methods differs from the traditional
horn gear method only in the way the carriers
are displaced to create the final braid geome-
try.Figure 18.27(a)shows a basic loom setup in
a rectangular configuration. The carriers are
arranged in tracks and columns to form the
required shape and additional carriers are
added to the outside of the array in alternating
locations. Four steps of motion are imposed to
the tracks and columns during a complete
braiding cycle, resulting in the alternate x and
y displacement of yam carriers, as shown in
Fig. 18.27(b-e).The formation of shapes, such
as T-beam and I-beam, is accomplished by
proper positioning of the carriers and the join-
ing of various rectangular groups through
selected carrier movements. The track and col-
umn braiding machine can also be used to
create 2-step braids and other similar 3-D
structures by simply adding a certain number
of axial yarns and removing most of the braid-
ing yarns (Du and KO, 1993a).

Track direction

Fig. 18.27 Formation of a rectangular 3-D track and column braid, using 4 tracks, 8 columns and 1 x 1
braiding pattern. (a) Initial loom setup; (b) Step 1: tracks move horizontally; odd tracks move to left and
even tracks move to right; (c) Step 2: columns move vertically; odd columns move down and even columns
move up; (d) Step 3: tracks move horizontally; odd tracks move to right and even tracks move to left; (e)
Step 4: columns move vertically; odd columns move up and even columns move down.
 Braiding 415

18.5.2 STRUCTURAL GEOMETRY from 5" in almost parallel yarn braid to

approximately 85" in a hoop yarn braid,
As with woven fabric, braids can be formed
depending on the mandrel dimension, the
with different yarn interlacing patterns by
machine speed ratio and the convergence
simply changing relative position of carriers
length (Du et al., 1990).
on the track ring. If one bias yarn continuously
The 2-D braid can be defined as a fabric
passes over one yarn and then under one yarn
which consists of only two layers of bias yarns
of the opposing group, the pattern is desig-
interlaced with each other. In 3-D braided
nated as 1/1 braid, or diamond braid as
structures, at least three layers of bias yarns go
generally recognized. Other simple interlacing
through the thickness in a zig-zag manner
patterns in common use include 2/2,3/3,2/1
along the diagonal direction. Similar to the 2-D
and 3/1 braids. Figure 18.28 shows the pattern
structure, longitudinal yarns can be incorpo-
of 2/2 braid with axial insertion. Among all
rated in the 3-D braid for the enhancement of
these patterns, the 2/2 braid is the most popu-
stiffness and strength in the length direction.
lar and has been referred to as regular,
Regardless of the difference in the carrier pro-
standard, plain or flat braid. The path of axial
pelling mechanism, there are basically two
yarns is independent of braid interlacing pat-
types of 3-D braiding looms: rectangular and
terns, they are always over one group of bias
circular. The former is usually used to fabricate
yarns, but under the opposite group.
solid structures such as panel, I- and T-beam
The formation of shape and fiber architec-
etc. and the latter for making thick wall tubular
ture are illustrated in Fig. 18.29 which depicts
the process of braiding over an axisymmetric structures. Figure 18.30(a) shows a schematic
shape of revolution. Braiding angle can range of a 3-D braided slab.

Fig. 18.28 Yarn structure in 2-D braid: braiding

yarns at & to braid axis, optional axial yarns at 0"
to braid axis.

Fig. 18.30 3-D braided solid slab (and its cross-sec-

tion as seen on SEM).
Fig. 18.29 Braid formation over a shaped mandrel.
416 Textile preforming
18.5.3 DESIGN METHODOLOGY
The unit cell geometry of 2-step braids has
been reported by Du et al. (1991). Based on
experimental observations, diamond and rib-
bon shapes for the axial and braider yarns,
respectively, are assumed in their analysis. The
unit cell was defined; pitch length and per-
centage of braider yarns were identified as key
process parameters which control the braid
microstructure and the jamming criterion for
the 2-step braid was given.
The traditional approach used in modeling
3-D braided composites is to artificially define
a unit cell geometry for a 3-D braided struc-
ture without providing any relationship
between processing variables and geometric
parameters. All fibers in the unit cell are
assumed to incline in four different diagonal
directions, as well as along the longitudinal
direction, if any. Fiber volume fraction is
assumed to be either known or measured. The
approach used in geometric modeling of tex-
tile structures is to first determine the
dimension, shape and fiber architecture of the
unit cell based on process and structural
analysis; using the unit cell geometry identi-
fied, the relationship between processing
variables and key geometric parameters can
readily be established.
The key geometric parameters of 3-D braids
(which affect reinforcement capability and
composite processability) include braider ori-
entation, total fiber volume fraction, volume
fraction of inter-yarn void and axial fiber per-
centage of total fibers. Although there are only
two simple process parameters adjustable to
control the microstructure of 3-D braids (speed
ratio between braiding and take-up and linear
density ratio of braider and axial yarns), the
process-structure model of 3-D braid is com-
plicated.
Normally, yarn bundles consisting of
numerous continuous filaments are used for
fabric preforms, thus, the fabric microstructure
has three levels: geometry of interfiber pack-
ing in the yarn bundle (fiber level),
cross-section of yarn bundles in the fabric
(yam level) and orientation and distribution of
fibers in the 3-D network (fabric level). The
unit-cell technique is commonly used to estab-
lish the geometric relation. In most of 2-D
fabrics a unit cell geometry is readily identi-
fied, but in complex 3-D fabrics it can be very
difficult to define.
The fiber volume fraction of a 3-D fabric
depends on the level to which yarns pack
against each other in the structure and the
level to which fibers pack against each other in
a yarn, as illustrated in Fig. 18.7. In addition to
the level of packing fraction, the fibers also
establish the yarn cross-sectional shape, i.e.
yarn packing in fabrics. This shape plays a
very significant role in determining how many
fibers can be packed into a fabric. One good
example is the yarn packing in 2-step braided
preforms (Du et al., 1991). Due to the use of
untwisted fiber bundles and high braiding
tensions, cross-section of axial yarns in the 2-
step braid is deformed to prismatic shapes,
giving most the compact yarn packing within
the braided structure. For the track-and-col-
umn braids, the braiding tensions are lower
compared to the 2-step braids and the cross-
sections of yarns actually have a polygonal
shape.
The microgeometric model for the track-
and-column braid has been investigated by
many researchers since the early 1980s
(Pastore et al., 1990b; Li et al., 1990). The most
recent one was given by Du and KO (1993a),
which does not only relate geometric parame-
ters and processing variables but also provides
limiting braid geometry due to yarn jamming.
In their analysis, the yarns are assumed as
rigid circular rods. This assumption is valid
when braiding at high yarn tensions. When
low yarn tensions are used, yarn crimp will be
introduced during braiding or during post-
preforming processing due to distortion. This
yarn waviness (crimp) may increase the fiber
volume fraction of the braid with the sacrifice
of directional reinforcing efficiency.
 Braiding 417

Figure 18.31shows an idealized braid cross- where IC is the fiber packing fraction (fiber-to-
section cut longitudinally at a 45" angle to the yarn area ratio). Due to the bulky fiber and
braid surface. There are four groups of yarns nonlinear crimp nature, it is difficult to fabri-
inclined at angle 8 with the braid axis (z direc- cate the braid with tightest structure. In
tion) in different directions; the yarns in each practice, the yarn orientation angle (braid
group are parallel to each other within a spe- angle) is determined from the yarn diameter
cific plane. Two groups of yarns are parallel to (d) and braid pitch length (kZ).The fiber vol-
the XI-z plane; the other two are parallel to the ume fraction is controlled by the braiding
y'-z plane. The cutting plane is so selected that angle and the braid tightness factor. The gov-
it cuts through the diameter of a group of yarns. erning equations are given below:
8
e = sin-1 {((k,/d)2 + 4)
(kZ2 2d) (18.21)

where is the fabric tightness factor, which is

within the range of 0 to ~ / 4This
. tightness fac-
tor must be so selected that the required fiber
volume fraction is achieved and also that the
over-jamming condition is avoided.
A Figure 18.32 shows the V , 4 relationship
prior to and at the jamming condition, based
on the governing equations. The fiber packing
fraction, K, is assumed as 0.785. As can be seen,
there are three regions of fiber volume frac-
tion. The upper region cannot be achieved due
to the impossible fiber packing in a yarn bun-
dle. Jamming occurs when the highest
C
Fig. 18.31 Braid cross-section cut longitudinally at
a 45" angle to the braid surface by the Y-y plane
ABCD. z is the braid length direction.
1

The braid has the tightest structure when

each yarn is in contact with all its neighboring
0,51=
0.4
0.3
0.2
yarns, in other words, the yarns are jammed
0.1
against each other. At the jamming condition,
the fiber volume fraction V ,as a function of the 0.04 I . , . , Y
0 10 20 30 40 50 60 70 80 90
braid angle 8 was derived by Du and KO
0 (")
(1993a):
cos8 Fig. 18.32 Relationship of fiber volume fraction to
v,=-K2K 1 + cos%
(18.20) braiding angle for various tightness factors. Fiber
packing fraction K is assumed to be 0.785.
418 Textile preforming

braiding angle is reached for a given fabric

tightness factor q. The non-shaded region is
the working window for a variety of V f 4 com-
binations. Clearly, for a given fabric tightness,
the higher braiding angle gives higher fiber
volume fraction and for a fixed braiding angle,
the fiber volume fraction is greater at higher
tightness factors.
Theoretically, the 2-D braid can be consid-
ered as a single layer of 3-D braid. For prepreg
or tape braiding without much change in yarn
width and for the braiding of structures with
constant cross-sections, the V f 4 relation is sim-
ple. For braiding of dry tows and structures
with variable cross-sections wherein a dynamic
interaction of the braiding machine and tow
geometry takes place, there is a need for a more
general representation of the kinematics of the Fig. 18.33 Schematic of the Novoltexa process.
braiding processes which allows for the tow
width to vary over a limiting geometry. Two
mathematical models have been developed, the thickness fiber reinforcement. For illustration
first is the kinematics model (Du et al., 1990) purposes, our analysis of fiber volume fraction
which provides the relationship between the distribution will be focused on orthogonal
braiding angle and the braiding process para- nonwoven 3-D fabrics.
meters and the other is the unit cell model (Du While woven 3-D fabrics have a long his-
and KO, 199313)which relates braiding angle to tory of development and is clearly a product
yarn geometry to predict fiber volume fractions of the textile industry, the class of orthogonal
V, along both the braiding and axial directions.nonwoven 3-D fabrics is a product of the
twentieth century, developed in the aerospace
industry for specific composite applications.
18.6 NONWOVEN Pioneered by aerospace companies such as
General Electric and AVCO, the nonwoven 3-
18.6.1 PROCESSING TECHNOLOGY
D fabric technology was developed further by
Nonwoven structures are fiber to fabric assem- Fiber Materials Incorporated. Recent progress
blies produced by chemical, thermal or in the automation of the nonwoven 3-D fabric
mechanical bonding or a combination of the manufacturing process was made in France by
above. Starting with discrete fibers or continu- Aerospatiale (Pastenbaugh, 1988), in Japan by
ous filaments (mostly tows), the fibers are Fukuta of the Research Institute for Polymers
randomly distributed or preferentially ori- and Textiles (Fukuta et al., 1982 and 1984) and
ented by dynamic combing (carding) or more recently by Mohammed (1989).
hydrodynamic (waterjet) methods. Orthogonal nonwoven (ON) 3-D fabrics are
The Novoltex@structure developed by SEI' fabricated by maintaining one stationary axis
as shown in Fig. 18.33 (Geoghegan, 1988)is an either by yarn pre-deposition or a spacer rod
example of a mechanically bonded structure which is subsequently retracted and replaced
wherein multiple layers of oriented or random by an axial yam. The placement of the planar
fiber webs are needled together to create an yarn systems is carried out by inserting the
integrated structure which has through yarns orthogonal to the axial yarn system in an
 Nonwoven 419

Fig. 18.34 Orthogonal nonwoven by direct method.

alternating manner. In Fig. 18.34, the method. 18.6.2 STRUCTURAL GEOMETRY

of direct formation of ON 3-D fabric is shown Structural geomeh.ies resulting from the vari-
(Stover et al., 1971)* By proper Of
ous processing techniques are shown in Fig.
the yarns prior to planar yarn placement, 18.35: (a) and (b) show the single bundle xyz
3-D fabrics of various shapes and densities can fabrics in a rectangular and cylindrical shape;
be produced. (c) demonstrates the multiple yarn bundle
possibilities in the various directions.

Fig. 18.35 Orthogonal

nonwoven fabrics.
420 Textile preforming

18.6.3 DESIGN METHODOLOGY against d y / d x ratios, assuming a fiber packing

fraction of 0.8. For all three levels of dJdx
A unit cell geometry for the orthogonal non-
ratios, the fiber volume fraction first decreases
woven 3-D fabric is shown in Fig. 18.36,
with the increase in d y / d xratio, reaches a min-
assuming circular cross-section for yarns in all
imum and then increases. As can be seen in the
three directions. The fiber volume fraction for
figure, the maximum fiber volume fraction is
about 0.63 at either high or low d y / d x ratios,
whereas the minimum fiber volume fraction of
about 0.47 is achieved when both d y / d x and
d z / d xratios are equal to 1.

18.7 SUMMARY AND CONCLUSIONS

In this chapter, we have first discussed the role
and importance of textile preforms in compos-
ite design processing and design, followed by
classifying them into linear (1-D), planar (2-D)
Fig. 18.36 Unit cell for orthogonal nonwoven struc-
and three-dimensional (3-D) fibrous assem-
ture.
blies. The objective of this chapter is to
the 3-D ON structure can be shown to have the describe the design methodology of the fiber
following form: architecture for representative textile preform
structures currently used for composite rein-
n forcements. After a brief introduction to the
Vf = -ICx
2 formation technology of each preform, its fab-
ric structure is shown and the geometry of a
dx‘(dy+ dZ)+ d$dX + dZ)+ q d x + dy)
(18.23) unit cell is defined. The relationship between
(dx + dy)(dx+ dz)(dy+ dZ) the engineering parameters (V,,0) and the key
where dx, dy and dZ are diameters of the yarns processing variables (such as preform pattern,
in x, y and z directions, respectively and IC is tightness factor 9 and linear density ratio etc.)
the fiber packing fraction of the yarns. within the range of achievable geometry is
Figure 18.37 plots the fiber volume fraction established from the geometric model.
A summary of preform fabrication tech-
0.65 niques has been given in Table 18.2. Table 18.3
gives a summary of the engineering and pro-
0.60
cessing parameters. Ranges of fiber
orientation angle and fiber volume fraction for
5 each fabric preform commonly used for com-
0.55 posite reinforcements are also included in
Table 18.3. It should be noted that although the
0.50 achievable range of fiber volume fraction is
restricted by theoretical fabric geometric limits
0.45 1 . , ...I..
,
Minimum fiber volume fraction
._
, , ._I due to yarn jamming, it is possible that a
10.’ loo 10’ lo2 lo3 lo4 higher fiber volume fraction can be achieved
in reality because of the compressible nature of
the preforms. A composite having a higher
Fig. 18.37 Process window of fiber volume fraction fiber volume fraction can be made simply by
for orthogonal nonwoven fabrics. squeezing the preform to a smaller mold
 Summay and conclusions 421

Table 18.3 Engineering and processing parameters for textile preforms

Preform Fiber orientation, 0 (") Vf Processing parameter bundle

Linear assembly 0 - yarn surface helix angle Bundle tension, transverse
Roving 0=0 0.6 - 0.8 compression, fiber diameter,
Yam 0=5-10 0.7 - 0.9 number of fibers, twist level
Woven 0, - yarn orientation in fabric plane Fiber packing in yarn, fabric
Oc - yarn crimp angle tightness factor, yam linear
2-D Biaxial Of = 0/90, -
Oc = 30 60 - 0.5 density ratios, pitch count,
2-D Triaxial Of= 0/90/+30-60, Oc = 30 60 - - 0.5 weaving pattern
3-D Woven O6 = 0/90, -
0- = 30 60 - 0.6
Non-woven Ox - fiber/yam orientation along x axis (2-D non-woven) fiber
0, - fiber/yam orientation along y axis packing in fabric, fiber
O2- fiber/yarn orientation along z axis distribution (3-D orthogonal)
Oxy - fiber distribution on fabric plane fiber packing in yam, yam cross
section, yarn linear density
ratios
2-D Non-woven Oxy = uniform distribution, -
0.2 0.4
3-D Orthogonal Or,O,O, = 0 0.4 - 0.6
Knit Os - stitch yarn orientation Fiber packing in yarn, fabric
Oi - insertion yam orientation tightness factor, yam linear
density ratios, pitch count,
2-D Weft knit Os = 30 - 60 -
0.2 0.3 stitch pattern
3-D MWK Os = 30 - 60, Oi = 0/90/+30-60 -
0.3 0.6
Braid 0 -braiding angle Fiber packing in yam, fabric
tightness factor, braid diameter,
2-D Braid -
0 = 10 80 0.5 - 0.7 pitch length, braiding pattern,
3-D Braid -
0 = 10 45 0.4 - 0.6 carrier number

during the process of matrix addition; how- Assuming a tightness factor 7 of 0.573, possi-
ever, a composite with a fiber volume fraction ble braiding angles range from 0 to 40".
higher than theoretical maximum will have a Young's moduli and Poisson's ratios of fiber
certain degree of fiber crimp and its fiber ori- and matrix are given as E, = 33.5 Msi, Em =
entation will also be distorted. 1.3 Msi, 2rf = 0.3 and urn= 0.11. The elastic con-
The geometric models of textile preforms stants of the carbon-carbon composite was
presented in this chapter provide a quantitative obtained from the Fabric Geometric Model
communication link between the preform (FGM) (KO et al., 1987).Figure 18.38 shows the
manufacturer, composite processors and prod- composite stiffness in different directions
uct design engineers. By reducing fiber within the working window of fiber volume
architecture and textile preforming processes fraction and fiber orientation. As can be seen,
into engineering and processing parameters Young's modulus, Edav in the axial direction
Vf, 8 and 17, rational composite design proce- decreases and in-plane shear modulus, Gh- lane,
dures and process control guides can be increases with the increase in braiding angfe 8.
established. For example, the mechanistic Young's moduli in both hoop and radial direc-
design of a composite product can be demon- tions, Ehmpand Eradial,have the same value at
strated using a tubular 3-D braided zero braiding angle, but depart and both
carbon-carbon composite as an example. increase as the braiding angle become higher.
422 Textile preforming
Braid Axis
6- Limiting fiber
architecture
0, , , . , .~ , , , . , . .
0 5 10 15 20 25 30 35 40 45 50 55 60
Braid angle, 8 (")
Fig. 18.38 Stiffness properties of 3-D braided car-
bon-carbon composite. Fiber packing and tightness
factor are assumed as IC = 0.785,~= 0.573; Young's
moduli and Poisson's ratios of fiber and matrix are
given as E , = 33.5 Msi, Em = 1.3Msi, z),= 0.3, urn= 011.
The other example of the application of the
fiber architecture models to the composite pro-
cessing is to predict the permeability of fabric
preforms. As suggested by the well known
Kozeny-Carman equation, there are two
major geometric parameters which greatly
affect permeability of fibrous materials, i.e.
porosity of fabric preforms E and characteristic
dimension of fibers @D,where @ is the shape
factor and D is the fiber diameter. Other para-
meters which also affect the permeability are
flow properties, pressure drop and part thick-
ness. These parameters have been shown to be
independent of preform fiber architecture.
From geometric analysis, one can construct
the V f 4 relationship and determine their
dependence on the process parameters. The
fabric porosity can easily be calculated from V ,
( E = 1 - V,), whereas the shape factor of fibers
@ is related to the fiber orientation 8 and the
flow direction in composite processing. From
our experiments, we have observed that @ =
1.5 when most of the fibers are aligned paral-
lel to the flow direction and @ = 0.75 when the
fibers are perpendicular to the flow direction.
The effect of the fiber volume fraction and
fiber diameter on the permeability of air flow
0.006
Pressure drop: 60 psd
s2
-r?
e.-x 0.004-
c
-
._
L2
0.002-
2
0.000 _1
0 3 6 9 12 15
Fiber diameter (pm)
.
Fig. 18.39 Effect of fiber volume fraction and diam-
eter on preform permeability.
can be quantified using the Kozeny-Carman
equation, as shown in Fig. 18.39, noting that
the permeability is in the unit of mass flow
rate per length of preform. In this example, the
shape factor @ is assumed to be 0.75 at a pres-
sure drop across the preform of 60 psi with a
fabric thickness of 0.5 in.
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Du, G.W., Popper, P. and Chou, T.W. 1990. Process
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Reinforcement of Composites. 1. Mater. Sci. 26:
3438-3448.
Du, G.W. and KO, F.K. 1992. Analysis of Multiaxial
Warp Knitted Preforms for Composite
Reinforcement. Proc. Textile Composites in
Building Construction 2nd Inter. Symp., Lyon,
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3-D Braided Structures. J. Rein. Plus. Comp. 12
(2): pp. 752-765.
Du, G.W. and KO, EK. 1993b. Analysis And Design
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1982. Application of Latticed Structural
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Fabrics to Artificial Bones. Bull. Res. Inst. Polym.
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KO, F.K., Pastore, C.M., Yang, J.M. and Chou, T.W.
1986. Structure and Properties of
Multidirectional Warp Knit Fabric Reinforced
Composites. In Composites '86: Recent Advances
in Japan and the United States, eds. Kawata, K.,
Umekawa, S. and Kobayashi, A. Proceedings,
Japan-U.S. CCM-111, Tokyo, pp. 21-28.
KO, F.K., Pastore, C.M., Lei, Charles and Whyte,
D.W. 1987. A Fabric Geometry Model for 3-D
Braid Reinforced Composites. Intern. S A M P E
Metals Conference: Competitive Advancements in
Metals/ Metals Processing.
KO, F.K. 1988. Braiding, Engineering Materials
Handbook, Vol 1, Composites, ed. Reinhart, T.J.
Metal Park, OH: AMS International, pp.
519-528.
KO, F.K., Whyte, D.W. and Pastore, C.M. 1988a.
Control of Fiber Architecture for Tough Net-
Shaped Structural Composites. MiCon '86:
Optimization of Processing, Properties and Service
Performance Through Microstructural Control,
ASTM STP 979, eds. Bramfitt, B.L., Benn, R.C.,
Brinkman, C.R. and Vander Voort, G.F.
Philadelphia: ASTh4 pp. 290-298.
KO,F.K. and Kutz, J. 198813.Multiaxial Warp Knit for
Advanced Composites. Proc. 4th Ann. Con$ Adv.
Composites, ASM International, pp. 377-384.
KO, F.K. 1989. Preform Fiber Architecture for
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(2): 401414.
KO, F.K. and Du, G.W. 1992. Processing and
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McCarthy, S. and Kim, Y.R. 1991. Resin Flow
Through Fiber Reinforcement During
Composite Processing. Proc. 5th Textile
424 Texfilepreforming
Structural Composites Symp., Drexel University,
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Processing-Science Model for Three-
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Engineering, Summer, pp. 12-13.
TABLE ROLLING OF COMPOSITE TUBES
John T. K a m e and Jerome S. Berg
19.1 INTRODUCTION
In the field of composites fabrication table
rolling is a major technique for utilizing pre-
impregnated fibrous tapes in flag or pennant
form for tubular structures. The individual
flags become part of the total wall thickness by
rolling the flags around a mandrel. The hard
mandrel provides the support during cure and
defines the inside dimensions of the tube.
Table rolling is utilized to fabricate a variety
of products including straight tubes usually
under 7.62cm (3in) in diameter and up to
3.66 m (12 ft) long and small diameter tapered
tubes such as fishing rods, golf shafts and ski
poles. Flags may consist of a wide variety of
fibers oriented either longitudinally (along the
axis of the tube) or offset at a bias angle, hence
the terms ’longitudinal and bias flags’. The
resin content (RC) and the fiber areal weight
(FAW) of the prepreg define the ply thickness.
Since external molds are seldom used for table
rolled tubes, a variety of polymer compaction
tapes are used to apply an external pressure.
These tapes provide the external pressure nec-
essary to debulk and prevent flag unravelling
before cure and to provide some heat driven
compaction during cure.
19.1.1 FIBERS AND RESIN
Carbon fiber form 234 M P (34
~ msi) to 620 M P
(90 msi), glass ’E’ or 8s’ we,
aramids, polyeth-
ylene and boron are some of the common fibers
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
19
in table rolled tube manufacture.
The most common resin used to coat the
fibers is the epoxy blend family, which is for-
mulated for specific product purposes. The
resin and fiber are combined and advanced
slightly to a selected ’tack‘ (stickiness) level.
This fiber and resin combination is called
’prepreg’. Prepreg surface tack has an impor-
tant adhesive quality in table rolling which
permits composite flags to adhere to one
another or the mandrel without slipping dur-
ing the table rolling operation.
Prepreg is offered by specification of resin
type and roll width. FAW from 130-160 g/m2
and RC from 30-36% are common in table
rolling. Higher modulus fibers favor a lighter
FAW to ease rolling. The epoxy in prepreg is
catalyzed, so care must be exercised in follow-
ing the prepreg vendor’s storage and handling
recommendations. Freezer storage can extend
the shelf life; therefore, the material generally
arrives on a freezer truck. Because air and
moisture are detrimental to the surface tack, it
is important to cut and consume the flags as
soon as possible after opening and unrolling
the prepreg. Dry and low tack prepreg can
influence and aggravate flag wrinkles and ply
slippage, leading to voids and dimensional
problems.
Address tack with the prepreg supplier to
~ find a suitable resin formulation for the table
roller’s manufacturing environment.
A Partial list of equipment and
tooling suppliers commonly utilized in table
rolling is presented in Table 19.1 at the end of
this chapter.
426 Table rolling of composite tubes

19.1.2 DESIGN
Figure 19.1 illustrates the relationship of the
mandrel, prepreg flags and diameters in table
rolling.

19.2 EQUIPMENT
19.2.1 SHEAR/SHEETER
A number of commercially available power
shears have hardened steel blades and
include automatic feed mechanisms for the
material rolls. Safety guards with interlocks
Fig. 19.2 Photograph of prepreg sheeter. (Courtesy
are needed to prevent finger and hand injury of Century Design Incorporated.)
(Fig. 19.2).
The tooling used in this machine is the 'Steel
Rule Die'.
19.2.2 ROLLER PRESS
The steel rule die, the prepreg and an impact
The roller press is a machine used to press sev- sheet (usually a soft plastic like polyethylene)
eral stacked layers of prepreg tape into are passed through the rotating pressure
individual patterns such as tapered pennants. wheels of the roller press. After compaction,

' -p Of longIt@Ml ma,

Fig. 19.1 Diagram of tapered mandrel, bias flags and longitudinal flags.
 Equipment 427

the impact sheet is removed to expose a stack ---'-.-' ---

,.-.. ._." -. .-
I

of ready-to-assemble flags which are now

nested between the blades of the die. The roller
press and dies act similarly to a kitchen cookie
cutter (Fig. 19.3). A sharp knife and straight
edge can act as a prototype or for small scale
production.

Fig. 19.4 Photograph of table rolling press.

(Courtesy of Century Design Incorporated.)

like fingers for achieving uniform pressure on

tapered parts. Both flat bed and segmented
bed versions are covered with canvas. This
pad provides sufficient resiliency and friction
Fig. 19.3 Photograph of a roller press including to permit flags to roll without slipping, yet
loading and unloading racks. (Courtesy of Century conform to the mandrel surfaces. A slight
Design Incorporated.) dusting of talcum powder can be used to pre-
vent prepreg from sticking.
Table rolling provides tighter and a more
19.2.3 ROLLING TABLE
uniform compaction of plies than hand rolling.
Originally, in the 1940s, prepreg flags were
hand cut and hand rolled like cigars to pro-
19.2.4 VERTICAL TAPE WRAPPER
duce the tubular structure. The fishing rod
industry was probably first to commonly use A variety of plastic and/or cellophane tapes,
rolled tubular structures. 1.27-2.54 cm (051.0 in) in width are used to
In the 1960s several devices with a mobile compact the table rolled plies of prepreg.
lower platen were developed. After activating Machines used to apply these tapes must per-
the machine, a pivoted upper platen is low- mit tape tensioning to debulk the product as
ered down upon the mandrel and a linear the tape is applied. Some applications call for
motion activator in the lower platen rolls the multiple passes through the tape wrapper to
mandrel into the prepreg flag. These machines increase the tape pressure for better com-
permit pressure ranges to be established, gain- paction. Additional wraps of tape are needed
ing maximum compaction and increasing the for thicker wall structures. Frequently, two
speed of rolling. The pivoted upper platen types of tape may be used: a release tape and a
permits the combinations of parallel tube or secondary compaction tape. Some tapes have
tapered (cone-like)tube rolling. If the mandrel a release backing which can allow a single
is parallel, then the pivot function of the upper pass of tape. However, these tapes are gener-
platen will be unnecessary. Figure 19.4 illus- ally more expensive. Apply the tape as soon as
trates a commercially available rolling table. possible after table rolling to prevent the flags
Current rolling tables include temperature from loosening. Figure 19.5 illustrates a verti-
controlled platens and platens with piano key- cal tape wrapping machine.
428 Table rolling of composite tubes
Fig. 19.5 Photograph of vertical tape wrapping
machine. (Courtesy of Century Design
Incorporated.)
19.2.5 HORIZONTAL TAPE WRAPPER
This machine represents an alternate to the
vertical tape wrapper. It is used frequently for
longer, heavier parts and also for very flexible
mandrels such as fishing rods. The mandrel is
affixed to a chuck or mechanical coupling
which rotates the parts while tape is applied.
The rollers provide support for the part while
motion is in place. The single or even dual tape
feed spools move with the tape carriage and
return to restart position (Fig. 19.6).
After cure, the wrapping tapes are removed
by slitting the tape longitudinally and peeling
the tape away from the cured part. Wrapping
tapes are then discarded.
Fig. 19.6 Photograph of horizontal tape wrapping
machine. (Courtesy of Century Design
Incorporated.)
19.2.6 MANDRELPULLER
Tubular parts which have been cured over a
hard mandrel are all subject to mandrel extrac-
tion. The mandrel puller generally connects to
a bolt on the larger shank end of the mandrel.
The end of the composite tube rests against a
stationary block shaped to permit passage of
the mandrel but blocking the tubular part.
Mandrel pullers are generally hydraulic or
pneumatic. Hydraulic pullers offer a con-
trolled extraction speed, while pneumatic
pullers are faster and useful in high volume
environments. Mandrel withdrawal is gener-
ally done prior to tape removal. Figure 19.7
shows a pneumatic mandrel puller.
The type of mold release used, correct size
of the stationary block and the mass plus
integrity of the cured part must be carefully
evaluated or end crushing of the part will
occur. Also, thin walled tubes or tubes with a
high degree of longitudinal plies can crack
during mandrel extraction.
19.2.7 CURING OVENS
Ovens used for curing the composite tubes can
be either electrically or gas heated and of batch
or conveyorized design. Temperatures rang-
ing from 121-191°C (250-375°F) are most
common for roll forming prepregs. Consult

Fig. 19.7 Photograph of pneumatic mandrel puller.
(Courtesy of Century Design Incorporated.)
the prepreg supplier for recommendations on
appropriate cure profiles. Fine tuning of the
cure profile is often needed to optimize partic-
ular roll forming operations and specific
products. Ovens with thermocouples are use-
ful in determining hot and cold spots, which
may indicate oven regulation for uniform tem-
perature control. This ensures a uniform gel
within the part.
19.2.8 CENTERLESS SANDER OR GRINDER
The wrapping tapes can leave a series of spiral
indentations approximately 0.5 mm (0.002 in)
deep in the composite tube surface. If a
smooth surface is desired for cosmetic reasons
or for geometry requirements the part can be
surface sanded or ground. A centerless sander
basically removes a user defined controlled
amount of surface material. A centerless
grinder provides a more accurate finish
dimension. Centerless grinders are common
for the high precision required for the tip ends
of golf shafts in which a tolerance of f 0.5 mm
(a.002 in) is not uncommon. In carbon fiber
golf shaft manufacture, these surface finishing
techniques are also used to tailor the product
stiffness by incrementally removing material
along the shaft length. This changes the shaft
stiffness characteristics.
Materials 429
19.3 TOOLING
19.3.1 MANDRELS
The mandrels used for table rolling are usually
hardened steel, sometimes aluminum or even
composite. The mandrels are designed to sup-
port the prepreg during rolling and curing and
provide the inside dimensions for the part.
Recalling that mandrels must be extracted in
'mandrel pulling', some negative taper is ben-
eficial.
Mandrel makers are skilled in the art of
metallurgy. They can select the materials and
heat treatments necessary to create a mandrel
resistent to permanent bending. However, in
many instances the mandrels can be
restraightened if damaged. Hard plated man-
drels generally provide a longer life since
scratched or dented surfaces will hamper
mandrel removal.
19.3.2 STEEL RULE DIES
These dies incorporate multiple blades
embedded in a rigid backing (usually marine
grade plywood) which cut the material in the
roller press. The prepreg tape (up to 20 layers)
is cut between the cutting die blades and a
polyethylene sheet sandwiched between the
rotating press wheels. Dies with one piece
blades provide the best and most continuous
cuts (Fig. 19.8(a)). Dies which include weld-
ments (as in a triangular shape flag) generally
dull faster since the weldments soften the cut-
ting edges (Fig. 19.8(b)) Ramps can be used
between the cutting blades in die designs to
keep the roller pressure off the blade ends. The
die builder can recommend blade height and
cutting edge type best suited for the task.
19.4 MATERIALS
19.4.1 MOLD RELEASES
Generally, mold releases for table rolling man-
drels consist of two components: a primary
mold release which provides a polymer bond
430 Table rolling of composite tubes

19.4.2 FIBERS
a L\ Rubber Dads
(Stacking The prepreg tapes can be made from longitu-
dinal tows or woven tows of the following
A reference)
fibers: aramid, glass, carbon and boron. All
these fibrous composite tapes can be cut into
flags and pennants needed for the table rolling
process. However, because of the brittle nature
blades
C utting\- of boron prepreg, boron is most often cut for
longitudinal flags. Refer to the appropriate
chapter for specific properties of these fibers.
U A

19.5 TYPICAL PROBLEMS

19.5.1 VOIDS
Voids are caused by entrapped air which is not
evacuated before resin gelation. The presence
of voids reduces the strength bearing capabili-
Cutting ties of the part, creates stress risers and can
blades contribute to surface finishing and cosmetic
problems.
Ramps Voids are first minimized by working with
the prepreg supplier to assure a high quality
material with uniform resin content and good
'wet-out' of the fibers. Also, the material sup-
Fig. 19.8 (a) Diagram of steel rule die for rectangu-
pliers (prepreg and wrapping tapes) must play
lar shaped flags. Ramps prevent blade damage.
@) Diagram of steel rule die for a triangular shaped a key role in developing a cure profile for the
flags. Ramps prevent blade damage. Weldments specific process and products.
can cause blade dulling. Voids are increased by flag wrinkles which
are indicative of rolling problems. The capabil-
ity to perform void content checks (ASTM
D3171) and photomicrographs of the laminate
to the mandrel surface to prevent adhesion; can be extremely useful to develop and
and a secondary mold release which acts as a improve tube processing. Laminate photos are
slip agent. also very useful in operator training. Few lam-
The secondary mold release is most benefi- inates are completely void free but void
cial in straight or slightly tapered mandrels contents lower than 1%are possible with table
and is reapplied between subsequent mandrel rolling and tape wrap compaction.
turns. A primary release can lose its effective-
ness after several hundred turns and must be 19.5.2 DRY AND DIFFICULT TO ROLL
stripped off and recoated. A variety of quality MATERIAL
mold releases are on the market. The fabricator
should work with the release supplier to Prepreg dryness (lack of tack) can be due to low
develop a coating program for the specific resin content, resin formulation, ambient condi-
application. Silicone based releases should be tions of the manufacturing environment, the
avoided if the tube is subjected to subsequent age or out time of the material. Insufficient tack
bonding and painting. can cause flag movement during assembly,
 Typical problems 431

wrinkles, voids and parts with a poor surface
finish. Resin content and formulation can be
adjusted to suit the manufacturing environ-
ment. Temperature and humidity control are
very helpful in maintaining consistent material
tack in the manufacturing shop. Avoid leaving
cut patterns exposed since moisture in the air
greatly affects the material surface tack and
sometimes renders it useless. Consuming the
material within two days is a good rule to
follow.
Warm lay-up and rolling tables can help
increase material rolling ability and are gener-
ally adjusted for slight material and
environmental changes. Off angle plies are dif-
ficult to roll adjacent to the mandrel and the
difficulty is magnified by the higher modulus
fibers. Tack tape is a narrow strip of reinforced
adhesive designed to aid the adhesion of bias
plies to the mandrel. Also, solvent based 'tack
resins' can be applied to the mandrel to ease
application of the first ply. Once the first ply is
tightly rolled, however, the material tack is
sufficient for subsequent flags.

Table 19.1 Table rolling equipment, material and tooling suppliers in USA

Equipment Tooling
Century Design Incorporated. Mandrels
3635 Afton Road Lynco Grinding Corporation
San Diego, CA 92123 5950 Clara Street
(619)-292-1212 Bell Gardens, CA 90201
(213)-773-2858

Materials Toray
5729 Lakeview Drive, NE
Prepreg Kirkland, WA 98083-2548
Newport Adhesives and Composites (206)427-9029
1822 Reynolds Avenue
Irvine, CA 92714 Cytec Engineered Materials, Inc.
(714)-253-5680 1440 North Kraemer Boulevard
Anaheim, CA 92806
Fiberite (714)-666-4349
4300 Jackson Street
Greenville,TX 75403 Chemlease
(903)-457-8554 P.O. Box 540083
Orlando, FL 32854-0083
Mold release (407)-425-2066
Frekote Products Dunstone Company, Inc.
Dexter Adhesives and 2104 Crown View Drive
Structure Division Charlotte,NC 28227
One Dexter Drive (704)-841-1380
Seabrook, NH 03874
(603)-474-5541 Steel rule dies
Ontario Die Company of America
Wrapping tapes 2735 20th Street
Flexicon Pacific, Inc. Box 610397
856 North Elm Port Huron, MI 48061-0397
Suite J (810)-987-5060
Orange, CA 92667
(714)-%33-9820
432 Table rolling of composite tubes
19.5.3 PART SLIPPAGE DURING CURE
The viscosity of the resin drops as the heat of
cure begins. Occasionally, tapered mandrels
and the constriction of the wrapping tape dur-
ing the cure can force a part to slip down the
mandrel. Golf shaft design is highly depen-
dent on mandrel reference position for proper
stiffness and geometry requirements. Slippage
can first be minimized by designing a short
semi-parallel section in the mandrel (as in the
butt section of the golf shaft). Slippage is also
reduced by overwrapping the tapes onto the
mandrel at both ends to secure the part. In
addition, the cure profile or the mold release
can be adjusted to limit slippage.
19.5.4 EXPOSED SURFACE VOIDS
Exposed surface voids after sanding or grind-
ing are indicative of poor rolling practices,
insufficient lamination pressure and question-
able material.
Exposed surface voids are sometimes
referred to as 'fiber pulls', which have a wood
grain appearance on parts with longitudinal
surface plies.
19.5.6 LONGITUDINAL PLY WAVINESS
Tapered parts with longitudinally oriented
fibers are prone to zones with a wavy or 'fiber
wash' appearance. The problem is amplified
with multiple taper mandrels and very low
viscosity prepregs. Cure profile modifications
or alternate resins can reduce the tendency of
'fiber wash'.
RESIN TRANSFER MOLDING 20
Lihwa Fong and S.G. Advani

20.1 INTRODUCTION ready for its removal from the mold when suf-
Resin Transfer Molding (RTM) is a closed ficient green strength is attained. Processes
mold process in which matched male and that are based on similar principles include
female molds, preplaced with fiber preform, Structural Reaction Injection Molding (SRIM)
are clamped to form composite components. and different versions of vacuum assisted
Resin mix is transferred into the cavity RTM (Figs. 20.1 and 20.2).
through injection ports at a relatively low pres- RTM offers the promise of producing low
sure. Injection pressure is normally less than cost composite parts with complex structures
690 kPa (or 1OOpsi). The displaced air is and large near net shapes. Relatively fast cycle
allowed to escape through vents to avoid dry times with good surface definition and
spots. Cure cycle is dependent on part thick- appearance are easily achievable. The ability
ness, type of resin system and the temperature to consolidate parts allows the saving of con-
of the mold and resin system. The part cures in siderable amount of time over conventional
the mold, normally heated by controller, and is lay-up processes. Since RTM is not limited by
the size of the autoclave or by pressure, new

Mixing Head

r -------1 Vent Port

I
1
I
I
I
I
-
I I
I I
I I
I I
Pumpunit
---------

Fig. 20.1 Schematic of the RTM process.

Handbook of Composites. Edited by S.T. Peters. Published

in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
434 Resin transfer molding

ISOCYANATE POLYOL

HYDRAULICS
MACHME MODE

HEAD

Fig. 20.2 Basic construction of a SRIM machine.

tooling approaches can be utilized to fabricate Advantages are:

large, complicated structures. However, the 0 Class A surface: Surface definition is supe-
development of the RTM process has not ful-
rior to lay-up. In addition, using matched
filled its full potential. For example, the RTM
tools for the mold, one can improve the fin-
process is yet to be automated in operations
ish of all the surfaces.
such as preforming, reinforcement loading, 0 Close tolerance: Parts can be made with bet-
demolding, and trimming. Therefore, RTM
ter reproducibility than with layup.
can be considered an intermediate volume
0 Design tailorability: Reinforcement and
molding process (Krolewski, 1990).
combination of reinforcements can be used
Several unresolved issues in RTM encoun-
to meet specific properties.
tered by composite engineers are in the areas
0 Fast cycles: Production cycles are much
of process automation, preforming, tooling,
faster than with layup.
mold flow analysis and resin chemistry.
0 Filler: Filler systems can be used to reduce
During the last decade, rapid advances in cost, improve fire/smoke performance, sur-
RTM technology development have demon-
face appearance, and crack resistance.
strated the potential of the RTM process for
0 Gel coat: One or both mold surfaces can be
producing advanced composite parts. The
gel-coated to improve surface performance.
advantages and associated disadvantages of
0 Good mechanical properties: Mechanical
the RTM process are summarized. As the
properties of molded parts are comparable
development of this process is rapid, some of
to other composite fabrication processes.
the disadvantages may be overcome by the
0 Good moldability: Large and complex
advances made in this technology.
shapes can be made efficiently and inexpen-

sively. In addition, many mold materials can
be used.
0 Inserts: Ribs, bosses, cores, inserts and spe-
cial reinforcement can be added easily.
0 Labor saving: The skill level of operator is
less critical.
0 Low tooling cost: Clamping pressure is low
compared to other closed mold operations.
Low volatile emission: Volatile emissions
are low because RTM is a closed mold
process. The worker is not exposed to
chemical vapors as with the lay-up process.
Disadvantages are:
Mold design: The mold design is critical
and requires good tools or great skill.
Improper gating or venting may result in
defects.
Mold filling: Control of flow pattern or
resin uniformity is difficult. Radii and
edges tend to be resin-rich.
Properties are equivalent to those with
matched-die molding (assuming proper
fiber wetout, etc.), but are not generally as
good as with vacuum bagging, filament
winding or pultrusion.
Reinforcement movement during resin
injection is sometimes a problem.
In the following sections, the resin transfer
molding process is discussed in terms of the
unit operations involved, to familiarize read-
ers with the basic steps of the RTM process.
The discussion covers details such as materials
of construction, mold design, preforming, cur-
ing, and demolding. Processing issues are
mentioned in each individual unit operation.
Relevant variations of RTM such as vacuum
assisted resin transfer molding and flexible
molding tools are summarized.
Process physics is described with emphasis
placed on the principles that govern the RTM
process; these are applied in the use of com-
puter simulations. Through the design tools
such as simulation codes for mold filling
analysis, engineers are able to predict or diag-
nose the problems in gating and venting in the
RTM process 435
design stage. The usefulness of such design
tools is discussed in detail, giving the relevant
advantages and disadvantages.
20.2 RTM PROCESS
The RTM process can be viewed as seven unit
operations. The general practice and process-
ing issues are described for each unit
operation.
20.2.1 FIBER REINFORCEMENT
Selection of the proper reinforcement type
should take into consideration loading condi-
tion, part geometry (size, thickness),
mechanical properties and surface finish. The
quantity of parts demanded also determines
the selection. The reinforcement normally car-
ries 90% of the load in a composite and
provides over 90% of the stiffness. The rein-
forcement in a composite can be designed to
match the strength requirements of the part.
The following characteristics should be con-
sidered when selecting fiber reinforcements:
Volume fraction: ratio of the volume of a
given mass of reinforcement to the volume of
the same component after molding;
Wash resistance: ability of a reinforcement to
withstand movement due to fluid motion or
solvation of the reinforcement binder by the
resin;
Wettability: ability of a reinforcement to reach
a condition wherein all voids in the reinforce-
ment are filled with resin;
Sizing: most fibers are coated with size for
better wettability and bonding but the size
may influence the cure kinetics during the
manufacturing.
Most standard reinforcement materials for
composites can be used, but fiberglass, carbon
and aramid are the most common in RTM.
One requirement is that the reinforcement
should hold its shape during the injection
436 Resin transfer molding
phase. Therefore, the reinforcements are gen-
erally stitched, woven or bonded together.
Reinforcement build-ups in certain areas can
easily be included. For example, woven roving
and fabric can be combined with continuous
strand mat and chopped strand mat in appli-
cations where higher strengths are required.
Hybrid systems composed of high perfor-
mance reinforcements such as carbon fiber and
aramid fiber can also be incorporated in RTM
laminates. Surfacing materials called veils can
be used in the preforms to hide the imprint of
fibers, for improved surface finish. Another
application of surfacing veil is to achieve a
resin-rich skin to improve corrosion resistance.
Stitched fabrics (Fig. 20.3(a))reduce stresses
inherent in the woven roving design and lead
to higher compressive strengths in the com-
posite. However, other constructions such as
8-HS style of weave (eight-harness satin
weave) in Fig. 20.3(b)have been used because
of improved wetting characteristics and com-
pressive strength compared to bidirectional
woven fabrics.
Continuous strand mat is multi-stranded,
laid in swirled configuration. The mats nor-
Fig. 20.3 (a) Stitched fabric; (b) eight-hamess satin weave.
mally have 4-6 wt.% of thermoplastic binder
added. They are thermoformable and can
therefore be used for highly complex shapes or
when the anticipated volume of production
makes them economical.
Different sizings can be obtained on many
reinforcements. Sizings can be tailored to the
type of resin system. Sizings are available that
are compatible with epoxy, vinyl esters or poly-
esters. The strength variation with type of
sizing can be as much as 20%, so this factor
needs to be considered in the choice of rein-
forcement.
20.2.2 PREFORM
For a flat part, the preform can be as simple as
a stack of reinforcements that fit in the mold
cavity. As preforms become more versatile,
various means of producing preforms are
available. Currently cut-and-sew is commonly
used to assemble preforms of various shapes
for aerospace applications. Other near net
shape techniques include braiding, spray-up
and thermoforming (Fig. 20.4).
I I t I
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
I
 RTM process 437

blank preparation heating zone stamping zone unloadinghrimming

zone zone

heatingcuring
resinbinder
1

1 cooling

A
t+ Vayum source

I N M '

demolding 1 forming
screen

directed fiber preform

Fig. 20.4 (a) Four station thermoforming preformer; @) spray-up process.

438 Resin transfer molding

If prefabricated preforms are not used, then Edge definition: The edges of the composite
some means must be found to hold the layers will be resin rich if the preform is not cut to fit
of reinforcement together as they are built up closely to the edge of the cavity or inserts;
on the tool surface. For example, unidirec-
tional reinforcement is subjected to washing Fiber distribution:Uniformity of fiber content
(washing is unplanned reinforcement move- in preforms, without excessive thinning, wrin-
ment due to resin movement) if proper kles or folds, is important;
precautions are not taken to prevent it. To Permeability:A measure of resin distribution
improve conformance of fibers, a tacky resin into the cavity. This quantity is also affected by
(e.g. epoxy), dissolved in suitable solvent (e.g. fiber volume fraction.
acetone), can be used as a spot glue to hold the
reinforcement layers together. The tacky resin Prefabricated preforms can be further bonded
will be washed out during the resin injection together, with or without a core, to achieve
cycle and will not interfere with the cure of the
part consolidation. For structural composites,
part. Sometimes veil can be used to hold the this eliminates the need for fasteners and
layers and prevent washing. adhesives to assemble discrete parts. New
Advantages are: thermoformable reinforcement mats can be
0 Fast loading: Preforms allow fast loading of
used for highly complex shapes or when the
the mold. anticipated volume of production makes them
0 Precise fiber placement: Preform placement
economical (Carvalho, 1991).
can be made precisely without misalign- Design of preforms should go hand in hand
ment. This allows high quality, close with part design. For example, preform corners
tolerance composites for advanced applica- are sensitive to radii of the shape. Figure 20.5
tions molded by the RTM process. shows the thickness reduction of preform over
0 Net shape preforms: If thermoformable
different radii. The preform thickness does not
reinforcements are used, the stamped pre- change appreciably compared to those around
forms have excellent dimensional stability. the corner when the radius is made larger than
0 No additional tool: For low production vol-
a critical value. However, if the radius is less
ume of the composite, the tool for
preforming can be the same as the tool for
molding.
The only disadvantage with use of preforms is
that there is an additional unit operation.
With the obvious advantages, use of pre-
forms is advisable when volume of production
allows their economical use. When designing
fiber preforms, following issues should be
considered:
Corners: The fiber in the bent corner of a pre-
form tends to move to the inside of a radius.
This can cause channeling of flow that leads to
poor mold filling patterns; 1 .o

Drapability:This characterizes the ability of a WRm

fabric or reinforcement mat to conform to con- Fig. 20.5 Effect of comer radii on preform thickness
tours of the tool; (Rmis the recommended radius).

than this critical value, dramatic movement of
the fibers to the inside of the radius occurs. As
a result, channeling becomes dominant in the
mold filling stage and induces irregular flow
patterns.
The edge of a preform is another source of
the race tracking of resin. In order to avoid
the channeling effect, the preform edge
should be cut to fit the edge of the mold cav-
ity. The task of obtaining a good edge
definition is normally difficult because of the
bulkiness of the layers and inter-layer move-
ment (sliding, rotating) during the mold
closing when prefabricated preforms are not
used.
Preforming of fabrics over tool geometry
other than simple flat type will induce shear
deformation in the fiber reinforcements. For a
biaxial reinforcement, shearing of the weave
Fig. 20.6 Draping fabric on a mold causes shearing of the weave.
XTM process 439
(Fig. 20.6) is necessary to conform to the con-
tours of the tool. This drapability problem,
therefore, has a two-fold significance in RTM.
Because of the fiber rearrangement, the
nonuniformity of fiber distribution should be
accounted for in the design of the composite.
Fiber volume fraction and orientation are no
longer that of the unreformed reinforcement.
Further, such preforms exhibit different char-
acteristics to resin flow. Designers should
account for this change in determining the
location of vent ports relative to an injection
port.
In practice, to modify the permeability of
preforms, various flow inducing media or
mechanisms have been suggested. Application
of such high porosity to the preform or inclu-
sion of a runner system in mold design can
alter the mold filling pattern.
440 Resin transfer molding

20.2.3 RESIN SYSTEM AND INJECTION Low viscosity: High viscosities can cause
mold pressures that are too high in both the
The resin used in the RTM process forms the
mold and the injection unit. Raising the tem-
matrix in the composite after solidification.
perature of the resin system is effective to
The solid structure is a result from polymer-
lower its viscosity, but pot life may be
ization. To select the resin system, one must
adversely affected.
take into account of the rheological change
and resin cure kinetics. Sufficient pot life: This is the time it takes
The formulation of the resin system the resin system's viscosity to reach a level
depends on many factors. For example, the that no longer be comfortably handled by the
resin system can be combined with promoters, equipment.
fillers, internal mold releases, pigments, etc.
Tg point: The glass transition temperature
Typical fillers, such as clay or calcium carbon-
should be as high as possible. As a rule of
ate, may reduce cost. The optimum viscosity
thumb, the glass transition temperature should
for RTM should be less than 500 cP s. Mixing is
be at least 30°C (50"F), and preferably 55°C
normally required to form a suspension.
(100"F),higher than the service temperature
Properties requirements (mechanical,
chemical, fire retardancy, etc.) can also affect Toughness: Toughness in a resin system is
resin selection; the resin mix can be formu- exhibited by its tensile elongation. If sufficient
lated to meet specific needs. Attributes to look damage tolerance is required, the elongation
for in resin systems are: should be at least 3%.
e consistent reactivity; Young's modulus: This modulus must be over
0 ability to wet out the reinforcement; some threshold value or the composite com-
e rapid cure after gel. pression strength will be less than the
optimum value. A high tensile modulus is
The ester-type resin mix is combined with an
required to adequately support the fiber rein-
appropriate catalyst, such as emulsified BPO,
forcement and prevent premature buckling.
MEKP, cumene hydroperoxide, at the mixing
head and transferred into the RTM mold. Low The effect of the resin system on hot-humid
profile additives have been developed espe- performance is important in the composite
cially for polyester resins to improve surface part. The modulus of a typical resin remains
appearance. In addition, epoxies, urethanes, essentially constant until the temperature is
vinyl esters, nylon and other hybrid resins are close to the ultimate T , when it falls off to
available for RTM. The newer resins may zero.
require modifications to the pumping/injec- Under wet conditions, the strength of the
tion unit to meter and condition the resin mix resin usually falls off at the same rate as the
prior to injection. These new systems offer a modulus because of the effect of absorbed
range of cost and performance options for the moisture. Absorbed moisture plasticizes the
RTM process. resin matrix and lowers the strength of the
Influencing parameters are viscosity, pot composite in non-fiber dominated directions.
life, tensile modulus, glass transition tempera- The amount of moisture absorbed by the resin
ture, tensile elongation and moisture matrix should be small, normally less than
absorbance. In considering a new resin system, 2%. This limits the amount of mechanical per-
the choice of the proper resin system for RTM formance degradation at elevated
must satisfy the following system criteria. temperatures.
Failure to meet these criteria usually means One final topic to consider is the injection of
that the resin system is impractical for RTM. the resin system (schematics shown in Figs.
 Mold materials 441

20.1 and 20.2). Items to control in the resin mix

to assure a consistent, smooth running process
include:
0 resin mix temperature;
0 ratio of catalyst or curatiire to resin;
0 resin mix viscosity;
0 amount of air entrained in the resin mix.
Presence of air in the mix can lengthen the
gel time/induce porosity in the composite (a)
and/or affect the mix viscosity.
Most successful production resin transfer
molding operations are now based on the use
of resin/catalyst mixing machinery using pos-
itive displacement piston-type pumping
equipment for accurate control of the resin to
catalyst ratio. Back pressure at the mix head
may change when a mixed resin is injected
into a cavity filled with the fiber reinforce-
ment. Static mixers greatly simplify the
process and are easily cleaned at the end of the
injection cycle. A static mixer sends the pro-
portioned resin and catalyst through flexible
Fig. 20.7 (a) Matched mold with rigid halves;
hoses to an injection head employing a (b) matched mold with a flexible mold half.
motionless mixer to thoroughly blend the
materials together immediately prior to injec-
tion step. Gate and vent: This critical part of the mold
design should allow complete wetout with
minimal resin wastage.
20.2.4 MOLD
Mold sealing: A perimeter gasket is necessary
RTM mold design and construction is the most to keep void content low. Tight sealing is
critical factor in successful resin transfer mold- important when vacuum is used.
ing. The mold must be constructed so that
resin reaches all areas. RTM molds require spe- Heatingkooling: A typical RTM cycle consists
cial considerations compared to other of a wide range of temperature for initiating
composite tooling. Figure 20.7 shows two pos- the chemical reaction, curing and final
sible configurations in RTM processing. The demolding. Hence, proper heating/cooling
mold must be designed to account for the fol- channels need to be designed.
lowing factors:
Mold materials: The material of construction 20.3 MOLD MATERIALS
dictates life cycle of mold, temperature control The low pressure requirements of RTM allow
and press requirement. the use of more types of mold materials than
can be used in other composites manufactur-
Cavity design: The RTh4 mold should consoli-
ing. The choice between metal molds and
date as many assembly steps as possible. A good
polymeric composite molds is chiefly one of
design should take advantage of this ability.
volume and processing temperatures. High
442 Resin transfer molding
volume and high temperatures dictate metal
molds.
Steel, the most suitable mold material, pro-
vides superior face life. Aluminum is good for
construction of prototype molds since the
metal is easy to machine, is lightweight and
has a reasonably high heat transfer rate, but
also galls easily. Cast aluminum and spray-
metal tooling are currently available and can
be used for higher volume applications. Cast
copper alloys are being considered for use in
RTM molds due to the potential for increased
throughput via heat management and better
durability.
Composites, for example reinforced poly-
ester and epoxies, are most frequently used for
making RTM molds. They can be expected to
last for approximately 2000 parts (Isorca,
1992).Higher production volumes may justify
the use of higher cost spray-metal or metal
tools.
In some cases, the mold must be backed up
in order to maintain its shape. Conventionally
the backup can be done cost-effectively with
core material or steel frames to add rigidity to
the cross section and to support composite
mold faces. The closure of the mold is
achieved by mating of the mold surfaces
against a perimeter gasket. Therefore, guide
pins are usually employed to align the mold
halves both laterally and vertically to keep
resin from leaking.
Advancement in adapting composite tool-
ing to the needs of RTM is underway. For
example, lengthening the life of the composite
tool face is desirable and effective to maintain
quality while keeping costs low. The factors
that cause deterioration of the mold face are
temperature fatigue and attack by solvents or
mold release agents. An electrolytically or
vapor deposited nickel shell is a new tech-
nique that will extend face life.
20.4 MOLD CAVITY DESIGN
One of the most important design rules for
RTM parts is to reduce the number of assembly
steps. Therefore, the mold designer should
incorporate this rule in the design of the mold
cavity. Instead of joining several substructures
or onto a major structure after molding, it is
structurally more effective and efficient to
incorporate them into the part before fabrica-
tion. This can be easily achieved by joining
substructure preforms when practical.
In production the number of molds or cavi-
ties required is determined by needed
throughput. This should take into account the
cycle time. For small parts, the designer can
incorporate several cavities in a mold.
High surface quality with excellent dimen-
sional control can be achieved by
electroplating the mold face with nickel. The
appearance surface of a part is usually placed
on the bottom of the mold. Pinholes are more
likely to collect on the top surface. Mold
preparation is similar to that used for hand
lay-up. Anew tool must to be treated with sev-
eral coats of release agent.
New mold materials provide flexibility in
mold design for RTM. For example, to demold
a part with vertical sides, it is common to
allow several percent draft in the vertical
dimension. Flexible silicone rubber has been
used for RTM molds in the form of a bladder
mold half which is capable of being inflated or
deflated depending on the process require-
ment. During mold filling, the flexible mold
wall is pressed against the rigid wall by inflat-
ing the bladder with a pre-determined
pressure. During the injection cycle, the mold
can deform to enhance resin flow. Upon com-
pletion of mold filling, the flexible tool can be
further inflated to consolidate the composite
component. Part removal in this case is easy
since the flexible half can be deflated. %s
technique allows fabrication of complicated
parts that are not ordinarily possible to
demold.
20.5 INJECTIONPORT AND VENT DESIGN
The injection port allows the resin to be trans-
ferred into the mold (Fig. 20.1) and its design

may be critical. The location of inlet ports must
allow the resin to reach all areas without
bypassing part of the reinforcement. Air vents
help control internal pressure, bleed out air
and provide a visual indication of mold filling.
Race tracking, or channeling, in the mold is
usually the reason why the resin bypasses
areas of the reinforcement. Since the resin will
not flow backwards, this tends to create dry
patches. The engineering way to ensure com-
plete initial wetout is to gate the mold
correctly in the design. This may be difficult
even for an experienced mold designer. Use of
computer simulations as a design tool has
become popular in conventional injection
molding. Without an engineering design tool,
gates and vents can be put in the mold after
molding some trial parts, but many trial runs
may be prohibitive in some applications. In
the next section, new engineering tools
adapted for RTM mold filling will be dis-
cussed to overcome the problem.
Mold designers have found that RTM
molds must be vented to allow the air within
the mold to be pushed out by the resin. Gate at
the lowest point and vent at the highest point
is generally a good design practice.
Experienced designers may use symmetry to
design the inlet ports and outlet vents to
remove entrapped air. Venting ports must be
placed to draw the resin through sections of
the part that are difficult to wet out. They are
best placed at dead ends where the resin
would not flow by itself.
After the resin has finished bleeding, both
injection and venting ports must be sealed off.
This allows pressure to build up in the mold,
and forces the resin to further wetout other
sections of the part. This packing stage allows
the part to gel under pressure, decreasing void
content in the finished part.
20.6 SEALING THE MOLD
The perimeter gasket seals the edges of the
mold to prevent loss of resin and injection pres-
sure. In addition, it is an absolute necessity
Heating and cooling design 443
when vacuum is used. Sealing the mold to
achieve cavity pressure of 690 kPa (100 psi) or
higher is necessary if the void content of the
part is to be kept low. The only practical way to
accomplish this is to use O-rings. Machining
the face of the mold to close tolerances is pro-
hibitively expensive. It is also usually
impossible to maintain the mold absolutely flat
to achieve a metal-tight seal.
O-ring design is well established. The slot
has to be cut so that the O-ring can deform
when the mold is closed and maintain a seal.
Either square or round O-ring grooves can be
used. The type of O-ring material used
depends on the maximum temperature the 0-
ring will experience during the fabrication
cycle and the type of solvent used to clean the
mold. Nitrile rubber material can be used sat-
isfactorily up to 120°C (250°F). Over 120°C
silicone rubber can be used to temperature
approaching 177°C (350°F). If help is needed
in sealing around inlet or outlet tubes, tacky
sealant can be used. This type of sealant is use-
ful for making an O-ring where grooves do not
exist.
20.7 HEATING AND COOLING DESIGN
The mold should have good temperature con-
trol. The RTM mold should be able to heat and
cool the part during the fabrication cycle. Most
resin systems cure faster at elevated tempera-
tures. During demolding, lowering the
temperature is sometimes helpful in removing
the part. Even molds that are intended for
room temperature-cured resins should be well
insulated so that environmental conditions do
not change the gel times and viscosity of the
resin. Some molds are heated or designed to
go into ovens to achieve faster cures at higher
temperatures.
Normally, the mold is heated and cooled
using either hot water or oil. The mold is con-
structed to allow the heating/cooling fluid to
flow through channels (Fig. 20.8) in its interior.
The fluid is heated and cooled by conventional
means, such as a gas-fired heater and heat
444 Resin transfer molding
heating
channel -
//////////////
TCO
topmold
platen V/HB la
resin
flow -oOoOo Ko0o 0o 0
oT
Fig. 20.8 Heating/cooling by flow channels in the RTM mold.
exchanger. For larger molds, the heating and
cooling times will be longer if the heat transfer
area does not increase in proportion to the
weight. At some point, the production cycle
time becomes limited by the rate at which heat
can be added or removed, and becomes inde-
pendent of the curing characteristics of the
resin system.
Under development is low thermal inertia
technology that allows the tool face to be
heated by electric wires buried in the face. The
construction of the mold face is such that the
heat flows into the mold face and not outward
toward the mold support structure. This is
accomplished by use of a foam core that insu-
lates the bulk of the mold from the tool face.
This novel technology, if successful, will allow
a more instantaneous transfer of heat where it
will do the most good - at the mold face.
20.8 MOLD FILLING
Resin injection is to pump the base resin sys-
tem to a mixing head through either a single or
two pot system. Impingement mixing of the
components occurs in the mixing head. The
catalyzed mix is then pumped through a static
mixer which completes the mixing of the two
components. The injection nozzle is attached
to the injection port on the mold and the resin
system is injected into the mold to pack the
mold to a predetermined pressure. When the
hh
=
mold is filled, the pumping system is shut off
and immediately flushed, and the part is
allowed to cure.
Successful configurations demonstrated in
the industry show a common factor: that is,
the flow of resin is symmetrical about the vent
ports, in a manner such that the volume of air
left in the reinforcement decreases. This com-
pression effect helps sweep the remaining air
out of the part.
When the flow path is arranged in such a
way that the resin flows into a configuration
with increasing volume, there is a tendency to
bypass part of the reinforcement. This situa-
tion can happen when core material is used.
For example, when there is reinforcement on
either side of a core, it is possible that slight
misalignment in the core thickness will cause
dry spots in the part. To overcome this prob-
lem, the resin must be introduced on either
side of the core simultaneously. Holes may be
drilled through the core to allow the resin sys-
tem to flow to the other side. When this is
done, the core floats on the wet reinforcement
and equalizes itself.
When the injection pressure is too high or
reinforcement tends to move in the mold, the
following remedies must be considered:
Multiple gates: partition the mold along the
flow path such that travel distance for resin is
reduced.

Runner system: allows the delivery of resin to
various parts of the reinforcement quickly
without using high injection pressure.
Flexible mold wall: allows the deformation of
the bladder wall to facilitate mold filling.
There are several techniques to modify the
flow patterns. Application of high porosity
media on the preform or inclusion of a runner
system in mold design can alter the mold fill-
ing pattern. This is helpful in reducing
injection pressure or displacing air.
All resin movement must be accomplished
within the time allowed before the onset of
gelation. Additionally, the resin injection
process should not cause movement of the
reinforcement and should be done at low pres-
sure so that the mold will maintain its shape
without requiring massive backing.
Vacuum may be used to facilitate filling the
mold and simultaneously assist in removing
air from the laminate. This requires good mold
sealing and the use of a vacuum pump.
Vacuum up to 740-760 mm Hg (29-30 in Hg)
has been reported in assisting RTM mold fill-
Matrix
Fig. 20.9 Rheological change during the curing process. (Reproduced from Macosko.)
Curing 445
ing (Mosher, 1995). Note that the tooling must
be large enough to accommodate the perime-
ter gasket, air vents, injection ports and guide
pins.
20.9 CURING
To convert a resin system into useful products
it must be cured or cross-linked by chemical
reaction into a three dimensional network. The
reaction usually involves either a step growth
polymerization, a chain growth polymeriza-
tion, or a combination of both. The
accompanying rheological change in the
process is shown in Fig. 20.9 (Macosko, 1989).
The curing step constitutes a major portion
of a typical RTM cycle. During curing, rheo-
logical property changes of the resin system
and heat transfer between the mold wall and
the resin dictate the cure cycle.
Simultaneously, modulus and strength begin
to build up at a rate depending on the type of
resin and catalyst used and the chemical kinet-
ics of the resin system. Curing can continue
after the part is demolded.
Time
446 Resin transfer molding

Cure cycle is dependent on part thickness, If the adhesion to the mold face is too strong,
the ratio of catalyst or curing agent to resin even exceeding the strength of the composite,
and the temperature of the mold and the resin it can be reduced by spraying release agents,
system. In some cases, the part is removed normally fatty ester soaps or waxes, on the
from the mold immediately after gel occurs. mold surface.
The part must develop sufficient green After the two mold halves separate, the part
strength for handling prior to its removal from can be removed from the cavity. Part removal
the mold. Green strength is the strength a com- methods range from the use of plastic/
posite exhibits after the resin gels, but prior to wooden wedges and rubber mallets to the use
complete cure. Gel time is the interval of time of knock out pins. A mold designed for low
between introduction of catalyst or curing throughput with hand operated clamps pro-
agent to a thermosetting resin and the forma- ducing a relatively simple, lightweight part
tion of a gel. Typical gel times range from would most likely be removed using a wedge
several minutes to about an hour depending and mallet. Sophisticated hydraulic ejection
on the factors mentioned above. systems can be used for high volume, complex
The glass transition temperature, Tg,for an or heavy parts. To be pushed out, the part
RTM resin system depends on thermal history. needs enough green strength to survive con-
For a given temperature, the Tg increases dra- siderable bending stresses.
matically with time until it levels off. As the The most common test for sufficient bend-
curing temperature is raised, the T reaches a ing strength is to fold over a corner of the part
steady-state value at a faster rate. &e steady- immediately after demolding. If the corner
state value for Tg is a function of the curing survives the bending without cracks or a
temperature, and usually approaches the cur- crease, the part is accepted. Otherwise, mea-
ing temperature. However, the limit is sures to improve its green strength include
bounded by the degradation temperature of any of the following steps:
the resin system.
0 allow the part more time to cure in the
mold;
20.10 DEMOLDING AND POST PROCESSING 0 increase the mold temperature;
0 modify or change the resin system, e.g.
The minimum the curing step must accom-
increase the catalyst level.
plish is to develop sufficient green strength so
that the part can be removed from the mold. There is often excess resin at the edges of the
While cost is an important factor, it is not the part and in the vents. Considerable trimming,
only criteria in choosing a method to remove a part of the post processing, is common when
part from an RTM mold. For example, part reinforcement is clamped in the parting line.
weight and complexity, and throughput are Trimming is required for almost all items
important considerations. In many ways, the made by the RTM process. Accurate preform
choice of ejection methods parallels the choice placement and precise alignment can reduce
of clamping methods. the labor in this step.
A few precautions are required to facilitate Postcure, one of the post processing opera-
demolding. Before opening the mold halves, it tions, is used for various reasons. A molding
is necessary to release the part from one mold cycle including postcure can increase produc-
surface. The force required is approximately tion throughput. While postcuring in an oven,
that to overcome the adhesive force between the temperature is not restricted to that
the mold and the composite. Typically, tears of allowed for the mold materials. Therefore a
surface skin or flash, both resin rich, can be higher conversion of reactive groups can be
found around the comers or edges of the part. achieved. It can also prevent the reaction
 Process physics and use of simulations as a design tool 447

exotherms of a resin system from damaging a

composite tool. It is important to hold the part
shape during the process of postcuring and
cooling to prevent distortion or warpage.

20.11 PROCESS PHYSICS AND USE OF

SIMULATIONS AS A DESIGN TOOL
The processing defects addressed in the previ-
ous section are often caused by lack of a
systematic treatment in RTM part design and
process planning. Among the unresolved
issues in RTM encountered by composite engi-
neers, those related to the physical processing
have developed rapidly during the last
decade. The advancement in RTM technology
demonstrates the potential of RTM becoming a
primary process for producing many compos-
ite parts.
In this section, the issues in reinforcement
preforming, alternative tooling, mold flow
analysis, and cure kinetics are revisited. The
focus is on the use of models to describe and
enhance the understanding of the physical
phenomena. The models are built on the
experimental evidence and observations, the
goal being to reduce the scope of experiments
in the engineering applications. Reducing
engineering experimentation is achieved by
combining three elements: mathematical mod-
els, numerical methods and computer
software, into a simulation. One example of
such software is LIMS (Liquid Injection
Molding Simulation) (Advani et al. 1993)
which has been developed specifically for
mold filling of complex structures in RTM and
can be used also as a design tool for manufac-
turing of complex structural parts as shown in
Fig. 20.10.
The topics will be presented in the order
found in the unit operations of RTM. Draping
of reinforcement plays the role of distributing
fibers in a way that depends on the tool geom-
etry. Simulation of reinforcement draping
allows an engineer to estimate the fiber con-
tent distribution. This distribution can change
the volume fraction as well as the orientation
Fig. 20.10 Complex structure manufactured by
RTM.
in the molded part and therefore is of extreme
importance.
Tooling and mold construction are critical
factors in successful RTM. By considering sev-
eral alternative configurations, both the
injection pressure and the filling time can be
reduced. These alternative designs are valu-
able as the injection pressure tends to rise
rapidly when inhomogeneous fiber distribu-
tions are present as a result of preforming.
20.11.1 PHYSICS GOVERNING RTM
PROCESSING AND NUMERICAL SIMULATIONS
Darcy’s law for flow through porous media is
conventionally used to describe the resin flow
in the fiber reinforcement. The generalized
form expresses the superficial velocity of resin
flow in terms of a factor, which is permeability
divided by fluid viscosity, multiplied by pres-
sure gradient. This expression together with
the mass conservation in the mold are solved
together using various numerical methods. A
typical example of this method combines finite
element method with control volume method
(Bruschke and Advani, 1990a, 1990b, 1991,
1994; Advani, 1994; Young et al., 1991a, 1991b).
The solution is moved forward in time after
448 Resin transfer molding

the pressure field is obtained during the filling surface. The length of the cell segment can be
process. changed as a result of slippage to accomodate
The pressure solution obtained from the this effect.
mold flow analysis can be used to position the A dome shaped part will serve as an exam-
gate and vent. This lends a design engineer ple of this draping simulation. First, a square
'infinite' options when facing the task of mold bidirectional mat is draped. The workpiece is
design. The design rules are no longer initially configured so that warp and weft
restricted to the rule of symmetry used by tows are perpendicular to each other. Then
experienced designers to position the inlet and draping starts at an arbitrary point on the tool.
outlet ports. Instead, a composites engineer The initial constraints used in this case study
would be able to optimize the overall design are prescribed along the central tows in both
based on criteria such as minimizing the injec- the warp and weft directions. The length of the
tion pressure. cell segment is assumed to be constant.
In the draped configuration shown in Fig.
20.11, the degree of deformation varies from
20.11.2 PREFORMING
cell to cell. The minor angles in the preform
For bidirectional mats, woven or stitched, range from 90" to a minimum of 35". The shear
draping an arbitrary tool surface depends on also results in fiber volume fraction increase
two deformation modes: shear deformation up to 70% for the dome. This information can
and inter-yarn slip (Potter, 1979).A mat of this assist a designer in material selection, setup of
nature is treated as a net that consists of many processing conditions and part design: a
cells (Van West, 1990).Therefore, draping over process engineer can use this information to
a surface of double curvature requires the net find out where to make necessary cuts in order
to map on the surface by changing the internal to accommodate for induced deformation. As
angles in each cell. The four sides of a cell are a rule of thumb, formability of preform mat
made up of fiber tows. These tows, under the relies on absorption of such deformation by
preforming condition, are inextensible. At the reinforcement material. A good material
high deformation regions in a reinforcement, can withstand high deformation without
slippage may be necessary to drape the tool wrinkle formation.

Fig. 20.11 Draped dome.

 Process physics and use of simulations as a design tool 449

20.11.3 ALTERNATIVE TOOLING or the preform is driven by the pressure differ-

ence. Therefore, the equation of motion is a
One benefit of this process is that it can con- function of the bladder as well as the rein-
solidate several complex three dimensional forcement material (Lucey, 1992). On the
parts into one molded piece. The key to preform part, the compressibility of the rein-
accomplish this is tool design. From the design forcement in the thickness direction plays a
point of view, a flexible mold wall is very major role. On the bladder part, factors such as
desirable to mold certain parts with difficult- inertia, damping, and rigidity of the elas-
or impossible-to-demold geometry. While a tomeric material can also be included when
hard tool makes clamping and demolding dif- they are significant.
ficult, the flexible mold provides a convenient From lateral compression tests, the
alternative for mold design of these types of load-deflection curve of the fiber reinforce-
parts. Figure 20.10 shows an example of possi- ment material behaves like a nonlinear spring.
ble features which may be molded using this The elastic constant of the preform depends on
concept. In this part, one can easily see the its state. Preform permeability is a function of
small draft angle and the stiffeners which can fiber architecture and porosity. Since the
make demolding difficult. Moreover, the porosity of the preform changes with the
beads and the flanged opening in the bulk- thickness, the permeability can be expressed in
head of this frame are features that are terms of the cavity thickness.
impossible to mold using conventional rigid Figure 20.12 was obtained from the numeri-
molds. cal simulation of two cases: one with rigid walls
To avoid unconstrained wall movement, and the other with a flexible mold wall. In the
the bladder pressure is higher than the injec- case with rigid mold walls, the pressure drops
tion pressure. The motion of the flexible wall linearly with respect to the flow distance. This is

0 0.2 0.4 0.6 0.0 1

Fig. 20.12 Pressure distribution in the 1-D mold near the end of mold filling for flexible and rigid tool.
450 Resin transfer molding

caused by the constant permeability of the pre- pressure drop and overall filling time which is
form inside the mold. The pressure curve for the impossible to attain simultaneously in conven-
case with a flexible mold wall reflects the fact tional tooling (Fong and Advani, 1995).
that the fluid flow in the filled region exhibits a
smaller pressure drop. This reduction is benefi-
20.11.4 GATING, VENTING AND VOID
cial to the molded parts as it causes less fiber
CAPTURE
washout and preform deformation due to the
resin. In this section, computer simulations for RTM
Figure 20.13 shows the results of computed mold filling are discussed to overcome the gat-
gap thickness of the 1-D mold with a flexible ing and venting problem. Mold filling
mold wall. The straight line shows the thick- simulation is an effective way of positioning
ness in a rigid tool. From this distribution, one injection and vent ports. Gating and venting
can see that the gap height is a function of time are critical in the mold design because they
during the filling process as well as a function determine whether complete wetout is achiev-
of pressure. Near the injection gate, the resin able under normal operating conditions.
pressure balances the applied pressure from A gate designed at the lowest part and vent
the bladder and increases the gap thickness to at the highest point is generally a good prac-
its maximum in the 1-D mold. As a result, the tice to allow the air within the mold to be
resistance to the incoming flow has reduced pushed out by the resin. Experienced design-
significantly as shown in the previous figure. ers may use symmetry to design the inlet
Through the numerical study, the potential ports and outlet vents. However, the picture is
of the flexible tool design has been demon- often complicated by the geometry or the
strated. It has the advantage of reducing the presence of inserts. The engineering way to

0.005

0.004

0.003

0.002

0.001

0
0 0.2 0.4 0.6 0.8 1

Fig. 20.13 Gap thickness variation in the 1-D mold near the end of mold filling.
 Process physics and use of simulations as a design tool 451

ensure complete wetout initially is to gate the the design tool. The situation would be much
mold correctly in the design. more complicated if mold filling is coupled
Figure 20.14(a) shows a square plate with with phenomena such as preform deformation
two cutouts in the part. The injection port is and channeling in the corners and along the
first positioned at the center of the lowest part. edges.
The flow fronts corresponding to the gate At the microscopic level, heterogeneities
design are indicated by the curved contours. always exist in the preform media. For exam-
Contours in this figure indicate different time ple, the fiber tow may have a permeability
steps. For example, the contours closer to the several orders lower than that of the inter-
gate represents area that is filled first and the stices. Therefore, micro-voids form when the
contours closer to the vent the last filled orientation of the fiber tow does not allow the
region. As a result of colliding flow fronts in displacement of the air inside the tow. A novel
the middle and top portion of the part, the fig- approach in mold filling analysis is reported
ure demonstrates the capturing of dry patches by modifying the equation of mass conserva-
or macro-voids. These voids can degrade the tion to account for the fluid absorbed by the
properties of the molded composite signifi- fiber tows (Fong and Advani, 1994). Void
cantly. Void capturing is important in the entrapment inside tows is found to be depen-
process simulation to avoid formation of such dent on the microstructure, the vent pressure,
defects. Figure 20.14(b) shows an alternative and the ratio of the difference in the perme-
design that eliminates venting in the middle of ability of the tows and the permeability of the
the part. As a result of injection in the corner, preform (Pillai and Advani, 1994;
the vent port has to be positioned differently. Ranganathan et al., 1994).
This demonstrates the power and simplicity of

Vent Port
4

I Injection port (b) I Injection Port

Fig. 20.14 Design of injection ports: (a) central injection; (b) corner injection.
452 Resin transfer molding

20.11.5 SENSOR CONTROLLED INJECTION Figure 20.16 shows the pressure calculation
from the mold filling simulation. The pressure
Sensor controlled injection is multiple injec-
drops linearly in the one dimensional flow. As
tion in an 'intelligent' way without involving a
the flow front progresses from the inlet toward
complex control algorithm. It requires place-
the vent under a constant flow rate boundary
ment of gates along the flow path at a number
condition at the inlet, the pressure build-up
of locations. The injection gate is also a sensor
looks like the schematic shown in the lower
capable of detecting the arrival of resin. These
left figure. For the multiple gate with sensor
gates are then activated or deactivated in the
controlled injection, the pressure at the first
order of first on, first off, and, therefore, allow
gate increases up to a limit when the flow front
the mold to fill in a series of steps.
hits the next sensor. When the next gate is
For example, Fig. 20.15 is a simple mold
open, the previous gate is shut off. So the pres-
which has four injection gates. To help visual-
sure build-up is only limited by the length of
ize the concept effectively, a 1-D mold is used.
the interval. Therefore, the maximum pressure
The T-column represents different time stages
seen in the mold is only a fraction of the pres-
in the filling process. In this example, only one
sure compared to the lower left figure.
gate is allowed to open at a time. As the injec-
tion starts at T1, the first gate is open and the
remaining three are closed. As the flow front
progresses through the mold, it hits the second
gate location at time T2. The injection unit
shuts off the resin to gate one and opens the
second injection gate. Instead of having the
resin flow through the whole length in the
n q--\n
mold, the length is divided up into a number E
of intervals. Therefore, the overall flow resis- a
tance decreases as the effort required is for the
resin to flow from one gate to the next closest
gate in the flow path.
Flow Length Flow Length

CONTROL SCHEME
Fig. 20.16 Representation of pressure during mold
filling.
T1 ON OFF OFF OFF
T2 OFF ON OFF OFF
T3 OFF OFF ON OFF Table 20.1 shows the results from two sets of
T4 OFF OFF OFF ON computer simulations. For either case, only
one gate is open at any time during the mold
filling stage. The first column uses constant
flow rate and the second column uses constant

/ Mold Table 20.1 Comparison of processing parameters

Gate with flow front sensor

PP Slnglegnfr s2nglegate

Single-gate injection 100% 100%

Fig. 20.15 Control scheme for a 1-D model. Sensor-controlled injection 48% 36%
 Process physics and use of simulations as a design tool 453
pressure. If only one injection gate is used, the
pressure under the constant flow rate bound-
ary condition will reach a maximum.
Compared to the sensor controlled injection
with four gates, the pressure at the gate is only
48% of the pressure reached by the single gate
injection. In terms of filling time, the two
molds are subject to a constant pressure
boundary condition. Results show that the
mold filling for the single gate injection takes
almost three times that for the sensor-con-
trolled injection.
An example is shown in Fig. 20.17, which
elaborates on how one can utilize a sensor to
eliminate a dry spot during molding. In Fig.
20.17(a), where no sensors are implemented
and the injection gate is at the location as
shown, a dry spot will appear in the middle of
the part. However, an extra gate in the middle
as shown in Fig. 20.17(b), if triggered at the
point the fluid reaches the midframe, can pre-
vent this void, as indicated by Fig. 20.17(c).
This feature is incorporated in a numerical
simulation such as LIMS and can be systemat-
ically studied for a given geometry to decide
the best strategy when in situ sensing capabil-
ities are incorporated in the fabrication phase
(Liu et al. (1995)).
t Vent
Fig. 20.17 Use of sensors to eliminatedry spots: (a) no sensor; (b) extra gate sensor; (c) void prevented.
20.11.6 MOLD FILLING WITH RESIN DELIVERY
SYSTEM
Conventionally, an injection port serves as a
point source where fluid is pumped. The
drawback of a point source is that the pressure
value tends to rise rapidly to an extent that
could be detrimental to the preform. By
extending the point source into other forms
proves to be effective in reducing the pressure
build-up. To implement this concept, one can
use multiple point sources as discussed previ-
ously. A line source has been popular in
vacuum assisted RTM because of its ability to
fill the mold using 1 atm of pressure.
A line source may be modified to serve as a
runner by allowing more fiberfree space in this
delivery system. This is the channeling effect,
now used to advantage in mold filling. Further
extending the fluid source may possibly yield
a 'plane' source. The actual implementation of
a plane source may include a high-porosity
layer in the stack-up of the reinforcement
mats. The layer can possess a permeability
several orders higher than that of the fiber pre-
form. The result of this is a three-dimensional
mold flow with fluid propagating rapidly
through the spreading plane or surface first
1Vent
454 Resin transfer molding
followed by percolation of the resin through
the thickness of the preform. For three-dimen-
sional flow, venting the mold may become less
intuitive. In practice, vacuum assistance can
provide part of the solution.
20.12 CONCLUSIONS
Resin transfer molding is a practical process
for much of the composite industry. The qual-
ity of RTM molded parts can equal that by
conventional autoclave processes and its eco-
nomic advantages are obvious. Although the
underlying principles of RTM appear at first to
be simple, this is often not the case. The chal-
lenge for RTM is to bring together the
disciplines of preforming, mold design and
process development with existing fibers and
resins. This can be best achieved through an
understanding of the physics governing RTM
and by current simulation technology.
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void formation, Proc. Intern. Conf. Comp. Engng,
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Lucey, A.D. and Carpenter, P.W., 1992,J. Fluid Mech.,
234, 121.
Macosko, C.W., 1989, RIM, Fundamentals of Reaction
Injection Molding, New York: Karl Hanser
Verlag.
Mosher, I?, 1995, An introduction to vacuum-
assisted resin transfer molding (SCRIMP), 50th
Techn. Conf., SPI, Comp. Inst., Session 8.

Pillai K. and Advani, S. G., 1994, The role of dual
permeability of fiber preforms in resin transfer
molding, Proc. 9th Am. SOC.Comp., p. 17.
Potter, K.D., 1979, Composites, lg 161.
Ranganathan, S., Wise, G.M., Phelan, F.R., Jr.,
Parnas, R.S. and Advani, S.G., 1994, A numeri-
cal and experimental study of the permeability
of fiber preforms, Proc. 10th ASM/ESD Adv.
Cornp. Con$, 309.
Scheidegger, A.E., 1974, The Physics of Flow through
Porous Media, University of Toronto Press.
Tucker, C.L., 1989, Fundamentals of Computer
Modeling for Polymer Processing, New York: Karl
Hanser Verlag.
References 455
Vanwest, B.P., Pipes, R.B., Keefe, M. and Advani,
S.G., 1991, The draping and consolidation of
commingled fabrics, Comp. Manufng, 2, pp.
10-21.
Young, W.B., Rupel, K., Han, K., Lee, L.J. and Liou,
M.J., 1991a, Polym. Comp., 12, 30.
Young, W.B., Han, K., Fong, L., Lee, L.J. and Liou,
M.J., 1991b, Flow simulation in molds with pre-
placed fiber mats, Polyrn. Comp., 12,391.
FILAMENT WINDING
Yu.M. Tarnopollskii, S.T. Peters, A.I. Bed’
21.1 INTRODUCTION
A winding operation is the basic fabrication
technique for forming load-bearing structural
elements made of polymer matrix-based
fibrous composites, which have the shapes of
bodies of revolution. A semifabricated product
(uncured preform) of previously impregnated
filaments, strands, tapes and fabrics is wound
layer by layer with controlled tension onto the
mandrel or previous layers. By varying the
angle of filament or tape placement, it is possi-
ble to control the reinforcement fiber angles
within the same layer and through the thick-
ness of the composite wall. During winding,
fiber tension generates pressure between lay-
ers of uncured composite; this pressure
influences the compaction and void content of
the article and contributes to more complete
utilization of the strength and stiffness of the
reinforcing fibers. If the contact pressure is
insufficient for compaction of the material,
additional layer-by-layer compaction of a
semifabricated product must be employed.
The wound article must be converted by
chemical and/or thermal means to the fin-
ished article. With heat treatment, the usual
method, the temperature can be constant or
can vary with time. The mandrel defines the
internal shape of the article. It is removed after
curing if the mandrel is not an element of the
structure. The winding process is illustrated in
Fig. 21.11,*.
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
21
Filament winding is a natural way to com-
bine two-dimensional reinforcement and, with
additional processes and devices, three-
dimensional reinforcement. Advanced
processes, combining filament winding and
braiding, allow fabrication of spatially sewn
structures.
The most important groups of wound arti-
cles are: thin-walled shells (their thickness is
negligible compared to their radius); com-
pound structures, including three-layered and
multi-layered shells with a light foam or hon-
eycomb plastic filler; and thick-walled
structural elements. For thin-walled shells, it is
most important to optimize the reinforcement
configuration. For compound surfaces, contact
pressure on the interface is a design parameter.
Also, there is the problem of monolithicity for
thick-walled structural elements, which is
closely related to the problem of control of
residual stresses. Most composites cannot sus-
tain a significant internal pressure over time
without leaking (weeping) through the other-
wise sound composite wall. The use of internal
liners made from rubber, plastic or metal can
provide a leak tight structure. The semifabri-
cated (uncured) article has extremely low
strength in the radial direction. Thus, the ratio
of elastic modulii along and across fibers can
reach lo3. As additional circuits are wound
with tension onto the earlier ’soft’ laminate the
previous circuits are compressed with a redis-
tribution of preset tension.
The process is typical for all types of filament
wound articles with specific processing
approaches for each3.Controlling the winding

TENSIONING
W
SEMIFABRICATED
MATERIAL
Fig. 21.1 Stages of winding process.
process may include specifymg fiber tensioning
and extra compaction pressure (internal or
external), or geometric parameters (configura-
tion of reinforcement lay-up along the length
and through the thickness of the article). The
reinforcement configuration is determined by
the design requirements of the article and can
be achieved with high accuracy. Winding, as a
way of obtaining preset reinforcement configu-
rations, is restricted in terms of available
winding angles. Filament lay-up on geodesic
lines on an external surface is easy. (A geodesic
line is a line linking two preset points of the sur-
face along a shortest path.) In non-geodesic
winding, filament tension can shift the filament
Introduction 457
CURING (HEAT BUILDUP,
CURING COOLING
q=t(t) EXTRA 6OMPACTiAN
REMOVAL FROM MANDREL
ARTICLE
INITIAL STRESSES
to the geodesic line, against the static friction or
viscous resistance of the binder, or mechanical
obstacles, such as pins, to keep the filaments on
non-geodesic curve.
Larger components will result in changes to
the system of residual stresses. To calculate,
analyze and control the values of residual
stresses, it is necessary to find the interrelation
between the winding parameters (mainly ten-
sioning) and the properties of the finished
product. By controlling filament tensioning
and the reinforcement configuration, it is pos-
sible to control strength and stiffness of the
material, residual stresses and pressures on
the mandrel or previous layers.
458 Filament winding

21.2 HISTORY OF WINDING following stages: winding of a preform; heat-

ing of a preform with the mandrel up to
Historically, the developments in winding
temperature of binder polymerization; curing
technology can be traced back to 1370 BC.
at constant or variable temperature; cooling to
There is an ancient Egyptian flask in the
below the glass transition temperature and
British Museum made by winding glass fibers
then to room temperature; and removal of the
from the melt onto a dissolvable mandrel.
article from the mandrel.
Embalmed mummies were wrapped with
As a rule, thermosetting binders are com-
tapes soaked in resin that were the natural pre-
monly used in winding, although recently
cursors of polyester resins. Rope wrappings
progress has been made with advanced ther-
were used for reinforcing the bamboo powder
moplastic binders. Among the reinforcing
rockets in ancient China. Guns with wire
fibers, the most widely used are fiberglass, car-
wound barrels for reinforcing and proper
bon, organic (aramid and p~lyethylene)~,~.
stress distribution were fabricated in Russia as
They can be used in the form of single fila-
early as 1869 and in Germany from 1900. In the
ments, rovings, woven and unwoven tapes,
development of fiber winding technology
strands and woven fabrics.
there have been three important stagesP6:the
adoption of the first patint in 19637; the cre-
ation of NOL-ring sample4for strength testing 21.3.2 MATERIALS FOR WINDING
in 1955; and the publishing of the first mono-
There is a distinction between winding with
graph wholly devoted to composite winding
prepreg, when the reinforcing material is
technology by Rosato and Grove in 1964R.All
impregnated with a binder by an outside ven-
these works addressed the development of
dor and subsequently partially polymerized to
thin-walled articles rather than the task of con-
a ' B stage and 'wet' winding, and when the
verting a semifabricated or uncured material
processes of reinforcement impregnation with
into a monolithic article, which is the primary
the binder and the winding operation are per-
objective for modern composites technology.
formed on the same equipment simultaneously.
The history of analytical development
The rarely used process of 'dry' winding
includes the paper by L. Euler on thread equi-
involves winding of the reinforcing material
librium on a rough surface, papers by P.
without any binder on the mandrel, followed
Laplace and G. Lame on equilibrium of shells
by vacuum or any other impregnation of the
loaded by pressure, a paper by A.W. Gadolin
on compound cylinders with preliminary article with the binder and curing. This latter
process will see increasing attention since it is a
tightness and his formulation of the problem
convenient and inexpensive method for pro-
on tension wrapping of pressure vessels by
viding a stable preform without edges for resin
wire and papers by A.P. Minakov on thread
transfer molding.
equilibrium on an arbitrary rough surface. The
The winding operation of thermoplastics
winding mechanics of an extendible wire have
can involve, in the case of in situ consolidation,
been described by R.V. Southwell. The state of
dilution of the high viscosity of the matrix
the art of the winding mechanics of compos-
material by heat or organic solvents. It is phys-
ites has been reviewed in detail2.
ically analogous to the effect of impregnation
in 'wet' winding or preliminary heating of a
21.3 TECHNOLOGY OF WINDING prepreg. Although a 'curing' stage is missing
21.3.1 STAGES OF PROCESS
in the winding operation of thermoplastics,
heat treatment and compaction, as a rule, will
The production cycle for most filament lead to significant changes in macromolecular
wound composites can be subdivided into the structure. These changes can result in physical

shrinkage analogous to chemical and thermal
shrinkage in the curing and cooling of ther-
mosetting plastics. The analysis of winding
techniques and general engineering winding
theory for thermosetting plastics are surveyed
in detail6.
21.3.3 GEOMETRY OF WINDING
The shape of the article to be wound is deter-
mined by the mandrel. The thickness of the
article is controlled by the number of circuits
wound (taking into account their compress-
ibility during winding and shrinkage during
cooling). The reinforcement configuration is
determined by controlling the wind angle,
which is the angle formed between the tangent
to the filament and tangent to the intersection
line of the surface to be wound with the plane
parallel to the running axis of winding. For a
body of revolution it will be the angle between
the filament and the wind axis.
The formation of a continuous layer with
finite thickness and bandwidths, and with
proper fiber geometry, requires a coverage
solution. If the bandwidth, the number of cir-
cuits to close and the winding angle are
carefully chosen, the adjacent circuits along
the axis will be linked in butt joints, forming a
smooth continuous covering. If the bandwidth
is greater, the adjacent circuits will form a lap
joint resulting in a rough surface. If the band
width is smaller, there will be a gap between
the adjacent circuits along the axis. This gap
can be partly or completely filled up by either
fiber or matrix of subsequent layers. Some
structures may be amenable to an incomplete
winding pattern. Winding of subsequent cir-
cuits is feasible either directly on the
preceding ones (winding of ribbed and honey-
combed structures, Fig. 21.1), or on the rough
outer surface formed from several preceding
layers. In the second version, the reinforcing
fibers undergo additional bending and inter-
weaving and the structure obtained may have
more voids and lower fiber volume than in the
case of winding with butt joints.
Technology of winding 459
Winding of more complex shapes aggra-
vates the problem of pattern closure. To obtain
a continuous layer, it may be necessary to vary
the bandwidth during winding. Also, it may
be advantageous to vary the fiber volume and
thickness by alternate compaction techniques.
21.3.4 EQUILIBRIUM CONDITIONS OF
FILAMENT ON THE SURFACE
Winding along geodesic lines is easier than
along non-geodesic lines. However, to obtain a
continuous covering on h e surface it may be
necessary to use non-geodesic winding. This
presents the problem of permissible deviations
from the geodesic lines. The angle of geodesic
deviation can be designated by v, i.e. the angle
between the main normal v to the curve, along
which the filament has been laid, and the nor-
mal to the surface n at the same point. The
curve on the surface is defined by the radius of
curvature Rc and the radius of twist R, and the
radius of normal curvature Rn (projection of
curvature radius of the curve on normal n to
the surface):
l / R n = cosv/Rc
and radius of geodesic curvature Rg:
l / R g = sinv/R,
The equilibrium equation for a filament on
the surface has the form (Fig. 21.2):
~
dN + FT+dQr = 0 (21.1)
ds
N (21.2)
~ Rn + F,, + p Q , - P = 0
N
-+F + p Qg = 0 (21.3)
RP
where N is tension of filament, s is the arc coor-
dinate on the curve, F represents surface
distributed forces, related to a unit length, p is
the linear mass density of filament, Q repre-
sents mass distributed forces, referred to a mass
unit, including dead weight and inertial forces,
460 Filament winding
Fig. 21.2 Condition of filament equilibrium on the surface.
t is the basis vector directed along the tangent
to the curve and P is the normal surface reac-
tion related to a length unit of filament.
Equation (21.l) describes the redistribution
of tension along the filament length due to fric-
tion, viscous resistance from lower-lying
circuits, viscous resistance of above-lying cir-
cuits and inertial effects. Equation (21.3)
represents the force, which tends to shift the fil-
ament onto a geodesic line and viscous
resistance of both the lower-lying and above-
lying circuits. In the simplest case of the
friction law I Fg I 5 kP where k is the friction
coefficient, from equation (21.2) (at Fn = Q, = 0) a value not exceeding the allowable strength
and equation (21.3) (at Q = 0) the following
relationship can be derive&
Rn
-=tanv<k (21.4) from equation (21.2) and the relationship
Rg
The ultimate permissible angle of geodesic
deviation is equal to v Iarctan k.
To obtain a monolithic (fully compacted)
material with successful chemical processes
(matrix crosslinking) in any type of composite
processing, some pressure must be maintained
through the completion of the curing stage of
the matrix. There are several potential sources
of pressure. The pressure p on the convex sur-
face comes from tension of the wound
material and is unique to filament winding; p
= P / b , where b is the width of the material to
be wound. For the simple case of circumferen-
tial winding of cylinders with a radius R, this
pressure is calculated according to the for-
mula:
N
P=m (21.5)
If this pressure is insufficient (if R is high), it is
necessary either to increase the fiber tension to
of the fiber band or tows or to employ addi-
tional methods. For helical angle winding (at
an angle t to the axis) of a cylinder, it follows
Rn = Rc = R / sin'p
that
p = N sin2
- (21.6)
bR P
The greater the angle deviation from the cir-
cumferential the less the compaction pressure
 Technology of winding 461

generated by the fiber band or tows being Helical winding

wound.
The wind eye reciprocates parallel to the axis
There are a variety of methods for creating
of the rotating mandrel and the article (Fig.
additional pressure (internal or external, local
21.3) and is the most common technique used
or general) by means of rollers, power trowels,
for tubular structures. By controlling the ratio
autoclaves, wrapping of a fiberglass or metal-
of rotational and translational speeds, it is pos-
lic tape under tension, wrapping of thermally
sible to control the wind angles of the
shrinking materials, extensible or squeezing
reinforcement. Three other techniques can be
mandrels, rubber bags, etc. Internal pressure
used: one or more wind eyes are stationary,
can be applied by an expanding elastomer, by
while the mandrel rotates and translates, the
pneumatic pressure to an expanding mandrel
wind eye rotates around the translating man-
or by the selection of a mandrel material with
drel, i.e. winding with a stationary whirling
high circumferential expansion properties.
arm type winder which is one of the widely
used methods of continuous fabrication of
21.3.5 REINFORCEMENT CONFIGURATIONS pipe; a wind eye rotates round a stationary
mandrel and executes a translational motion
There are three basic types of reinforcement
along its axis. Winding with a whirling arm
configurations: circumferential, helical and
type winder is a popular method of insulating
polar. There are up to six degrees of freedom
metallic pipelines. Circumferential winding is
between the mandrel and the wind eye in typ-
a particular case of helical winding with a
ical advanced winding machines today and
wind angle of close to 90" (related to the band-
more motions are possible. Wind eyes can
width and the mandrel diameter).
have three additional degrees of freedom
(three rotational motions). The combination of
several motions may allow more effective or
rapid reinforcement placement on a complex
surface.

Circumferential or hoop winding

The wind eye is stationary, except for travel
along the length of the mandrel at a band-
width per revolution and the mandrel together
with the article rotates about one axis, i.e. for
winding of rings, discs, profiled rings and
discs (the ultimate case of profiling is the
winding through an opening), short pipes,
cones and other bodies of revolution. During
circumferential winding, the shape of a cross
section is decided either by the shape of the
mandrel or by localized inserts, or by varying
the bandwidth additional hoop layers. Some
large and small-scale articles have been fabri-
cated by rotating the wind eye about the
stationary mandrel. Circular rings, ellipses,
ovals and other shapes can be fabricated by a
circumferential winding technique.
I
r
Fig. 21.3 Lathe type winder.
Polar winding
This type of winding combines several differ-
ent winding processes. It has the same
combination of motions as helical winding,
but the shortest axis is the axis of rotation. This
technique combines two rotational motions.
During simultaneous rotation of the mandrel
around its axis and the wind eye around an
axis nearly perpendicular to it, a race-track
462 Filament winding
pattern is generated (Fig. 21.4). This process
enables the fabrication of vessels with differ-
ent sized polar openings or closed ends. There
are a number of alternative techniques. First,
the wind eye executes a rotational motion in
two planes. It is a very complex technique and
is used only for unique articles. Second, the
rotational motion of the mandrel is in two
planes (Fig. 21.5), sometimes supplemented by
a reciprocating motion of a wind eye or turn-
ing of its head.
Fig. 21.4 Racetrack winder.
Fig. 21.5 Polar winding by the mandrel rotating in
two planes.
Thirdly, there is a group involving three
motions, two of which are rotational in two
planes and one is translational. To this group
belong, for example, a race-track type of wind-
ing, where a wind eye executes a motion along
a closed but not circular trajectory. The trajec-
tory shape affects the variation of the winding
angle over the surface of the article. Pendulum
winding is analogous to lathe winding, but
instead of translation motion of a wind eye,
there is a reciprocating motion along a curvi-
linear trajectory. One version of winding with
a whirling arm-type winder is when a wind
eye rotates and moves along some curvilinear
trajectory.
Fourthly, there is a group involving two
rotational motions executed alternately (a pla-
nar-polar winding). Applications of this
method include chord winding (Fig. 21.6) of
composite flywheels.
3 1’
Fig. 21.6 Scheme of chord winding. Numbers des-
ignate the order of chord lay-up : 1-1’, 2-2’, 3-3’ for
chords on the right side of mandrel; 1’4, 2’-3 for
chords on the reverse side of mandrel; D is a disc
mandrel; H is a pendulum mechanism.
The fifth group consists of three rotational
motions. Kinematics of this process may
involve a combination of two rotations around
nonperpendicular axes and a combination of
two rotations around two perpendicular, but
noncrossing axes (winding of a torus).
Even more complicated types of winding
including combinations of circumferential, heli-
cal, polar winding with axial lay-up and/or
braiding have been describedzJOJ1. One of the
examples of fabricating large-size articles by a
combined method is shown in Fig. 21.7.
 Technology of winding 463

Fig. 21.7 Combined winding of large-scale articles.

Winding pattern control explosion of the sporting goods business all

over the world. Many golf shaft manufactur-
In the simplest winding machines, control of
ers have studied or are studying the possibility
the ratio of speeds of different motions is done
of using filament winding rather than flag
by rigid kinematic coupling (usually gears or
wrapping for production of carbon/graphite
chains). With modem winding machines dif-
reinforced golf shafts. Filament winding offers
ferent motions can be regulated individually
lower labor costs, because of the possibility of
with greater accuracy by computer control. In
winding many shafts at once (Fig. 21.9), the
the gear and chain machines, looseness and
possibility of lower material costs with unlim-
wear of the mechanical elements have been
ited possibilities for varying the axial and the
occasionally responsible for poor winding pat-
torsional stiffness along with the advantage of
terns. Winding inaccuracies can result from
no seams, such as would be generated by flag
combined fiber delivery and winding machine
wrapping with unidirectional tape, along the
positional errors. These errors can be analyzed
shaft’s length. Tennis racquet manufacturers
by winding with a controlled material, such as
are also considering a filament wound rac-
fine copper wire, over the mandrel surface.
quet, again because of the expected lower
Typical feedback resolutions on computer con-
labor costs and ease of control of stiffness.
trolled winding machines range from
Along with the new machines much better
lWm/bit to 10” m/bit for linear axes and
fiber delivery systems have been offered, with
from 0.02 to 0.001 degrees/bit for the rota-
electronic fiber tensioners with roll diameter
tional axes. The speed sensitivity has been
sensing, provisions for setting tension from
greatly improved with the newer control sys-
the main control panel and rewind capability.
tems by tracking both velocity and position for
The machine manufacturers have devel-
each axis. This makes it possible to change
oped menu-driven, user friendly computer
winding speeds during the winding.
programs for which the user inputs need only
The standard for the industry now is the 6-
be part geometry, wind angle, band width and
axis filament winding machine (Fig. 21.8).
number of circuits desired.
These have been built in the USA, UK and
One of the most helpful innovations intro-
Germany and are marketed worldwide. These
duced by the filament winding machine
machines, in general, can be programmed by
manufacturers has been the ability to work
the manufacturer, by third party software sup-
with the machine control computer programs
pliers or by the customer. The newest venue
off-line on a common PC within the standard
for the machine manufacturers has been the
464 Filament winding
Fig. 21.8 6-Axis computer controlled filament winding machine. Machine motion indicated by arrows.
(Courtesy of McClean Anderson, Inc.)
operating systems such as DOS or Windows.
This allows the design engineer to participate
in the selection of machine parameters such
as number of circuits to close and the number
of crossovers, which influence structural
properties.
For much of the history of composite fabri-
cation by filament winding, only the large
aerospace manufacturers had computer pro-
grams to predict slipping or bridging of the
wet fiber band on a non-geodesic path. Now
these programs are available from third party
suppliers and they include 3-D display of the
mandrel and the fiber path, the friction at
each section and the deviations from geodesic
and desired winding angles. They also dis-
play the more mundane information, such as
laminate thickness, winding time, length of
fiber used and laminate weight for any figure
of revolution and general nonsymmetric
parts (Fig. 21.10). The programming extends
to nonaxisymmetric parts also, such as
elbows.
21.3.6 MANDRELS
The mandrel, which determines accurate inter-
nal geometry for the component, is generally
the only major tool. Low-cost mandrel materi-
als such as cardboard or wood can often be
used when winding low-cost routine parts.
For critical parts requiring close tolerances,
expensive mandrels designed for long-term
use may be required. For high-temperature
cure 315°C (600"F), graphite mandrels with
low thermal expansion may be advantageous,
however some attention should be paid to the
potential difficulties of mandrel removal. Gas
containment pressure vessels often require
metal liners because composites are porous;
these metal liners can also serve as mandrels'*.
Mandrels are either removable or nonre-
movable (remaining as a part of the wound
structure). Removable mandrels are classified
according to the removal technique as:
0 entirely removed (for example, tubular
mandrels with or without taper and with
release agent);
 Technology of winding 465
----.,--*---- *. - . ~ . - . . .

Fig. 21.9 20-Spindle golf shaft filament winding machine. (Courtesy of ENTEC, Salt Lake City, UT, USA.)

0 collapsible (the mandrel is disassembled low-melting temperature alloys. Of these

and removed piece by piece); materials, the water-soluble sand mandrels
0 breakable or soluble (plaster, sand or salts). and the breakout/washout plasters are most
commonly used.
The selection of a mandrel involves several
trade-offs. These include part size and com-
plexity, size of openings, resin system and its
curing cycle and the number of components to
be fabricated. The basic requirements for a
mandrel, whether it will be removed from the
part after winding or remain as a part of the
structure, are:
0 It must be stiff and strong enough to sup-
port its own weight and the weight of the
applied composite while resisting the fiber
tension pressure from winding and curing.
0 It must be dimensionally stable and should
have a thermal coefficient of expansion
greater than the transverse coefficient of the
composite structure.
Components such as rocket motor cases or
pressure vessels have closed or reduced-area
end openings that require the use of dissolv-
able or fusible mandrel materials. Some of
these materials are: water-soluble sand man- Fig. 21.10 Cadwind display of complex mandrel
drels, breakout plasters, soluble plaster, and fiber path. (Courtesy of Material SA, Brussels,
soluble or meltable salts, eutectic salts and Belgium.)
466 Filament winding
Water-soluble mandrels are primarily used
in rocket motor cases and pressure vessels
where mandrel removal through small open-
ings is desired. The sand/polyvinyl alcohol
(PVA) mixture is cast into female molds that
have preassembled components, such as insu-
lation, wind axis, lightening tubes and polar
bosses. The sand mixture is cured and the two
mandrel ends are assembled and bonded.
Spider/plaster mandrels are often used to pro-
vide a high-tolerance mandrel surface. The
plaster is cured, then overwrapped with tetra-
fluoroethylene tape or other separator film.
Following cure, tooling is removed, the plaster
is chipped or washed out and the release tape
is removed, leaving the desired inside dimen-
sions. Metal-supported plaster is generally
used for relatively large parts of 3-6 m.
Segmented collapsible mandrels, used for long
tubes, are specialized and expensive, but the
advantages of their reusability and the continu-
ous winding process renders expensive tooling
worthwhile for high-production applications.
The main considerations for mandrels are
stiffness, hardness, strength, coefficient of
thermal expansion and heat resistance.
Mandrel removal from the part is equivalent
to application of the pressure of opposite sign
and new shearing stresses at the interface
between the part and the mandrel and must be
done with some care.
21.3.7 RESIDUAL STRESSES
The residual stresses caused by the tension of
the reinforcement and compaction undergo
essential changes during elevated temperature
exposure. The thermoelastic stresses as a result
of the difference in thermal expansion of the
mandrel and composite article and the
anisotropy of thermal expansion of composite
in a statically indeterminable type of structure
are added to the system of residual stresses.
The majority of wound articles end up with
these stresses. The resulting fields of residual
stress in wound articles are comparable in
scale to fields of allowable stresses. Taking into
account these fields, their analysis, develop-
ment and application of the methods of
controlling the fields are important aspects in
the manufacturing of defect-free structures,
especially thick-walled components.
21.4 THIN-WALLED STRUCTURAL
ELEMENTS
21.4.1 TYPICAL ARTICLES
The basic problems in the design and manufac-
ture of thin-walled composite shells are related
to the optimization of shape and reinforce-
ment configuration^'^. Fibrous composites
show their best performance under tensile
load acting strictly along the fibers, while the
matrix serves only to distribute the load uni-
formly among fibers. A rational reinforcement
configuration for a thin-walled composite
structure is similar to that of a guyed structure
working under the same loads. The winding
technique is a natural process and is the most
widespread production process for thin-
walled structural elements.
The most widely used elements are cylin-
drical shells, such as pipelines which operate
under a combination of external or internal
pressure, bending and axial tension-compres-
sion. Cylindrical sections of missiles,
cylindrical shells with semi-spherical closed
ends used as tanks or pressure vessels,
toroidal shells for electrical applications; and
conical shells, which include nose fairings of
aircraft and rocket motors, are also common.
21.4.2 SHAPE CONFIGURATIONS OF WOUND
PARTS
Filament-wound shapes generally include
cylindrical, spherical, conical, or dome-end
configurations.These bodies of revolution best
exploit the advantages of high-speed winding.
Spherical shapes contain the maximum
possible volume with minimum surface area.
Hence this shape is commonly used for pres-
sure vessels. Because the radius of curvature is

equal in all directions, the best reinforcement
pattern is an isotropic combination of wind
angles. This pattern is readily obtained by
winding a series of great circles, each stepped
out from the preceding pattern by the width of
one winding band.
Cylinders and shafts can be wound on a
cylindrical mandrel by providing an adequate
pattern reversal length at each end. The cured
part can be removed from the mandrel by
using a stripping die. Winding patterns consist
of hoops or helical patterns as desired to react
to design loads. For torsion-type loading, k45"
helicals provide the most efficient load path.
Thick-wall effects are a major consideration in
the design of composite shafting.
With flat cylinders, the width is just a frac-
tion of the thickness. These parts can be
fabricated using hoop windings alone. A typical
application is in flywheels. Thick-wall effects
and delaminations are potential problems that
must be carefully considered. Fabrication tech-
niques using programmed winding tension,
high strain resin systems and low temperature
cures help to overcome these problems.
The combination of cylinders with domes
is typical of rocket motor cases and pressure
vessels. The winding patterns and dome
shapes must be carefully chosen to prevent
fiber slippage and to react adequately against
the pressurizing forces on the domes. Ideal,
or isotensoid, domes or end closures for fila-
ment-wound vessels have a general surface
of revolution that requires a numerical solu-
tion. The two types of dome contours
generally considered are geodesic (constant
stress) and polar (planar) ones, each of which
requires its own derivation. The only geomet-
ric variables affecting the dome shape are the
radius of the cylindrical portion of the pres-
sure vessel and the radius to the center of the
filament band at the polar opening. There are
several winding considerations. Winding pat-
terns must be stable, the dome must be
shaped with properly sized openings and
there must be balanced stress fields in a cylin-
drical section.
Thin-walled structural elements 467
21.4.3 SPECIFIC FABRICATION FEATURES
One of the main problems in obtaining the
designed shape for thin-walled composite
structures is the problem of warpage. The
bending stiffness of structure is proportional
to the cube of the thichess, while residual
stresses, as a function of thickness, increase
more slowly. Therefore, warpage can be a
problem with thin-walled articles. The reasons
for warpage are :
Inhomogeneity of material properties in
structures can be ascribed to local imperfec-
tions, inaccuratewind angles, inhomogeneity
of temperature field during cure and
changes in binder composition or volume
within the wall.
Mandrel removal; pressure and shearing
stresses on the interface between the man-
drel and article can be distributed
nonuniformly as a result of different ther-
moelastic behavior of the mandrel and
composite article, especially for complex
shapes.
Anisotropy of composite shrinkage and dif-
ferent relaxation rate of components of
residual stresses can cause inhomogeneity
and anisotropy of relaxation characteristics.
In the production of thin-walled articles it is
most important to have a high degree of wind
angle fidelity.
21.4.4 SANDWICH AND COMPOUND THIN-
WALLED STRUCTURES
Sandwich structures incorporate a low density
filler to increase bending stiffness to increase
bending moment of inertia. Foam and honey-
comb plastics are most often used as low
density fillers. These materials serve not only
to increase the separation between the load-
bearing layers, but also to act as sound and
heat insulation. Sandwich structures are
widely used in aviation and construction.
Typical design problems are associated with
optimization of the thicknesses of load-bearing
468 Filament winding
layers and the filler and selection of the rein-
forcement angles. When winding the outer
load-bearing layer the winding tension has to
be low enough to avoid damage to the low
density filler. Stress distribution during wind-
ing depends essentially on the compliance of
the mandrel6.In sandwich structures the outer
load-bearing layer of the filler serves as the
mandrel for the outer skin lay-up.
21.5 THICK-WALLED STRUCTURES
21.5.1 ENGINEERING THEORY OF WINDING
The development of engineering winding
mechanics must involve the study, description
and sequential consideration of the peculiari-
ties of composite behavior under loading
perpendicular to the plane of reinforcement.
During the winding process the physical-
mechanical properties of the composite
undergo great changes. The composite proper-
ties remain linear and practically do not change
in the reinforcement direction. The compliance
in the transverse direction is essentially nonlin-
ear during the stages of winding, heat build-up
and curing of the article and can vary by three
orders. The possibility of applying a universal
rheological model to such a material is beyond
the present state of the art. The engineering
approach assumes that the material behavior in
each of the stages of the process follows a spe-
cific rheological law. Passing from one stage of
cure to another results in an abrupt change in
ncr
Fig. 21.11(a) Relative pressure (A)on the mandrel
in winding. 1is a metallic tape winding; 2 is a com-
posite winding.
material properties. To define these changes, a
simplified hypothesis about the progression of
the stress state has been developed.
Experiments with tensometric (instru-
mented) mandrels have served as an impetus
for the development of an engineering theory
(Fig. 21.11). The distinction between the wind-
ing process of a semifabricated composite
article and that of an isotropic metallic tape was
made by examining an 'integral force parame-
ter' - the dependence of the pressure - on the
mandrel related to the number of circuits n
being wound. A sigruficantpart of the applied
pressure is consumed in the deformation
process of the lower-lying circuits. By using
instrumented mandrels it has been possible to
evaluate the variation in winding pressure for
every stage of the process. In the curing
process, constant pressure on the mandrel is of
special interest and makes it possible to
develop several variations of the theory of
residual stresses, omitting the polymerization
stage. It establishesthe dependence of the resid-
ual stresses d,and 0 : on the geometry of the
article h / R , material anisotropy p2 = E, / E ,
winding angle p(x, Y), the number of circuits n,
winding tension N(x, r ) and parameters of the
curing process (q is contact pressure, T is tem-
perature and t is curing time).
Fig.21.11(b) Pressure variation on the mandrel. 0-1
is a winding stage; 1-2 is heating after winding; 2-3
is heating prior to curing; 3 4 is polymerization at
constant temperature; 4-5 is cooling on the man-
drel; N p I X is the ultimate pressure (- - -) on the
mandrel in elastic tape winding, R is a radius of the
wound article, q,, is a residual pressure on the man-
drel after cooling.
 Thick-walled structures 469

Residual stresses in thick-walled articles

differ essentially from those in thin-walled
structures, both in nature and magnitude. In
thin-walled articles these stresses can cause
the loss of monolithicity and reduction in
load-carrying capacity.
To analytically describe the force variation
in the winding process, the circular models
were based on the simplest linear approxima-
tion of the nonlinear strain diagram or 5 (Fig.
21.12). The basis of the solution is that the
process of continuous tension winding can be
modeled by a system of concentric rings,
which are first mounted on the mandrel and
Fig. 21.12 Models of winding stages. (a) a linear cir-
then on each other under contact pressure cular model (1965); (b) a spirally circular model
equal to the tensioning of the ith layer. The (1971); (c) approximation of the deformation char-
range of thicknesses and operating pressures, acteristics of winding materials used for a nonlinear
were broadened when it became impossible to circular model (1973); PI, PI,,
PI,, are coefficients of
consider only one linear section of the stiffness anisotropy of the composite in the process
stress-strain curve of the material. This of winding; (d) a model of a growing body, R =
required model refinement. The modification R(w),o is a parameter of growth.
of this model has played an essential role in
the development of technology of winding
thick-walled articles, It was established that
21.5.2 METHODS FOR CONTROLLING
the total winding pressure on the mandrel had
RESIDUAL STRESSES
increased nonlinearly, approaching asymptoti-
cally an ultimate value
Programmed winding
p = No arctan sinh nK
~ Programmed winding involves variation of
KR,
winding tension in accordance with a speci-
where K = P(c/R,), Ri is the inner radius of the fied program with the aim of eliminating fiber
ring to be wound and c is the band thickness. buckling and compensating for thermoelastic
The critical number of circuits ncrwas estab- tensile stresses which arise during cooling of
lished beyond which the winding pressure on the article with the mandrel. Crack formation
the mandrel did not increase. and loss of monolithicity can occur at this
stage. By properly selecting the correct tension
program it is possible to transfer the radial
K
stresses or into compression and eliminate the
Where excessive force conditions of winding danger of fiber buckling.
appear, a circular area through the thickness of The range of variation of tensioning N,,, is
the article appears, where the circuits pass into limited by the strength of the semifabricated
compression leading to instability in the form article to be wound, the contact pressure 4 =
of irregular curvatures and buckling of the N,,,/R and by the overall dimension of the
reinforcement. These defects are common to part to be wound R. New methods have been
thick-walled wound articles. employed for developing thick-walled wound
structures: winding with layer-by-layer cur-
ing, introduction of compensating interlayers
470 Filament winding

and winding with extra pressure. These meth-

ods, along with programmed winding, have
facilitated the design of thick-walled articles
with wall thickness comparable and some-
times equal to the inner radius. Another
means is reinforcing thick-walled articles in
the radial direction with a radial reinforce-
ment. This method makes it possible to
significantlyincrease shear stiffness and trans-
verse tensile strength.

Winding with extra external or internal

pressure
This method can be accomplished by layer-by-
layer compaction in the winding process, by
spinning rollers, by wrapping fiberglass or
metallic tape and by extensible (Fig. 21.13)
mandrels with programmed compaction pres-
sures to force extra compaction of the article.
Compaction of the wound article can also be
performed with these same processes during
heating and curing. Control of residual Fig. 21.13 The extensible mandrel (a) and the pre-
stresses can be achieved by varying the mag- form stretched along the axis (b).
nitude of extra pressure and the time of
removal. For a step-by-step compaction tech-
nique the following operations (winding of a cations of programmed winding. The advan-
part of the article, compacting, pressure tages of layer-by-layer winding however
release) are repeated. In this case, the residual result in an significant increase in the dura-
stresses can be altered by varying the interme- tion of the process of manufacturing for
diate thicknesses of the article and the thermoset-polymer composites. Therefore, a
magnitudes of the applied pressure in each consideration of the number of individual
step. layers based on a theoretical analysis is very
important for process economics. For interme-
diate curing, both the usual curing methods
Winding with layer-by-layer curing
and accelerated ones (i.e. radiative or catalytic)
The basic idea of this method is similar to step- are appropriate.
by-step compaction in that it decreases the
compliance of the already wound circuits. This
A method of temperature gradients
is a result of partial or complete curing of a
group of wound layers, followed by winding There are methods for controlling the residual
of the next group of layers. As the number of stresses by varying the process parameters in
curing steps, into which the process is divided, the heat build-up and curing stages.
increases, layer-by-layer winding approaches Thermoelastic behavior of anisotropic bodies
some idealized ultimate process of winding a differs greatly from the thermoelasticbehavior
’cured’ material (similar to thermoplastics). of isotropic bodies. The methods of tempera-
The layer-by-layerwinding extends the appli- ture gradients must compensate, at least
 Applications 471

partly, for the thermoelastic stresses which 21.6 APPLICATIONS

arise from anisotropy of thermoelastic proper-
ties, by artificially developed and controlled 21.6.1 PRESSURE VESSELS
temperature gradients. Different modifica- Most advancesin filamentwinding have been
and Objectives for using the method Of made in the course of development of pressure
temperature gradients are possible. Among
vessels, particularly rocket motor cases. In
them are the curing in an inhomogeneous tem-
these structures the reinforcement is loaded
perature field, the creation of temperature
only in tension and winding the
gradients during the cooling process, or mod- arrangement of fibers along the directions of
ification Of the Polymer matrix through the principal stresses. It uses the main advantages
thickness of the article for the purpose of con-
of composites, such as high strength and stiff-
trolling the gradient Of heat during a ness in the reinforcementdirection, and avoids
curing chemical reaction.
-
shear stresses which are dangerous for com-
posites. Rocket motors come in many sizes,
A spatial reinforcement from the graphite/epoxy filament wound case
for the Space Shuttle to pressure vessels as
A number of methods for controlling residual small as 0.152 m in diameter for orbital adjust-
stresses at the expense of variation of the rein- ments to spacecraft. Metal-lined pressure
forcement configuration have been worked vessels are widely used in aerospace, aircraft,
out. By controlling portions of the elastic, marine and commercial applications. The
strength and thermo-physical properties Skylab Oxygen Tank shown in Fig.
21.14 is an
either by changing their level or generating
example of such a structure. The tank, 1.143 m
artificial inhomogeneity, it is possible to affect
in diameter and 2.286m long, operated at
the level and distribution of residual stresses. 31 MPa with a demonstrated life up to 1000
There are methods for the reduction of cycles in temperature service range of
anisotropy of composites, such as an extra -53-71°C.
radial reinforcement by short needles, wind-
ing while braiding a three-dimensional
reinforcing framework, hybrid reinforcement
and decreasing of fiber volume content,
Another method of controlling the residual
stresses is to introduce compliant interlayers
of rigid foam or other material. The third
group of methods creates an artificial inhomo-
geneity by substituting a homogeneous
structure for a compound one which has dif-
ferent elastic and thermophysical properties.
This is done by creating a smooth macro-inho-
mogeneity of properties by varying the bulk
reinforcement coefficient, or the ratio of two
types of reinforcement in hybrid composites,
or by changing the reinforcement angle or
chemical composition of matrix through the
article. The basic methods for controlling the
residual stresses are summarized in Table 21.1.
Fig. 21.14 Skylab Oxygen Tank5. (Courtesy of
Brunswick Corporation.)
472 Filament winding

Table 21.1 Methods of controlling residual stresses in wound articles

Method Techniques
Forced A programmed winding
Pressing and rolling during winding process and after it
Chemico-technological Curing in regime of spreading of reaction front
Curing in nonhomogeneous temperature field
Variation of matrix composition through the article
Continuous or layer-by-layer curing during a winding
Controllingphysical fields Controlling of cooling rate
Method of temperature gradients
Influence of electromagnetic fields at curing
Controlling of reinforcement Additional radial reinforcement
schemes Introduction of thermocompensatinginterlayers
Variation of reinforcement coefficient
Application of hybrid composites
Creation of artificial nonhomogeneity
Creation of compound structures
Winding with braiding

21.6.2 THIN-WALLED SUPPORTED amount of attenuation. By increasing the pres-

STRUCTURES sure of a water-filled test vessel, deep water
depths could be simulated for calibration of
Thin metal-lined pressure vessels over-
sonic equipment, while the equipment is sus-
wrapped with Kevlaf reinforcement for the
pended just a few feet under water. A 2.4 m
Space Shuttle and various medium class satel-
diameter acoustic pressure vessel with 0.10 m
lite systems and metal fuel tanks overwrapped
wall thickness rated for multiple cycle life
by composites for military aircraft are
included here. The applications in aircraft
34.4 MPa working pressure is shown in Fig.
21.15. Special winding programs were
structures include entire composite aircraft
fuselages as well as many secondary struc-
tures. Two prototype fuselage test sections for
Beech Starship with different stiffening con-
cepts have been developed, both filament
winding concepts used high strength graphite
and Shell resin 9400. The first technique used a
filament-wound isogrid network, 1.8 m diam-
eter, 2.4 m long geodesically reinforced test
section to prove the concept. The second
approach used a honeycomb-stiffened struc-
ture with graphite epoxy skins and
lightweight composite tooling.
One of the earliest uses of composites for
marine application was in the use of acoustic
transmission of radar signals. Fiberglass-rein-
forced plastic structures have an ability to Fig. 21.15 Eight foot (2.4m) diameter acoustic pres-
transmit sound waves with a minimum sure vessel5.(Courtesyof Brunswick Corporation.)

required in concert with multiple compaction
and cure cycles due to the thickness of the ves-
sel. Composites combining low density,
stiffness and high strength with superior
sound damping properties are very promising
materials for submarines and deep-submer-
gence devices. Filament wound composites
offer cost savings in terms of materials and
process both for primary and secondary struc-
tures on submarines.
21.6.3 NETTED-RIBBED SHELLS
The middle layer of a sandwich composite
structures is usually fabricated by an alterna-
tive technology. Winding technology can be
used not only to manufacture facing layers,
but also for middle layers by winding a net-
work of helical ribs. Netted-ribbed composite
shells (Fig. 21.16) are widely used in aerospace
because of low dead weight, a9 antenna
frames, solar batteries, etc.I4.
21.6.4 WINDING WITH BRAIDING
Winding with braidingi0 allows the manufac-
ture of articles of complex shape with
sophisticated reinforcement techniques. These
structures possess high resistance to bending,
torsion, tension, compression and to local
Fig. 21.16 Carbon-epoxy filament wound isogrid
space structure.
Applications 473
loads. The advantage of this technology has
been demonstrated in high resistance to
impact loads. The impact failure is localized
within several spatial cells of the structure.
21.6.5 THICK-WALLED STRUCTURES LOADED
IN TORSION
Progress has been made in the development
of thick-walled wound rods loaded in torsion.
A characteristic example is shafting for
shipd5. The advances in the mechanics and
technology of winding of thick-walled large-
scale elements have substantially solved this
problem. It is well known that fibrous com-
posites behave poorly when loaded in torsion.
Ways of increasing load-carrying capacity
involve increase in shear strength of a ply and
the adherence to the optimal law of shear
stress distribution over the radius of a rod.
Increase in the strength of a ply is accom-
plished by properly selecting the optimal
angle in the plane of fiber lay-up and the
number of starts and crossovers during wind-
ing. Shear strength in torsion zuLT= 400 MPa
has been attained and a shaft was fabricated
with wall thickness equal to the inner radiusi6.
Thick-walled wound structures can also be
manufactured by multidirectional braiding of
a system of one tow. The main difficulties of
this process are the complexity of preform
impregnation and necessity of compacting
over the external surface to increase fiber vol-
ume and to ensure monolithicity of the article.
This promising technology can also be used
for braiding over the external surface of unidi-
rectional thick-walled elements, to reduce the
danger of delamination due to low transverse
tensile strength. Another possibility to
increase the torsion strength of thick-walled
products is the spatial placement of straight
fibers along the surface contours of one-sheet
hyperboloids, whose centers are shifted along
the longitudinal shaft axis for a specified step.
The slope of straight contours of one-sheet
hyperboloid can be governed by the wind
angle of the applied fibers, which are originally
474 Filament winding
parallel to surfaces. The spatial arrangement
of reinforcement results not only in the
increase of transverse tension and interlami-
nar shear strength and in the localization of
fracture within several spatial
21.6.6 COMPOSITE FLYWHEELS
The ultimate storage energy W" of a rotating
body is proportional to tensile strength of the
material at"and body volume V , i.e. (W" =
k,oW) and is independent of the material den-
sity p. The ultimate angular speed of flywheel
depends on the material density and conse-
quently, composite flywheels are high-speed
structures. Mass energy storage capacity Wmu
is proportional to specific strength of material
Wum= WU/m = kma"/p
where m is flywheel mass and volume energy
storage capacity Wvuis
Fig. 21.17 A full-scale specimen of the hull of underwater vessel of reinforced plastic before test in a pres-
sure chamber19.
where V , is the overall flywheel dimension.
Advanced composites are the most promising
materials for inertial energy storing systems
because of high specific strength, high tensile
strength along reinforcing fibers and compara-
tively safe modes of failure. The possibility of
quick release of all stored energy is one of the
advantages of flywheels. The highest mass
energy storage capacity is achieved with rim
flywheels made by a circumferential winding
technique (km -+ %).This is true only for thin
rings. Increasing volume energy storage
capacity requires growth of the radial thick-
ness of the rim.
With increasing radial thickness the prob-
lem becomes bidirectional, i.e. not only
circumferential but also radial stresses must be
considered. The low transverse tension and
shear strengths of unidirectional composites
limit the ultimate rim thickness. This is why

previously developed methods of increasing
load-carrying capacity of thick-walled articles
appear to be extremely useful in the design
and fabrication of composite flywheels1s.The
high effectiveness of methods of increasing
transverse tensile strength of composites by
improving the matrix-fiber adhesion, i.e. by
plasma surface treatment of carbon fibers,
may be of greater value for thick wall fabrica-
tions. Use of chord winding is another way to
increase radial tensile strength and provides a
solution to solve the following problems: how
to connect the rim, shaft and hub of the fly-
wheel and how to increase shear strength and
stiffness.
21.6.7 DEEP SUBMERGENCE DEVICES
Deep submergence composite devices with the
depth of immersion up to 2000 m (manned)and
up to 6000 m (unmanned)l9 have been built. A
hull with 22m length, 8 m diameter and 250 t
total mass was entirely manufactured by wind-
ing on numerically controlled machines. The
full-scalehull (2.4 m diameter and 17t mass) for
an underwater vessel made up entirely of fiber-
glass plastic (metal fraction in the structure less
than O.lo/0) withstood an external pressure
350 MPa is shown in Fig. 21.17. Tests methods
for wound articles have been described in detail
in References 15 and 20.
REFERENCES
1. Peters, S.T., Foral, R.F. and Humphrey, W.D.
1987, Filament winding. In International
Encyclopedia of Composites, (ed. S.M. Lee) pp.
503-518. New York: VCH.
2. Structural Composites. A Handbook, 1994, (eds.
Yu.M. Tarnopol’skii and V.V. Vasiliev)
Lancaster: Technomic.
3. Peters, S.T. 1987, Filament winding. In
Engineered Materials Handbook, Vol.1, Composites,
pp. 503-509. Ohio: Metals Park.
4. Handbook of Composites, 1982, (ed. G. Lubin)
New York Van Nostrand Reinhold.
5. Peters, S.T., Humphrey, W.D. and Foral, R.F.
1991, Filament Winding Composite Structure
References 475
Fabrication, 2nd printing. Covina: SAMPE.
6. Tarnopol’skii, Yu.M. and Beil’, A.J. 1983,
Problems of the mechanics of composite wind-
ing. In Handbook of Composites, (eds. A. Kelly and
Yu.N. Rabotnov), Vol. 4, Fabrication of
Composites, (eds. A. Kelly and S.T. Mileiko) pp.
45-108. Amsterdam: North-Holland.
7. Concise Encyclopedia of Composite Materials, 1989,
(ed. Anthony Kelly) Oxford: Pergamon Press.
8. Rosato, D. and Grove, C.. 1964. Filament
Winding: Its Development, Manufacture,
Applications and Design. New York: John Wiley.
9. Tsai, S.W. 1994, Theory of Composites Design.
Dayton, Paris and Tokyo: Think Composites.
10. Textile Structural Composites. 1989, (eds. T.W.
Chou and F.K. KO) Composite Materials Series,
Vol. 3, (series ed. 8. Pipes) Amsterdam: Elsevier.
11. Tsyplakov, O.G. 1974 (Part l), 1975 (Part 2),
Scientific Fundamentals of Technology of Fibrous
Composite Materials. Perm: Perm Book Publisher.
12. Humphrey, W.D. and Peters, S.T. 1987, Filament
winding. In Engineered Materials Handbook, Vol.
2, Engineering Plastics, pp 368-377. Ohio: Metals
Park.
13. Obraztsov, I.F., Vasiliev, V.V. and Bunakov, V.A.
1977. Optimal Reinforcement for Composite Shells
of Reuolu tion, Moscow: Mashinostroyenie.
14. Bunakov, V.A. and Protasov, V.D. 1992, Netted
composite cylindrical shells. In Proc. 1st
USSR-USA Symp., Mechanics of Composites,
Vo1.2, Composite Structures, (ed. Yu.M.
Tarnopol’skii), pp. 89-98. Riga: Zinatne.
15. Wilhelmi, G., Appelman, W. and Loo, F. 1986,
Composite shafting for naval propulsion sys-
tem. Naval Engng., July, 129-136.
16. Tarnopol‘skii, Yu. M. and Zakrzhevskii, A.M.,
1994, Thick-walled composite rods loaded in
torsion. Mechanics Comp. Mater 30(4) 40-47.
17. Tarnopol’skii, Yu.M., Zhigun, I.G. and
Polyakov, V.A. 1992, Spatially Reinforced
Composites. Lancaster: Technomic.
18. Portnov. 1989. Composite flywheels. In
Handbook of Composites, (eds. A. Kelly and Yu.N.
Rabotnov), Vol. 2, Structures and Design, (eds.
C.T. Herakovich and Yu.M. Tarnopol’skii) pp.
531-582. Amsterdam: North-Holland.
19. Advanced Materials and Processes. 1993.
Scientific Technical and Advertising Article
Collection 1, 70-72. St. Petersburg: CRISM
Prometey.
20. Tarnopol’skii, Yu.M. and T. Ya., Kincis. 1985.
Static Test Methodsfor Composites. New York: Van
Nostrand Reinhold.
FIBER PLACEMENT 22
Don 0. Evans

22.1 INTRODUCTION When starting a course, the tows are

restarted and cogpacted onto a surface. As the
Fiber placement is a unique process combining
course is being laid down, the processing head
the differential tow payout capability of fila-
can cut or restart any of the individual tows.
ment winding and the compaction and
This permits the width of the band to be
cut-restart capabilities of automatic tape lay-
increased or decreased in increments equal to
ing. During the fiber placement process,
one tow width. Adjusting the band width
individual prepreg fibers, called tows, are
avoids excessive gaps or overlaps between
pulled off spools and fed through a fiber deliv-
adjacent courses. At the end of the course, the
ery system into a fiber placement head (Fig.
remaining tows are cut and the head is posi-
22.1). Here they are collimated into a single
tioned to the beginning of the next course.
fiber band and laminated onto a work surface
During the placement of a course each tow
which can be mounted between a headstock
is dispensed at its own speed, allowing each
and tailstock.

FiberPkementHead r

T i Restart Rollers

Collimated Fiber Band Y

ControlledHeat

Fig. 22.1 Fiber

placement head.

Handbook of Composites. Edited by S.T. Peters. Published

in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
 Introduction 477

tow to independently conform to the surface
of the part. For example, when the head lami-
nates a curved path, the outer tows of the fiber
band pull more length than the inner tows.
A rolling compaction device, combined
with heat for tack enhancement, laminates the
tows onto the lay-up surface. This action of
pressing the tows onto the work surface (or a
previously laid ply) adheres the tows to the
lay-up surface and removes trapped air, mini-
mizing the need for vacuum debulking.
Figure 22.2 is a diagram of a Cincinnati
Milacron 'Viper' Fiber Placement System
(FPS). This system has seven axes of motion
and is CNC controlled. The machine consists
of three position axes (carriage, tilt, crossfeed),
three orientation axes (yaw, pitch, roll) and an
axis to rotate the mandrel. All of these axes are
necessary to make sure the processing head is
normal to the surface while the machine is
laminating tows. The machine also has 24 pro-
grammable electronic bidirectional tensioners,
which are mounted in a creel. These tensioners
provide individual tow payout and maintain a
precise tension. The fiber placement head is
mounted on the end of the wrist. The head
precisely dispenses, cuts, clamps and restarts
individual prepreg tows.
To increase productivity some machines are
equipped with dual mandrel stations (Fig.
22.3). This setup allows two sets of lay-up
tools to be placed on the machine, ensuring a
constant supply of work for the head. During
routine manual operations such as hand lay-
ing small plies, inspecting plies, or vacuum
debulking on one part set, the head simply
shifts to the other mandrel and picks up the
program where it left off.

X-axis (arm crossfeed)

Y-axis (arm tilt)
Z-axis (carriage longitudinal movement)
&axis (pawmandrel rotation)
i-axis (head yaw)
$-axis (head pitch)
-axis (head roll)
-axis (redirect roller angular position)
-axis (tow restart linear position) Fig. 22.2 Fiber placement
system.
478 Fiber placement
Fig. 22.3 Fiber placement machine dual station.
22.2 MATERIALS
A fiber placement machine can dispense
prepregged fibers that are commonly used by
the aerospace industry such as carbon, KevlaP
and glass. These fibers need to be impregnated
with a resin and formed into tows or slit tape.
The width of tow or slit tape used by fiber
placement range from 3.2 mm (0.125 in) to
6.4mm (0.250 in) After the tows are impreg-
nated with a resin matrix they are flattened to
a desired width and wound onto a 7.6 cm (3
in) diameter by 28 cm (11 in) long core in a
helical pattern. A typical length for a 2.3 kg (5
lb) spool of prepregged IM7-12K tow, 3.2 mm
(0.125 in) wide, is 3350 m (11 000 ft).
Slit tape is fabricated by running a 7.6 cm
(3 in) wide tape through a slitter creating
smaller widths of slit tape. These slit tapes are
then wound onto a number of 7.6 cm (3 in)
diameter by 28 cm (11 in) long cores. When the
slit tape is wound onto the spool a backing
film which is wider than the slit tape must be
added. If the backing film is not used, the slit
tape cannot be removed from the spool
because of stringers, which will occur during
the despooling operation. The edge of the slit
tape separates and stays on the spool while the
rest of the tape is despooled. This will cause
the tape to eventually break. During part fab-
rication this backing film is removed before
the fiber reaches the fiber placement head.
When selecting a tow that is to be used by a
fiber placement machine, it is important to
consider the cross sectional area of the fiber.
This cross sectional area will be a major factor
in determining the ply thickness of the lami-
nate. This is because the width of the tow is
fixed and the thickness of the tow varies
depending on the cross sectional area of the
fiber and the resin content.
The following equations can be used to
determine the thickness of a given tow. Since
resin content is usually given as a percent of
resin by weight, it is first necessary to calculate
the resin volume fraction, which is the percent
of resin by volume.
where rvf = resin volume fraction, rwf = per-
cent of resin by weight fraction, rd = resin
density (g/mm3), r f = fiber density (g/mm3).
Using the resin volume fraction the thick-
ness of fiber can be calculated using the
following equation:
(22.2)
where fh = tow thickness (mm),fa = fiber cross
sectional area (mm2),fw= tow width (mm),rvf
= resin volume fraction.
For example the thickness of a Hercules
IM7 fiber impregnated with a Hercules 8551-7
resin containing a 32% resin content by weight
and flattened to 3.2 mm (0.125 in) would be
0.14 mm (0.0055 in).
To increase or decrease the thickness of the
tow, the cross section of the fiber must be
changed by adding or subtracting 6K or 12K
fiber bundles. With slit tape this is not a prob-
lem because the thickness of the tape is
determined when it is prepregged and before
it is slit to width.
 Tooling considerations 479

The tow width of the material is very guided through a fiber delivery system and
important in controlling the gap between the head, but high tack is needed when it is being
prepregged tows. For example if the fiber compacted onto the surface.
placement head is designed to lay down tows Materials that have a low tack can be
that are 3.24.38 cm (0.125+0.015in) wide, the despooled with a fiber tension of 0.45 kg (1lb)
tows will be compacted onto the surface in or less. These low tensions are achieved
3.2 mm (0.125in) spacings. If the tow is exactly because the resin does not stick to the spool or
3.2 mm (0.125in) wide, there will be no gap the components of the fiber delivery system.
between the tows. If the tows are 2.5mm This lower fiber tension is needed while fiber
(0.100in) wide, there will be a 0.63 mm placing concave areas. A higher tension will
(0.025in) wide gap between the tows. If the cause the fiber to bridge over concave areas.
tows are 3.8 mm (0.150 in) wide, there will be Materials with low tack levels also have less
a 0.63 mm (0.025in) overlap. tendency to deform or rope while being pulled
Figure 22.4 shows a typical width his- through the fiber delivery system. They also
togram of a spool of tow material. To develop transfer less resin to the components of the
this histogram a spool of tow was run through fiber delivery system and head. This reduces
a measuring device, which measured the the number of times that these components
width at 1100 locations. The average width is need to be cleaned because of resin build up.
3.20 mm (0.126 in) and the standard deviation Resin build up in the head causes it to mal-
is 0.13 mm (0.005 in). A typical width his- function.
togram of a slit tape will show an average The tack of most resins can be reduced by
width of 3.18 mm (0.125 in) and a standard lowering their temperature. To accomplish
deviation of 0.08 mm (0.003 in). Maintaining this, most fiber placement machines are
the quality of tow and slit tape will greatly equipped with an air conditioned creel. The
improve the quality of the composite laminate fiber placement head also has some means of
and the reliability of the process. cooling the components that come in contact
The ideal fiber placement material has no with the tow material. To achieve the desired
tack at 21°C (70°F) and high tack from 27°C to tack required to adhere the tow material to the
32°C (80°F to 90°F). Low tack is needed when surface, the area where the material is com-
the material is being pulled off the spool and pacted onto the surface is heated. This is
accomplished by blowing hot air at the nip
point of the compaction roller (Fig. 22.1).

73 20 mm
0.13 mm

: 3.56mm
2.74 mm

I # of Samples. 1100
22.3 TOOLING CONSIDERATIONS
The tooling for fiber placement provides the
shape of the part being fabricated and a suit-
able surface for the machine to lay tows onto.
It also has features that can be used to associ-
ate the electronic data’s coordinate system,
which describes the laying surface, to the
machine’s coordinate system. The electronic
data must accurately represent the finished
2.03 2.54 4.06
tool. The smaller the surface of curvature is,
TowWdth (mm)
the more important it is that the electronic data
accurately represent the finished tool. If the
Fig. 22.4 Tow width histogram. electronic data does not accurately represent
480 Fiber placement

the lay-down surface the tows will be placed

in the wrong location and there is a chance
that the machine could collide with the tool or
part. It is also important that the electronic
data is in a format that can be used by the
offline programming system. If data is in the
wrong format, the length of time it takes to
program the part is increased and sometimes
there is a loss of surface accuracy. If no elec-
tronic data exist then the tool needs to be
accurately measured and this information
needs to be converted into electronic data that
can be used by an offline programming sys-
tem.
Tooling for fiber placement needs to meet
criteria that are not necessarily required for
other processes. The tool surface must have
sufficient strength so that it does not deflect as
the head compacts tows onto it. When the tool Fig. 22.5 Tooling features.
surface deflects, the tows will not be placed in
the correct position and they will buckle after
the tool springs back into position. Tows that having to rotate the mandrel and they must
are buckled will no longer carry the desired also be described in the electronic data coor-
design loads. Another consideration is that the dinate system used by the part programmer.
tool surface needs to extend 152 mm (6 in) past The probed coordinates are used by the offline
the largest part boundary. This extended area software to create a transformation matrix
is used by the head to roll off and onto the part that will convert the part’s electronic data
as it is starting and ending a course. This coordinate system to the position of the tool in
extended area also needs to be part of the elec- the machine’s coordinate system.
tronic data, because the offline software also If the tool has to be removed from the
uses this area as it is generating the courses machine and then replaced in after each part,
when deciding where the ply boundaries are. it is important that the tool is designed with
This extended area is also used as a place to features that allow it to be located in the same
apply the bagging sealant tape for vacuum position each time it is put back in the
debulking (Fig. 22.5). machine. This will eliminate repeating a time
The tool must also be designed with fea- consuming alignment procedure. If the tool is
tures that can be used to associate the part’s mounted between a headstock and tailstock it
electronic data coordinate system to the is desirable to attach the ends of the tooling
machine’s coordinate system. This can be shafts to the headstock and tailstock with non-
accomplished by perpetually molding or locking tapered adapters. This makes it easier
machining three cross hairs onto the tool sur- to load the tool and when the tapers are tight-
face, in the area of the 152 mm (6 in) ened they are self locating. The tapered
extensions. To provide accurate results, the adapters also need to incorporate a keyway on
cross hairs need to be placed as far apart as the headstock end so the tool can be located in
possible. These three cross hairs are probed by the radial direction. A tool mounted to a flat
the machine to detect the location of the tool plate should be located by a three-point locat-
in the machine’s coordinate system, without ing system incorporating pins or keys.

22.4 PLY SHAPE
Fiber placement is used to fabricate simple
parts such as flat panels or complicated parts
such as an inlet duct, which is square on one
end and round on the other (Fig. 22.6).The ply
shapes can be any size or geometric form. A
ply shape can also include interior ply bound-
aries which create holes.
When generating ply shapes, the designer
must consider the shortest tow length the
machine can lay down. This length is the dis-
tance from the start of the lay-down point to
where the tow is cut in the head. Figure 22.7
shows exterior and interior ply shapes of an
I I I
Fig. 22.6 Fiber placing an inlet duct.
aircraft structure. The black areas are the areas
that cannot be fiber placed because the length
of the required tow is less than the shortest
allowable fiber length. These areas could be
laid in by hand, or the ply shape could be
adjusted, as in Fig. 22.7, so that the required
fiber length
" is longer" that the shortest cut
Ply shape 481
length. The exterior ply boundaries can the
extended in the areas where there are mini-
mum cut length problems. These extended
areas can later be cut off. Interior plies must be
reshaped to match the fiber angles.
The designer must also consider the end
locations of the tow. Each tow is cut at a 90"
angle; because of this the ending angle of the
tows may not match the angle of the ply
boundary. Figure 22.8 shows three different
ply boundary conditions for a 45" ply. The
Outer Pb bunday 45'
Inner Ply bunday -5.
Boundaries With Missing Tows
Adjusted Boundaries With No MissingTows
Fig. 22.7 Ply boundary adjustments.
amount the tows can cover the ply bound-
aries is specified by the percent of ply
boundary coverage. A 100% value is typically
used on the larger ply boundaries that are
later trimmed to shape. This makes sure that
all of the fibers go to the edge of the bound-
arv. A 50% value is used on interior plv I d
482 Fiber placement
PLY BOUNDARIES
0% 50% 100%
Fig. 22.8 Ply boundary conditions.
boundaries. The 50% value allows some of
the fibers to go past the ply boundaries; but it
makes sure that the correct volume of mater-
ial has been placed in the ply. The percent of
ply boundary coverage is specified in the
offline programming software.
22.5 STEERING
The ability to steer the fiber band allows the
designer to maintain a constant fiber angle on
a complex surface, or align the fibers with
some applied stress. Steering is made possible
because of differential payout and because the
impregnated tow has enough tack to over-
come any sliding forces. Differential pay out
of the individual tows is one of fiber place-
ment's key features. This feature is required to
allow each tow within the fiber band to main-
tain a unique length as the laminating action
of the head pulls the tows off the spools and
compacts them onto the part surface. When
the head is required to laminate a curved
path, the outer tows of the band will pull
more length than the inner tows. Similarly, as
the head laminates over a contour, some tows
must dispense more length than others. This
allows the fiber placement machine to steer
the fiber band.
Steering can be defined as the binormal
radius of curvature along a fiber path. An
example (Fig. 22.9) shows O", 45" and 90"
courses laid on a cone shaped mandrel. On
the right side of the figure, the same courses
are shown on the unwrapped mandrel sur-
face. On the unwrapped mandrel surface it is
easier to see which courses are being steered.
The 0" course is straight showing that no
steering is necessary. On the 45" course the
amount of steering changes as the course is
laid from the larger end to the smaller end of
the cone. The steering radius on the larger end
is 58.4cm (23.0in). It decreases to 20.3 cm
(8.0 in) on the smaller end. On the 90" course
the center line steering radius of the 2.54 cm
(1.0 in) wide course is 28.7 cm (11.3 in). The
90" course also illustrates the need for differ-
ential payout. The fibers on the inside steering
radius are 32.14 cm (12.653 in) long. The fibers
on the outside steering radius are 35.11 cm
(13.821 in) long. This is a 2.97 cm (1.168 in)
difference in length.
Tape is typically laid along it's 'natural
path', but can be steered by small amounts. A
tape laying machine can steer a 7.6 cm (3 in)
wide tape along a 20.3 m (800 in) radius with
small amounts of buckling. The buckling
occurs because the fibers on the outside steer-
ing radius are in tension and the fibers on the
inside steering radius are in compression. A
typical fiber placement machine using
3.2 mm (0.125 in) wide materials can steer a
fiber band along a 63.5cm (25in) radius
without buckling the individual tows. When
steering a radius smaller than 63.5 cm (25 in),
the tows will begin to buckle if laid on a flat
or a convex surface or 'Venetian blind' if laid
on a concave surface. 'Venetian blinding'
occurs when the fibers on the inside steering
radius of the individual tows are adhered to
the surface and the outside steering radius
fibers are in the air.
 Dropping and adding tows 483

' 0 DEGREE COURSE

ON MANDREL
0 DEGREE COURSE
FLAT LAYOUT

p., /STEERING: 58.4 R

A5 DEGREE COURSE
ON MANDREL 45 DEGREE COURSE
FLAT LAYOUT

STEERING: 30.0 R
LENGTH: 35.11 cm

STEERING: 27.4 R
LENGTH: 32.14 cm

ON MANDREL 90 DEGREE COURSE

FLAT LAYOUT

Fig. 22.9 Steering.

the compactor lays the ends onto the surface

22.6 DROPPING AND ADDING TOWS
To start a course, the delivery head is posi-
tioned to the start point and the tows are fed
out under the compactor. While following the
fiber path, the delivery head can change the
fiber band width by adding or dropping indi-
vidual tows. This feature allows all or any
combination of tows to be removed or added
to the band width in increments equal to one
tow width. With this capability, it is possible
to decrease the band width to prevent adja-
cent courses from overlapping each other. A
course is ended by cutting all of the tows as
of the mandrel.
Each tow is cut at a 90" angle. When adja-
cent courses are placed next to each other, this
can leave a triangular gap or overlap (Fig.
22.10). The designer can use the off-line soft-
ware to specify the percent of overlap between
courses. A zero percent specification will leave
a triangular gap between courses. In this case
the outside tow of the course being laid is
dropped when it touches the adjacent course.
On the other extreme, a 100% overlap will
leave a triangular overlap and no gaps. The
100% overlap specification can leave a part
484 Fiber placement

TRIANGULAR GAP
\

/'
,' 0% OVERLAP
/'

a
,'

'.
'. '.
u
50% OVERLAP

TRIANGULAR OVERLAP-/'\ /
u
100% OVERLAP

Fig. 22.10 Overlap between courses.

'bumpy' because of the overlaps. The 50% which is to be manufactured by fiber place-
specification is most commonly used because ment. The first is concave surfaces and the
the smaller gaps and overlaps tend to average second is areas with small radii of curvature.
out each other as the laminate is built up. The When consideringa part with a concave sur-
other technique that helps average these trian- face area, the designer must make sure the
gular gaps and overlaps is to offset each ply byfiber placement head can fit into the concave
one and a half tow widths. This ensures that area without hitting the surface of the part.
the small triangular gaps and overlaps do not There are some techniques that can be used to
align on top of each other. overcome some of these limitations. To help the
head fit into a concave area the offline software
has a feature known as collision avoidance.
22.7 SURFACE GEOMETRY
The software knows the part and head geome-
Fiber placement can automate the fabrication try. It constantly checks to see if the two are
of many composite part geometries that in the colliding. If they collide, the software will rock
past could only be laminated using hand lay- the head off the surface normal away from the
up. The types of surface geometries that can be collision. Figure 22.12 shows a part with a
fiber placed range from fan blades to full 360" small concave area being fiber placed. As the
asymmetrical shells (Fig. 22.11). There are two head stays normal to the surface and
surface features that the designer needs to pay approaches the concave area, it will collide into
special attention to when designing a part the part, as shown in the upper exploded view.
 Surface geomety 485

Fig. 22.11 Fiber placing a fan blade.

SURFACE NORMAL
2 COLLISION POINT

NO COLLISION AVOIDANCE

SURFACE NORMAL 7

C"
1
'-,a I-
I O " COLLISION AVOIDANCE

Fig. 22.12 Collision avoidance.

486 Fiber placement
To correct this problem, the software rocks
back the head 10" off normal, as shown in the
lower exploded view.
There are limits to how much the head can
be rocked off the surface normal. If the head
hits on both front and the back sides, the soft-
ware cannot avoid the collision and the area
should be redesigned. Rocking the head to the
front and back slightly affects the effective
applied compaction force and the minimum
cut length. Rocking the head sideways also
affects the effective applied compaction force
and requires extra compactor compliance.
Examples of small radii of curvature are
shown in Fig. 22.13. On the convex surface
the compactor cannot completely come in
TOOL SURFACE
SMALL CONVEX RADIUS
Fig. 22.13 Small radii of curvature.
contact with the surface. The part can still be
fiber placed but the number of tows in the
fiber band should be reduced to match the
compaction line width. On the concave sur-
face the radius should be increased to allow
the compactor to contact the surface, other-
wise the tows will bridge over the small
radius of curvature.
22.8 INSPECTION
Fiber placement is a very repeatable process
and requires only a small amount of in-process
inspection, but it is important to perform a rig-
orous first article inspection. This inspection is
used to verify that the part program fabricates
a part that meets all of the design require-
ments. This detailed first article inspection
should not need to be repeated unless the part
program has been changed.
The first article inspection should start with
a dry run of each ply. Dry running a program
means to run the machine through the pro-
gram without laying down tows. Dry running
of a program verifies that the electronic data
7
SMALL CONCAVE RADIUS
describing the tool surface matches the actual
tool surface. It also verifies that the transfor-
mation matrix, used to associate the part's
electronic data coordinate system to the tool's
position in the machine's coordinate system, is
correct. This is accomplished by watching the
compactor as it follows the part surfaces. Dry
running also verifies that collision avoidance
worked properly.
 Further reading 487

Table 22.1 Inspection criteria

Discrepancy Criteria Correction procediire

A gap that is greater than Add a tow to fill the gap.

2.54 mm (0.1 in) wide and
is longer than 76.2 mm (3.0 in).
Wandering tow at start A wandering tow that leaves a Pick up the tow and reposition.
and end of course gap greater than 2.54 mm (0.1 in)
wide and is longer than 50.8 mm
(2.0 in). If the tow is captured under
another tow, do not repair the
captured tow.
Twisted or folded tow A twisted or folded tow that is longer Remove twisted or folded tow and
than 76.2 mm (3.0 in). replace.
Wrinkles at start of course A wrinkled tow that is wrinkled more Pick up the wrinkled end of the tow
than 19.05 mm (0.75 in). and straighten it out.
Bridging of tows Bridging is more than 1.57 mm Use a heat gun and hand pressure
(0.062 in) high. to remove bridging or vacuum bag
the part for a maximum of 15 min at
full vacuum.

The next step in first article inspection is to
load the machine with tows and fiber place
each ply. After each ply is fiber placed, the ply
is inspected for the correct fiber angle, ply loca-
tion, band-to-band overlap and for missing
tows. The easiest way to inspect for fiber angle
and ply location is to have a Mylar template
that has the ply boundary plotted onto it and a
line for the fiber angle. The template needs to
be located with alignment marks or pins that
are part of the tool. A Mylar template will not
work on surface geometries with curvatures in
both directions. For these geometries, a formed
inspection tool should be fabricated.
After the first article inspection, subsequent
parts need to have each ply visually inspected
for excessive gaps and overlaps, lost tows,
twisted tows, wrinkled tows and bridging
tows. Table 22.1 is an example of a typical in-
process inspection criteria. Another criterion
used to evaluate gaps is to take a 30.5 cm (12in)
scale and lay it on the ply normal to the fiber
direction.All the gaps along the 30.5 cm (12 in)
distance are measured and summed. If this
value exceeds a pre-determined design crite-
rion the area is reworked.
FURTHER READING
Barth, James R. 1990. Fabrication of Complex
Composite Structures Using Advance Fiber
Placement Technology. 35th Intern. SAMPE
Symp., 2-5 April 1990.
Enders, Mark L. and Hopkins, Paul C. 1991.
Developments in the Fiber Placement Process.
36th Intern. S A M P E Symp., April 1991.
Enders, Mark L. 1991. The Fiber Placement Process.
Intern. Conf: Comp. Mater., (ICCM/8), July 1991.
Evans, Don O., Vaniglia, Milo M. and Hopkins, Paul
C. 1989. Fiber Placement Process Study. 34th
Intern. S A M P E Symp., 8-11 May 1989.
Evans, Don 0. 1993. Design Considerations for
Fiber Placement. 38th Intevn. S A M P E Syrnp.,
10-13 May 1993.
PULTRUSION 23
Brian A. Wilson

23.1 INTRODUCTION ment and manufactured the equipment to pro-

duce structural elements by the method. A
The word pultrusion is used to describe a com-
typical pultrusion machine is shown in Fig.
mercial fabrication process for the production
23.1. The process has a relationship to extru-
of fiber reinforced composite elements. First
sion, which is used primarily with metals and
mention of the process is recorded in a patent
describes the process of forming a shape using
in 1951 with much of the early work in the
a closed die and pushing normally hot metallic
1950s attributed to W. Brandt Goldsworthyl.
materials through the die. Pultrusion differs in
He performed much of the process develop-

Handbook of Composites. Edited by S.T. Peters. Published Fig. 23-1Typical Pulkusion machine. (Courtesy of
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 W. Brant Goldsworthy and Associates Inc.)

that it takes advantage of the strength of the
longitudinal fibers in the section to pull the
extruded shape through the forming die and
the heated curing die to create a constant cross
section structural element from a composite
materials system. Hence the name pultrusion.
Use of this-processhas now expanded both in
the USA and around the world with many
manufacturers equipped to produce the simple
structural elements which are the main pultru-
sion products. The process was labeled for the
first 30 years or so of its existence as a com-
mercial production method. This was owing to
the nature of the method, using longitudinal
fibers and a simple thermoset resin system to
produce a structural shape which had its pri-
mary strength in the longitudinal direction and
properties in the transverse and third axis
relating only to those of the resin system. The
ability to incorporate three-dimensional
strength first occurred in the mid 1960s when it
became possible to include layers of mat/fab-
ric and circumferentially wound layers of fiber
both w i t h the body and on the surface of the
structural shapes. Multi-directional reinforce-
ment was used extensively starting in the
1970s2,3 . These developments, plus the intro-
duction of thermoplastic resin matrices, have
brought the pultrusion process into the manu-
facturing arena of the aerospace, defense and
aircraft businesses as a relatively inexpensive
and repeatable method of producing a constant
cross-section structural element48 *.
In this chapter, the basic process, variations
on the process, pultrusion equipment, materi-
als including fiber, fabric, resin matrices,
additives, tooling, curing, structural connec-
tion methods, equipment manufacturers,
pultrusion fabricators and potential markets
and applications will be reviewed"".
23.2 THE BASIC PROCESS
The basic pultrusion process as originally con-
ceived consisted of creating a cured composite
shape by pulling a bundle of resin impregnated
fibers through a heated die, providing sufficient
The basic process 489
curing energy in the heated die to cure the com-
posite into a hard structural product and using
the resulting shape as a unidirectional strength
element for commercial structures.
The primary advantages of pultrusion are
as follows:
~roductioniscontinuous~
0 labor requirements are low;
0 material scrap rate is low;
0 the requirement for support materials is
eliminated, i.e. breathers, bleeder cloth, sep-
arator film, bagging film, edge tape.
23.2.1 VARIATIONS IN PROCESSING
The original process of pulling a bundle of
unidirectional fibers through a curing die
remained without variation until the middle
of the 1960s. At this point, pultruders, both in
Europe and the USA, developed the process of
adding fabric in strip or sheet form and fiber
mat to the pultrusion system in order to pro-
vide transverse strength and shear strength in
the corner sections of complex pultruded
shapes. In addition, the concept was devel-
oped for a filament winding head to be added
to the pultrusion machine to provide a hoop
wrap around a pultruded form. This process is
known as 'pull winding' and is primarily used
with tubular or rod shapes. It is not feasible to
add the filament winding process to a struc-
tural shape that has a concave curvature, such
as angles, channels and I-beams. A typical
process of pull winding is shown schemati-
cally in Fig. 23.212.
During the 1970s, the concept of pull form-
ing was developed by Brandt Goldsworthy.
Three versions of this forming process were
developed.
The first was actually named 'curved pultru-
sion' by Goldsworthy Engineering. The method
was developed under a NASA contract and
resulted in a pure, constant radius section with
a constant cross section. A curved die was used,
with a reduced radius, smaller than the
required part radius. This allows for a degree of
490 Pultvusion

COUNTER-ROTATING

MANDREL
AND

LAYER 1. LAYER 2. LAYER 3. LAYER 4. LAYE&S. FIBERS

FIBERS WOUND FIBERS FIBERS WOUND FIBERS

Fig. 23.2 5-Layer tube on double head pull winder. (Courtesyof Pultrex Ltd.)

spring back after the product is removed from response to a specific production require-
the diel3. The die was split along its length, in rnentl4,l5.The pull forming process still uses
the vertical plane. One half of the curved unit the basic principles of pultrusion since it has a
was fixed in place. The internal radius portion continuous strand of fiberglass roving within
of the die was further split in half vertically, the product and this roving is used to pull the
along the central radius plane, forming two product through the sequence of the forming
quadrants. Each of the quadrants had a slightly process. Goldsworthy Associates have
longer circumferential length than the fixed designed two versions of this process, a
half. The two moving quadrants moved past curved pull forming and a straight pull form-
the fixed part of the die at the processing speed ing. These two versions of the process are
of the pultrusion. When each moving quadrant briefly described in the following paragraphs
had exited the plane of the fixed die, it moved but it should be noted that a major difference
rapidly in a circular fashion to contact the end between pull forming and pultrusion is that
of the following quadrant as it too passed pultrusion is a generic process which can be
across the face of the fixed die. used to make many different cross-sectional
shapes and products by changing the die in
23.3 PULL FORMING
the machine (which creates the cross-sectional
shape) and the materials of fabrication. Pull
The pull forming process is a highly sophisti- forming however, is essentially a custom
cated variation of the pultrusion process in process which must be tailored to a particular
which both curved and straight product sec- product design.
tions are fabricated with the ability to change
cross-sectional dimensions of the product. It
can be thought of as a combination of pultru- 23.3.1 CURVED PULL FORMING
sion and compression molding. The pull In the curved version of the pull forming
forming process was developed by process, a curved structure is manufactured
Goldsworthy Associates and was created in using a selected combination of roving and

mat/fabric to satisfy the performance require-
ments of the produ~t'~J~. The die is a multi-
cavity die. Several of these dies are mounted on
the face of a wheel and are curved with the
radius of curvature of the die matching the
radius of its position on the wheel. The die is
open faced and is also open on the two ends for
entry of the fiber preform. The preform is
impregnated with resin in the same manner as
for pultrusion and the fiber and mat/fabric
combination is pulled into the curved mold or
die by the rotation of the wheel. As the preform
is pulled into the die, a stainless steel band
moves against the open face of the die and com-
presses the impregnated preform into the
contour which is in essence a compression
molding cavity. After the die is closed, it is
heated to cure the resin and following cure, the
stainless steel band peels away from the face of
the die/mold. A fixed pin which is mounted
adjacent to the wheel strips the product out of
the mold and into a storage bin. When the stain-
less steel band is moved against the mold it is
held in place by an automated clamping system
until the product is fully cured at which point
the clamping system releases the band which
then retracts into a 'parking' position. The
Fig. 23.3 Curved pull forming process. (Courtesy of W. Brandt Goldsworthy and Associates Inc.)
Pull forming 491
machine is shown in Fig. 23.3.
It should be noted that the process does dif-
fer from pultrusion in that the fiber preform is
placed into the mold rather than being pulled
through it. Also, while the cross section of the
mold can change, the resulting part is a con-
stant volume design, equivalent to the volume
of the preform which is initially compressed
into the mold.
23.3.2 STRAIGHT PULL FORMING
Straight pull forming was also invented by
Goldsworthy Associates in response to a spe-
cific customer requirement for the automated
manufacture of hammer handles. In this
process, the fiber is pulled as a preform through
the automated machine. Many single cavity
dies are mounted on a belt. As the fiberglass
roving moves through the system, a section
of bulk molding compound (BMC) is cut
from a rope of this material, is opened up
longitudinally and placed around the roving
and clamped onto it. The BMC is then com-
pressed in a small briquetting press which
travels with the fiber preform as it moves
through the system. Following the compression
492 Pultrusion

molding of the BMC, the press releases and the process variation has not been successful to
balance of the fiberglass roving is fed in and date and further development will be required.
encapsulates the BMC material. Following the
encapsulation, a shrink film is placed around
23.4 PROCESS EQUIPMENT
the wet package and the process goes through a
heated tunnel which shrinks the film around The pultrusion fabrication machine consists of
the product. Finally, the product is run through six different parts (Fig. 23.4): the creel; the
the frame of a C-shaped die in a press which resin bath; the forming die; the heated curing
provides the final compression molding and die; the pullers; the cut-off saw.
curing of the hammer handle. The product is
pulled from the die and cut off and the dies con-
23.4.1 CREEL
tinuously exit the belt and are recycled back to
the front end of the process. The creel is the beginning of the pultrusion
This type of pull forming is a highly auto- process and is the material storage system from
mated, sophisticated process which requires which the fibers and mat, veil or fabric are
considerable capital investment for the design, drawn in the correct sequence to match the
manufacture and set up. Each potential prod- design requirements of the structural shape.
uct, which would be a candidate for the pull Since pultrusion is a long run continuous
forming process, must have its design analyzed process, fiber rovings are provided in the max-
and the process modified to respond to the cus- imum size configuration possible. Continuous
tom requirements of the particular product. glass rovings are normally provided in 'center
With the increasing popularity and explo- pull' packages between 14 and 23 kg (30 and 50
ration of the resin transfer molding process in lb) in size. These center pull packages are typi-
recent years, the pultrusion process has been cally stored on a bookshelf style creel. These
reviewed for the potential of developing a creels have from three to six shelves and are
repeatable, precise cross-section of a preform capable of storing anywhere from 45 to 120
using a loose fiber bundle and an adhesive packages of this type of fiberglass. These creels
binder in place of the resin system. This are normally mounted on casters to create a

Mat
Roving racks
racks A Material

Pulling
mechanism Cutoff saw

V Resin tank Finished

Preforming product
guides

Fig. 23.4 Schematic of pultrusion process. (Courtesy of W. Brandt Goldsworthy and Associates Inc.)

mobile system. The casters are provided with a
foot locking device to enable them to be locked
in place when this is required. The glass roving
is pulled vertically from the package through
ceramic-lined holes in the shelves above. The
roving is collected above the creel and turned
90" by means of a ceramic textile type thread
guide and then moved forward to the material
accumulating section just prior to the resin
bath and forming die. A series of ceramic
guides or rollers can be provided in the fiber
path in order to tailor the tension in the fibers
to the required level. The pulling of fiber from
the center of the package will automatically
insert a twist in the fiber as it is led into the pul-
trusion machine. To eliminate this, some
fiberglass rovings are provided in a center pull
twistless condition where the natural twist has
been off-set by a 'built-in' reverse twist.
Continuous fibers of fiberglass, carbon,
aramid and polyethylene are normally sup-
Fig. 23.5 Carbon fibre spool on package holder with quick braking action. (Courtesy of Texkimp Ltd.)
Process equipment 493
plied on 'way wound' packages on standard
diameter cardboard cores. A typical carbon
fiber package mounted in a payoff creel is
shown in Fig. 23.5. These fiber packages are
designed to provide fiber payoff from the exte-
rior of the fiber package and hence avoid
twist. While fiberglass is normally supplied in
the heavy center pull spools, it can also be
obtained in the outside payoff type package.
All of the cardboard cores are a standard three
inch diameter with the exception of the aramid
which is 90 mm (3.5 in) inside diameter.
This style of package requires the use of a
multiple spindle creel design in which the
packages are oriented normally horizontal but
usually with a slight upward camber. Creels
are available with package positions up to
1500 or 2000 on a single creel or combination
of creel frames. A loaded multiple spindle
creel is shown in Fig. 23.6. Ceramic guides are
used to move the fibers to the front of the creel
494 Pulfrusion

(12-24 in) on cores of 75-100 mm (3-4 in) in

inside diameter. This special mat/fabric creel
must be able to accommodate rolls of these
dimensions and resulting weight and permit
the rolls of material to be installed in a varying
sequence of locations to match the design of the
final structure. This type of material creel will
normally provide horizontal feed. However, if
vertical mat or fabric is required, then an inde-
pendent custom unit must be provided. These
units are usually of a carousel-type configura-
tion. Figure 23.7 shows a typical mounting for
feeding veil rolls into the system.

Fig. 23.6 Loaded multiple spindle creel. (Courtesy

of Texkimp Ltd.)

and into the pultrusion system. Tension

requirements in this type of system are usually
provided by spring attached tension straps
which rub on a pulley attached to the package
holder. This provides a braking action. The
straps can be either independently loaded
with weight or can be connected to a central I
mechanical system, such that tension for all of
the spools can be varied by a single adjust- Fig. 23.7 Feeding external veil material into pultru-
ment handle. Fiber packages for this type of sion system. (Courtesyof Creative Pultrusions Inc.)
system are normally 5 kg (11 lb). With this
small size of package, it is normal for a large Clearly, the overall creel system for materials
number of packages to be located on this type supply must be able to provide any combina-
of creel assembly. In addition, package simula- tion or arrangement. It should be noted that in
tion bars are normally provided with these every fiber and fabric system used for pultru-
types of creels to give a uniform tension and to sion, there should be sufficient continuous
eliminate the possibility of a fiber from a small roving in the system to sustain the required
or 'almost used' package touching and abrad- pulling force. As the various materials travel
ing a near-by forward mounted, full package. forward towards the resin application area it is
Stationed immediately after the fiber creel is important to control the alignment of the vari-
the specialized type of creel which is designed ous fibers and fabric/mat strips which are
to accommodate rolls of mat, veil or fabric. going into the configuration. This will prevent
These materials are usually supplied in roll knotting and twisting of the fiber reinforce-
form with diameters between 305-610 mm ment and also will ensure that the various fiber

materials remain in the correct relationship to
each other and are placed in the correct zone of
the pultruded product according to the prod-
uct design requirements. This can be best
accomplished by the use of orifice plates, creel
cards combs and rollers (grooved and flat) to
precisely and accurately place all the materials.
The materials commonly used for these guides
and rollers are primarily titanium oxide
ceramic, stainless steel, tool steel alloys and
chrome plated steel. These materials are also
used for the various rollers associated not only
with guiding the sheet materials but also with
controlling them during their passage through
the resin impregnation zone.
23.4.2 RESIN IMPREGNATION
Virtually all pultrusion processes utilize a
resin impregnation bath to facilitate the
impregnation of the resin into the fiber struc-
ture. The position of the resin impregnation
bath in the production line can be varied and
the manner in which the resin is applied to the
fiber can have many different versions. A resin
dip bath is most commonly used. During this
process the fibers are passed over and under a
series of rollers or bars which both spread the
fiber to more easily accept the resin and also
provide a massaging effect which 'kneads' the
resin into the fiber bundles and structure.
The wetting speed of the fibers depends
upon their pretreatment and on the resin for-
mulation. Wetting is also affected by the type
of sizing agent on the fiber, the possible pres-
ence of remaining lubricant on woven fabric
and finally the type of binder which is used in
mat and veil products. The resin bath is uni-
formly used for products that utilize all roving
in their construction or for products that are
easily formed from the flat fiber ply which
emerges from the resin bath. However, in
many of the more sophisticated products
which are now made from pultrusion, it is
impractical to dip all of the materials in the
resin bath. When vertical mats are required or
hollow profiles are produced, a tailored resin
Process equipment 495
bath is frequently used which matches the pre-
form shape or orientation of materials which
pass through it. These types of tailored chan-
nels or baths can also be used to orient the flat
materials properly. This method permits the
resin impregnation to take place without mov-
ing the reinforcements away from their
optimum path or shape.
23.4.3 VERTICAL PULTRUSION
The vertical pultrusion process should be men-
tioned at this point since the primary difficulty
in creating a vertical pultrusion is the place-
ment and use of a resin bath. In the
arrangement for vertical pultrusion the equip-
ment used is essentially similar to that for the
horizontal methodI8.Most equipment operates
in the vertical position with the exception of the
resin bath and roving creels which are generally
positioned horizontally and the roving is fed in
the regular manner, horizontally through the
resin impregnation bath. This bath is located
above the entrance to the forming die and the
fibers exiting from the bath are turned 90"
across a roller and then proceed vertically into
the forming die. The advantage of using this
vertical procedure is that a uniform arrange-
ment of impregnated fibers can be achieved
across the section being formed. The effects of
gravity are removed from the fiber arrange-
ment. During the horizontal process, gravity
plus any nonuniform tensioning across the
fiber group will result in some fibers sagging
under their weight with resin and hence not be
properly located as they enter the forming and
curing dies. An additional advantage of the ver-
tical process is that it is possible accurately to
locate the internal mandrels whch are neces-
sary for hollow shapes and tubes. This is
particularly important in the fabrication of
heavy, thick wall tubes. In the horizontal
process, these internal mandrels will frequently
deflect under their own weight and cause a
nonuniformity of wall thickness around the
hollow profile or tube. In addition, the vertical
process allows the use of several different fiber
496 Pul trusion
entry points to the forming process with multi-
ple resin baths. In the horizontal procedure, the
multiple entry points have to come from the side
of the main fiber path and it is not as easy to coa-
lesce the fibers into a single merged preform.
23.4.4 USE OF THERMOPLASTIC MATRIX
RESINS
Thermoplastics cannot be applied to roving
easily using the standard resin bath, even with
heating. Thermoplastic resins impregnated on
roving are generally available as preimpreg-
nated (prepreg) materials and are supplied by
specialty companies who are experts in the
prepreg process. Thermoplastic matrices
improve the toughness of the composite and
this is their major end use advantage. In gen-
eral they have high softening temperatures
and high physical properties coupled with a
low fluid viscosity in their melted form. The
prepregs are normally prepared using solvents
and this provides some difficulty against envi-
ronmental regulations in order to remove and
dissipate the majority of the solvent. Some sol-
vent has to be retained in the process in order
to have the material be sufficiently pliable for
machine and manual handling. In addition to
the improved toughness of the thermoplastic
composite, an important advantage of thermo-
plastic pultrusions is the ability to heat and
reshape the product after f ~ r m i n g ' ~ - ~ ~ .
23.4.5 RESIN BATH LIFE
In a continuous pultrusion process, the pot life
of the resin should be several days. However,
if the volume of the resin bath can be kept
small in relation to the resin being withdrawn,
shorter pot-life resin, i.e. 3 4 h can be used.
Shorter pot-life resins result in smaller batches
and mixing becomes time consuming.
23.4.6 THE PULL WINDING TECHNIQUE
The pull winding process was developed in
Europe and was used frequently by European
fabricators to provide pultruded tubular struc-
tures both round and square23,24. The process
combines the standard continuous unidirec-
tional fibers of the pultrusion process with
hoop wound continuous fibers. The longitudi-
nal fibers are used for axial and bending
resistance while the hoop fibers are used for
hoop tension and compression resistance. The
combination of the two processes of pultru-
sion and winding provides virtually unlimited
possibilities. However, the increasing com-
plexity of the process limits these
combinations. Normally, longitudinal fibers
are positioned at the inside and outside sur-
faces of the tube with one or two hoop wound
layers positioned internally in the tube wall.
These hoop wound layers are not truly 90"
hoop wound layers because of the slightly
helical nature of the winding and the lateral
movement of a wound roving, one band width
of advance with each circumferential pass.
Depending on the diameter of the tube, the
winding angle is typically anywhere from
80-87". The winding can be performed in
both clockwise and counterclockwise direc-
tion and in addition to the hoop tension and
compression resistance can also provide a
degree of torque strength to the tubing.
Single and double head pull winders are used
with these techniques. The pull winding
process is shown in Fig. 23.2 and the proce-
dure for the use of these systems is self
explanatory. The important control feature of
the pull winding process is the control of the
winding speed and position with respect to
the linear motion of the pultruded form
through the machine. This is achieved by
sensing the speed of the longitudinal motion
accurately and using a microprocessor con-
trol to coordinate the speed of the rotating
head motor. This relationship defines the
pitch of the winding which is defined as the
linear distance moved during one revolution
of the head. With the microprocessor control
the pitch can be varied, thus providing varia-
tions in fiber content and angular position, as
required. A paper by D.E. Shaw Stuartz5
 Process equipment 497

defines the primary advantages of pull wind- used for forming dies include Teflon@,high
ing over other methods of tube manufacture as: molecular weight polyethylene, chrome plated
0 it is a fully automatic continuous process; steel and a variety of tool steel alloys. The fabri-
it is dimensionally accurate and repeatable; cation of the forming die is a custom process
which is best performed at the pultrusion fabri-
0 it produces tubes with a good external
appearance and finish; cator by a skilled tool maker/machinist.
0 it can have built-in color;
it can be made with thinner wall sections
23.4.8 INJECTION PULTRUSION
than conventional pultrusion or filament
winding. In this modification of the resin impregnation
process, the resin is directly injected into either
the forming die or into the initial segment of
23.4.7 PULTRUSION DIES the pultrusion die. The resin is injected into the
die under pressure and is forced into the inter-
Two types of dies are used in the pultrusion
stices of the fiber system. The principal
process: the forming die and the heating or cur-
advantage of this system is that it limits the
ing die. Forming is normally accomplished
release of volatile resin components and reac-
immediately after the impregnation process
tion products.
although some shaping with the roving and
An additional advantage of this process for
mat/fabric inserts in a dry condition can take
laboratory or research and development pul-
place prior to entering the resin impregnation
truders is that it enables a rapid resin change
processing step. Forming dies or guides are
without removal and cleaning of all of the
normally attached to the heating or curing die
resin bath components. In addition, dry fibers
in order to provide the correct relationship
are not impregnated with resin before entering
between the forming and the heated curing
the die and therefore they can be positioned
step. For tubular or hollow profile pultruded
accurately, even with complex profile cross
products, a central mandrel support is neces-
sections and multiple mat and fabric entries.
sary internal to the fiber form and it is
The schematic of the injection pultrusion sys-
necessary to extend this mandrel as a cantilever
tem is shown in Fig. 23.8. A typical resin
through the pultrusion die. It is also important
injection pultrusion die is shown in Fig. 23.9.
to resist the forward drag on this central man-
In addition to the advantages listed above,
drel which will occur from the surface tension
there are several disadvantages which must be
and adhesive forces of the resin on the roving or
weighed in a process trade off, before resorting
mat. Materials must form in sequence around to the injection pultrusion method. These dis-
this mandrel and must alternate from one mate-
advantages are:
rial to another to prevent any weak areas at
overlapping joints. The sizing of the slots, holes 0 a more complicated die design;
and clearances in the forming die must be care- 0 more parameters to control;
fully designed so that excess tension on the dry 0 analytical support is required to predict wet
or impregnated fiber is avoided. The fiber is out behavior and design of the resulting
weaker in this condition than in the cured con- dies;
dition and filaments may be independently 0 fibers in the die are very tightly compressed
broken and distortion of the mat and fabric can and resin penetration is difficult, particu-
take place. The forming die can also be larly with large wall thicknesses;
designed to permit excess resin removal. This 0 the tightly packed fibers can act as a filter
prevents an abnormally high hydrostatic force and partially remove resin additives, partic-
at the curing die entrance. Materials commonly ularly those in suspension.
498 Pultrusion

Fiber
rack
doth
J racks

I
S - moving

-
pulling mechanisms cutoff saw
disengaged
\
Lc t
I
\ /
preforming
I hydraulic rams
finished
pressurized product
guides
resin tank

Fig. 23.8 Injection pultrusion process. (Courtesyof American Composite Technology Inc.)

injection port thermostats

23.4.10 POSITIONING OF THE HEATED DIE
The heating/curing die must be firmly
mounted to the frame of the pultrusion
machine in order to react the pulling forces,
which are created in pulling the product
through the process. These forces are typically
in the range of 5440-7250kg (6-8tons).
‘1 6% thermostats
However, some of the larger machines which
are capable of producing parts up to 1.52 m
matrix
injection i (60 in) wide and heights of 0.60 m (24 in) (with
fiber +
I zone
1 cure
zone
narrower parts) can require pulling forces up
COmprBsEmn
zcne to 16 320-18 000 kg (8-20 tons). The mounting
method must not only permit these types of
Fig. 23.9 Resin injection pultrusion die. (Courtesy loading but must also be capable of mounting
of American Composite Technology Inc.) height adjustment in order to accurately align
the axis of the die with the pullers which move
the product out of the die. Following align-
23.4.9 HEATING AND CURING DIES
ment and clamping, the mounting system
There are three considerations in the design must also not allow any deflection which
and use of a heated die for the curing of a pul- might provide an angular or dimensional mis-
truded composite section. The first of these is match of the machine.
the positioning of the die relative to the
machine access, the second is the actual
23.4.11 DIE HEATING
method of heating to induce the necessary
energy into the composite material to fully cure Die heating is probably the most critical con-
the resin system. The third includes the design trol parameter of the whole pultrusion
features and construction materials for the die. process. The die heating profile will control

the rate of polymerization of the resin system
and the position of the resin gel point front
w i t h the die. It also influences the degree of
resin exotherm profile throughout the various
wall thicknesses of the pultruded structure.
The curing dies are typically heated with elec-
tric strip heaters or hot oil jackets. The thermal
curing using these two methods of heating is
slow, owing to the fact that the tool steel of the
die is a poor conductor and limits the rate of
heat injection to provide a uniform cure. The
thermal energy which is required to cure the
composite material must all be applied
through the outer surface of the composite
shape. The heat input is required to produce
gelation of the resin throughout the composite
part. When the composite structure being pul-
truded has thick sections, this necessarily
requires a longer heat input which slows
down the pultrusion rate. Increasing the rate
of heating to permit a faster pulling speed will
not necessarily solve this problem and may
result in premature curing of the outside skin
of the profile with early onset of the exotherm
in the resin system and potential overheating
and cracking of the exterior surface of the part.
Temperature conditions of the die are con-
trolled by the internal placement of
thermocouples and this can result in individ-
ual control of heating rates in various
segments of the die.
Instead of using strip heaters or hot oil jack-
ets, it is possible to heat the curing die by
means of heated platens and a press. These
heated platens will usually have several zones
of heating control with imbedded thermocou-
ples to sense the platen temperature. T h s
method provides a uniform heating condition
to the die. However, since the thermocouples
are sensing the platen heating temperature
rather than the die or product temperatures,
the temperature differential between these
zones must be well documented. This permits
the platen heating temperature to be set to pro-
vide an adequate heating level in the
composite product and absorb all of the con-
duction and radiation losses from the system.
Process equipment 499
Use of the platen system will allow change out
of dies with very little system down time.
During start up and also during shut down
periods it is necessary to provide a cooling
method at the front of the die to prevent early
gelation of the resin system. During these
phases, the entire die will heat up rapidly
without the composite being pulled through it
and acting as a heat sink. The cooling can be
done dynamically through cold air impinge-
ment or by using a water jacket or tubes
through which cold water will be pumped.
Instead of these dynamic methods, a simple
static method would be to provide an
unheated zone at the beginning of the die to
act as a heat sink and conduct away the excess
heat during start up or shut down actions.
These same unheated or cooled sections may
also be useful at the exit of the die to remove
contained heat from the product prior to its
exit.
It has been mentioned that the heating pro-
file within the die is the primary factor which
controls the speed of throughput of material in
the process. This was recognized early in the
development of the pultrusion process by W.
Brandt Goldsworthy and he added a radio fre-
quency preheated system to his pultrusion
machine designZ6rz7. The use of radio frequency
heating in conjunction with the traditional die
heating methods can significantly increase
running speeds. This technique is basically
limited to unidirectional reinforced rods, bars
and shapes and cannot be used if carbon fibers
comprise the reinforcement. Data from
Goldsworthy Engineering Inc. shows speed
increases of up to 400% based on a 2.54mm
(0.1 in) wall thickness pultrusion. Speed
increases of 100% (i.e. doubling the speed) are
accomplished at wall thicknesses of 2.54 mm
(0.1 in).
During recent years it has become possible
to evaluate the internal die profile with regard
to both temperature and pressurez8.The sen-
sors which are used to provide that data are
essentially similar to strain gages with output
leads attached to them. The pressure sensor is
500 Pultrusion

a unique development resulting from the heating zones in order to maintain control
music industry. These sensors were originally over the resin gel, curing and cooling of the
used as striking pads in electronic keyboards pultruded section within the die. In addition,
and the manufacturer has now developed if one of the cavities in the multi-cavity tool is
them to measure pressure forces transverse to damaged, the complete tool is not out of pro-
the plane of the sensor. The output from the duction since the remaining useable heating
sensor is transmitted via a pair of thin strain zones can be modified to continue to provide
gage type wires. It is thus possible to insert an acceptable product.
both of these sensors (temperature and pres- The dies are usually made from steel, which
sure) into the fiber resin system prior to can be hardened tool steel, or steel alloy which
entering the curing die. The sensors will then is treated, hardened and plated before use. The
travel through the die internal to the product die must be relatively thick walled so that it
and will record both the temperature and the can be heated uniformly and retain the heat
internal pressure in the die from the entrance input. Thick wall design also reduces distor-
to the exit. Once the sensors have traveled tion under temperature and pressure. It has
beyond the exit from the die, the connecting been suggested that the cross-sectional area of
wires can be cut. The section of product which the steel should be at least ten times that of the
contains the two sensors and the lead wires is pultruded part. The steel used should be hard
then cut out and discarded. The resulting data since it has to withstand the abrasive action of
provides a complete process description from the composite being drawn through it. A typi-
the entrance to the exit of the die. cal hardness is a Rockwell C rating of 30,
which can be obtained with a prehardened
tool steel. Dies are manufactured from multi-
23.5 DESIGN FEATURES AND MATERIALS
ple pieces that are machined and joined
In considering the design of the heated curing together to create a design profile cavity. As
die for a pultrusion system, it is possible to use the various sections of the die are connected
a single cavity tool, a multi-cavity tool or sev- together they must be properly aligned. This
eral single cavity tools mounted in parallel. can be done using dowels for permanent
The choice between these three will depend alignment or by machining an alignment
upon the size, complexity, dimensional toler- groove on the outside part of the die which
ance and surface quality of the pultruded can then be used for a hard metal key which
product. Individual or single cavity dies are a can be driven into the groove to provide a pos-
frequent choice of pultruders, particularly for itive alignment for the entire tool. The die
medium to large or sophisticated shaped assembly is then match drilled and tapped for
products. Use of the multi-cavity tool or sev- the assembly bolts which hold the parts of the
eral single cavity tools mounted in parallel is die in position against the high internal pres-
generally restricted to very competitive and sure developed during the process. Following
low cost shapes such as round and square alignment and assembly, the exterior surface
cross section rod. The choice between an indi- of the assembled die is ground flat. The inter-
vidual die and a multi-cavity die is frequently nal cavity surfaces are polished using
dependent upon the experience and prefer- polishing wheels and buffing compounds to a
ence of the manufacturing engineer in the high surface finish 0.254-0.762 wm (10-20 kin).
pultrusion company. The multi-cavity tool can At this point a bell mouth is machined
be an efficient arrangement for production around the entrance of the die to provide a
conditions. In this case the die is two to three smooth entrance for the resin impregnated
times the length of a single cavity tool. The fiber form. The radius will vary in size from
longer die makes it possible to use different a small radius for small simple structural

profiles to a relatively large radius for a large
and complex composite profile particularly
where the fiber content is high. The bell mouth
is polished and the finished die is hard chrome
plated to a thickness of 0.025-0.050 mm
(0.0014.002 in) with a Rockwell C hardness of
approximately 70. The dimensions and surface
quality of the pultruded product are a direct
reflection of the condition of the die. Dies will
thus not be removed from production to be
inspected unless the shape or quality of the
product begins to change. Chrome plated dies
will normally have a life of 61 000-150 000 m
(200 000-500 000 ft) of product run with their
initial chrome plate application. Up to 305 000 m
(1x lo6ft) of product have been produced from
some hard chrome plated dies. Chrome plated
dies require frequent inspection to insure that
their internal shape and dimension is main-
tained. They should also be inspected for wear
of the chrome plated surface since the wear
process will proceed much more rapidly if the
tool steel surface is exposed from under the
chrome. Once the die has worn and produces
product beyond allowable dimensional toler-
ances, the die may be replated and repolished
back to original dimensions. This process may
be repeated several times.
23.5.1 CLAMPING AND PULLING
Three different types of clamping and pulling
systems have been used in the pultrusion
industry. Of these three, only two are now
encountered. The original system used on the
earliest machines in the 1950s and early 1960s
employed a single clamp. This clamp was
hydraulically controlled and contoured pads
were used for gripping the part. The unit con-
taining this single clamp was pulled by a
continuous chain for a distance of 3.2-3.7 m
(10-12 ft). Areversible motor was used to drive
the chain and following the pull stroke, the
puller/clamp released the product and
returned to the beginning of the pulling stroke,
clamped the product and pulled againz9.The
obvious disadvantage of this system is that the
Design features and materials 501
pultruded profile remains stationery until the
puller returned to the beginning of its stroke.
Because of the alternating pull and pause
mechanism this system was known as the
'intermittent puller'. This system is still used
on some very early machines, however, it is
certainly not in widespread use.
A modificationof the clamping/pulling sys-
tem has become popular which provides a
continuous pull. The clamping, pulling and
unlocking cycles of this system are coordinated
by the control system of the machine. The drive
system used can be either a hydraulic cylinder,
a threaded ball screw such as is used on lathes,
or a chain drive mechanism. The clamping
pads are still formed to match the contour of
the profile being pulled. The two puller heads
must operate in the space originally designed
for the single puller. Consequently, limited lat-
eral movements of approximately two feet
each are sustained by the two pullers. The two
puller system is shown in Fig. 23.10.
Fig. 23.10 Conventional two puller system.
(Courtesy of Pultrex Ltd.)
Continuous belt pullers are used on basic com-
mercial machines. These pullers can be used
with single or multiple cavity molds. The
cleated chain or caterpillar version of the con-
tinuous belt machine has many individually
contoured puller pads attached along the
chain length. The number of these contoured
502 Pultrusion

puller pads depends on the complexity of the aramid fiber to date has been the high pressure
part but generally varies between 12 and 60 water jet and presumablythis could be adapted
pads. This large number of pads permits a for use on a pultrusion machine. The inherent
lower unit pressure between the clamping pad disadvantage of the high pressure water jet is
and the pultrusion. The caterpillar type its cost which is from $50 000-100 000. A com-
machine was designed and built in 1958 by promise solution to this problem would be to
Brandt Goldsworthy, Dennis Franks and Tom cut off the sections as smoothly as possible,
Bailey. Caterpillar type machines are preferred using the diamond saw, to a slightly over
and still widely used in the industry. length condition with very rough ends. The
product length can then be subcontracted to a
waterjet cutting source for final trimming. This
23.5.2 CUT-OFF STATION
will result in some wastage.
Every pultrusion machine utilizes a cut-off saw
to cut the pultruded profiles to the required 23.6 MATERIALS
length for shipment and use. This saw is fre-
quently of a radial arm type as shown in Fig. Fiber properties to aid the designer are shown
23.11, but can be also a chop saw, orbital or elsewhere in this text. Following the selection of
band saw. It is mounted on a platform which the fiber type to suit the required design factors,
moves down the pultrusion exit table at the the fiber must be oriented in the correct direc-
same speed as the pultruded product. Carbide tion. It is understood that all of the fiber types
and diamond tipped saw blades are used for must be available in continuous form in order
the cutting of glass and carbon pultrusions. to be useable in the pultrusion process. The
However, these saw blades are not effective for most commonly used form of continuous rein-
cutting aramid fiber pultrusions. This fiber is forcement is roving. This is available in single
known for its properties of toughness and and multiple strand configurationsm.Glass rov-
resistance to abuse. These properties lead to ings are designated by their yield which is the
difficulty in machining, grinding and cutting. number of yards per pound of material. The
The most successful method of cutting two most commonly used versions are at
112yd/lb or 224 in/kg or 112 or 124 m/kg (56
1 or 62 yd/lb). The glass rovings are typically
supplied in 18.1 kg (40 lb) hollow cylindrical
packages with a center pull payout. A similar
center pull spool is also available for both
aramid and polyethylene fibers. Carbon fiber is
typically available in either a 3K, a 6K or a 12K
!!- filament. It should be noted that the tow sizes of
- the
1 carbon are much smaller than the glass rov-

\ ing and package weights are 1-2 kg (2-5 lb)

with an outside payoff designed for a package
holder style creel system. New versions of the
- carbon fiber roving are available now in 40K,
160K and 320K tows. Use of these tows allows
the fiber to be laid down very rapidly and con-
sequently these versions of carbon fiber are
attractive to pultruders. Typical properties of
Fig. 23.11 Conventional cut-off saw. (Courtesy of fibers used in PultruSiOn are shown in Table
Creative Pultrusions Inc.) 23.13', 32.

Table 23.1 Typical properties of the major fibers used in the pultrusion process
Property E-glass S-glass
(Aramid)
Density, 2600 2491
kg/m3
Tensile strength, 3447.5 4585.2
MPa
Tensile modulus, 72.4 86.9
GPa
Elongation at 4.8 5.4
break, %
All the rovings discussed will yield the highest
possible longitudinal properties. Fibers as rov-
ings result in the maximum fiber content to be
achieved in pultrusion. If the longitudinal rov-
ings are used under near perfect conditions, a
65% fiber volume percent level should be
achieved. In a product which utilizes 100%
roving this material is normally in the longitu-
dinal direction or axis of the pultruded
product. Properties in the other two directions
are dependent upon the resin system and the
mechanical properties of the matrix resins are
much lower than fiber properties. Transverse
strength problems are overcome by inserting
transverse fiber materials into the pultrusion.
This is done either by using fabric or continu-
ous strand mat. The latter is most commonly
used. While the fabric is a standard woven tex-
tile form, the continuous strand mat has fibers
oriented in a random mode, bonded with a
thermoset resin binder which holds the mat
together adequately for processing in the pul-
truded section. While mat is available in any of
the fibers which have been previously dis-
cussed, the most common available mat is an
E-glass version that has coarse fibers in an
open or porous construction. This mat can be
used either as a center ply in a pultruded
structure or on the outer surface of the struc-
ture. Use of the mat greatly improves the
transverse physical and mechanical proper-
ties. It should be noted, however, that the mat
Materials 503
Keular Spectra Carbon Carbon
(Type T300) Inter. modulus
~~
1470 968 1720 1770
2964.9 1170.0 1896.1 2560.9
131.0 26.0 379.2 473.6
2.3 3.7 0.5 1.81
is porous and its use on the exterior surface of
a pultrusion might well leave porosities or
voids in the surface. To counter this problem, a
very fine filament, E-glass mat, commonly
known as veil, can be used as the surface ply.
Its presence during the pultrusion process will
tend to bring more resin to the surface of the
pultrusion and this will achieve a smooth, uni-
form surface, devoid of porosity or voids. The
veil mats can also be placed internally in the
composite and recent improvements in their
structural properties have made this possible.
The random fiber mats in E-glass are used
in weights of 0.15-0.6 kg/m2 (0.5-2 oz/ft2).
The inclusion of these mats in the pultruded
structure means that some of the longitudinal
fibers will have to be removed to allow for the
volume of the mat, veil or fabric. With the use
of fabric or mats in the structure, the resin con-
tent by volume will increase in order to fill the
openings in the mat or fabric. Thus while the
transverse strengths increase, the longitudinal
strengths usually decrease. Mats are also avail-
able in carbon fiber.
The random fiber structure of strand mat
provides fibers in all directions. However, this
random orientation does provide some prob-
lems in that the fibers may not provide a
symmetrical balance within the structure. The
initial solution to this problem was the use of
woven fabric. However, the lack of tension in
the fabric results in a lower strength capability
504 Pultrusion
of the pultrusion since under load, the fibers
in the fabric will have to straighten and
become tensioned prior to being able to
accept load. One way of solving this diffi-
culty is to use non-woven biaxial fabrics
which are stitched or knitted together at the
crossover points. Because of the nature of fab-
rication of these nonwoven materials, any
ratio of fibers in the two directions can be
provided. It is also feasible to utilize k45"
fibers in conjunction with the 0 and 90" fibers.
The biaxial fabrics are normally used as inter-
nal plies and not on the external surface. This
is due to the nature of the nonwovens in that
their transverse fibers will tend to be dis-
placed by friction with the walls of the die
during pulling. Fabrics using a +45" orienta-
tion without any longitudinal fibers are
usually impractical for the pultrusion
process. It should be noted that hybrid com-
posites with tailored properties are possible
using combinations of the fiberglass, carbon
and aramid materials. The designer will read-
ily determine the mechanical properties
which are required from the nonwoven or
woven fabrics. The rule of mixtures will
apply for combination proper tie^^^.
When pultruded composites are used in
outdoor weather conditions, the surface of
the composite may be degraded with time by
sun, wind, rain and ultraviolet exposure. In
order to solve this problem, additional resin
needs to be provided at the exterior surface of
the pultrusion. This is done by incorporating
the very fine filament veil mats which are
typically fabricated from polyester or nylon34.
These veil fabrics are available in a variety of
weights and weaving patterns. They help the
pultruder by providing a tough surface mate-
rial which will protect the die wall from the
abrasive nature of the fiberglass or aramid. In
addition, the resin rich surface is created
without any obvious fiber weaving patterns,
plus the veil materials can be screen printed
with company identification or decorative
effects35.
23.6.1 MATRIX RESINS
Of all of the technology considerations in the
pultrusion process, the most critical material is
the resin system and its f~rmulation~"~~. Resin
selection controls mechanical characteristics,
electrical insulation, corrosion resistance,
operating temperature and flame and smoke
properties. It also has a significant effect on the
process speed because of the required cure
cycle for any particular resin. The selection of
a resin system will also affect the production
cost of the process. The two most commonly
used resin types in pultrusion are the isoph-
thalic polyester and the vinylester. These two
comprise over 90% of all resins used in pultru-
sion. Epoxy resins and phenolic resins are also
being increasingly used. Phenolic resins were
traditionally avoided by pultruders because of
their condensation reaction during cure.
Condensation reactions produce large vol-
umes of water vapor and this typically causes
voids, channels, delaminations and porosity
when there is no provision to remove it. While
the pultrusion die does have an entrance and
an exit, nonetheless the system is essentially a
closed, pressurized volume. Table 23.2 pro-
vides typical mechanical properties for resin
systems most generally used in pultrusion and
several other chapters discuss the broad range
of matrix materials39.
23.6.2 PHENOLICS
In consideration of the use of phenolic resin
systems, the disadvantage of the condensation
type reaction was certainly sufficient to cause
delays in the potential use of phenolic resin in
the pultrusion process. The amount of water
vapor which is generated in the condensation
process is very large and it has always been
assumed that a phenolic pultruded structure
would look somewhat like a sponge. However,
phenolic systems have been pultruded in
recent years and a phenomenon has occurred
which is not well understood. During pulling
of a phenolic/fiberglass structure through the
 Materials 505

Table 23.2 Typical mechanical properties for resins Federal Department of Transport and the var-
used in the pultrusion process ious state departments of transportation have
imposed fire controls on composite materials. It
Property Polyester Vinylester Epoxy is required that they will not bum or stimulate
Density, 1100 1100 1300 combustion, have minimum required smoke
kg/m3 levels and also will not produce toxic fumes
Tensile strength, 77.2 81.2 75.4
under flame impingement and high environ-
MPa mental temperature conditions. Considering all
of the resins in the composite industry, pheno-
Tensile modulus, 3.3 3.4 3.3 lic resins will come closest to matching these
GPa
flammability specifications. Because of these
Elongation at 4.2 4.5 6.3 factors, it is anticipated that the use of phenolic
break, YO resin systems in pultruded products in the
Flexural strength, 122 134 115 future will increase dramatically.
MPa
Flexural modulus, 3.2 3.1 3.3 23.6.3 COMPARISON OF RESIN SYSTEMS
GPa
In recent years, there has been use of epoxy
Heat distortion, 77 99 166 and phenolic resins in pultrusion. G.A. Hunter
"C
of Shell Development Company compared the
properties of resin systems42.He provided a
three zone model of the pultrusion process
pultrusion die, a high pressure jet of steam is within the curing die (Fig. 23.12). The sketch
noted at the exit from the die. How and why provides an excellent background for compar-
the steam is caused to come off in this manner ison of resin proper tie^^^.
is not known. However, in the experiments Of the four primary resin systems used in
which have been run, the resulting pultrusion the pultrusion process, the polyester and
has not had any porosity problems and the vinylester resins account for more than 90% of
processing tests are noted as being successful. the marketplace. Phenolic and epoxy resins
Specific pultrusion grades of phenolic resin make up the balance of the market. In com-
systems are now available from plywood paring resin systems, one should review the
manufacturing corporations such as internal contours and the heating profile of the
Weyerhauser and Georgia Pacific. The avail- heated resin die and examine the change in
ability of these resins would certainly indicate resin morphology as it proceeds through the
that the anticipated processing problems have die. The model of the pultrusion process given
not occurred40, 41. The importance of phenolic in Fig. 23.12 which shows the three zones of
resins is in their resistance to fire and their low the heated die and the transition of the resin
smoke and toxicity production under fire con- phase from liquid through the gel zone into
ditions. All forms of composite materials, the solid phase. The first zone shown in Fig.
including pultrusions, are being used increas- 23.12 is where the material enters the die at
ingly in mass transit, aircraft and civil room temperature and expands as it absorbs
engineering applications. In all of these areas heat which causes the hydraulic pressure in
of application, increasing contact of the com- this zone of the die to rise. As the material pro-
posite material systems with the general gresses into zone 2, or the gel zone, it has
public is occurring. Because of this, the fire absorbed more heat, is beginning to cross link
smoke and toxicity requirements of specifica- and changes from a viscous liquid into a non-
tion control groups such as the FAA, the flowing jelly type of material, then into a
506 Pultrusion
~~

"THE GEL ZONE"

STRIP HEATER

&&( LIQUID PHASE

ZONE 1
..
i.
..
.
SOLID P H A S E

ZONE 3
iVlSCOUS SHEAR i i SLIDING FRICTION FORCES i
iFORCES *........ .*......-.I
**a..............
ZONE 2 I..

: COHESIVE FORCES :

Fig. 23.12 Three zone model of the pultrusion process. (Courtesy of Shell Development Company.)

rubber-like texture. As the material cures to a gel zone will expand or contract.
hard solid, shrinkage occurs which releases Joseph Sumerak in 1985 quantitatively
the hydraulic pressure forces and the product described the internal dynamics of the pultru-
shape retracts from the internal surface of the sion process. Taking test results from
die. This is zone 3. In this zone, because of the Sumerak's earlier work, Hunter showed the
release of the product from the surface of the relationship of pull loads to processing speed
die, the sliding frictional forces are very slight. for catalyzed and uncatalyzed resin systems
Depending upon the thickness of the part and (Fig. 23.13)w7. For the uncatalyzed resin case,
the process speed, the bullet-nose shape of the the rising pulling load associated with

looot7
1
P W I T H 20 P H R C L A Y

t 800 -
D - PULL LOADS ATTRIBUTED TO
VISCOUS SHEAR AND FRICTION O F
CATALVZED RESIN
0 - P U L L L O A D S A T T R I B U T E D TO
* 700- PURE VISCOUS SHEAR OF THE
U N C ATALYZ E D R E S I N
A
I 600 -A CALCULATED PULL LOADS
ATTRIBUTED TO VISCOUS
u)
S H E A R O F T H E CATALVZED

0
400-
J
J
3 300-
n
200 -

0 12 24 36
LINE SPEED, INIMIN.

Fig. 23.13 Pull loads compared with line speed for different types of resin systems. (Courtesy of Shell
Development Company.)

increased processing rate, or line speed, is the
result of increasing shear forces over the
length of the die. In the case of the catalyzed
resin and referring back to Fig. 23.12, viscous
shear forces are generated only in the front
portion of the die, i.e. zone 1. Within the gel
zone, cohesive forces come into play for a
small length of the die which is followed by
the transition to the rubbery cured material
which provides substantial friction forces. As
the resin hardens and shrinks away from the
surface of the die, the frictional forces are
reduced significantly. It is obvious that the
pull load is significantly higher for the cat-
alyzed resin system, particularly as the line
speed increases. This proves that the major
portion of the pultrusion loads are generated
in the gel zone and are cohesive forces and
frictional forces resulting from the interface of
the resin and the die.
Sumerak showed that a significant part of
the internal pressure does develop inside the
B
4
-1- -
---
INITIAL CURE CYCLE
SECOND HEAT CYCLE
0
>
-2-
STARTING VOLUME - 9.098 ML
NET VOLUME LOSS - 0.<5
VOLUMETRIC SHRINKAGE
-3-
1 . r l r . l :
Fig. 23.14 Volume change of polyester resin during cure. (Courtesy of Shell Development Company.)
Materials 507
die and is proportional to the speed of pro-
cessing. Hunter provided evidence that the
pressure loss in zone 3 of the die occurs well
before the material cools. Thus it is not thermal
contraction but volumetric shrinkage due to
the cure of the resin. The coefficient of thermal
expansion of the steel material of the die also
enters into this equation. For a differential
temperature of 121°C (250"F),the hottest tem-
perature section of the die for a 12.7 mm
(0.5 in) diameter pultrusion will be 0.3% larger
than the entrance. Thus pressure and volumet-
ric shrinkage together play a major role in
pultrusion dynamics. Insufficient pressure
causes sloughing problems and insufficient
shrinkage can cause excessive pull loads. The
resin rate of shrinkage affects the rate of pres-
sure decay and is controlled linearly by the
cure rate of the resin. Thus a delicate balance
between pressure, cure rate and shrinkage
must be obtained for a clean pultrusion
process to take place.
ML
- 6.04 %
1 1 1 . 1 I ,
508 Pultrusion
23.6.4 SHRINKAGE
Hunter ran shrinkage tests on a typical poly-
ester resin and a standard Shell epoxy resin
system42.The volume change of the polyester
and the epoxy resin are during cure are shown
in Figs. 23.14 and 23.15. The data shows that
the polyester shrinks almost twice the degree
of epoxy. However, Hunter reports that the net
shrinkage is not nearly as important as the
profile of that shrinkage. The polyester contin-
ues to expand after the gel point which is
followed by a high shrink rate that gradually
tapers off. In comparison, the epoxy resin
shrinks before it gels and continues to shrink
at a steady rate until it is fully cured. This
information sheds new light on the under-
standing of the pultrusion characteristics of
epoxy resins compared to polyesters. In most
composite manufacturing processes, the appli-
cation of pressure during the curing phase of
the resin is always beneficial to the resulting
product. Pultrusion is no exception to this rule
and it is beneficial to generate pressure in the
pultrusion die up to the point where the resin
3t. A GEL POINT
-2-
NET VOLUME LOSS - .32 MLS.
VOLUMETRIC SHRINKAGE
-3-
Fig. 23.15 Volume change of epoxy resin during cure. (Courtesy of Shell Development Company.)
is fully cured. Similarly, the pressure during
the gelation phase ensures that the product is
tightly held against the surface of the die and
consequently a smooth surface will be gener-
ated with the pressure preventing sloughing.
Thus, from a comparison of the test results, it
is obvious that the polyester shrinkage profile
is superior to the epoxy in terms of providing
gelation and cure under pressure. In addition,
the sudden high initial rate of shrinkage fol-
lowing gelation for the polyester resin is also
beneficial in that it results in a fast pressure
drop and hence frictional force reduction.
In comparison, the epoxy resin begins to
shrink well in advance of gelation and gels
under a condition of declining hydraulic pres-
sure. Thus much of the hydraulic pressure is
lost by the time that gelation occurs due to the
effect of volumetric shrinkage. Following gela-
tion, the rate of shrinkage is very slow such
that it causes the friction forces to only reduce
gradually. Thus in the gel zone for epoxy
resins there is insufficient hydraulic pressure
to prevent sloughing. This explains why a
i 22.8" C QUENCH
- 3.57 %

problem is frequently encountered when
epoxy resin is substituted directly for a poly-
ester without consideration of the curing and
shrinkage properties. Hunter postulates that a
simple solution has been found to compensate
for these shrinkage characteristics in epoxy
resin systems. The presence of fillers, whether
fiber or powdered, in the resin system, reduces
the amount of total volumetric shrinkage. Also
the pressure from thermal expansion is
directly proportional to the amount of filler or
fiber reinforcement volume. Thus the increase
in reinforcement to resin volume ratio, either
by fiber or powder fillers, will reduce the
shrinkage tendency and the hydraulic pres-
sure will be increased at the same time. Even
though the epoxy resin shrinks prior to gela-
tion, sufficient pressure will remain to prevent
sloughing. This explains why it is always ben-
eficial to have a higher fiber to resin ratio for
epoxies in the pultrusion process than for
polyester resins.
00
50
00
50
I I
75 100 125
GEL TIME TEMPERATURE, DEG. C
Fig. 23.16 Gel time compared with temperature of epoxy and polyester resin. (Courtesy of Shell
Development Company.)
Materials 509
23.6.5 CURE RATE
As previously mentioned, shrinkage rate is a
direct result of the known cure rate of the resin.
It is beneficial in the pultrusion process to have
a high shrinkage rate to initiate a quick pressure
drop to reduce frictional pull loads. From this
point of view, it is important for the epoxy to
have a fast cure rate. This will also provide a
shorter gel zone which will result in a faster
processing rate. Cure rates of polyesters may
be varied chemically by changing the amounts
and types of peroxide catalysts which are used
to initiate them. It is not simple to change the
cure rate of an epoxy resin chemically.
Curing agents for epoxy resins are selected
based on the desired performance parameters
for the epoxy in the final product or structure.
Some considerations of pot life and manufac-
turing process also influence this selection.
Thermal accelerators can be used. However,
the effect of increasing cure rate accelerator
I I
150 175 200
510 Pultrusion
content may be to reduce the pot life. Hunter
ran experiments to provide data on gel times
of epoxy resin at different accelerator levels.
In addition, he checked on the gel times of
polyester resin using two different curing
agents. Figure 23.16 shows the data which
resulted from these two evaluations. The data
on the epoxy resin system shows that signifi-
cantly more heat is required to generate the
same gel times even though the accelerator
content is doubled. Figure 23.17 shows the
viscosity versus time of the epoxy resin at two
accelerator levels and two temperatures. This
graph clearly indicates that pot life is sacri-
ficed by increasing the accelerator level. Pot
life is also affected by temperature and Fig.
23.17 illustrates that a small increase in tem-
perature will reduce the time to double the
initial viscosity by almost half. Heat can be
generated during the mixing process of the
epoxy formulations and because of this it is
important to minimize the mixing times when
using high shear mixers that generate heat
within the body of the resin system. The
implication of the experimental data pre-
sented in these figures is that the most
efficient method of increasing cure rate in the
epoxy resin is to increase the die temperature.
4 0 0 0 ~0- P T D . A C C E L E R A T O R
3500 -
W
u)
0 3000-
n
2500-
2
w
0 2000-
>.
1500-
u)
2 1000-
-
u)
5 500-
01 I I I I
0 1 2 3
Fig. 23.17 Epoxy resin viscosity compared with time and temperature. (Courtesy of Shell Development
Company.)
23.6.6 REINFORCEMENT VOLUME
The general relationship of glass fiber content
to pull loads in epoxy resin system is shown in
Fig. 23.18. These data were derived from an
experiment in the Shell laboratories where the
reinforcement volume was decreased and the
pull loads were recorded until sloughing
The fiber volume was then
increased until the sloughing was eliminated
and was increased further until pull loads
became too large. The data shows that there is a
plateau in the pull load curve spanning approx-
imately 2% of the glass fiber content range. This
is the optimum level for pultruding the
12.7mm (0.5in) diameter epoxy rod used in the
test program. Below the optimum range,
sloughing occurs owing to the insufficient
hydraulic pressure at the gel point. Above the
optimum level, the pull loads rise owing to the
high pressure both during and after the gel
zone (referring back to Fig. 23.12). Both poly-
ester and epoxy systems respond similarly to
the different types of reinforcement materials
which are contained within the pultruded
structure. For both of these resin systems, the
minimum reinforcement level to prevent
sloughing when using a continuous mat and
roving is somewhat less than that for an all rov-
LEVEL AT 2 l . C
I I 1 1 1 1 1 1 I J
4 5 6 7 8 9 1 0 1 1 1 2 1 3
TIME, H
 Materials 511

1000
112" DIAMETER ROUND
P R O C E S S E D AT 1 2 " I M I N
112 VLO. SINGLE END ROVING

-
47-64 ENDS
000 16 x CLAY

0
2 600 - TOO LOW, TOO HIGH,
4 LOADS ARE
A
OCCURS EXCESSIVE
2
3
n
400 -

78 79 00 01 02 03 04 05 86 07

GLASS CONTENT (NON-COMBUSTIBLES), % B Y WT.'

'OF W H I C H A P P R O X I M A T E L Y 2 X IS R E S I D U A L C L A Y

Fig. 23.18 Epoxy resin pull loads compared with glass content. (Courtesy of Shell Development Company.)

ing part. Table 23.3 lists the target reinforcement
volumes for the epoxy system for a variety of
reinforcement systems. These values were gen-
erated by following the same procedure as for
the data in Fig. 23.18. The data shown in Table
23.3 are qualitative rather than quantitative val-
ues. They may be used to estimate the required
reinforcement volume.
Table 23.3 Target fiber volume ranges for epoxy
pultrusion
All glass roving reinforced composites
Multi-end type rovings
Single end type rovings
Glass roving and continuous mat
reinforced composites
3.175 nun (1/8in) thick cross sections
6.35 nun (1/4 in) thick cross sections
Carbon fiber reinforced composites
All unidirectional tows
(57-65VOlYO)
23.6.7 DIE TEMPERATURE CONTROL
In polyester pultrusion, there is a wealth of
prior experience7 which can be used to pro-
vide a temperature set point to produce the
desired surface and internal quality of the part
with the controller being a thermocouple
located some short distance from the entrance
to the die. This creates a situation which is
independent of the actual exotherm tempera-
ture in the curing process.
For epoxy pultrusion it is vital that the peak
wt.% exotherm be understood and controlled. It
should not exceed 225°C (437°F) in the hottest
region of the part and die. At this temperature
78 homopolymerization will take place within
77-81 the epoxy resin system and the resin does not
need the curing agent to stimulate the cure.
The mechanical and physical properties of the
6447 structure are degraded under these conditions
71-74 by the presence of the unused curing agent.
For most thin profiles (up to 12.7 mm (0.5 in)
thick), a single heating zone is sufficient. The
67-74 thermocouple should be located in the center
512 Pultrusion

CIT

1 2 ' /MINUTE

1 8 ' S T R I P HEATERS

1'- -
----
TEYPERATURE ON THE SURFACE OF THE ROD
TEYPERATURE I N THE CENTER OF T H E R O D

I 1 I I 1 I I I
0 6 12 18 24 30 36 42 48
DIE LENGTH, IN

Fig. 23.19 Die temperature profile of single zone heating. (Courtesy of Shell Development Company.)
of the strip heater to minimize the overshoot in the epoxy resin system. If the temperature
and lag time for the temperature controller. set point is too low, the resin cure rate will
For a 12.7 mm (0.5 in) thick cross section the decrease which increases the size of the gel
temperature set point of 200°C (392°F) on the zone. At the same time, the rate of shrinkage
surface of the die will yield an internal peak and the rate of hydraulic pressure decay is
exotherm temperature of 225°C (437°F).Figure reduced and this results in more pressure
23.19 is a graphic example of this single strip within the larger gel zone which increases pull
heater profile. Figure 23.20 depicts the graph loads. As the die temperature increases, the
of the temperature set point versus pull loads conditions begin to favor reduced pull loads.

700 -
m
A

600 -
0
A
A
4
3
n 500 -

400
140 150 160 170 180 190 200
DIE CONTROL TEMPERATURE, "C

Fig. 23.20 Pull load compared with die control temperature. (Courtesy of Shell Development Company.)
 Materials 513

With section thicknesses up to 12.7 mm (0.5 23.6.8 RESIN MIXING

in) a two zone heating profile can be used and
this will probably eliminate the need for radio
frequency (RF preheating) to prevent internal
cracking. The pull loads are much lower and
the temperature decay rate is less than the sin-
gle zone heating profile. Thus the two zone
version will result in a higher degree of cure
than the single zone.
For thick pultrusions with sections beyond
12.7 mm (0.5 in), the RF preheating method
results in faster processing rates without crack-
ing. Figure 23.21 illustrates the die temperature
conditions for the same 12.7 mm (0.5 in) diam-
eter rod pultruded with RF preheating.
Preheating serves to reduce the temperature
differential between the die entrance and the
gel zone which results in less volumetric expan-
sion due to temperature and hence less
pressure. The temperature lag between the sur-
face and the center of the part is also reduced by
RF heating, thus the gel zone is smaller which
reduces pulling loads. Increase of the process-
ing rate through the machine will bring the
pressure, the gel zone size and the pull loads
back to normal conditions. This is how RF heat-
ing permits faster processing rates without
increasing the pull loads beyond the standard
levels.
The best approach to mixing resin system com-
ponents is to precisely follow the stated recipe
for the amount of material to be added and the
degree of mixing following the addition. As the
ingredients such as catalyst accelerator, pig-
ments, viscosity and extenders, internal mold
release and fillers are added, the resin is mixed
for a very short time of up to one minute (Table
23.4). The curing agent is left out of the mix
until the mix is ready to be added to the pultru-
sion resin bath. The addition of filler materials
requires a high shear mixing and this should be
minimized since it generates significant quanti-
ties of heat. Just prior to start up, the curing
agent should be added and blended at a
reduced mixer speed (high shear mixing is only
needed for filler addition.)Following start up of
the system, make-up replenishment resin
batches should be scaled to the depletion rate
for the run.If the resin consumption is 7.5 1 (two
gallons) per hour, add 7.5 1 (two gallons) per
hour. This addition will assist the pot life of the
epoxy resin and will dilute it with fresh resin on
a frequent basis. If a small bath size can be used,
this will increase the dilution effect of the
replenishment material. Depending on the size
of the bath, this technique can enhance the pot

CIT
200c
Q
18' /MINUTE
r

18' STRIP HEATERS

250k

W
I- 50- ----
-TEMPERATURE ON THE SURFACE O F THE ROD
TEMPERATURE I N THE CENTER OF THE R O D

01 I 1 I 1 I I I I I
0 6 12 18 24 30 36 42 48
DIE LENGTH, I N

Fig. 23.21 Die temperature profile with FF heating. (Courtesyof Shell Development Company.)
514 Pultrusion
life of the resin by 800% or more. A large master
batch of the resin can be mixed and set aside in
advance of the production run.This batch with-
out the curing agent will be stable for up to
three days. The curing agent can then be added
to a small make-up batch and mixed in just
prior to the addition to the system resin bath. A
typical formulation used in batch mixing is
shown in Table 23.4.
Even with the best of conditions in terms of
a small resin bath and frequent addition of
new batches, the resin mix will ultimately
become too viscous for good fiber wetting. A
good tip is to provide a large hole in the resin
bath with an appropriate plug. This allows a
quick drain and a clean and refill with only a
momentary pause in the process. With this
step, the pot life of the resin bath will be reset
to zero. It should also be noted that the plug in
the drain hole should not be threaded since a
very small amount of resin can cure and lock
up the threads. A preferred plug would be
hard rubber with a rim, similar to the knock
out drain plugs in the floor of an automobile.
23.7 START-UP PROCEDURE
A key factor in trouble free start up is to use
the minimum required amount of reinforce-
ment. However, if too much reinforcement is
eliminated in start up, sloughing will take
place in the die because of insufficient total
pressure in the gel zone. Once the sloughing is
Table 23.4 Two part batching for long production runs
Part 'A'
(in order of addition) [PHR, (wt.%)]
1. Epon@resin 9310 100.00
2. Epon Curing Agent@9360 0.67
3. Mold Accelerator 837 Wiz Int. 1846 0.70
4. Zylac 907 0.40
Blend the above for 30 s then add clay
5 . ASP400P 20.00
Blend clay for no more than 5-10 min
Courtesy: Shell Chemical Co.
initiated there may be potential for significant
build up on the surface of the die and this may
be difficult to remove. The most troublesome
spots in the die are the low pressure, remote
areas such as a comer or a small radius. There
is a standard process used in pultrusion of
purging the die with pure mold release just
prior to entry of the resin. Experience and
recent tests have shown that the pure mold
release is not necessary and may lead to
related problems. The normal types and quan-
tities of mold release recommended for use
with epoxy were determined by tests at resin
suppliers. Any levels of mold release in excess
of those recommended will not provide addi-
tional benefit to the process. A high
concentration of mold release may result in a
'squeeze off' at the die entrance which could
work its way back into the resin bath. If a pre-
lubrication step is used, this squeeze off resin
quantity must not be allowed to get back into
the resin bath.
Prior to the resin entering the bath, the die
temperature must be stabilized at the set point.
For most parts an initial throughput speed of
25.4-30.4 cm (10-12 in) per min is recom-
mended until the cured stock is in the pullers,
to minimize loads imposed on the dry fiber.
Process rate increase can then be made gradu-
ally and for epoxy resins the processing speeds
normally will not exceed 45.7 cm (18 in) per
min. It would appear that 30.4-35.5 cm
(12-14 in) per min provides the best combina-
Part 'B'
Epon Curing AgenP
9360
33 PHR based on resin weight
OR
Recompute based on the total weight of Part 'A'
(33/121.77) 100 = 27.1
and use
27.1 PHR to Part 'A'

tion of processing parameters, pull loads and
surface gloss. If RF preheating is used, perform
the start up without it at a reduced speed
15.2-20.3 cm (6-8 in) per min to minimize pull
loads. When cured stock is through the die and
in the pullers, the RF preheater can gradually
be started up. The resin temperature entering
the die should be monitored and as it reaches
about 71°C (160°F)gradually increase the pro-
cessing speed. Do not recycle the resin which is
squeezed off at the die entrance.
23.7.1 TROUBLESHOOTING
The standard problem encountered with
epoxy resin pultrusions is poor surface finish
or sloughing. The reasons for this have been
discussed earlier in this chapter. If the rein-
forcement level is low then the cure for this is
to obviously add some reinforcement.
However, if the redorcement level is in accor-
dance with the specifications, then additional
reinforcement will increase the pull loads
beyond standard. In this case the die tempera-
ture profile is probably too low. There is an
instrument on the market known as the
Gelstar Thermal Analyzer. The thermal ana-
lyzer can be used to obtain a temperature
profile within the die. From this, the size of the
gel zone can be estimated. This is proportional
to the lag time between the die and internal
temperature profiles. If the temperatures
appear to be within limits but the lag time is
too large then the processing rate is too fast for
the particular cross section within the die. At
this point either reduce the process rate or use
RF preheating to minimize the problem. These
steps will reduce the size of the gel zone.
If sloughing is encountered, the part should
automatically clean itself up. The typical
purge techniques that are common in the
industry can be used with epoxy resins. If a
portion of the die refuses to clean up, a trick is
to insert a copper kitchen ‘Chore Boy’ in the
area of the part which has the problem. This
will often push the offending plug out or catch
onto it and pull it out. The copper gauze will
Additives 515
provide a mild scrubbing action that will clean
the surface of the die.
23.7.2 SHUT DOWN
Standard shut down procedures have been
developed for polyester resins. The key step is
to remove the resin bath or bypass the rein-
forcement around it. The dry reinforcement
should be completely pulled through the die.
None of it should be cut out or removed. At
this point the die will be free from build up
and ready for a restart.
The resin drain from the bath should be
placed in a container in an area with good ven-
tilation and spill protection. A metal or plastic
tray with a surrounding high lip will be satis-
factory for spill protection. The resin containers
should only be half full. Eventually when it
does exotherm, it will become hot, expand and
may overflow the container if it is too full.
23.8 ADDITIVES
Inorganic fillers are used to reduce shrinkage at
polymerization. They also extend the volume of
the resin phase to provide a low cost formula-
tion. These are primary additives. Fillers can
frequently constitute the largest proportion of a
formulation, second only to the base resin.
Fillers are classified according to their particle
size, as either coarse fillers or fine. Coarse fillers
have an average particle size in excess of 8 pm
and are generally the nonfibrous type with low
surface area and low oil absorptions. They can
be highly loaded into the resin and are easily
wetted out by the resin system. Their disadvan-
tage is that they tend to provide poor
compound cohesiveness and to introduce local-
ized resin rich pockets and possibly to increase
fiber agglomeration during secondary molding
processes (as in pull forming).The large particle
size filler can be filtered out by a high density
roving preform which can lead to large voids in
the interior of the pultruded structure.
The most common of these fillers are cal-
cium carbonate, aluminum silicate and
516 Pultrusion
alumina trihydrate. Silica and coarse talcs are
also examples of coarse fillers. Calcium car-
bonate is primarily used as a volume extender
to provide the lowest cost resin formulation
where performance is not critical4s.
Fine fillers have an average particle size of
5 pm or less and have high surface areas which
can produce high viscosities in the formula-
tions. These fillers provide a high order of
cohesiveness and will tend to lubricate the
pultrusion system. They also help to reduce
localized shrinkage owing to their more com-
plete distribution within the polymer. Kaolin
clays, hydrous alumina silicate, fine talc, col-
loidal silica and precipitated calcium
carbonate are examples of fine fillers. Clay
fillers are used to improve corrosion resistance
and where electrical properties are required.
They also impart a superior surface finish to
the pultruded product. Alumina trihydrate
improves flame and smoke generation proper-
ties and occurs in applications where
consumer or governmental codes are imposed
to decrease flammability.
Fillers used in the pultrusion process
should contain less than 0-5% free water con-
tent and should be uniform and free from
contamination. Foreign material in the filler
may cause localized reaction with off gassing
of volatile byproducts and voids or could
affect the uniformity of coloring within the
pultrusion. Fillers are mixed into the resins in
quantities up to 50% of the total resin formula-
tion by weight (100 parts filler per 100 parts
resin). Limits of filler addition are based on the
viscosity of the system which results from the
particle size of the filler and the characteristics
of the resin. Wetting agents are sometimes
used to add a volume of filler material without
increasing formula viscosity. Wetting agents
can be added to the filler by the supplier or as
an additive during the formulation process for
the resin. Air release agents are added in the
same manner and will result in more efficient
packing by reducing entrapped air in the liq-
uid resin. They also tend to reduce void
content in the finished product.
23.8.1 PIGMENTS
Pultruded products are normally associated
with bright colors and these colors are nor-
mally created by adding suitable colored
pigments to the resin system which are then
cured into the matrix material. Pigments are
generally of three types: (a) dyes; (b) organic
pigments; (c) inorganic pigments. These three
pigments are characterized by their own indi-
vidual proper tie^^^. Dyes have good
transparency and acceptable brightness.
However, they have poor heat resistance and
tend to migrate in solution. Organic pigments
also have acceptable brightness and brilliance
but are not normally as good as the dyes.
Weather resistance and W absorption tends
to be a problem and the colors may deteriorate
and fade after long periods of W exposure.
Inorganic pigments are generally the materi-
als of choice. These are usually natural or
synthetic metallic oxides, sulfides, or other
salts which are heat treated and converted to a
dry powder at 600-1100°C (1112-2012°F).
Inorganic pigments have superior properties of
brightness to those of organic pigments or dyes
and are very resistant to weather and migra-
tion and have a very high stability under light
exposure. The major problem, however, in
incorporating these pigment additives into
resin formulations are the effects which they
have on the cure cycle of the resins. It is possi-
ble for them to be involved in the
polymerization reaction during the curing of
the resins and to become chemically attached
into some of the reactive sites. This has a strong
effect on the properties of the resulting com-
posite material and will require a change in the
temperature/time curing cycle. A large per-
centage of pultruded composite components
are used outdoors and W exposure is a prob-
lem. Under these circumstances, titanium
dioxide, an excellent UV absorber and
whitener, is used as a part of the formulation.
Its presence would also naturally create a paler
color in the pultruded composite and hence
additional quantities of inorganic pigment are

normally required to make the color bright.
Zinc sulfide is also a UV absorber which is fre-
quently used in pigment systems. Both
titanium dioxide and zinc sulfide seem to have
little effect on the ultimate mechanical and
physical properties of the pultrusions such as
the strength, moduli and impact resistance.
23.8.2 STRUCTURAL CONNECTIONS
Pultruded FRP composites can be joined using
various methods of assembly including
mechanical fastening (with plastic or metallic
bolts or screws or by doweling with dowels or
rivets), mechanically interlocking connections
(where molded or laminated inserts lock into
the sections being fastened), adhesive bond-
ing, or a combination of these methods50.
When structural components are assembled
special attention must be given to the rigidity,
geometry, fabrication and assembly require-
ments involved. It has been determined that
mechanical fastening and/or mechanically
interlocking connections are most suitable for
structural connections. Some connections
depending upon the geometry and the stresses
developed in connection can be strengthened
by also adhesive bonding in addition to
mechanical fasteners. Each of these systems
have their own advantages and disadvantages
which are discussed in the following para-
graphs.
23.8.3 MECHANICAL FASTENERS
If properly designed and fabricated, mechani-
cally fastened connections are the most
reliable method of joining pultruded struc-
tural sections. In recent years a significant
amount of information through empirical test-
ing and prototyping of connections has
become available on the bolting and riveting
of composites. There are many standard refer-
ences in this field51-53.
The advantages of a mechanically fastened
joint are:
Additives 517
0 surface preparation of the composites is
not required;
0 inspection of the joint is relatively easy;
0 the joint can be assembled and connected
up to full strength rapidly;
0 ability to disassemble and reassemble.
The disadvantages of a mechanically fastened
joint are:
in preparing the joints, holes must be
drilled and sealed, structural members
must be trimmed and any required gusset
plates must be fabricated;
drilling of holes cuts the longitudinal
strength fibers in the area of the hole. This
can cause high stress levels and stress con-
centrations;
strength of the joint is dependent upon the
bearing strength of the composite material;
the strength of mechanically fastened
joints is also dependent upon the strength
of the fastener.
Fastener parameters include:
0 clamping force/installation torque limits;
0 washer size for transmission of load;
0 fastener size;
0 hole size and tolerance;
0 joint type;
0 geometry of the fastener layout;
0 composite thickness;
0 rate of loading and the direction;
0 static or dynamic loading;
0 failure criteria;
0 high stress concentrations around fas-
tener.
23.8.4 ADHESIVE JOINTS
Adhesive joints have become popular for the
connection of the composite materials since
there is not degradation of the composite itself
by the bonding process. Adhesives are usually
available in solid, paste or liquid form and are
classified as either inorganic or organic materi-
als. The majority of the structural adhesives are
derived from the organic group and can be
518 Pultrusion
thermosetting resins, thermoplastics, or elas-
tomers. These adhesives are known for their
properties of being strong, tough, insoluble and
useable over a wide temperature rangeM.The
primary advantages of an adhesive joint are:
0 the properties of the composite material
remain intact and are not degraded;
0 adhesives are generally stronger than the
composite material being bonded, conse-
quently any failure mode is usually forced
into the surrounding primary structural
material;
0 good distribution of joint stresses;
0 adhesive bonding can be used to bond dis-
similar materials;
0 adhesive joints can be particularly forgiv-
ing. Flaws in the joints do not generally
degrade the strength of the joint. The main
reason for this is that the critical stress
location in a bonded joint is usually at the
end of the overlap and flaws tend to occur
in the center of the joint where the stress
level is low;
0 good fatigue and impact loading charac-
teristics.
Disadvantages of the adhesive bonded joints
are:
0 surface pretreatment such as cleaning and
etching must be carefully performed;
0 the preparation and mixing of the adhe-
sive in the correct proportions is critical.
Manufacturers instructions must be fol-
lowed precisely;
0 there is a time limit or shelf life of the
adhesive following its preparation;
0 the component parts must be carefully
located ;sing holding tools and fixtures
and maintained in position with pressure
across the joint during the curing of the
adhesive;
0 while adhesive joints are normally
designed and stressed in shear, there is an
additional failure mode owing to peel
stress. This is a tensile stress which devel-
ops a maximum value at the free end of a
double or single lap joint. The stress can be
particularly severe in thick, double lapped
joints;
0 adhesive bonded joints take time to cure
while the resin is setting up and hardening.
During the cure cycle, the component parts
must be restrained in a fixed position.
23.8.5 MECHANICAL ADHESIVE
COMBINATION
Some connections are stronger using a
mechanically fastened/adhesive bonded joint.
Advantages of mechanically fastened/adhe-
sive bonded joints are:
0 higher overall capacities;
0 greater resistance to environmental and
thermal deteriorations;
0 less subject to peel stress failure than
‘bonded only’ joint;
0 improved fatigue and impact characteris-
tics;
0 increased joint rigidity.
The disadvantage of mechanically fas-
tened/adhesive bonded joints is that they are
labor intensive.
23.9 APPLICATIONS FOR PULTRUDED
PRODUCTS
Applications for pultruded products are many
and varied but generally are commercially ori-
ented. The process shows up in the consumer
and recreation market, electrical equipment
products, corrosion resistance, civil engineer-
ing and construction and transportation
(automotive, truck, bus and rail).
23.9.1 CONSUMER/RECREATION
The combination of strength, stiffness, fatigue
resistance and aesthetic design and coloring
makes pultruded products ideal for the con-
sumer recreation market. Applications are:
fishing rods, archery bows and arrows, hockey
sticks, tent poles, ski poles, playground equip-
ment, fence posts and baseball bats.
 Applications for pultruded products 519

23.9.2 ELECTRICAL EQUIPMENT

In this marketplace, strength, electrical insula-
tion and safety are primary attributes of
pultruded The following are the
most significant applications:fuse holders, lad-
ders, tool handles, electrical conduits5(', cable
traysy and power rail covers for subway trains.
Figure 23.22 shows a set of pultruded ladders
and Fig. 23.23 shows the installation of a
power rail cover for a subway train.

Fig.23.23 Third rail cover for rapid transit rail sys-

tem. (Courtesy of Creative Pultrusions Inc.)

23.9.3 C M L ENGINEERING/CONSTRUCTION
MARKET
In this market the properties which are
required are strength, modulus, corrosion
resistance and nonslip surfaces. Applications
are: gratings, stairs, guard rails, bridges and
platform^^^, crash barriers, ladder cages,
structural supports614, sign posts and signs,
light and pedestrian bridges.
Figure 23.24 shows an installationof gratings
and hand rails in a chemical plant. Figure 23.25
shows a pedestrian bridge and Fig. 23.26 shows
the Aberfeldy foot bridge in the UK. This latter
applicationis one of the most interesting devel-
opments in the application of pultruded
sections. This bridge was designed and erected
by Maunsell Structural Plastics Division of
Fig. 23.22 Pultruded ladders. (Courtesy of Creative Maunsell Engineering in London. The bridge
Pultrusions Inc.) spans the River Tay in Scotland and C O M & S
520 Pultrusion
,,
Fig. 23.24 Grating and handrail installation.
(Courtesy of North West Fibre Mechanics Ltd.)
Fig. 23.25 Pedestrian bridge in Pennsylvania.
(Courtesy of Creative Pultrusions Inc.)
Fig. 23.26 Aberfeldy footbridge. (Courtesy of
Maunsell Structural Plastics Ltd.)
two sections of a golf course. The bridge is a
double cable stay design and all of the compo-
nents are made of composite materials with the
bridge decking and guard rails being pultruded
products. Maunsell has also installed a com-
posite vehicular bridge at Bonds Mill in
England which was opened in 1994.
23.9.4 TRANSPORTATION MARKET
This market is potentially very large. It
includes automotive, trucks, busses, light rail,
subway trains and passenger trains. The prod-
ucts which are being pultruded for this large
array of industries are as follows: drive shafts
for trucks66,leaf springs67,68, bumpers, frames
and cross members, transportation container
bodies, roll up doors, refrigerated truck com-
ponents, frames for light rail cars, interior
structure for passenger trains and subway
load carrying beds for small trucks
and frangible airport approach masts.
 References 521

Figure 23.27 shows a bus interior, fabricated

from pultruded sections and Fig. 23.28 dis-
plays a frangible airport approach mast.

23.9.5 MISCELLANEOUS
Another market which is using pultruded
products is the oil and gas industry for off
shore oil well platforms. Application here is
for floor gratings, hand rails, stairs and storage
buildings and living quarters on the platforms.
Another emerging application is in the con-
stant cross section blade for the Darius design
of windmills for alternate power.
This is just a brief review Of the current aPP1i- Fig. 23.27 Bus interior showing pultruded compos-
cations. The future of the pultrusion process and ites. (Courtesy of Creative Pultrusions Inc.)
its applications is only limited by the scope of
human imagination. The market will continu-
ously increase and it is predicted that by the
year 2000 the total volume of pultruded prod- ..” .- -----c?9.

ucts will have tripled over the 1995 levels.

REFERENCES
1. Goldsworthy, W. Brandt, US Patent, 2 871 911
Apparatus for Producing Elongated Articles
from Fiber-reinforced Plastic Material; Issued
2/12/59.
2. Birsa, R. and Taft, P., New Materials Approach
for Providing Transverse Strength in Pultruded
Shapes, RP/C Reinforced Plastics/Composites
‘84; Composites go to the Market; Papers pre-
sented at Technical Sessions of the 39th Ann.
Conf., New York. Jan 16-19,1984, Session 1-A,
p. 4, 627, SPI Reinforced Plastics/Composites
Institute.
3. Taft, P. and Birsa, R., Transverse Strength for
Pultruded Parts, Plusf. Engng., 1984,40, (5), 634.
4.

5.

6.

Barking: Elsevier Applied Science, 1986,p. 1-46, Fig. 23.28 Frangible airport approach mast.
012. (Courtesy of Creative Pultrusions Inc.)
522 Pultrusion

7. Martin, J., Pultrusion, Plastics Products Design 19. Beever, W.H. and O’Connor, J.E., Pultruded
Handbook. Part B. Processes and Design for Thermoplastic Composite Structures, Int.
Processes, (ed Miller, E.), New York: Marcel S A M P E Symp. Proc., 32, 1309,1987.
Dekker Inc., 1983, p. 37-74. 20. Beever, W.H. and OConnor, J.E., Polyphenylene
8. Martin, J. and Sumerak, J.E., Pultruded Sulphide Pultruded Type Composite Structure,
Composites - The Case Against Aluminum 42nd Ann. Conf., Plastics/Composites Inst.,
Extrusions, Pultrusion Technology, Inc., RP/C 1987.
Reinforced Plastics/Composites ‘84; 21. Wood, AS., Pultrusion is Poised for New
Composites go to the Market; Papers presented Growth and It Won’t be All Thermosets, Mod.
at Technical Sessions of the 39th Annual Plast. Int., 1976, 6(6), 47-9.
Conference, New York. Jan 16-19, 1984, Session 22. Goldsworthy, W. Brandt, Thermoplastic
1-D, p. 5, Confer. 627, SPI Reinforced Plastics/ Composites: The New Structurals, Plast. World,
Composites Institute. 1984,42(9),56-8.
9. Laguan, O., Pultrusion: Economic Aspects, 23. Kidd, A.C., Winding and Profile Production -
Applications and Design, Rev. Plast. Mod., 1985, Tape, Filament, Pultrusion-Extrusion,
50(349), 61-6 (Spanish). Reinforced Plastics, In Proc. Electrical Symp.,
10. Spencer, R.A.P., Developments in Pultrusion, In Bristol, Feb 1975, Paper 5, p. 18 Preprint 627-61
Developments in GRP Technology - 1, (ed. Harris, 24. Smith, A., Pull Winding Techniques Improve
B.), Barking: Applied Science, 1983, p. 1-36, Pultruded Products, Pop. Plast., 1988, 33(4),
6272. 42-3.
11. Martin, J.D., Pultrusion: The Other Process, 25. Shaw Stewart, D.E., Pullwinding Conf. Proc.,
Plast. Engng., 1979,35(3), 53-7. 2nd Int. Conf. on Automatic Composites, Paper
12. Beck, D.E., New Processes and Prospects in 15, Noordwijkerhout, The Netherlands, 26-28
Pultrusion, Goldsworthy Engineering Inc., Sept. 1988.
Composite Solutions to Material Challenges: 26. Goldsworthy, W. Brandt, US Patent, 3 674 601
38th Ann. Conf Preprint, Houston, Tex., Augmented Curing of Reinforced Plastic Stock;
February 7-11, 1983, Session 6-B, p. 4, Confer. Issued 7/4/72.
627, SPI, Reinforced Plastics/Composites 27. Goldsworthy, W. Brandt, US Patent, 3 793 108
Institute. Augmented Curing of Reinforced Plastic Stock;
13. Roubinet, P., Curved Pultrusion, Composites Issued 2/19/74.
Plast. Renf. Fibers. Verre Text, 24(4), July/Aug 28. Parry, T.V. and Wroksky, AS., Effect of
1984,69-73 (French). Hydrostatic Pressure on the Tensile Properties
14. Goldsworthy, W. Brandt, New Technology for of Pultruded CFRP, J. Mater. Sci., 1985, 20(6),
Continuous Reinforced Plastics Processing: Its 2141-7.
Called ’Pulforming’and It Permits Extrusion of 29. Bibbo, M.A. and Gutowski, T.G.,Analysis of the
Variable Cross Section Parts and Curves, Mod. Pulling Force in Pultrusion, Antec 86. Plastics -
Plast. Int., 1979,9(9),Sept, 100-1. Value Through Technology. Proc. 44th Ann.
15. Goldsworthy, W. Brandt, Pulforming - The Techn. Conf., Boston, April 28-May 1, 1986, p.
Changing Shape of Composites. 1430-2.012. SPE.
16. Ewald, G.W., Curved Pulforming - A New 30. Anon, Pultruded Fibre-Reinforcements, Plast.
Manufacturing Process for Composite News (Aust.),Nov. 1979, 20.
Automobile Springs, Working Together for 31. Hill, J.E., Goan, J.C. and Prescott, R., Properties
Strength, 36th Ann. Conf., Washington, D.C., of Pultruded Composite Containing High
February 16-20, 1981, Session 16-C, p. 1-6, Modulus Graphite Fibers, S A M P E Qtly, 1973,4,
Confer. 012 SPI Reinforced Plastics/Composites (2), 21-7.
Institute. 32. Spencer, R.A.P., Advances in Pultrusion of
17. Goldsworthy, W. Brandt, Pulforming Makes Carbon Fibre Composites, Carbon Fibres, 2nd
Curved Pultrusions, Brit. Plast. Rubb., Nov 1985, Int. Conf., London, Feb 1974, Paper 21, 140-7,
p. 36. Confer. 51FlC.
18. Nepasicky, J and Kannebley, G., Advantages 33. Evans, D.J., Designing with Pultrusions: From
and Limitations of Vertical and Horizontal the Idea to the Application, Composite
Pultrusion Processing. Examples of Typical Solutions to Material Challenges: 38th Ann.
Applications. Conf Preprint, Houston, Tex., February 7-11,

1983, Session 6-A, p. 5, Confer. 627, SPI
Reinforced Plastics/Composites Institute.
34. Browning, J., Synthetic Surface Veils for GRP
Laminates, Int. Reinf. Plast. Ind., 1986, 5(5) 14/6.
35. Werner, R.I., Improvements in Means of
Evaluating Weathering Characteristics of
Pultrusions, Rising to the Challenge: 35th Ann.
Conf. New Orleans, LA, Feb 1980, Section 4-E,
p. 6, Confer. 627. SPI Reinforced Plastics/
Composites Institute.
36. Heritt, R.W., New, High Performance, Fast
Curing Epoxy Resin System for Composites,
Composite Solutions to Material Challenges:
38th Ann. Conf. Preprint, Houston, Tex.,
February 7-11,1983, Session 19-D, p. 7.627, SPI,
Reinforced Plastics/Composites Institute.
37. Kershaw, J.A., New Epoxy Resin Systems for
Pultrusion, Shell Development Co., Composite
Solutions to Material Challenges: 38th Ann.
Conf Preprint, Houston, Tex., February 7-11,
1983, Session 6-42, p. 4, 627, SPI Reinforced
Plastics/Composites Institute.
38. McQuarrie, T.S., New Generation Resins for
Pultrusion, 33rd Ann. Conf., Washington, D.C.,
Feb 1978, Section %E, p. 5, Confer. 627 SPI
Reinforced Plastics/Composites Institute.
39. Howard, R.D. and Sayers, D.R., Development of
New Methacrylate Resins for Use in Pultrusion,
RP/C Reinforced Plastics/Composites '85. 40
Years of Innovative Technology;Proc. 40th Ann.
Conf., Atlanta, GA, January 28-February 1,
1985, Paper 2-A, p. 5, 627, SPI Reinforced
Plastics/Composites Institute.
40. Boinot, E and Daspet, Y., Phenolic Resins: A
Boon to the Building and Transport Industries,
Composites Plast. Renf. Fibres Verre Text, 26, 3,
May/June 1986,97-100.
41. Lo Scalzo, E., Phenolic Resins in Advanced
Composites, Mat. Plast. Elast., 1988, 3, p. 124-9
(Italian).
42. Hunger, G.A., Pultruding Epoxy Resin,
Reprinted from 43rd Ann. Conf. and Focus '88.
Proc. 43rd Ann. Conf. SPI Reinforced
Plastics/Composites Institute
43. Kiernan, D., Tessier, N. and Schott, N.,
Modification of Epoxy Resins for Improved
Pultrusion Processing, US Army Materials &
Mechanics Research Center, RP/C Reinforced
Plastics/Composites '85, 40 Years of Innovative
Technology; Proc. 40th Ann. Conf., Atlanta, GA,
January 28-February 1,1985, Paper 2 4 , p 6 627,
SPI Reinforced Plastics/Composites Institute.
44. Sumerak, J.E., Understanding Pultrusion
References 523
Process Variables, Mod. Plast., March 1985.
45. Sumerak, J.E. and Martin, J.D., Pultrusion
Process Variables and their Effect Upon
Manufacturing Capability, RP/C Reinforced
Plastics/Composites '84; Composites go to the
Market; Papers presented at Technical Sessions
of the 39th Ann. Conf., New York. Jan 16-19
1984, Session 1-B, p. 7, Confer. 627, SPI
Reinforced Plastics/Composites Institute.
46. Sumerak, J.E., Understanding Pultrusion
Process Variables, Mod. Plast., 1985,62(3),58-64.
47. Sumerak, J.E., Understanding Pultrusion
Process Variables for the First Time, Conference,
Atlanta, GA, January 28-February 1, 1985,
Paper No 2-B, p. 8, Confer. 627, SPI Reinforced
Plastics/Composites Institute.
48. Armstrong, R.F., Calcium Carbonate,
Encyclopedia of Chemical Technology, Vol. 4, 2nd
ed., Wiley Interscience, New York, 1964.
49. Anderson, R. and Riddel, R., Effects of Pigments
on Pultrusion Physical Properties and
Performance, Molded Fiberglass Co.; Morrison
Molder Fiberglass Co., Composite Solutions to
Material Challenges: 38th Ann. Conf Preprint,
Houston, Tex., February 7-11, 1983, Session
6-H, p. 4, Confer. 627, SPI Reinforced Plastics/
Composites Institute.
50. Rufolo, A., Design Manual for Jointing of Glass
Reinforced Plastics, US Naval Material
Laboratory Report, Navship 250-6341, August
1951.
51. Hodgkinson, J.M., de Beer, D.L. and Matthews,
EL., The Strength of Bolted Joints in Kevlar R.P.,
Proc. Composite Design for Space Application,
The Netherlands, (esa SP-243) 15-18, October
1985.
52. Hollaway, L. and Baker, S., The Development of
Nodal Joints Suitable for Double Layer Skeletal
System made from Fibre/Matrix Composites,
Part 7, Paper 21, Proc. 3rd Intern. Conf. on Space
Structures (ed. Nooshin, H.), Barking: Elsevier
Applied Science, 1984.
53. Green, A.K. and Phillips, L.N., Crimp-Bonded
End-Fittings for Use on Pultruded Composite
Sections, Composites, 1982,13(3),219-24.
54. Hart-Smith, L.J., Adhesively Bonded Joints for
Fibrous Composite Structures, Douglas paper
7740, Long Beach, California, 1986.
55. Anderson, R., Use of Pultruded Reinforced
Plastics in Energy Generations and Energy
Related Applications, Working Together for
Strength, 36th Ann. C o d , Washington, D.C.,
February 16-20, 1981, Session 22-B, p. 1-3,
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Confer. 012. SPI Reinforced Plastics/Composites
Institute.
56. Morara, F. and Eva, G., GRP Conduits and
Poles, Agrosistemi, Macplas, 1985, 10(67),
136-9.
57. Pultrusions for Cable Rack, Brockhouse Group,
Eur. Plast. News, 1982, 9(4), p. 36.
58. Mallick, P.K., Qiauw, L.K. and Fesko, D.G.,
Design and Evaluation of a Pultruded Hybrid
Beam, Working Together for Strength, 36th Ann.
Conf., Washington, D.C., Febraury 16-20, 1981,
Session 1 7 4 , p. 1-5, Confer. 012. SPI Reinforced
Plastics/Composites Institute.
59. Head, P.R., GRP Walkway Membranes for
Bridge Access and Protection, 13th Reinforced
Plastics Congress, 1982, Brighton, November
8-11,1982, Paper 20,97-91, BFP Publn. 293, BPF,
Reinforced Plastics Group.
60. Head, P.R., Pultruded Box Beams, Fibreforce
Composites, Ltd.; Maunsell Structural Plastics;
UK Dept. of Transport; Windfoil Ltd.
61. Anderson, R.A. and Thomas, C., Development
of Large Hollow Rectangular Tubes for
Structural and Electrical Markets - A Unique
Application for Pultrusion, Rising to the
Challenge: 25th Ann. Conf., New Orleans, LA,
Feb 1980, Section &A, p. 5, Confer. 627. SPI
Reinforced Plastics/Composites Institute.
62. Starr, T.F., Structural Applications for Pultruded
Profiles, TECHNOLEX, Composite Structures 2;
Proc. 2nd Intern. Conf. Composite Structures,
Paisley, September 1616,1983, p. 192-216,627.
63. Tickle, J.D., Halliday, G.A., Lazzarou, J. and
Riseborough, B., Designing Structures With
Pultruded Fibre Glass Reinforced Plastic
Structural Profiles as Compared to Standard
Steel Profiles, 33rd Ann. Conf., Washington,
D.C., Feb 1978, Section SF, p. 8, Confer. 627.SPI
Reinforced Plastics/Composites Inst.
64. Owens-Corning Fiberglas Europe SA, Fiberglas
in Action: FRP Lighting Poles, Burssels, 1977,
Publn, 13-Ch. 4-5, p / 4 12 ins. 16/2/77
6272-6R.
65. Mutch, W., Composite Utility Pole, Plast. World
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66. Kliger, H.S., Yates, D.N. and Davis, G.C.R.,
Driveshafts: The Next Step for Composites?,
Aufomot. Engng, 1980,88(3),1OC-3.
67. Roubinet, P. and Delacroix, B., Industrial
Development of Composite Leaf Springs,
Composites Plast. RenJ Fibres. Verre Text., 26,(3),
May/June 1986, p. 79-83 (French).
68. de Goncourt, L. and Sayers, K.H., Composite
Spring Systems, Composites Plast., Rent Fibres
Verre Text, 1988,28(3), 145-50 (French).
69. BTR Permali RP Ltd, Pultrusion Protects
Passengers, Europ. Plast. News, 15(3), 1988,46.
PROCESSING THERMOPLASTIC 24
COMPOSITES
James L. Throne

24.1 INTRODUCTION
Machinery

Thermoplasticpolymers are seldom converted

into products without the time-dependent Product Requirements Shape or P a r t
Production
application of temperature, pressure, shear or Requirement
Electrical
other types of mechanical manipulation. The Environmental
mechanical manipulation of plastics is called Rigidity
Tempera tu r e
'polymer processing'. Many polymer Possible
processes and combinations of polymer Polymer Families Processes

processes are used in modern commercial

manufacturing. The selection of a process to
produce a thermoplastic polymer product
from pellets, powder, or other granular forms

I ti
begins with general characteristicsof the prod-
uct itself. The two primary concerns to be met F i b e r Type
F i b e r Length
in the manufacture of any polymer product Other Adducts

are:
0 Will the finished part meet all required, Concerns

specified and desired design criteria? I

0 Can the product be produced at the mini-
mum cost for the projected market size?
The first concern focuses primarily on the
ability of the polymer to meet mechanical and
environmental challenges throughout its func-
tional lifetime. This is shown as the left branch
of the Fig. 24.1 schematic'. The second concern
deals with the economic ability to process the
acceptable polymers into the useful product,
and this is shown as the right branch of Fig.
24.1.
Commercial polymers are rarely pure. Even
'neat' polymers or polymers that contain no
Handbook of Composites. Edited by S.T. Peters. Published
in 1998by Chapman & Hall, London. ISBN 0 412 54020 7
Compound Grades
I
Economics 1
F i n a l Polymer
Fig. 24.1 A schematic for choosing the proper poly-
mer and an attendant process'.
fillers, reinforcements or foam cells, usually
have one or more adducts or additives that
alter the basic characteristics of the polymer.
Table 24.1 gives a short list of some of the
adducts used with thermoplastics*. Some of
these, such as coupling agents, are vital in
achieving the desired final solid mechanical
performance of other adducts, such as fillers
and reinforcements. Typical fillers used in
526 Processing thermoplastic composites
Table 24.1 Adducts in thermoplastic polymers’
Antioxidants
Antistatic agents
Colorants and pigments
Coupling agents
Flame retardants
Fillers
Foaming agents
Heat stabilizers
Mold release agents
Odor suppressors
Plasticizers
Processing aids
Emulsifiers
Lubricants
Reinforcing fibers
Ultraviolet stabilizers
Viscosity depressants
thermoplastic polymers are given in Table
24.23. Typical fibrous reinforcements used in
thermoplastic polymers are given in Table
24.34. Filled, reinforced and foamed thermo-
plastics offer great breadth of solid mechanical
properties. In many cases, they offer substan-
tial processing challenges, as well. Nearly all
thermoplastic processes shape the polymer in
its fluid state (The most notable exception to
this is thermoforming, where forming occurs
when the polymer is in a rubbery state.
However, thermoforming depends on the pro-
duction of sheet that is produced by
calendering or extruding the polymer in its
fluid state.) Fillers and reinforcing fibers
increase the viscosity of the polymer, making
it more difficult to shape. As expected, pro-
cessing difficulty increases with increased
filler or reinforcement loading.
There are more than twenty major types of
polymer processes5.Not all these processes are
suitable for thermoplastics and not all thermo-
plastic processes are suitable for filled,
reinforced or foamed thermoplastics. Table
24.4 lists most of the thermoplastic processes
that are used with neat, filled or reinforced
poIymers. Several of these processes are dis-
cussed in detail shortly. As is apparent, fillers
and fibers increase the polymer processing dif-
ficulty. In certain instances, as with continuous
reinforcing fibers, conventional thermoplastic
processing cannot be used.
Part geometry is one way of classifying suit-
able polymer processes, Table 24.56. This
classification is further amplified in Table
24.67. Again, not all these processes are suit-
able for processing all polymers with all
combinations of fillers or reinforcements. As
noted in Fig. 24.1, the cost of the polymer is
only one aspect of the overall economics of
product manufacture. Table 24.7 gives a rela-
tive comparison of the process costs for filled
and reinforced polymers8.
Extrusion and injection molding are the pri-
mary methods for producing foamed, filled
and discontinuous-fiber reinforced thermo-
plastics. As an example of the growth in
molding thermoplastic composites, in the
1950s esentially all injection molded thermo-
plastics were neat or unfilled and
unreinforced. By the early 1990s, filled,
foamed and reinforced polymers accounted
for,more than 25% (wt) of all injection molded
parts. In certain instances, blow molding and
rotational molding are possible.
Thermoforming or rubbery sheet deformation
is now being applied to continuous fiber rein-
forced polymers. These processes are
described below, with the objective of compar-
ing general operating conditions of neat
polymers with thermoplastic composites. The
technical details of these processes are given
elsewhere9-I4.Two axioms apply:
0 Axiom I: If the neat polymer is processed in
conventional polymer processing equip-
ment, composite versions of that polymer
are usually processed in adapted or modi-
fied versions of that equipment.
0 Axiom 11: Processing is always more diffi-
cult with composite versions of processable
neat polymers.
An important corollary also applies:
 Rheology,fiber flow and fiber orientation 527

Table 24.2 Fillers for thermoplastic polymers3

Silica products Metallic oxides

Minerals Zinc oxide
Sand Alumina
Quartz Magnesia
Novaculite Titania
Tripoli Beryllium oxide
Diatomaceous earth Aluminum trihydrate
Synthetic amorphous silica
Wet process silica Other inorganic compounds
Fumed coloidal silica Barium sulfate
Silica aerogel Silicon carbide
Molybdenum disulfide
Silicates Barium ferrite
Minerals Mica
Kaolin (China clay)
Mica Metal powders
Nepheline silicate Aluminum
Talc Bronze
Wollastonite Lead
Asbestos Stainless steel
Synthetic products zinc
Calcium silicate Carbon
Aluminum silicate
Carbon black
Glass channel black
Glass flakes Furnace black
Hollow glass spheres Ground petroleum coke
Cellular glass nodules Pyrolized products
Glass granules or cullet Intercalated/exfoliated graphite
Calcium carbonate Cellulosic fillers
Wood flour
Chalk
Limestone Shell flour
Precipitated calcium carbonate Comminuted polymers

0 Corollary I: Adding foam, fillers or rein- economic importance of polymer processing

forcements to neat polymers will never
improve their processability.
24.2 RHEOLOGY, FIBER FLOW AND FIBER
ORIENTATION
Rheology is the study of polymer flow. Shear
flow and elongational flow dominate polymer
processing. The great length of polymer chains
results in extensive entanglements and com-
plicates the study of neat polymer flow. The
and the technical challenge of predicting
molten polymer response to applied load have
resulted in an incredibly rich literature15z1.
Neat polymer melts are considered as vis-
coelastic non-Newtonian fluids. Viscosity is
the measure of fluid resistance to applied load.
The viscosities of oil and water are material
constants, independent of shear rate. Fluids of
this type are called Newtonian fluids. In
steady-state shearing flow, polymers typically
exhibit shear-dependent viscosities, as with
528 Processing thermoplastic composites

Table 24.3 Fibers for reinforcing thermoplastics differences. Shear rate-dependent viscosity
and normal stress differences represent poly-
Cellulose fibers mer material functions and are not material
a-Cellulose constants.
Pulp preforms
Cotton flock
Jute
Sisal
Rayon 'p
a
Synthetic organic fibers
Polyamide (nylon, PA)
Polyester (PET)
Polyacrylonitrile(PAN)
Polyvinyl alcohol (PVOH)
E
v)

Carbon fiber l o 2 2

Asbestos fiber m-' mo m1 lo2 m3

Shear Rate, s-'
Fibrous glass
Filaments Fig. 24.2 Shear-rate dependent viscosity of low-
Chopped strand density polyethyleneat 180°C(356°F) with titanium
Reinforcingmat dioxide filler in volume YO.(Adapted and redrawn
Glass yarn from Ref. 22 by permission of the Academic Press.)
Glass ribbon
Whiskers
Aluminum oxide (Corundum)
Titanium dioxide The inclusion of particulates further compli-
Boron cates the rheological behavior of polymers
Boron nitride (Fig. 24.2). The effect of filler loading on
Boron carbide steady-state shear viscosity of polymers is
Metallic fibers approximated by:
Aluminum
Stainless steel zw = Y + K j " (24.1)
Copper
Tungsten where zw is the shear stress at the wall, f is the
shear rate, and Y, K and n are empirical con-
stants. This Hershel-Bulkley is the
power-law equivalent of the Bingham model
for Newtonian plastic fluids. As anticipated,
low-density polyethylene in Fig. 24.2=. When increasing particle surface area to volume
the shearing force on a Newtonian fluid is increases the viscosity of the polymer, even at
released, the fluid resistance instantaneously the same loading level and particle size distri-
ceases. When the shearing force on a poly- bution (Fig. 24.325). Increasing particulate
meric fluid is released, the fluid exhibits a loading levels usually decreases polymer vis-
measure of time-dependent reorganization, coelasticity as measured by the first normal
the extent of which depends on the extent and stress difference (Fig. 24.426).
duration of the applied forces. Viscoelastic flu- It has been suggested that the shear-rate
ids exhibit fading memory of deformation dependent viscosity of particulate and fiber-
history. This is manifested by normal stress filled polymers can be predicted from a
 Xheology,fiberflow and fiber orientation 529

Table 24.4 Effect of adduct type on thermoplastic polymer processability

Degree of difficulty (0 = Easy, 9 = Difficult, X = Not done)

Polymer process Neat Filled" Short-fiber Longlfiber Continuous Continuous
reinforced reinforced organicfiber inorganic
reinforced fiber
reinforced
Extrusion 0 3 5 8 b b
Sheet
Single screw
Extrusion 5 8 b b
Profile
Single screw
Extrusion 4 5 b b
Profile
Twin screw
Extrusion 5 7 b b
Compounding
Twin screw
Extrusion 2 5 8 X X X
Foam
Pultrusion X X X X 9 8
Injection molding 1 3 6 8 X X
Injection molding 2 4 7 X X X
Foam
Blow molding 2 X
Thermoforming 1 9
Compression molding X 5
Rotational molding 2 X

a Short aspect-ratio adducts.

Pultrusion replaces conventional extrusion for continuous filament thermoplastic polymers.

temperature-invariant master curve: polymer temperature needed for the viscosity

determination (K),T, = Tg + 50 (K), and T is
MFI, -
log,oMFL, - the glass transition temperature (K)27. &e
1 experimental results for many polymers and
8.86 (T, - Ts) 8.86 (T, - Ts) filler and fiber types show good agreement
- with the master curve.
101.6 + (T, - Ts) 101.6 + (T, - Ts) (24.2) Blow molding and thermoforming are poly-
where MFI is the melt flow index determined mer processes that employ melt or rubbery
using a melt flow indexer die of L / D = 3.8, phase stretching. Elongationalviscosity shows
according to ASTM D1238. T , is the ASTM rec- an increase in value with increasing filler load-
ommended test temperature (K), T2 is the ing in a manner similar to shear viscosity, Fig.
530 Processing thermoplastic composites

Table 24.5 Part geometry as means of classifying

processes for filled and reinforced thermoplastic
polymers6

Linear forming
Extrusion (sheet)
Extrusion (profile)
Pultrusion
Formation of a solid body by injecting
into a cavity
Unfoamed injection molding
Foamed injection molding
Formation of a hollow object
Blow molding
Rotational molding
Sheet forming
Thermoforming

24.528.As a first approximation, the elonga- 104 I , I , , , I 1 I , 1 1 1 1 ,

tional viscosity for filled polymers is 10-2 10-l 100

determined in a fashion similar to that for
shear viscosities, using equation (24.1)29.For
many neat polymers, the elongational viscos-
ity is proportional to three times the shear
viscosity. For filled polymers the proportional-
ity is substantially greater than three and is
usually shear rate-dependent34
Fiber flow in a shear field is far more com-
plex than particulate flow. Independent fiber
closed-orbit rotation as a consequence of
shear is dominant in very dilute suspensions.
Shear Rate, s-’
Fig. 24.4 Shear-rate dependent first normal stress
difference for polystyrene at 180°C (356°F)with car-
bon black filler in volume %. (Adapted and
redrawn from Ref. 26 by permission of Academic
Press.)
As fiber concentration increases, fiber interac-
tion inhibits independent fiber motion. At
moderately high fiber concentration or for

Fig. 24.3 Shear-rate dependent vis-

)
cosity of polypropylene at 200°C
(392°F) with two types of fillers
having particle sizes of 44pm or
less. (Adapted and redrawn from
m3
m-3 m-* 1 6 o, , , Ref. 25 by permission of Academic
Shear Rate. s 1 Press.)
 Thermal properties offlled and reinforced thermoplastics 531
005 01 02 03 0 4 05 07
Elongation Rate, s”
Fig. 24.5 Elongation-dependent elongational vis-
cosity for polypropylene at 200°C (392°F) with
calcium carbonate in volume %. (Adapted and
redrawn from Ref. 28 by permission of Academic
Press).
long fibers, fiber interaction acts to momen-
tarily align fiber segments into bundles. The
nature of the polymer flow field then deter-
mines whether these momentarily aligned
fiber bundles remain oriented as the product
is produced. Increased shear implies
increased fiber interaction. Fibers not oriented
in the flow direction are subjected to
increased bending stresses around the fiber
bundles. The result is fiber length degrada-
tion. In addition to increased normal stress
difference with increasing fiber loading, fiber
reinforced polymers exhibit substantial shear
stress and normal stress difference overshoot
at flow inception. These overshoots are attrib-
uted to the interactions of fibers moving from
an isotropic random state to the more ordered
shear flow state31. Depending on flow
strength and fiber aspect ratio and volume
fraction, these overshoots can be sustained for
several minutes.
24.3 THERMAL PROPERTIES OF FILLED AND
REINFORCED THERMOPLASTICS
Most polymer processes depend on energy
interchange between the environment and the
interior of the melt or solid polymer. Fillers,
reinforcing fibers and cells dramatically affect
the thermal properties of polymers. Typically,
polymers have lower thermal conductivities
than inorganic fillers and fibers and higher
thermal conductivities than gases that are
used as foaming agents. Thermal conductivity,
heat capacity, density and thermal diffusivity
are the most important.
24.3.1 THERMAL CONDUCTIVITY
10
Both the solid and fluid thermal conductivities
of a filled polymer depend on the relative filler
content and the shape of the filler. The
Halpin-Tsai equation modified by N i e l ~ e n ~ ~
yields useful values:
kc - 1+AB$ (24.3)
kP 1 - BO$
where A = kE - 1, and & is the Einstein coeffi-
cient, Table 24.833. $ is the filler volume
fraction, P is the maximum packing fraction,
Table 24.9%, k, is the thermal conductivity of
the composite, kp is the thermal conductivity of
the neat polymer, and kf is the thermal con-
ductivity of the filler. B and (T are given as:
(24.4)
(24.5)
The Einstein coefficient, k,, is a measure of the
shape of the filler particle. kE = 2.5 for regular
shapes such as spheres and becomes large for
fibrous or acicular particles. The packing frac-
tion, P, for uniformly sized particles varies in
value from 0.52 for random packing to 0.91 for
532 Processing thermoplastic composites

Table 24.6 Classification of polymer processes by size and shape for filled and reinforced thermoplastic
polymers7
_______

Processes 2 2 3 4 5 6 7 8 9 2 0 2 1
Blow molding Hollow, Platen x x X X
thin
wall
Calendering Sheet Width of X X
roll,
Compression molding Platen X X X x x x
Sheet extrusion Sheet Width X X
of roll,
Die
Profile extrusion Linear Die X
Injection molding Platen X X X x x x x x
Injection molding Platen X X x x x x x
(foam)
Pultrusion Linear Die X
Rotational Hollow X x x x x
Molding
Thermoforming Thin wall Platen X X
1 = Shape limitation
2 = Factor limiting maximum size
3 = Complex shapes
4 = Controlled wall thickness
5 = Open hollow shapes
6 = Closed hollow shapes
7 = Very small items
8 = Plane area greater than 1m2
9 = Inserts
10 = Molded-in holes hexagonal packing. For fillers with random
11 = Threads sizes, P is typically about 0.85 to 0.9.
Thermal conductivity is a tensor quantity,
with unique values in each of the three princi-
pal directions. Because filled polymers are
Table 24.7 Ranking of polymer processes according relatively isotropic, the principal values of
to unit costs thermal conductivity are usually equal. For
continuous carbon graphite filament compos-
Process cost ites, the thermal conductivity in the fiber
direction is usually much greater than that in
Calendering
Injection molding Very low the transverse directions. The packing frac-
tions are determined from Table 24.9 for the
Blow molding fiber and crossfiber directions. For random
Foam injection molding mats, the typical packing fraction value is
Profile extrusion Low
Rotational molding about 0.5 in the cross-fiber direction.
Sheet extrusion
Thermoforming 24.3.2 HEAT CAPACITY
Compression molding Medium
The polymeric heat capacity or specific heat is
Pultrusion the isobaric change of enthalpy with tempera-
Machining High ture:
 Thermal properties of filled and reinforced thermoplastics 533

Table 24.8 Values of the Einstein coefficient, k,, for various types of fillers33

Filler type k,"

Spheres, one size, maximum packing 2.50
Spheres, random close packing 2.50
Spheres, random loose placing 2.50
Rods or ellipsoids, random packingb
Aspect ratio = 2 2.58
=4 3.08
=6 3.80
= 10 5.93
Mixed sizes, irregular shapes, minimum surface area 4.00
Mixed sizes, plates flakesc 5+
Agglomerates of spheresd 2.5/$,
Agglomerates, generally'. kd40
a
Correction factors for the mechanical case of Poisson's ratio, Y , of the matrix:
V Factor
0.50 1.00
0.40 0.90
0.35 0.87
0.30 0.84
0.20 0.80
At high rates of shear and low @a, for the rheological case, these shapes tend to orient and to reduce &.
These values may be approximated from oil absorption data or more precisely determined by intrinsic viscosity.
@, is the volume fraction of the agglomerate that is spherical.
e
@ is the volume fraction of particles in the agglomerate and k, is the appropriate value for the particle shape.
These values are generally less than the maximum packing fraction for the particular particle shape.

Table 24.9 Effect of filler particle shape and packing type on maximum
packing fraction, P, for uniformly sized particlesM

Particle shape Packing type Maximum packing fraction, P

Sphere Hexagonal close packing 0.7405
Sphere Face-centered cubic 0.7405
Sphere Body-centered cubic 0.60
Sphere Simple cubic 0.5236
Sphere Random close packing 0.637
Sphere Random loose packing 0.601
Fiber Parallel hexagonal packing 0.907
Fiber Parallel cubic packing 0.785
Fiber Parallel random packing 0.82
Fiber Random orientation 0.52

are constant. The enthalpies of most amor-

= (%) P
(24.6) phous polymers such as polystyrenics, acrylics
and polyimides are nearly linearly dependent
The specific heats of fillers and reinforcements on temperature and so their specific heats are
534 Processing thermoplastic composites

nearly constant. Semicrystalline polymers adduct loading. Thermal diffusivity also

such as polyolefins, liquid crystal polymers
and polyketones have enthalpies that exhibit
the effects of melting and so their specific
heats are temperature-dependent. The specific
heat of a mixture of materials is given as:
increases with increasing void fraction in cel-
lular composite^^^. As a result, the rates of heat
addition and of heat removal increase with
increasing adduct loading.

(24.7) 24.4 EXTRUSION

Extrusion is a means of producing continuous,
where xi is the weight fraction and cp, is the linear products in a steady state fashion. Both
specific heat of the ith species. single-screw and twin-screw extrusion
processes are used to produce sheet and pro-
files from composite thermoplastics.
24.3.3 COMPOSITE DENSITY
Single-screw extruder length-to-diameter
The density of a mixture of materials is given ( L / D ) ratios range from 15:l to 48:l with 18:l
as: to 30:l being usual. Twin-screw extruder L / D s
range from 12:l to 30:l. Figure 24.6 is a
(24.8) schematic of a typical singlescrew extrudes6.
The process is generally characterized as hav-
where pc is the density of the mixture, xi is the ing four sequential segments37,38:
weight fraction and pi is the density of the ith
0 Solids conveying, where the polymer pel-
species.
lets, flake, powder or granules are conveyed
from the extruder hopper to the conveying
24.3.4 THERMAL DIFFUSMTY flights of the extruder. The particulates are
Thermal conductivity is the key material prop- compacted and begin to heat by shearing
erty in steady state heat transfer. The heat flux, contact with the metal screw and barrel.
9, is proportional to the thermal driving force Table 24.10 tabulates the polymer character-
as: istics that are important during solids
conveying. Methods of determining some
dT of these properties are discussed in Sections
9 =k- (24.9)
dx 24.2 and 24.3.
where T is temperature and x is distance 0 Plasticating or melting, where the gap
through the composite. between the barrel and the root of the screw
The proportionality is thermal conductivity. is reduced, the polymer melts and the com-
In transient heat transfer, thermal diffusivity is pressed solid cake breaks up. The degree of
the proportionality, as: compression usually depends on the mor-
phological nature of the neat polymer.
(24.10) Crystalline polymers need greater compres-
sion ratios than amorphous polymers.
where t is time and a is thermal diffusivity, Polymers with particulate adducts need a
given as: lower compression ratio than neat poly-
mers. Table 24.10 also includes the polymer
a = - -k- - (24.11) properties that are important in plastica-
PCP tion.
0 Melt pumping, where the fully fluid
For most filled and reinforced polymers, ther-
mal diffusivity increases with increasing polymer is pressure- and temperature-
 Extrusion 535

Table 24.10 Polymer properties important in extrusion

Solids conveying
Frictional coefficients of particulate polymers with various metallic surfaces
Temperature-dependent thermal properties of particulate polymers:
Thermal diffusivity
Thermal conductivity
Heat capacity
Bulk density
Polymer density
Temperature dependent modulus of polymer
Temperature dependent yield strength of polymer
Plasticating
Temperature dependent and shear rate dependent melt viscosity,
Density of polymer melt
Density of polymer cake in solid bed
Polymer melt thermal conductivity
Melt pumping
Melt viscosity dependency on
Temperature
Shear rate
Pressure
Polymer melt thermal conductivity
Viscous dissipation
Thermal and shear degradation potential
Extruder die
Polymer shear sensitivity
Degradation potential - temperature limitation
Melt fracture potential
Extrudate swell
Rheological characteristics
Normal stress difference
Temperature dependent elongational viscosity

conditioned for the extruder die. The pri-
mary polymer property is shear viscosity.
Other important properties are given in
Table 24.10.
0 Extruder die, where the polymer melt is
shaped a n d presented to the take-up
equipment39. The extruder die shape
depends on the product being produced.
For example:
- if the extruder die is slot-like, the result-
ing product is a planar sheet;
- if the extruder die is cylindrical, the
resulting product is a rod;
- if the extruder die is annular, the result-
ing product is a hollow pipe or tube. This
tube or pipe is also a parison for extru-
sion blow molding;
- if the extruder die is irregular, the result-
ing product is called a profile. Some of
the major polymer properties that are
important in profile extrusion are given
in Table 24.10.
Extrusion dies are dissipative. That is, the
polymer exhibits pressure drop through the
die equal to that provided at the tip of the
extruder screw.
536 Processing thermoplastic composites

\ H o m b F e e d Throat Thermocouple Well Barrel

I I 'Main Thrust Bearing

Heate; Band

Q
Motor

Fig. 24.6 Schematic of conventional single screw extruder without extrusion die. (Redrawn from Ref. 36 by
permission of Carl Hanser Verlag.)

Twin-screw extruders are used extensively
in producing linear composite products. Figure
24.7 is an illustration of a cylindrical intermesh-
ing twin-screw d e ~ i g n ~ ~ lTwin-screw
~l.
extruders are classified according to the relative
screw rotational directions, whether the screws
intermesh and the relative screw speeds, Table
24.11. Comparative twin-screw performance is
given in Table 24.12. Despite some important
shortcomings, twin-screw extruders are desired
for low shear and controlled feed rates, impor-
tant aspects of compounding composite
thermoplastics as well as extruding them into
uniformly consistent products.
Increasing time in the shear field results in a
linear decrease in fiber length (Fig. 24.847).
Fiber length degradation is much less influ-
enced by screw speed than mixing time. As a
result, twin-screw compounding extruders
provide less fiber length degradation than do
tandem compounding single screw extruders.
In fiber-reinforced extruded products, the
average fiber orientation for discontinuous
fibers is up to about 20" from the axis4s.The
orientation is the result of converging flow
from the extruder screw tip to the die end.
(Converging flow is one of the standard die
design critia for neat polymer extrusion.
Accelerating flow allows molecuIar alignment
in the axis direction and tends to minimize
extrudate swell shear d e ~ e n d e n c y ~ ~ . )
Extrudate swell decreases with increasing

Cornpresnion Precompression
Metering Gas-Meit Mixing Preheating Feed
I_ \ I L & L
I- I I

Fig. 24.7 Schematic of standard configuration of cylindrical twin screws40.(Redrawn by permission of Carl
Hanser Verlag.)
 Extrusion 537

10
I 1 I I
0 10 20 33 40
TiO, Volume Percent 96

Post-Injection Molding
Fig. 24.9 Effect of volume fraction of titanium diox-
m ide on extrudate swell ratio for high-density
0 e polyethylene at 180°C (356°F). Capillary L / D = 28
and shear rate = 10 s-l. (Redrawn from Ref. 50 by
permission of Academic Press.)
05 10 15 2.0 ' 25

Mixing Length, Diameters

Fig. 24.8 Effect of residence time in shear field on

glass fiber length in injection molding and extru-
~ion~ (By
~ . permission of Society of Plastics
Engineers.)

Table 24.11 Classification of twin-screw extruders

Intermeshing screws'
Corotating screws
Low speed extrusion for profiles, foams, filled polymers, short-fiber profiles
High speed extrusion for compounding and devolatilization
Counter-rotatingscrews
Conical extrusion for profiles
Cylindrical extrusion for profiles
Non-intermeshing screwsb
Counter-rotating separated screws
With blades for kneading, compounding
High speed for in situ polymerization
Corotating screws
Not used in practice
Counter-rotating tangential screws
High speed for compounding, devolatilizing
Low speed for plasticating fluffy, bulky regrind
a
Intermeshing screws are also classified as h l l y or closely intermeshing or partially intermeshinp
Non-intermeshing screws are also classified as separated non-intermeshing and tangential non-intermeshing
screws4z.
538 Processing thermoplastic composites
filler loading (Fig. 24.950)and with increasing
fiber orientation in the hoop direction.
Orientation in the extrusion direction is
desired for profiles that are designed for
strength in the bending direction. For pipe and
tubing, on the other hand, the strength in the
hoop direction is half that in the axial direction
for an isotropic polymer. Reinforcement and
hence fiber orientation is desired in the hoop
or cross-extrusion direction. This is achieved
by using a diverging die section following the
converging section (Fig. 24.1O5I).The amount
*-
Annular Die
Fig. 24.10 Expanding mandrel extrusion die with
converging section for extrusion of highly fiber-
reinforced polymers. (Redrawn from Ref. 50 by
permission of Society of Plastics Engineers.)
Hopper
f r l
\
Plasticating Screw
Nozzle
Non-Return Valve
Fig. 24.11 Schematic of plasticating and injection portion of conventional reciprocating screw injection
molding machine. The nozzle inserts into the sprue of the mold mounted on the press shown in Fig. 24.12.
(Redrawn from Ref. 55 by permission of Carl Hanser Verlag.)
of hoop reinforcement is related to the channel
width expansion52.
24.5 INJECTION MOLDING FILLED AND
REINFORCED THERMOPLASTICS
Injection molding is a means of producing dis-
crete products on a cyclic b a ~ i s ~The ~,~~.
injection molding machine consists of two
major parts: the plasticating and pumping sec-
tion, and the clamping mechanism.
24.5.1 THE PLASTICATING AND PUMPING
SECTION, FIG. 24.1155
A single Archimedean screw similar to an
extrusion screw acts to convey and compress
the solid thermoplastic, plasticate and melt the
polymer and melt convey or pump the poly-
mer melt through a non-return valve or check
ring to an accumulation region ahead of the
screw. As the polymer accumulates between
the screw tip and the nozzle, it pushes the
screw backward away from the nozzle, effec-
tively shortening it. When a suitable amount
of polymer is accumulated, the mold is closed,
the nozzle abuts the sprue, the screw advances
and the melt is pushed into the mold. Injection
molding screws have L / D ratios of 15:l to 30:l.
Hydraulic Piston
W
\
Frame Electromechanical Drive
 Injection molding filled and reinforced thermoplastics 539

Table 24.12 Advantages and disadvantages of twin-screw extrudersM

Advantages
Controlled compaction of powders in feed zone
Powder feeding independent of friction with screw or barrel
Starved feed decouples feed rate, screw speed and extent of viscous shear heating
Rapid but gentle heating and plasticating of thermally sensitive polymers
Kneading action provides superior thermal and melt mixing and homogenization
Control of pressure build-up by proper element selection
High outputs at low speeds, minimizing shear heating
Ability to custom design processing sections
Gas injection easy to locate
Addition of adducts, fillers, reinforcing elements relatively straight forward
Comparatively little wear on extruder elements when processing aggressive fibers, fillers
Comparatively little fiber attrition
Disadvantages
Equipment cost per unit output very high
Output limited when compared with tandem extruders
Screw wear harder to predict
More difficult to mix gases into polymer melts in direct gas injection
Maintenance tends to be specialized, expensive
Although flexibility in changing mixing elements touted, no real way of determining a priori what
mixing elements are best for optimum throughput"
Pressure build-up entering the die is less effective
The thrust bearing remains the primary mechanical weakness
a Recently, computer models have been developed to aid in understanding polymer flow in certain elements such as for-
ward pumping screw elements, backward pumping screw elements and kneading disc elements45.Owing to the
complex geometry, twin-screw extruder configuration and element design has not achieved the sophistication of sin-
gle screws46.

The length ratio of solids conveying to plasti-
cating to melt pumping is 50:25:25. Injection
molding screw compression ratios are usually
the same as those for extrusion.
24.5.2 THE CLAMPING SECTION
Figure 24.1256shows a fully hydraulic clamp,
one method of holding the mold halves closed
against the pressure of the injecting melt. The
clamp consists of a stationary platen and a
moveable platen. The platens are guided open
and closed along tie bars. The polymer is intro-
duced through the sprue, a hole in the
stationary platen. The moveable platen con-
tains a means of applying pressure to hold the
mold halves closed. Hydraulic and mechanical
methods are common means although new
electric drives are considered to need less
maintenance. In addition, means for ejecting
the part from the mold cavity are usually
attached to the moveable platen. The polymer
is transferred from the accumulator section of
the screw into the mold cavity by ram-
advancement of the screw at relatively high
shear rates of 100-10000 s-l, with transfer
times of seconds. Since polymers are com-
p r e ~ s i b l eat~ ~injection pressures and exhibit
decreasing density with increasing tempera-
pressure is applied to the polymer in the
mold cavity, runner system and transfer lines
after the cavity is filled, until the polymer cools
sufficiently to hydraulically seal the mold cav-
ity. This packing pressure is most important in
540 Processing thermoplastic composites

Tailstock Platen

Oil Inlet for Closin

Oil Inlet for Opening

L Traversing LMoving Platen Stationary Platen

Cylinder

Fig. 24.12 Schematic of hydraulic clamping portion of conventional injection molding machine. (Redrawn
from Ref. 56 by permission of Carl Hanser Verlag.)

Table 24.13 Polymer properties important in injection molding

Particulate polymer frictional coefficients

Solid and liquid polymer thermal properties
Thermal diffusivity
Thermal conductivity
Heat capacity
Particulate bulk density
Pressure and temperature dependent melt density
Polymer shear sensitivity
Degradation potential - temperature limitation
Shear and temperature dependent viscosity over the shear rate range of 0-10 000 s-I
Melt fracture potential
Extrudate swell
Rheological characteristics
Normal stress difference
Temperature dependent elongational viscosity
Melt compressibility
Volume expansivity
Isothermal compressibility
Pressure dependent shrinkage
Crystallization kinetics
Heat of crystallization
Rate of crystallization
 Injection moldingfilled and reinforced thermoplastics 541

the injection molding of all polymers, includ-
ing heavily filled and reinforced compounds.
A tabulation of polymer properties impor-
tant in injection molding is given as Table
24.13. Note that many of these properties are
important in extrusion, as well.
For filled and reinforced polymers, mold
design is critical. There are several elements to
a mold:
result exhibit differential shrinkage values that
increase with increasing loading (Fig. 24.13j9).
As a first approximation, the flow of a filled
molten thermoplastic can be considered simi-
lar to the flow of the neat polymer, regardless
Cross-Flow

Sprue and runner system. The sprue

directs the polymer from the injection
molding machine nozzle into the mold
body through the stationary platen wall.
The runner system directs the molten poly-
mer to the appropriate cavities.
The gate. Polymer flows into a mold cavity
through a constriction called a gate. The

?
size and location of the gate are critical to
injection mold part performance, as noted
below.
; Diameter

Mold temperature control. Coolant lines

are normally placed parallel to the machine
platens. Adequate coolant flow to all part
surfaces is important in minimizing part
distortion and warpage. Warp = CuplDiameter
Part removal system. Typically, parts are
I I
molded under substantial pressure of
10-15 MPa. Ejector pins and rings are used
to press the part from the mold surface after
the mold has opened. In addition, other
Cross-Flow -
I
devices such as sliding cores and unscrew- Relative Measure
ing devices are employed to meet certain of Warp
design criteria.
Crystalline neat polymers exhibit greater over-
all shrinkage and more differential shrinkage
0.5
than amorphous neat polymers. Filled poly-
mers exhibit lower overall shrinkage but may W
4-
show substantially greater differential shrink-
age, called warp or cupping, than neat 10 20 40
polymers. Typically, the value for shrinkage of
a filled or reinforced polymer is less than that Glass Fiber Content, %(wt)
for the neat state of the polymer, and the value
shows substantially less injection-pressure sen-
Fig. 24.13 Differential shrinkage, cupping and
sitivity. Fiber-reinforced polymers exhibit warping of glass fiber reinforced polyacetal
reduced in-flow shrinkage and greater cross- homopolymer (polyoxymethylene).(Redrawn from
flow shrinkage than neat polymers and as a Ref. 59 by permission of Carl Hanser Verlag.)
542 Processing thermoplastic composites

of the loading level. The amount of force
needed to transfer the polymer from the injec-
tion molding machine to the mold cavity
increases with increase in apparent shear vis-
cosity. Since the transfer pressure is usually
fixed by the machine hydraulic system, the
transfer rate usually decreases with increasing
mold system (Fig. 24.1463).(It has been mathe-
matically shown that the fountain flow effect
holds for cylindrical and planar flow field&.
Even at very high fiber loading, individual
fibers or fiber aggregates align themselves
with the flow streamlines6z.)As is apparent
from Fig. 24.15@,there is no appreciable shear

--
filler loading. Usually, sprue, runner and gate field in the center core. As a result, fiber
dimensions are increased to accommodate the
wall
lower compressibility of the filled polymer
melt. Solid particles tend to migrate away
from planes of highest shear. Since shear is
Shear Rate
greatest near the mold confining surfaces,
parts of highly filled polymers tend to have
resin-rich surface layers. These layers are typi-
cally 10-100 p in thickness. Similarly, weld
lines or planes perpendicular to meeting flow
fronts, also tend to be resin-rich and are usu-
L- Centerlune

ally weaker than regions on either side of the

weld line60. Increasing levels of filler tend to
minimize the problem of jetting, where a neat
polymer forms a thread rather than a radial
disk as it enters a mold cavity from the gate.
For fibrous reinforcements, where the L I D
aspect ratio is greater than about lO:l, orienta- wan
tion during flow is very important. The fiber Fig. 24.15 Typical shear rate and velocity profiles
rotation attempted in the shear field is compli- for nonisothennal flow during injection mold filling
cated by the fountain-like flow of the of a cavity. (Redrawn from Ref. 64 by permission of
polymeric mass as it advances through the Society of Plastics Engineers.)

Fiber Bundle Orientation

Advancing Flow-Front

Flow Streamlines

Cdd Wall

Fig. 24.14 Fountain flow in injection molding, showing fiber bundle behavior along a streamline and
development of frozen layer at cold walls. (Redrawn and reinterpreted from Ref. 63 by permission of
Society of Plastics Engineers.)
 Injection moldingfilled and reinforced thermoplastics 543

bundles move preferentially from the molded;

upstream organizing region transverse to the
center axis toward the flow front. In doing so,
they orient as the advancing front is formed.
As shown in the schematic, the interface
between the molten core and the frozen skin
grows rapidly into the melt once the advanc-
ing front has passed. The oriented fibers are
aligned parallel to the flow direction. As with
extrusion, the surface at the mold surface is
resin-rich and, in many cases, essentally fiber-
free. When the mold is full, the structure
shows three, five, seven and even nine layers
in cross section (Fig. 24.16'j5,@j):
the resin-rich surface layer, up to 10 mm
(0.4 in) in thickness;
a relatively thin layer of fibers oriented in
the flow direction, with some of these fibers
tipped toward the flow axis;
a relatively thick layer of fibers oriented
transverse to the flow direction, with a sub-
stantial amount of in-plane randomness,
0 at the very center, a very thin plane of fibers
that are oriented in the flow direction.
The general nature of flow into an injection
mold cavity through a constriction or gate is
radial. Since there is substantial in-plane
stretching, fiber orientation in the gate region
of long narrow molded parts are quite similar
to fiber orientation in center-gated axisymmet-
ric molded parts. If there is no in-plane
orientation, cores typically have random pla-
nar orientation. Typically, the thickness of the
transverse fiber orientation in the core
decreases with distance from the gate. For cer-
tain polymer-fiber combinations and certain
injection speeds and mold temperature, the
resin-rich surface layer may not be apparent.
In fact, fiber prominence on molded part sur-
faces is apparent at long flow length-to-cavity
thickness ratios, in regions very near the gate
when the flow is turned as it enters the mold
cavity, at low neat polymer viscosities, for cold

-
depending on the nature of the part being polymer melts, and at slow injection rates.

Flow Direction

Transverse Orientation
Inflow Orlentation In-Flow Orientation
Fiber-Free Layer Transverse Orientation

Fig. 24.16 Schematic of the development of fiber orientation in injection molding,showing disappearance
of fiber-free surface layer and centerline transverse fiber orientation as flow proceeds into the mold cavity.
(Redrawn and reinterpreted from Ref. 65 by permission of Society of Plastics Engineers.)
544 Processing thermoplastic composites

Furthermore, the center line or plane of in-axis
fibers is usually the result of continuing injec-
tion as the flow channel freezes closed. The
resulting high shear orients the fibers in the
flow direction. This layer may not be apparent
in all fiber-reinforced parts. In very thin parts,
fibers are nearly always oriented parallel to
the mold surface67.The flow in an injection
Weld lines are particularly bothersome with
fiber-reinforced polymers. The primary con-
cern is the undesirable fiber orientation at the
interface between two advancing flow fronts
(Fig. 24.17”O). Trpically the reZative weld line
strength decreases with increasing filler load-
ing and aspect ratio71(Table 24.14).

- -
mold is mathematically modeled using
Hele-Shaw or creeping flow6*,69.

Flow Direction Flow Direction

Weld Line

Weld Line

Fig. 24.17 Fiber orientation at the interface of two impinging flow fronts, creating a weak weld line.
(Redrawn from Ref. 70 by permission of Carl Hanser Verlag.)

Table 24.14 Relative weld line strength for neat and reinforced polymer^^*,'^
~~~

Polymer Tensile strength retention for various glass loadings, YO

0 10 20 30 40
Polypropylene 86 47 34
SAN 80 40
Polycarbonate 99 86 64
Polysulfone 100 62
Polyphenylene sulfide 83 38 20
Nylon 66 (PA-66) 83-100 87-93 56-64

24.6 THERMOFORMING AND
COMPRESSION MOLDING
For neat polymers, thermoforming and com-
pression molding are different disciplines74,75.
Thermoforming begins with a formed sheet of
plastic that is heated to the rubbery state of the
polymer, usually a few degrees above its glass
transition or melting temperature. The rub-
bery sheet is then pressed with relatively little
differential force into or onto a cooled single-
sided mold and held there until the polymer
temperature is substantially below the form-
ing temperature. (In traditional vacuum
forming, the space between the sheet and the
mold surface is evacuated, thus applying dif-
ferential pressure of up to 0.1 MPa. In pressure
forming, air pressure is applied to the free sur-
face of the sheet, thus applying differential air
pressure of up to 1Ml'a76.) The desired part is
then trimmed from the web. Compression
molding is usually reserved for thermosetting
polymers, but certain thermoplastic polymers
such as UHMWPE, PTFE, and certain poly-
imides are compression molded. These
polymers are characterized as having very
high viscosities even at temperatures hun-
dreds of degrees above their melting or
processing temperature^^^. A polymer of this
type is compressed as a powder into a pre-
form, heated in a convection oven to the
processing temperature, and transferred to a
compression molding press where it is com-
pressed between heated mold halves. Typical
molding pressures are 7-35 MPa. The mold is
then cooled until the formed part temperature
is substantially below the polymer processing
t e m p e r a t ~ r eTable
~ ~ . 24.15 gives polymer prop-
erties important in thermoforming.
For filled, foamed and reinforced polymers,
the boundaries between thermoforming and
compression molding blur. Frequently, the
composite sheet forming process is simply
called stamping79.Fillers and discontinuous
fibers stiffen the polymer so that even at the
upper forming temperature of the polymer,
substantial differential force is required to
Thermoforming and compression molding 545
Table 24.15 Polymer properties important in ther-
mof orming
Temperature dependent polymer hot strength
Elastic modulus at forming temperature
Elongational viscosity at the forming temperature
Strain-rate hardening at high elongation
Other properties that are important in extruding
polymer sheet
Temperature dependent thermal properties of
rubbery solid polymer:
Thermal diffusivity
Thermal conductivity
Heat capacity
Polymer density
form the composite from the planar state to a
useful product. Mechanical means such as
matched dies, or hydraulic forces using super-
plastic aluminum or polyimide films, replace
pneumatic forces when the differential form-
ing pressures exceed 1 MPa. The foamed
polymer, on the other hand, cannot be heated
to the same forming temperature as the
unfoamed polymer without dramatic cell col-
lapse. As a result, foamed polymers are
formed at temperatures substantially below
forming temperatures for the unfoamed poly-
mers. Mechanical forces, such as matched dies,
are used for forming foamed polymer sheet
into useful products. Typically, the ratio of
polymer modulus at forming temperature to
applied pressure, E ( T ) / P , should be in the
range of 2-10 with a value of 5 most typical for
traditional thermoformingsO.As an example,
the temperature-dependent flexural modulus
of glass fiber-reinforced polyetherimide is
shown in Fig. 24.W. At 200°C (392"F), the
modulus of neat PEI is 2 MPa. The pressure
required to thermoform this polymer at this
temperature is about 0.4 MPa. For 30% (wt)
glass fiber-reinforced PEI the modulus is
7MPa and the required pressure is about
1.4 MPa. Pneumatic pressures at this level are
possible, but mechanical forming is preferred.
In many cases, the elastic modulus of the com-
posite exibits similar temperature dependency
to the elastic modulus of the polymer matrix,
546 Processing thermoplastic composites
10, I I
I I I I
0 50 103
Temperature, "c
0 xa zm
Temperature. "F
with the isothermal value of the modulus
increasing monotonically with increasing filler
or fiber loading (Fig. 24.19a2).
Thermoforming is a surface-generating
process. That is, the total area of the finished
part plus web is greater than the total area of
the initial sheet. The dominant method of gen-
erating surface is biaxial stretching of the
rubbery solid polymer. The shape of the tem-
perature-dependent tensile stress-strain curve
oo 10 20
Glass Fiber Content. %(wt)
33
Fig. 24.19 The effect of glass fiber loading on flexural
modulus of polysulfone at 25°C (77'F). (Redrawn
from Ref. 82 by permission of Carl Hanser Verlag.)
I
Fig. 24.18 Temperature dependent
150 0 flexural modulus of glass fiber rein-
forced Dolvetherimide. (Redrawn
from Rei. s'l by permission of Carl
3M Hanser Verlag.)
of the rubbery sheet is key to the forming
process. Figure 24.20 is a schematic of a temper-
ature-dependent stressstrain curve for a neat
polymer that exhibits a yield at low tempera-
t u r e ~ The
~ ~ . effect of filler and discontinuous
fiber on the shape of this curve is shown in Fig.
24.21M.Typically, the initial slope of the curve,
the tensile modulus increases, the yield point
disappears and the elongation at break
decreases rapidly with increasing fiber or filler
loading. This implies that the forming of com-
posite thermoplastics requires high
temperatures, substantial forces and the parts
40
Elongation
Fig. 24.20 Schematic of temperature dependent
stress-strain curve for a neat polymer exhibiting a
yield point.

Elongation
Fig. 24.21 Schematic of the effect of fiber content on
isothermal stress-strain curve for a polymer
exhibiting a yield point when unreinforced.
n n
Bottom Mold Half
Bottom Platen
Mold Open
Fig. 24.22 Schematic of a mold designed to slip-form continuous fiber-reinforced composite. (Redrawn
from Ref. 88 by permission of Society of Plastics Engineers.)
Thermoforming and compression molding 547
so produced are restricted to relatively shallow
draws. Typically, polymers containing nonwo-
ven continuous fiber mat and short- and
long-fiber chopped fiber mat are formable with
matched metal dies. Composites containing
woven fiber mat are not as formablea5.For very
long glass fiber- and continuous fiber-rein-
forced composites, the extensibility of the sheet
is so restricted that even shallow draw parts
cannot be formed without substantial polymer
migration (the squeezing of the polymer matrix
from the fiber bundle is called ‘percolation’),
compression buckling, pleating wrinkling and
fiber breakage when standard matched die
molding techniques are used. (Note that this
problem is not unique to fiber-reinforced ther-
moplastic composites. Paper, organic synthetic
paper and mixed fiber paper are nonwoven
fiber structures that are very difficult to form
into deeply drawn product^^,^^.) It is well
known that buckling, folding and pleating are
minimized by keeping the sheet under tension
throughout the forming process. Further, for
composites with limited extensibilities, the
material that makes up the formed shape must
come from the region outside the formed
Drive Shaft
Cartrldge Heater
Mold Closed
548 Processing thermoplastic composites

lntraply Shear
Resin Percolation Through Fiber Bundle

Transverse Squeezing Flow

F
IP
I,

Fig. 24.23 Schematic of fiber-resin matrix interaction during deformation for several types of deforma-
tions. (Redrawnand reinterpreted from Ref. 93 by permission of Society of Plastics Engineers.)

shape. Slip forming is the principal method for

accomplishingthis (Fig. 24.Zm90).The key is to
supply sufficient tension to the sheet to mini-
mize folding but not an excess amount that will
tear the very hot ~ h e e t ~ l , ~ ~ .
Bulk mechanical deformation of the rein-
forced sheet is not the only concern when
I Heater I
forming reinforced sheet93.Figure 24.23 shows
several fiber-matrix interactions that take
place locally during composite thermoform-
ing94.Intraply shear, interlaminar shear or slip
and interlaminar rotation are local shearing
effects that involve the fiber. Local resin flow
between fibers, fiber bundles and plies allow Mold Open
local distortion of the matrix. Matrix percola-
tion and squeeze flow are predominantly resin Formed Sheet
effects. Voids and delaminations are micro- I PI
scopic defects that are attributed to local
fiber-matrix interactions during forming.
Compression molding is flow molding or
‘squeezingflow’ of polymer between two mold
halves (Fig. 24.2495).The flow behavior for a
filled or short-fiber reinforced polymer mimics Mold Closed
that for the neat The flow is usually
characterized as planar radial with the wave- Fig. 24.24 Schematic of flow molding, flow form-
front being fountain-like as with injection ing or squeezing flow of nonwoven fiber-reinforced
molding. Fiber orientation is quite similar to thermoplastic resin composite. (Redrawn from Ref.
that observed with center-gated injection mold- 95 by permission of Society of Plastics Engineers.)
 Other processes forfilled and reinforced polymers 549

Compression molding is also used with halves close on the parison, pinching it
long fibers or continuous fibers. In one exam- between the mold halves. The remaining por-
ple, a fiber preform is inserted in the mold tion of the parison is then inflated against the
cavity and a heated neat polymer preform is mold walls (Fig. 24.25). Parison thickness con-
placed on top. The press is closed to 35 MPa or trol is the key to uniform wall thickness.
more, squeezing the polymer into the fiber pre- Parison thickness uniformity is governed by
form. The process works best if the polymer is extrudate swell as the polymer exits the die
crystalline and has a very low melt viscosity at and by parison sag owing to the parison
the molding temperature. Compression hanging weight. The former is a function of
molded composite parts are usually more com- the viscoelasticity of the polymer in general
plex than thermoformed composite parts. and the normal stress difference in particular.
Voids, warping, fiber prominence at the part The latter is a function of the mass of the pari-
surface intially against the mold and resin rich- son, the extrusion time and the elongational
ness at the other surface are typical problems viscosity of the polymer. Neat polyethylenes
attributed to the forming process. exhibit extensive extrudate swell. Fillers and
fibers reduce the extrudate swell in propor-
24.7 OTHER PROCESSES FOR FILLED AND
tion to the filler or fiber loading (Fig.
REINFORCED POLYMERS
24.91°1J02).Filler loading increases parison dif-
ferential weight. And fillers and fibers cause
As noted above, foamable, filled and short-
fiber reinforced thermoplastics are usually
processed in fashions similar to the neat ther- Mold Half Mold Half
moplastic. Filled and reinforced hollow Parison
structural parts are fabricated by blow mold-
ing and rotational molding. Rotational
molding is also used to produce multilayer
structures having foam cores97.
Polyolefins account for approximately 90%
(wt) of all non-disposable industrial products
produced by blow molding and nearly all
products produced by rotational molding.
Mica flake reinforced HDPE to 30% (wt) has Mold Open
been accumulator blow molded into flat struc-
380" Pinch-Off
tural parts and ducts for automotive, truck
and agricultural vehicles since the early
1 9 6 0 ~ ~ ~Graphite-filled
-'~~. HDPE is blow
molded into conductive electrical boxes and
doors. Glass fiber-reinforced HDPE is blow
molded into flotation devices, sailboards and
kayaks. Accumulator blow molding machines
are used to extrude a large quantity of plastic
in a short period of time. The filled or short-
fiber reinforced polymer is plasticated at a Formed Part

constant rate in a conventional screw Mold Closed

extruder. The melt is stored in an accumulator
until the mold is cleared, then extruded in sec- Fig. 24.25 Top view schematic of lay-flat squeezing
onds into a parison or vertical tube. The mold of extruded parison in structural blow molding.
550 Processing thermoplastic composites

Table 24.16 Polymer properties important in blow molding

Shear and temperature dependent viscosity over the shear rate range of 0-10 000 s-'
Melt fracture potential
Nonisothermal melt strength or temperature dependent elongational viscosity
Extrudate swell
Rheological characteristics
Normal stress difference
Temperature dependent elongational viscosity
Polymer strain recovery
Molecular weight dependency
Molecular weight distribution dependency
Particulate polymer frictional coefficients
Solid and liquid polymer thermal properties
Thermal diffusivity
Thermal conductivity
Heat capacity
Particulate bulk density
Pressure and temperature dependent melt density
Polymer shear sensitivity
Degradation potential - temperature limitation
Effect of orientation on gas permeability of polymer
Strain-oriented crystallinity levels and effect on
Barrier properties
Permeability
Tensile strength

I i!
II II

tlne
Shafia

C h d n Drira

Fig. 24.26 Schematic of co-axis

rotational molding for filled or
lightly reinforced p~lyolefins'~~.
 Other processes for filled and reinforced polymers 551

the parison to cool more quickly. As a result,
parison wall thickness control must be
changed radically when blow molding filled
or reinforced polymers. Table 24.16 gives a list
of polymer properties important in blow
molding.
Rotational molding is an atmospheric
process in which polymer powder is charged
to a metal clam-shell mold. The mold is rotated
about the polar or major and equatorial or
minor axes (Fig. 24.261°3),while being heated in
a forced air convection oven for several min-
utes, until the powder sticks to the mold
surface, melts and densifies into a void-free
hollow object. The mold is then air- and/or
water mist-cooled, the part removed, the mold
recharged and the process repeated.
Polyethylene is the major rotational molding
polymer, with particle sizes ranging between
50 pn and 500 pm. Coarse particle fillers hav-
ing particle sizes of about 50 pm or more, such
as CaCO,, milled glass and glass cullet are suc-
cessfully molded to loadings of 30% (wt). Fine
particle fillers such as TiO,, carbon black and
talc fluidize readily in the tumbling environ-
ment of the mold and so rarely yield useful
products. Fibers with aspect ratios of 1000 or
less can be successfully molded if the maxi-
mum fiber content is less than about 15% (wt).
Lower fiber loadings may be necessary for cer-
tain mold geometries and certain types of
polyethylenes. If the fiber loading is too high,
the fibers orient at right angles to the mold sur-
face, producing an unacceptable setaceous
inner surface104.One method of forming a hol-
low composite is to impregnate nonwoven
fiber mat with up to 30% (wt) electrostatically
charged polymer powder, then sinter the struc-
ture to fuse the powder to the fibers. The hot
structure is then manually pressed against the
mold surfaces prior to adding additional poly-
mer powder, closing the mold, rotating it,
heating it to the forming temperature, and
cooling it in standard fashion105.Evacuating
the mold through the rotating concentric shafts
is helpful in minimizing voids but is usually
quite difficult to achieve successfully. Table
24.17 gives a list of polymer properties needed
for rotational molding.

Table 24.17 Polymer properties important in rotational molding

Particle size distribution

Temperature dependent thermal properties of particulate polymer
Thermal diffusivity
Thermal conductivity
Heat capacity
Bulk density
Polymer density
Molecular characteristics
Molecular weight
Molecular weight distribution
Crystallization kinetics
Heat of crystallization
Rate of crystallization
Crosslinking characteristics
Reaction rate
Level
Zero-shear viscosity at melt temperature
552 Processing thermoplastic composites

Table 24.18 Effect of fillers on processing properties

Processing property Effect of filler

Viscosity Increases
Melt flow Decreases
Compounding Machine dependent, usually complicates the process
Processing temperature Increases
Temperature No effect or cools faster
Injection pressure Increases
Flow in injection mold Mold dependent but usually decreases
Injection mold shrinkage Decreases
Injection mold cycle time No effect
Thermoforming sheet sag Decreases
Thermoforming pressure Increases
Thermoforming depth of draw Decreases
Thermoforming part surface quality Decreases
Extrudate surface quality Decreases
Extrusion die pressure Increases
Melt extrudate swell Decreases, sometimes dramatically
Melt fracture severity Decreases
Foam cell size No effect to decreases

24.8 SUMMARY REFERENCES

Filled polymers tend to process in manners
similar to their neat polymer counterparts. The
general trend is to increase the melt viscosity
of the polymer at low shear rates and to
decrease the relative effect of viscoelasticity of
the polymer. Table 24.18 shows this for most of
the processes described above. Short-fiber
reinforcements show more local flow orienta-
tion than fillers but, by and large, process
parameters are not dramatically influenced by
their presence. Long-fiber reinforcements on
the other hand show substantial local flow ori-
entation in all polymer melt processes. This
orientation is controlled to a limited extent by
the design of the dies and molds. Table 24.18
summarizes many of the important processing
variables for filled and discontinuous fiber-
reinforced polymers. Flow of continuous
fiber-reinforced polymers is restricted to local
squeezing flow around the fiber bundles and
so thermoforming, compression molding,
stamping and diaphragm forming are the
major ways of forming these thermoplastic
composites into useful products.
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6. Progelhof, R.C. and Throne, J.L., Polymer
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Table 5.3.

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97. Shutov, F., lntegral/Structural Polymer Foams,
Berlin: Springer Verlag, 1986, Chapter 10.
98. Peters, D.L., Kowalski, R.C. and Hughes, J.K.,
Blow molded reinforced HDPE for structural
applications, SAE Tech. Paper No. 830077,
1983.
99. Rosato, D.V. and Rosato, D.V., Eds., Blow
Molding Handbook: Technology, Performance,
Markets, Economics. The Complete Blow Molding
Operation, Munich: Carl Hanser, 1989, p. 481.
100. Rathgeber, J., Evolution of an imaginative tech-
nology - double wall blow molding, in Blow
Molding Handbook: Technology, Performance,
Markets, Economics. The Complete Blow Molding
Operation, Munich Carl Hanser, 1989 (D.V.
Rosato and D.V. Rosato, Eds), pp. 828-829.
101. Han, C.D., Multiphase Flow in Polymer
Processing, London: Academic Press, 1981,
Figure 3.26, p. 109.
102. Minagawa, N. and White, J.L., The influence of
titanium dioxide on the rheological and extru-
sion properties of polymer melts, J. Appl.
Polym. Sci., 1976, 20, 501-523.
103. Throne, J.L., Rotational molding, in Polymer
Powder Technology, (M. Narkis and N.
Rosenzweig, Eds.), Chichester: John Wiley,
1994, Fig. 3.
104. Ramazzoti, D.J., Rotational molding, in PZastzcs
Engineering Handbook of the Society of the Plastics
Industry, Inc., (J. Frados, Ed.), 4th Edn, New
York Van Nostrand Reinhold, 1976, p. 353.
105. Crawford, R.J., Rotational moulding of plastics,
Prog. Rubb. Plast. Technol., 1990,6(1),1-29.
TOOLING FOR COMPOSITES 25
Jerry L. Cadden and Paul F. Sadesky

25.1 INTRODUCTION lized for tooling, but no one material solves all
The manufacture of composite details and of the problems, particularly when factors
such as cost, longevity and tolerances are con-
assemblies requires that some kind of accurate
sidered. The primary objective of any tool for
repeatable tool surface be provided, indexed
composite fabrication is to make an accurate
to an engineering database or reference model
repeatable part, within the confines of the
and be capable of withstanding repeated expo-
sures to the cure cycle environment of high process parameters defined by the composite
temperatures and pressures. Once the specific material supplier and the detail performance
manufacturing process has been selected (i.e. characteristics of the end use customer. Design
vacuum bag lay-up or resin transfer molding), of the initial tool becomes the most pressing
decisions regarding tolerances, heat up rates, initial issue of tooling for composites.
coefficients of thermal expansion, tool
longevity etc. influence the construction of the 25.2 TOOL DESIGN BASICS
tool from an engineering design and material
selection standpoint. Individual composite 25.2.1 COEFFICIENT OF THERMAL EXPANSION
parts or details will require a variety of sup-
port tooling beyond the initial cure tool, such One of the most critical parameters in the
as master model reference patterns, trim or design of tooling for composites is the differ-
router tools, precision hole location drill tools, ence between the coefficient of thermal
assembly fixtures, ply locating templates and expansion (CTE) of the tool being designed
other shop aids. Planning must ensure that a and of the composite detail being fabricated.
point of reference is established that will con- During the cure cycle of the composite lay-up
trol all tooling in any one part family. This will on a tool, the lay-up expands during the heat
guarantee that critical dimensional tolerances up cycle. The specific rate of expansion is
are maintained within the relationship directly related to the type and combination
between different tools supporting the fabrica- of resin or matrix and fibers or reinforcement
tion of one composite detail or assembly. In used. The tool will also expand and contract
addition, coordination between various com- at a specific rate determined by the material
posite details will ensure that and construction techniques utilized. If the
interchangeability or replacement is main- CTE values for the laminate and the tool dif-
tained throughout entire structures. There is fer significantly, stresses may result in the
an extensive list of materials which can be uti- laminate causing the occurrence of dimen-
sional, strength and part stability problems.
The greater the difference between the CTE of
Handbook of Composites. Edited by S.T. Peters. Published the composite detail and the tool, the more
in 1998by Chapman & Hall, London. ISBN 0 412 54020 7 pronounced the effect will be.

One of the effects that occurs as a function of
these dimensional differences is called spring-
back. Composite details, when cured, hold the
specific molded shape, as defined by the tool,
as a result of the cured combination of resin
and reinforcement. The springback, or more
accurately defined as a warpage condition,
occurs when the composite detail is cured into
a tool, that at a specific temperature has one
definite dimensional tolerance and then upon
cooling to ambient temperature, contracts to its
original ambient dimensions. The composite
detail, based on the resin chemistry, cures dur-
ing the specific period when tool expansion is
at it greatest. Warpage occurs when stresses are
induced to the composite as the tool begins to
return to the ambient dimensions, because the
composite detail is being forced to conform to
the new dimensional range against the dynam-
ics of the state it reached during cure. This
condition will increasingly become greater as
the temperature difference between ambient
and cure temperature increases and the dimen-
sional size of the tool increases. A common
method of minimizing the effects of springback
or warpage of quasi-isotropic composite
details during and after cure cycling is to deter-
mine the CTE of the composite part being
fabricated and the CTE of the tooling material
selected. During the design of the tooling, care-
fully match as closely as possible the
appropriate tooling material CTE to that of the
composite detail.
Other conditions that might lead to a
warpage of the laminate include an unbal-
anced laminate orientation where the number
of layers or plies of material are more domi-
nant in one direction than another. This
condition is separate from any function of the
tool and must be considered during the design
of composite detail.
25.2.2 USING CTE IN THE DESIGN OF
TOOLING FOR COMPOSITE
Two methods are commonly used to minimize
the effect of CTE when designing tooling for
Tool design basics 557
the fabrication of composite details. One
method is careful selection of the appropriate
tooling material. Each of the commonly used
tooling materials available has a specific CTE
value (Table 25.1). When selecting the appro-
priate tooling material based on the issue of
CTE compatibility only, first determine the
CTE of the composite detail being fabricated.
The specific expansion rate will be determined
by the combination of the resin and reinforce-
ment utilized along with the particular fiber
orientation that is incorporated into the lami-
nate. For example, the CTE of the more
common unidirectional carbon fibers used in
most composite epoxy laminates is approx. 4.5
x 104/OC (2.5 x 10"/OF ). The strength of the
reinforcement material lies along the direction
of the fiber, not perpendicular to it. If a lami-
nate is balanced, quasi-isotropic, with
individual laminate layers or plies equally dis-
tributing loads throughout the laminate, the
CTE of the laminate will be consistently equal
in all directions. If one direction is dominated
by more material plies than any other direc-
tion, the CTE value will vary, with the
dominant direction having the lower CTE.
Once the CTE of the laminate is determined,
using the appropriate chart select the tooling
material with the closest match to the laminate
value.
The other method of accounting for CTE
variations between the detail being fabricated
and the associate tool, besides material selec-
tion, is the use of shrink factors in the
calculation of dimensions prior to tool fabri-
cation. If requirements dictate that when
fabricating the tool, a material with an incom-
patible CTE to the detail being manufactured
must be used, steps may be taken to mini-
mize the effect of this variation. During the
design phase of the tool, accurate estimates of
the actual tool size at its greatest expansion
point or at the highest temperature during
the cure cycle must be made. The percentage
difference between this calculation and the
dimensions at ambient must be applied to the
base design as a 'shrink factor' reducing the
558 Toolingfor composites

Table 25.1 Properties of commonly used tooling materials

Material Coefficient of thermal expansion, Density, Thermal conductivity,

x 10-fipc g/cm3 cal cm/s cm2"C
(x 1 c 6 / a F ) (iwt3) (BTU in/hft2 O F )

Aluminum 23.7 2.7 0.48

(13.6) (170) (1400)
Electroformednickel 13.3 8.6 0.19
(7.4) (540) (564)
Carbon/epoxy prepreg 4.5 1.61.5 16 x 10-4
(2.5) (87-94) (4.6)
Glass/ epoxy 13.1 1.6-2.0 6x
(74 (100-125) (1.7)
Invar 36 3.4 8.0 0.016
(1.9) (504) (48)
Invar 42 5.4 8.1 0.016
(3.0) (507) (48)
Monolithic graphite 2.16 1.76 0.28
(1.2) (110) (840)
High carbon cast steel 9.7 7.3 0.12
(5.4) (456) (360)
Steel 12-14 7.8 0.10
6.7-7.8 (490) (300)
Wood (mahogany) 22 0.7 0.90
(12) (44) 2600
Urethane board stock 50 0.77 n.a.
(28) (48)

size of the tool by that same percentage. For
example, if a specific tool at 177°C (350°F) has
a growth factor equaling 1.27mm (0.050 in) of
growth over ambient dimensions, this same
factor would be applied as a reduction of the
overall tool dimension while at room temper-
ature. This method of applying a shrink
factor to allow for variations of CTE between
tools and details must be approached cau-
tiously when complex shaped surfaces are
involved. This is due to the potential for the
composite details to become entrapped
within the geometry of the tool as the tool
returns to the ambient temperature dimen-
sions. Since the composite detail was cured
while the tool was at the larger dimension, if
the detail is confined to the tool surface or
restricted from movement due to complexity
in the tool surface, the composite detail could
become entrapped, resulting in dimensional
abnormality in the laminate and possible
damage to the composite detail or the tooling
surface. A variety of other factors should also
be considered such as tool durability, tool
usage rates, thermal conductivity of the mate-
rial and machinability or fabrication cost.
Each of these factors must be weighed indi-
vidually before final selection is made.

25.2.3 MATERIAL CHOICES IN THE DESIGN OF
TOOLING FOR COMPOSITE
The use of CTE is not the sole determinant for
selection of a tooling material. For example, as
defined in Table 25.1 monolithic graphite
which as a tooling material has a CTE value of
2.2 x 104/OC (1.2 x 1O4/'F) has good machin-
ability at a relatively low cost compared to
other tooling materials, but exhibits poor
durability when utilized in the high usage of
production environments. InvaP 36, however,
displays a similarly low CTE value, displays a
much higher level of damage resistance but
has poor machinability and also has a high
acquisition cost. Careful selection of the
appropriate material for tool use must include
review of the following criteria:
0 anticipated tool usage (expected life of tool);
0 cost available for tool fabrication;
0 materials available for tool construction;
0 available methods of tool manufacturing;
0 level of dimensional tolerances required
from composite detail.
Anticipated tool usage
The life expectancy of any tool fabricated for
the lay-up and cure of composite details is
dependent on a variety of factors. Material
selection, shop handling procedures and cure
cycle times all affect the ability of the tool to
withstand long usage. Certain materials dis-
play characteristics that allow longer tool life,
however the advantage and disadvantage of
each material must be analyzed prior to selec-
tion. In addition, each of the tooling materials
presently used is sensitive to damage specific
to that material. If short term usage is antici-
pated, temporary tooling such as wet lay-up
epoxy or polyester tooling (dependent on
detail cure temperature) may be acceptable,
however master models and intermediate
transfer tooling would be necessary to main-
tain the correct surface tolerances. To
minimize the costs associated with master
models and intermediate transfer tooling,
Tool design basics 559
machining the final tool surface directly from
a computer model can be accomplished using v
a material capable of the final cure tempera-
tures. Monolithic graphite and a variety of
epoxy and polyester tooling boards would
allow this with monolithic graphite offering
the highest quality and lowest CTE at a com-
parable cost to the board stocks available.
These costs would be similar to laminated
tooling without the intermediate and time
consuming steps necessary to complete the
laminated tool. However, in a high usage pro-
duction program, these materials can be
damaged more easily than the composite lam-
inate or metallic tools currently in use.
Continued advances by the suppliers of com-
posite tooling prepregs have drastically
increased the ability of composite laminate
tools to support a high number of cycles at
cure temperature.
Another factor directly affecting the
longevity of tooling fabricated from composite
materials is the effect of proper employee
training in the care required of such tooling.
Improper handling techniques will drastically
shorten the expected life of composite tooling.
Employee caused damage such as cutting on
the surface of the tool, using sharp instru-
ments to facilitate the removal of details after
cure and improper application of release
agents are the most readily identified causes of
shop induced damage. Special handling pro-
cedures and employee indoctrination can
minimize this type of damage. While all tool-
ing, both metallic and non-metallic, is
susceptible to damage, tooling fabricated from
composite materials is especially sensitive to
surface damage caused by employee careless-
ness.
Cost available for tool fabrication
Cost of tool fabrication is difficult to quantify
since material procurement and labor cost
vary widely throughout the industry.
However, comparisons can be made between
the different tooling materials and methods
560 Toolingfor composites

of manufacturing to assist the user in deter- up fiberglass or graphite tooling. Equipment

mining the optimum approach based on a obligations can be as minimal as a calibrated
cost/performance comparison. Comparisons surface table and measuring instruments for
must include all necessary steps to deliver a the accurate setup and weighing of mixed
completed tool family. There is a temptation resins and a general knowledge of the systems
to compare tooling cost for just the lay-up involved. Use of composite prepreg materials
mold in vacuum bag processing and ignore requires additional employee skills levels plus
the procedures and tooling necessary to the additional equipment expenditures of an
obtain that final surface. In direct compari- oven or autoclave to cure the materials accord-
son, a machined lay-up tool will appear to be ing to manufacturers’ instructions. Increasingly
substantially more expensive when com- stringent facility requirements involving the
pared to a lay-up tool fabricated from a installation of a controlled environment, such
composite prepreg. However, when the asso- as a ’clean room’, have been recommended by
ciated costs of reference patterns, additional material suppliers. As the complexity of the
splashes to obtain the correct surface and tooling rises, so does the requirement for ade-
possible autoclave or oven processing time, quate employee training and engineering
are factored in, the tool machined directly support.
from numerical control (NC) data, which will To support the fabrication of complex,
eliminate the need for all the intermediate highly accurate machined tooling, machine
steps mentioned, will become more compara- tools with sufficient work envelopes are
ble in price. required in the correct axis of motion to sup-
port the complexity of tooling surfaces.
Three-axis machine tools will support basic
Materials available for tool construction
simple contours, with 4,5 and 6 axis machines
Because of the advent of computer-aided capable of machining the much more complex
design and manufacturing systems compound contour surfaces. A sufficient com-
(CAD/CAM) to support tool fabrication, there puter-aided design and manufacturing
are more materials now available. Baseline (CAD/CAM) system is required to supply
methods such as plaster master models and software commands in order to drive machine
plastic-faced plaster transfer tooling will tool directional and cutting speeds. In addi-
always have a specific application within tool- tion, if board stock materials are chosen for
ing, but as the use of CAD/CAM increases reference patterns, the skill and equipment
beyond aerospace into all regimens (e.g. sport- necessary to assemble, bond and seal the
ing goods, medical and transportation), such material after machining are required.
tooling practices that depend more on the skill
level of shop personnel than on the accuracy of
Level of dimensional tolerances required
a machine tool are rapidly being replaced.
from composite detail
Based on the type of manufacturing method
Available methods of tool fabrication
and the type of material selected, different lev-
Methods of manufacturing vary, dependent on els of dimensional tolerances are possible.
equipment and personnel resources available. Initially, the designer determines the level of
Plaster type master models, intermediate trans- dimensional tolerance for the composite detail
fer tooling and wet lay-up type molds take being fabricated. Compliance to this tolerance
minimum facility requirements. Basic shop skill is critical in meeting structural demands and
levels require a familiarity with resins and conformance to any form, fit or function
geometry in order to support simplistic wet lay- requirements.

In the early days of advanced composites,
applications were limited to aerospace, which
invoked strict dimensional requirements for
both tooling and detail parts. These require-
ments continue within aerospace today. With
the expansion of composite usage into other
areas, such as sporting goods and automotive
applications, the range of acceptable dimen-
sional variations has increased but visual
requirements are much more stringent than
before. The variation of CTE between differ-
ent materials for tooling has a major effect on
dimensional tolerances. In addition, some
materials display sensitivity to environmental
conditions that have an adverse effect on
dimensional stability. Tooling, such as refer-
ence patterns or master models manufactured
from urethane board stocks or plaster models,
are hygroscopic and may absorb moisture
from the atmosphere. This condition will, at a
minimum, cause dimensional changes related
to the level of moisture absorbed. Also, this
condition could be excaberated if the moisture
contamination is extensive and the model is
taken to elevated temperatures. At higher
temperatures, the moisture will expand and
may result in possible significant changes in
structural integrity. Urethane or epoxy board
stock materials have greater resistance to
moisture. However, if machined and used for
reference patterns they are both still suscepti-
ble to contamination, which could result in
dimensional changes and possible failures in
the bond joints between the block surfaces.
Additional steps must be taken to protect all
models manufactured from these materials to
prevent these types of contamination. Sealers
must be applied and the items must be segre-
gated from potential sources of
contamination. Monolithic graphite offers
advantages over these materials because it is
inert and resists contamination from the envi-
ronment. Lay-up molds manufactured from
both ferrous and nonferrous materials must
be protected from oxidation. Failure to main-
tain a nonoxidized lay-up surface will require
restoration of the tooling surface which could
Tool design basics 561
result in dimensional changes occurring dur-
ing this process.
The highest level of tolerances available are
obtained by machining the tooling surface
directly from the computer model. Certain
master model materials such as plaster and
some board stock materials have a limited
temperature exposure level which inhibits the
ability to pull composite laminates directly off
their surface. Intermediate tooling must be
fabricated either to obtain the correct surface
level from the master or to be capable of with-
standing elevated temperatures within an
autoclave or oven, above that of the original
model. By machining directly from the engi-
neering database, the need for intermediate
surface splashes to obtain the correct surface is
eliminated. Each time a splash or the original
surface model is duplicated, a 'stackup' or
accumulation of the tolerances for each model
is combined, resulting in a much greater range
of tolerances in the final tool. For example, if a
plaster master is fabricated to k0.25 mm
(a.010 in) tolerance and each of two addi-
tional splashes have the same tolerance range,
prior to fabrication of the final lay-up mold,
the beginning tolerance range is now d . 7 6
mm (4.030 in). If a tool is machined directly
from NC data, the tolerance stackup is elimi-
nated and only the range of the individual
machine tool applies. Machine tools, depen-
dent on the condition and environment of
machining, are capable of providing 4.128
mm (4.005 in) accuracy or greater.
25.2.4 DESIGNING TOOLS FOR RESISTANCE TO
FAILURE
Because of the abusive environment experi-
enced by tooling during the fabrication of
composite details, life expectancy of tooling
will always be short of anticipation. Repetitive
cycling from ambient to over 177°C (350"F),
inadequate care and handling procedures,
incorrect fabrication techniques have all led to
a variety of defects resulting in premature
temporary or permanent failure of the tool.
562 Toolingfor composites
Failure modes common to composite lay-up
tools fabricated by both wet lay-up and
prepreg methods generally involve fiber sepa-
ration. This is due to a variation in CTE
between the resin matrix and the fiber.
Generally, the neat resin systems used in most
composite tooling systems have a CTE of 65 x
104/"C (36 x 104/"F) The graphite fibers used
in most prepreg tooling systems have a CTE of
around 4.5 x 104/"C (2.5 x 104/"F). During
exposure to cure cycles where temperatures
will vary from ambient to 177°C (350°F) and
above, the difference in CTE between the
fibers and the resin will eventually cause dis-
bonds between laminate layers resulting in
leaks internally within the tool. In addition,
the expansion of the resin is somewhat con-
trolled by the fiber reinforcement in the x and
y axis. Because no reinforcement exists in the z
plane linking the individual layers together,
the difference in CTE between the resin and
reinforcement becomes more pronounced.
Failures between the individual plies increase
because of the lack of reinforcement restrain-
ing the resin from the repeated expansion and
contraction.
Furthermore, when laminating layers of
either prepreg or wet lay-up tooling, by cut-
ting each of the plies into pieces 304-457 mm
(12-18 in) square, no continuous fiber path
will pass through the tool. By discontinuing
these pathways, leaks occurring along the
fiber path will be minimized. In addition,
because each layer or ply consists of sections
without any continuous fiber path, stresses
within the laminate will be lower, minimizing
warpage during use. A majority of failures in
composite tooling may be directly tracked to
leakage around tooling holes or plumbing fit-
tings. Tooling hole fittings are exposed to
repeated shocks during the removal of cured
composite details. If steel bushings are used,
the difference in CTE will possibly lead to
cracks in the tool surface which will become
potential leak paths. One solution is to install
Invar 36 bushings in laminated tools which are
closer in CTE to the parent tool. Also, when
laminating the initial tool, apply additional
plies of pregreg in the area of the bushings to
increase support in those areas to resist move-
ment during part removal.
Another possible solution to the problem of
delamination between layers of prepreg tooling
is the application of glass transition tempera-
ture values (TJ to extend the life expectancy of
a tool. Most tooling resin systems are formu-
lated with a Tg value at or slightly above the
maximum use temperature of the resin system.
As a function of the resin chemistry, glass tran-
sition temperatures decay or reduce with each
exposure to the cure temperature that the sys-
tem was designed for. This decay, in
incremental steps will continue until well
below the cure cycle temperature that the tool
was intended to be cycled at. When this point is
reached, the resin will begin to break down
with a mechanical failure of the bond between
the resin matrix and the fiber reinforcement.
The solution to this problem is to use a
resin system with the highest possible Tg
value available. For example, if the tool is
intended to be cycled repeatedly at 177°C
(350"F), a T value of the resin system in the
220°C (425"h) range will allow more cycles. It
is common among some aerospace compa-
nies to now fabricate composite tooling for
epoxy laminates from a bismaileimide or a
cyanate ester resin system with Tg values
higher than 260°C (500°F). This allows the
inevitable decay of the Tg value to span a
greater difference allowing the life of the tool
to be extended. The same principle may be
applied for any prepreg system from poly-
esters to the higher temperature resin
systems. One consideration in using this
method requires the selection of a master
model material capable of exposure to the
elevated temperatures that the higher tem-
perature systems require during cure. Plaster
and most of the board stocks available are not
capable of these higher temperatures and
intermediate splashes or surfaces would have
to be provided. Monolithic graphite does pro-
vide a surface capable of exposure to higher

temperatures in addition to having the lowest
CTE available, allowing tools fabricated from
these resin systems to be taken directly off the
model surface without need for intermediate
surfaces.
Employee-induced damage of tooling can
play a much greater part in the reduction of
expected tool life. Correct indoctrination into
the importance of the tool to the fabrication of
accurate details must be stressed. Most of the
employee-induced damage will occur either
during the lay-up procedures, the removal of
cured composite details from the tool surface,
or preparation of the tool surface prior to the
next lay-up. During lay-up of details, damage
will be the result of employees using knives or
other sharp objects during the trimming of the
composite material. If proper care is not
taken, the employee will not only cut the
material but also cut into the tooling surface.
While not as detrimental to a metallic tool,
damage of this kind may be catastrophic to a
tool fabricated from a composite material. The
cut will allow a breach in the vacuum
integrity in addition to allowing resin to pen-
etrate beyond the surface of the tool. Also,
when laminates are removed from tooling
after completion of the cure cycle, damage
occurs when personnel use sharp equipment
to force the completed detail from the tool.
The greatest care must be given when
attempting to remove the detail, to prevent
inadvertent damage if the detail fails to
cleanly release from the tool surface. Damage,
not only to the tool, but also to the detail may
result. To prevent this damage from occur-
ring, proper steps must be taken. Employees
must be indoctrinated in the proper tech-
niques of tool maintenance and lay-up
procedures and must be provided with
acceptable tooling aids to assist in the safe
removal of cured details from the tool surface.
Soft wood or plastic wedges must replace
hammers and hard-faced chisels for detail
removal and tool surface preparation. Tools
must be designed with adequate laminate
thickness to prevent damage to the tool if
Master models 563
struck with a hard object. Carriers designed to
transport the tool to and from work station
must also function as a protective barrier to
prevent the tool from striking walls or beams
within the shop environment. Support tool-
ing, where applicable, must be designed to be
as lightweight as possible to prevent injury to
the employee and damage to the tool surface
when handled.
25.3 MASTER MODELS
A master model is considered to be just that -
a master source identified with holes, scribe
lines, trim lines or any other feature of the
part that requires duplicating to other tools.
The master model is the physical representa-
tion of the design or a point of reference to
which all support tooling, both for fabrication
and inspection, would be indexed. Because
this surface will provide the reference pattern
for all subsequent operations beyond initial
fabrication, such as assembly fixtures index-
ing a variety of details from different
locations, extreme care must always be taken
in protection of the master model. Master
models may be fabricated from a variety of
materials. Common materials include plaster,
machined urethane or epoxy board stock,
monolithic graphite or most ferrous and non-
ferrous metals. Each material offers distinct
advantages and disadvantages. To determine
which material is the most feasible, the entire
tooling family philosophy must be reviewed.
Master models are generally stored indefi-
nitely so that they may be referred to over the
life cycle of the manufactured parts. In cases
where cost and/or time schedules are impor-
tant, temporary models are produced and
then destroyed once they have been used.
However, because of the hygroscopic nature
of plaster, care must always be taken to pro-
tect the master model from the environment
to maintain accuracy. Adequate storage con-
tainers, allowing for complete protection,
must be utilized throughout the life
expectancy of the model.
564 Toolingfor composites

25.3.1 PLASTER MASTERS 25.3.2 TEMPLATE! METHOD

One of the oldest methods of producing a mas- There are several techniques of building a
ter is from plaster. Plaster is made from the plaster master determined by the shape of the
mineral gypsum (CaSO,). which is finely part. If the part is not symmetrical and does
ground and calcined (dehydrated) to produce not have a constant cross section or the size is
a fine powder with uniform properties. With large, the master model is made from a series
the addition of water to form a workable of templates secured to a flat base to form a
slurry, a reaction occurs which produces heat three dimensional full scale model of the part.
and the inert gypsum on drying. Plaster is Space between the templates is relative to the
manufactured in various textures or grades degree of abruptness of the contour. For nor-
which support the level of detail required on mal gentle contours a space of 15.24-20.32nun
the model. Coarse grades are used to build up (6-8 in) is common. Templates are usually
the master model surface and then followed made from 0.317 mm (0.125 in) thick alu-
by the fine grades which allow precise details minum to prevent corrosion. For temporary
such as trim lines or other identifications to be masters, steel is sometimes used, but, because
scribed into the surface. Depending on the of the amount of moisture used in the mixing
grade being used, plaster has a setting expan- and application of the plaster, steel templates
sion of approximately 0.080% and a thermal may rust (Fig. 25.1).
expansion in the dried state of a maximum of If electronic data is available, the templates
0.027/ "C (0.0156/ OF). can be NC machined or cut with a water or

REFERENCE LINE
REFERENCE LINE

Fig. 25.1 Skeletal structure for template plaster master.


laser jet directly from the flat pattern generated
by the data. Section cuts taken at specific sta-
tion lines from two-dimensionalblueprints can
be used to saw out a template. Except for the
NC machining method, deburring is generally
required to remove spurs or sharp edges from
the templates prior to use. Holes are drilled
into the templates for threaded rod spacers and
screen support rods. For larger models, air pas-
sages are cut into the bottom of the template to
allow for even curing of the plaster. Once suffi-
cient templates have been prepared, bluing is
applied to a flat ridged steel table and scribed
with an awl to denote the location of each tem-
plate. Flatness of the table is critical and should
be within 0.127 mm (0.005 in). Tooling balls
which indicate the x, y and z direction are
sometimes placed on the table corners as refer-
ence points for the system. Tooling balls can
vary in size but a common size is 12.7mm
(0.5 in) diameter on a 6.35 mm (0.250 in) diam-
eter x 12.7mm (0.5in) long pin. The pins, each
with a 'ball' on top are placed into location
holes and optically sighted relative to the posi-
tion of the each ball location. Location can also
be treated relative to a position on the master
such as a station line. Each template is attached
90" to the base table with angles and held to
within 0.127 mm (0.005 in) of the reference line
at the base, the face square to the base to within
0.076 mm (0.003 in) in 304.8 mm (12 in) and
within 0.127 mm (0.005in) of the base reference
line. Threaded rods are secured with sheet nuts
on each side of the template to provide rigidity
to the template face. Wire mesh is placed
between the templates and secured to the
threaded rod with wire hooks approximately
101.6 mm (4 in) below the top surface of the
template. This is used to hold the plaster in
place. Plaster is mixed with hemp and placed
against the screen to approximately 9.5 mm
(0.375 in) below the template surface.A second
layer without hemp is added to this surface to
approximately 12.7 mm (0.5 in) A sawtooth
scraper is used to build a striated surface and
allowed to dry. A final mix is made with the
fine grade of plaster and using a flat spring
Master models 565
steel blade, the plaster is 'faired' or swept flush
between the templates to form a smooth accu-
rate surface. Because of the propensity of
plaster to absorb moisture, it should be sealed
after the surfacehas had adequate time to cure.
Commercially available lacquers can be used
to seal the surface and provide a suitable pro-
tection within the shop environment.
25.3.3 FOLLOW BOARD METHOD
A method widely used when a constant cross
section is to be built is the follow board. A flat
surfaceis required with an accurate side surface
to act as a guide rail. A template of the contour
is prepared from a rigid 3 mm (0.125 in) mini-
mum sheet of aluminum or steel and attached
to a wooden guide support. Plaster is mixed
and built up on the surface to within 3mm
(0.125 in) of the final contour. Partial drying is
recommended before the final plaster mix is
applied. This will prevent shrinking and crack-
ing of the plaster surface which would affect
accuracy. Using the template and guide sup-
port, the plaster contour is formed by pushing
the template evenly over the surface (Fig. 25.2).
FOUOW
BOARD
- /
FOLLOW BOARD METHOD
FOR PRODUCING PLASTER MASTER
Fig. 25.2 Follow board method for producing plas-
ter master.
25.3.4 SWEEP METHOD
A third method called a sweep is best utilized
when a symmetrical surface s;ch as a cone or
566 Toolingfor composites

hemispherical shape is involved. As with the
follow board method, a flat surface from which
a frame can be constructed of the shape to be
produced is required. For large shapes, inter-
mittent templates should be placed within the
framework to allow support for the sweep and
provide adequate support for the sweep to fair
against. The sweep itself is usually made from
sheet metal 3 mm (0.125 in) minimum thick-
ness and supported by a wooden guide or
other mechanical guides that can ride the sur-
face of the flat surface table. Smaller shapes, of
course, do not require this extent of rigging.
Plaster can be reinforced with saturated hemp
fibers, mixed into the slurry and applied to
form rough shapes and to form strengthening
ribs on the back surfaces of casts. All master
models fabricated from plaster require, in
addition to sealing with commercial grade lac-
quer, suitable storage containers if the model is
required to be stored for any period of time
outside the shop environment.
operation significantly. The system, known as
Automated Tool Manufacture for Composite
Structures (ATMCS),is an expert system with
macros which dramatically speeds up the tool
design process. ATMCS takes the composite
detail surface model into either IBM Catia or
EDS Unigraphics I1 and creates the tool
required around the part model.
The system, acting through a series of
inquiries made to the tool designer, selects the
optimal configuration, material, manufactur-
ing process and design. The design is then
created around the part model, with signifi-
cant savings in time. Although the system was
developed initially for the aircraft industry
and is presently used for basic open-faced lay-
up molds, it could be expanded for many
different types of tools and processes such as
resin transfer molding and injection molding
in other industries.
25.4 COMPOSITE TOOLS

Composite tools are usually made from epoxy

25.3.5 NC MACHINING
resin matrix and either E-glass or carbon fibers
Because of the widespread use of CAD (com- as reinforcement. Depending on the life cycle
puter aided design) systems, older methods required, tools can be made from prepreg or
which utilized two-dimensional prints to by 'wet' lay-up procedures. Prepregs generally
build master models are now used less fre- require curing within an autoclave because of
quently. With CAD systems, a great deal of the elevated pressure specified by the manu-
accuracy can be transferred into the master facturer. Because of the increased compaction
model via the NC machining operation. Table available when curing in an autoclave, tooling
25.1 lists various materials widely used today fabricated from prepregs are capable of a
for NC machined master models. From a CAD greater number of cure cycles than the wet lay-
model of the part, a tool manufacturer must up method. In addition to greater compaction,
design a tool from the surface data supplied. autoclave curing offers better control of resin
Advances with CAD/CAM systems seek to content and uniformity of reinforcement.
minimize the operator input to the system and However, for shop aids such as trim tools,
transfer design responsibility to the computer. room temperature curing epoxy systems are
One example of this technology is demon- recommended.
strated in a system developed by a
multicompany team lead by the Northrop
25.4.1 LAY-UP MOLDS
Grumman Corporation for the US Air Force
Manufacturing Technology Directorate at Lay-up molds are used to form the shape of
Wright Patterson Air Force Base. This system, the part to be produced and have the part
while not totally removing the tool designer periphery scribed on the surface as well as
from the design process, does streamline the the location of any required cross hairs and

tooling holes. Tools can be made directly
from a NC machined master model or from a
plastic faced plaster splash taken from a mas-
ter model not capable of elevated
temperatures and pressures. The choice of
glass or carbon fiber/epoxy for the mold is
generally governed by the complexity and
CTE of the part to be fabricated. Lay-up
molds must be capable of maintaining a vac-
uum tight environment while being subjected
to high temperatures and pressures.
25.4.2 PREPREG METHOD
There are a considerable number of prepregs
available as epoxy 'B' staged glass or carbon
reinforced cloth. Prepregs can be obtained in
rolls or as precut squares or rectangles. The
weave style can vary depending on the
amount of drape to be encountered but gener-
ally plain or satin weaves are readily available.
The resins are tailored for tack, out time and
glass transition temperatures at a minimum
and are around 40% by volume of the prepreg.
(Tooling prepreg manufacturers have very
detailed procedures that they recommend for
their specific system. These comments are not
meant to supersede the recommendation of a
manufacturer, but rather to place emphasis on
important steps that should not be overlooked
for tool fabrication.)
Within the last several years, an innovation
for tooling prepregs is the capability for low
temperature curing 61°C (145°F) in an auto-
clave, followed by a free standing post cure at
177°C (350°F) after removal of the tool from
the master. This has allowed the use of plastic
faced plaster and urethane based tooling
boards for direct lay-up of composite tools.
Monolithic graphite with a low CTE and capa-
bility to withstand 315°C (600°F) under
autoclave pressures can be a good choice.
The first step prior to prepreg application on
the master surface is to ensure that the prepreg
and the master surface are absolutely clean and
free of debris and that the surface is smooth
and without pin holes. A quick vacuum check
Composite tools 567
is always a good idea at a minimum of 6.2 kPa
(25 in Hg). A loss of 500 Pa (2 in Hg) within 5
min with the pump nonoperating is acceptable.
Apply masking tape around the tool periphery
for later application of the sealant tape. It is
absolutely necessary, regardless of prior his-
tory of the master surface, that it can be
released with a suitable hard wax or other
release agent. The prepreg manufacturer may
recommend a specific release agent for his
prepreg system and it is advisable to follow
those instructions due to the possibilities of
chemical reaction occurring between the resin
system of the tool and the release agent used
(Table 25.2). After the cleaning and releasing
processes have been completed, release coated
tooling pins should be placed into the holes of
the master. These are generally index and
locating holes that have bushings and are used
to position or align one tool to another, or to a
production part. Bushings can be installed dur-
ing lay-up of the tool or potted in after final
cure of the tool.
In general, a face or gel coat layer is not
used by most manufacturers today. The reason
is associated with the difference in CTE of a
neat resin on the face and the CTE of the
underlying reinforced prepreg which over the
life span of a tool can cause cracking and craz-
ing of the face and subsequent loss of vacuum
integrity. If a gel coat is used it should be of
minimum thickness to minimize these effects
over time.
A lightweight (style 7781) cloth is the first
layer applied to prevent mark through to the
surface from heavier cloth. Carefully lay each
ply onto the surface and work out wrinkles or
air bubbles and maintain the warp direction of
each ply in the 0" direction. An overlap
between the plies should be 3-6 mm
(0.125-0.250 in). Some manufacturers recom-
mend a debulking step at this point to ensure
no air entrapment at the interface and a
smooth surface on the tool. Debulking is
accomplished by application of a peel ply net
to the edge of the laminate and working out
wrinkles and air bubbles. A resin dam (sealant
568 Toolingfor composites

Table 25.2 Cures for common mold release problems

Problem Cause Solution

Non-adherance of paint or
adhesive to part
Poor release with small particles
of visible on mold surface
No paint or adhesive sticks to
part
Multiple release not possible
Failure to obtain any release even Inadequate cleaning of the mold
though release was applied
Generally poor release with
patches of white transferring to
the part
Build up of mold release, layers Use manufacturer’s
of incompatible mold releases, or recommendations for layers and
too much release in formulation cure schedules. Avoid adding
incompatible layers such as
silicone, wax and flurocarbon.
Check with manufacturer for
possible revision or custom
formulation to allow multiple
releases and adequate paint
adhesion
Porosity in mold Thoroughly clean mold with an
appropriate solvent and then
add a mold sealer before the
release coat
Check for the presence of silicones Remove silicones from plant
in the area. Silicone mold releases where painting or adhesive
can be transferred over long bonding is performed
distances
Poor release in some areas, Apply one or two additional
particularly in severe contours coats of release to severe contour
areas
Strip out the part and thoroughly
before application of release has clean the mold, then apply and
interfered with the ability of the fully cure release agent. Also
release to bond to the mold or the check shelf life of release
release has been improperly
cured. Shelf life of release may
have expired
Mold surface not properly cleaned Remove all release and
which results in poor bonding of thoroughly clean mold with an
release to mold appropriate solvent before
reapplication of release. Follow
manufacturer’s
recommendations for cure cycle

tape) can be placed around the perimeter to
prevent resin flow (Fig. 25.3). Next, lay-up one
ply of Teflon@beyond the resin d a m and attach
to the resin dam. Using the manufacturer’s
recommendation, holes should be placed into
the Teflon ply to allow for resin bleed. Pre-per-
forated film can be obtained for this purpose
and provides greater control over the size a n d
spacing of the holes. If only one lightweight
ply has been applied, no holes are required to
permit a higher resin content on the tool sur-
face. Over this layer, one ply of polyester
breather cloth or 7500 style glass cloth is
applied. A nylon vacuum bag is placed over
the entire stack and a vacuum of at least
625mm (25 inHg) is applied for at least one
hour. Removal of the bag, breather, separator
film and peel ply should be done very carefully
to avoid lift up or shifting of the prepreg lay-
ers. The orientation for each additional ply

Tdl
Fig. 25.3 Laminate pre-bleed stackup.
should be such that a balanced system is main-
tained to minimize stress build up in the
laminate. Prepreg manufacturers will clearly
stipulate the lay-up sequence.After the second
or third ply has been laid down, knurled bush-
ings should be placed onto the tooling pins
and pressed down to seat them. Subsequent
plies will be placed over the bushings to inte-
grated them into the laminate. After the
seventh or eighth ply, the pins can be removed
so that later plies can cover the bushing com-
pletely to prevent vacuum leaks. In some
instances a pad or build up of plies over the
bushing is recommended. An alternate
method is to pot the bushings into the lami-
nate after the final cure. To do this a tapered
wax or rubber plug should be placed over the
pin to allow space for the potting compound
after the final cure. Each ply should be care-
fully worked into corners and radii making
sure all entrapped air is removed. Wrinkles
should also be carefully worked out before
another ply is placed over it. If a persistent
wrinkle or air bubble can not be rolled out,
then carefully slit the pockets with a sharp
knife and work it down into the surface. In the
excess area of the tool, thermocouples can be
strategically located between the plies for
recording during the autoclave run. As a rule
of thumb, debulking should be performed
Composite tools 569
Vacuum Line
Vacuum Vacuum Bag Sealant
,,Breather
Laminate \
Release Film
after every 4-5 plies. Final build up of the lam-
inate should be at least 0.013 mm (0.375 in) or
whatever is recommended by the prepreg
manufacturer. Final vacuum bagging is per-
formed in the same manner as for debulking
with a layer of peel ply, perforated Teflon,
polyester breather and vacuum bag. Prepreg
manufacturer will provide a detailed heat up
rate and cure temperature for their system and
this should be carefully followed. Most sys-
tems can be initially cured at up to 63°C
(145°F) and 586-689 kPa (85-100 psi) of pres-
sure for 14 h.
After the autoclave cycle, carefully remove
the bag and films from the laminate to avoid
lift up from the master surface. Attachment of
the egg crate structure (support or back-up
structure, Fig. 25.4) to the laminate is very
important to minimize any potential residual
stresses built into the laminate or stresses from
the egg crate itself. Leave the laminate on the
master surface and attach board structure of
the same material to the surface of the lami-
nate. If the laminate is glass/epoxy, the egg
crate material can be made from glass/epoxy
or aluminum honeycomb sandwiched
between glass. The point is to avoid stresses
caused by the difference in CTE between the
egg crate and laminate by using similar mate-
rials.
570 Toolingfor composites
Fig. 25.4 Support structure details.
The egg crate should be cut to the contour of
the laminate with a standoff of 3.17mm
(0.125 in). This prevents hot spots during pro-
duction part curing and also mark off into the
tool laminate. The egg crate should be con-
structed so that it will lie flat on the surface.
The intersections of the board stock are held
together with cloth and resin with at least
three strips per junction. To ensure minimal
stress to the laminate from the egg crate struc-
ture, it is advisable to remove the structure
from the laminate and cure the strips holding
the structure together at 177°C (350°F).
After curing, the structure can be placed
back onto the laminate and 'tied' into the lam-
inate with at least three strips of cloth and resin
around the periphery of the egg crate. Shims
can be used to provide for the standoff. If the
type of master used for the lay-up permits an
oven cure at 177°C (350°F) (Le. metal or mono-
lithic graphite) the post cure can be performed
without removal of the tool from the master.
However, if the master material will not toler-
ate this temperature, careful removal of the
tool from the master must be done prior to the
post cure.
Separation of the tool from the master
should be done carefully to avoid damage to
the master or the tool itself. Tooling pins
should be removed prior to separation. Tools
with severe contours may require plastic
wedges to be inserted around the tool periph-
ery until it releases. Once the tool is separated,
the surface should be inspected for pinholes or
roughness. Pinholes can be filled with resin
and the roughness can be smoothed out with a
fine grit sandpaper. Edges of the tool can be
sawed to even up the periphery and then
 Composite tools 571

sanded lightly with 220 grit sandpaper to occur in corners or the bottom of contours. Too
remove any loose fibers. Care must be taken much resin will result in cracking and crazing
that no fibers are lifted by sanding along the later in the tool life cycle. Also, ensure that all
length of the fibers. air bubbles have been worked out by repeat-
Once the tool has been cleaned up, the edly applying the brush back and forth across
required check for vacuum integrity is accom- the surface. To ensure that all air has come to
plished by placing a layer of polyester the surface while brushing, pause occasionally
breather cloth on the surface and a vacuum and allow the air to rise to the surface where it
bag over it. The acceptance criterion is gener- can be brushed out. Air that remains
ally that there be no loss greater than 500 Pa entrapped either on the tool surface or within
(2inHg) in 5 min at a minimum of 6.2 kPa the layers of cloth could result in possible blis-
(25inHg) at the start of the test. If possible, ters and delamination later during tool usage.
depending on the complexity of the tool, place The resin supplier will provide mix ratios for
the tool back onto the master and check for resin and hardener as well as pot life and gel
any warp or out of contour problems. times. Tooling cloth generally comes in rolls
and is either a satin or plain weave with the
warp direction noted. Sufficient squares or rec-
25.4.3 WET LAY-UP METHOD
tangles can be precut from the roll prior to
The wet lay-up of composite tools can be for laminating. Sections over 609 mm (24 in)
room or elevated temperature use. The differ- become too cumbersome to work on the tool
ence is in the resin selection. Procedurally, the face, therefore smaller sections are advised.
process is the same except for the cure cycles. The first 2-3 plies should be from light weight
The master or tooling aid should be cleaned of cloth such as 7500 glass or 2534 carbon which
all defects and debris such as scratches and will prevent mark through to the surface. The
loose fibers. Solvent clean the surface to gel coat should be advanced with time prior to
remove any residual resin or oil. Check for application of the first ply. If enough tack is
vacuum integrity using a criteria of a maxi- not present, the ply will sink too deep into the
mum loss of 500 Pa (2 in Hg) at a minimum of gel coat and be visible on the tool surface. One
6.2 kPa (25 in Hg) starting vacuum. simple test is to place a finger onto the surface
Place masking tape around the periphery and release. If the gel coat has not advanced
for later use for sealant tape. Regardless of the adequately, the fingerprint will disappear. If
prior history of the tool, it should be released the fingerprint remains, the gel coat has
with a suitable hard wax or release agent. advanced far enough to withstand the
Tooling pins should be released and placed repeated pressing of subsequent layers of
into the holes provided on the tooling aid. cloth. Using the mix ratios provided by the
For wet lay-ups, two resins are used, one for supplier, mix enough resin to cover the surface
the gel or face coat and one for laminating. The of the gel coat in the time allotted by the pot
gel coat is generally the same as the laminating life or around 30min. Approximately 40g
resin but with additives to thicken it to make it (0.088 lb) per 0.009 m2 (1ft2)of tool surface for
adhere to the contour of the master or tooling each ply should be adequate. Application of
aid. Resin manufactures can supply both room the first several plies should be done carefully
temperature and high temperature systems. to avoid pushing through the gel coat surface.
Apply the gel coat to the surface using a To ensure complete wetting of the ply, a
short bristled brush or squeegee. Work the short bristled brush or squeegee can be used to
coating as evenly as possible over the surface carefully work the ply into the laminating resin.
at a thickness of approximately 12 mm All wrinkles and air entrapped areas should be
(0.030 in). Do not allow excessive build up to worked out before another ply is added and if
572 Toolingfor composites
necessary, use a sharp knife to slice through the
ply wrinkle in order to work it down. Bushings
should be placed over the tooling pins at this
point and worked into the resin to seat them. A
heavier cloth such as 7587 glass or 2548 carbon
can be used for the remaining plies. Since the
cloth was precut into squares or rectangles and
the warp direction was maintained, each ply
should be placed at 45" to the previous ply.
Overlaps of 6.35 mm (0.250 in) between plies
should be maintained but a seam should never
be placed over a seam from a previous ply.
After each ply, add additional resin to cover the
surface. Place the next ply and work the resin
up through it by pressing the cloth with the
brush. If there is not sufficient resin to com-
pletely wet out or saturate the ply, additional
resin should be used. Saturation of the cloth
with resin on a table separate from the lay-up
surface and then transferring the saturated ply
to the tool can cause air entrapment and bridg-
ing of the ply. After the fourth ply, or prior to
the resin curing, apply a peel ply to the surface
for a compaction cycle. The peel ply when
removed before other operations will eliminate
the need for sanding the surface prior to bond-
ing. This is followed by a Teflon film with
perforations every 250-300 mm (10-12 in).
Cover this with a heavy glass or bleeder cloth to
bleed off excess resin during compaction.
Finally, place a nylon vacuum bag over the sur-
face using sealant tape to attach to the surface
and apply a vacuum of at least 6.2 kPa
(25inHg). Hold this vacuum for 10-12h or
overnight or until the peel ply can be removed
without disturbing the laminate layers.
Following this cycle, the bag and peel ply can
be removed along with the tooling pins and
lamination can commence as previously
described. Debulking should be performed
after every 6 plies or before the resin begins to
cure. Final laminate thickness should be 9.5 mm
(0.375in). It is probably a good idea to build up
the bushed hole area with additional plies to
ensure vacuum integrity.
After the final ply has been applied, the
compaction step is repeated with the peel ply,
FEP, bleeder and the vacuum bag. Depending
on the resin system and the tooling aid mater-
ial used, a precure is recommended and
should be supplied by the manufacturer.
Fabricate an egg crate structure using 9.25 mm
(0.375 in) thick board stock of similar material
to the laminate to avoid stresses caused by the
difference in CTE between the egg crate and
laminate. If the laminate is glass/epoxy, the
egg crate material can be made from
glass /epoxy or aluminum honeycomb sand-
wiched between a glass laminate. The egg
crate should be cut to the contour of the lami-
nate with a standoff of 3.17 mm (0.125 in). The
standoff prevents heat differences or hot spots
on the tool surface during production part cur-
ing and also prevents mark off from the back
up structure pressing upward into the tool
surface laminate. The egg crate should be con-
structed so that it will lie flat on a surface. The
intersections of the board stock are held
together with cloth and resin with at least
three strips per junction. To ensure minimal
stress to the laminate from the egg crate struc-
ture, it is advisable to remove the structure
from the laminate and cure the strips holding
the structure together at 177°C (350°F). This
will allow the tool surface to be tied into a sta-
bilized support structure and minimize
warpage during subsequent cure cycles.
After the support structure is cured, the
structure can be placed back onto the laminate
and attached or 'tied' to the tool laminate with
at least three strips of cloth and resin around
the periphery of the egg crate. Shims can be
used to provide for the standoff to prevent
warpage. If the type of master used for the lay-
up permits an oven cure at 177°C (350°F), then
the post cure can be performed without
removal of the tool from the master. However,
if the master material will not tolerate this tem-
perature, careful removal of the tool from the
master must be made prior to the post cure.
Allow the tool to stand at ambient temperature
for a minimum of 24 h prior to post cure.
After the final 177°C (350°F) post cure,
inspect the surface for pinholes and repair any
 Composite tools 573

blemishes with gel coat resin. A final vacuum the same thickness and place any bushings
check at 635 mm Hg (25 in Hg) with a loss of through the second layer and flush to the first
no more than 51 mm (2 in) is acceptable. layer. Place a ply of 7500 glass cloth onto this
layer and work in to impregnate the cloth.
Allow to cure to the fingerprint test. Mix a
25.4.4 PLASTIC FACED PLASTER
third batch of the resin but add about 10-15%
Plastic faced plasters (PFPs) are tooling aids by weight of wet plaster to the mix and apply
that minimize the wear and tear on masters by to a thickness of 2.5 mm (0.1 in). Do not wait
duplicating the master surface with a suitable for curing but proceed with a layer of plaster
unit that can be used for a variety of purposes. approx. 25.4 mm (1in) thick. Allow this to
PFPs allow for tooling to be directly fabricated partially dry and then finish the tool by
from the master surface without exposing the adding plaster and hemp to the surface to a
master model to adverse environmental con- thickness that will allow support for the size
ditions, such as autoclave temperatures or of the tool [50-76 mm (2-3 in) for a 914 mm x
pressures. If taken directly from a master sur- 914 mm (4 ft x 4 ft) tool]. Support structure
face, the PFP is the reverse of the master can be built in for small tools using plaster
contour. An intermediate plaster splash is and hemp to make strengthening ribs on the
required to get back to the master contour back surface. For large tools, steel pipe or tub-
with a PFP. If the surface required is directly ing can be tied into the back structure with
from the master model, the PFP will be taken plaster and hemp ropes. Approximately 24 h
directly from the master surface. If the surface is required to dry and cure the system and
is above or below the master surface, appro- depends on the thickness and size. Drying in
priate steps must be taken by either taking an oven up to 60°C (140°F) will provide a sta-
additional splashes with or without layers of ble system for use. PFPs can be used in an
tooling wax to achieve the appropriate dimen- autoclave (with vacuum integrity) up to
sion. approximately 105°C (220"F), however a limit
Prepare the master surface by cleaning thor- of one or two runs is all that can be expected.
oughly and removing blemishes, debris and PFPs provide tooling aids for a variety of
pinholes by filling with a compatible filler other room temperature shop applications.
compound. Release the surface and any tool-
ing pins with a hard wax or release agent. If
25.4.5 DRILL TEMPLATES
the master model is plaster, a hard wax can be
used with a minimum of three applications, Drill templates or fixtures are used primarily
dried adequately and buffed between each to drill and locate precision holes in the pro-
application per the manufacturers directions. duction composite part. While their use is
From the resin supplier, request a water- limited to hole location and drilling, their
proof or hydrophobic resin system which will function may also be combined with other
cure in the presence of water from the plaster. support tooling, such as a trim/router fixture
Apply the resin evenly 0.76 mm (0.030 in) to minimize tooling expenditures. Drill fix-
thick to the master surface with a short bris- tures are fabricated using a room temperature
tled brush and work out air bubbles as they cured fiberglass/epoxy laminating and face
appear. Ensure that no bristles are pulled coat system. Because the tool is used in the
from the brush to contaminate the resin shop environment in ambient conditions, no
Allow the resin to cure to a point that a fin- vacuum integrity or elevated temperature
gerprint may be imprinted lightly into the requirements are needed. Location of the holes
resin and will remain for a period of time can be obtained from the master model sur-
after touching. Then apply a second coat of face. In addition, to facilitate concurrent tool
574 Toolingfor composites

manufacturing, a Mylar@film sheet (0.010 in)
or thicker may be used as a transfer medium
by relocating the position of the holes to the
surface of the Mylar and then using the Mylar
as a temporary master surface while fabricat-
ing the fixture. Prior to fabrication, it must be
determined if the fixture is to mount on the
outside surface of the part (OML) or the inter-
nal surface of the part (IML). Since master
models normally represent the OML surface,
most support tooling such as drill and trim fix-
tures may be fabricated directly off this
surface. Occasionally the surface required will
be a specific distance above or below the sur-
face of the master model. If the surface is
above, tooling sheet wax at the specific dimen-
sion required must be placed on the master
surface prior to fabrication of the tooling aid.
Sheet wax is commercially available in numer-
ous thickness to accommodate most
requirements. If the surface required lies
inside the master model surface, a 'splash'
consisting of plaster and hemp reinforcement
must first be pulled from the master surface
and then the splash surface can be waxed to
the specific dimension inside the master sur-
face. Tool pins are placed in the tooling aid.
After the face coat and two layers of glass have
been applied, the drill bushing is seated onto
the surface with additional lamination over
the bushing to provide an integral lock to the
tool. Template thickness can vary depending
on use, but 9.5 mm (0.375 in) in thickness is
typical.
trim and routing operations are always con-
ducted at ambient temperatures, CTE is not
considered in the design of this type of tooling.
Procedures for laminating the room tempera-
ture cured system are similar to those for drill
fixtures. Periodic debulking is not required
and the tool is not required to maintain any
vacuum requirements. Thickness can vary
depending on final use but is usually about
9.5 mm (0.375 in). If the tool is to be used for
routing, a set back or offset will have to be
determined as defined by the type of routing
equipment used. This set back must be identi-
fied on the surface of the tool to alert
personnel to which equipment is acceptable
for use with the tool. Failure to use the correct
set back will result in an under trimmed or
over trimmed condition. A witness or verifica-
tion line is usually scribed on trim fixtures as a
reference to which edges may be checked for
damage. This allows shop personnel to
quickly verify the accuracy of the trim fixture
with minimal inspection equipment. With drill
fixture tooling, a determination must be made
as to what surface the trim fixture is applied. If
the tool is to represent the same surface of the
master model, then the tool may be directly
taken from that surface. However, if the sur-
face required is internal or external to the
master, appropriate steps including plaster
splashes or waxing must be completed to
obtain the correct surface.
25.4.7 PLY LOCATING TEMPLATES

25.4.6 TRTM AND ROUTER TEMPLATES Ply locating templates are used during the lay-
up of the production part and designate
These shop aids are used to trim and rout locations for the plies and indexing of detail
cured composite parts to a specific dimen- parts. In addition, these templates may also
sional tolerance. Accuracy is required for these show individual ply orientation and designate
tools in order for the composite detail to fit special features of the part such as splice areas
precisely with adjacent details. Trim and or hardware attachment points. Occasionally,
router templates can be fabricated directly honeycomb core placed within composite pro-
from the master model, composite tool or a duction details must be potted with a syntactic
tooling aid such as a PFP (plastic faced plas- core material to prevent core collapse when
ter). They are generally fabricated using room hardware is attached. Reference locations of
temperature cured epoxy/glass systems. Since all attachment hardware may be transferred

from the master model to produce a core pot-
ting template. Core may then be accurately
potted, laminated and then drilled after curing
by referencing the location from the potting
template. Similar templates may be produced
to locate individual details or other assemblies
that have to be located during detail construc-
tion. Slits or eyebrows are cut into the laminate
to locate the edge of the production part ply
and color coded and identified accordingly.
All templates are fabricated from room tem-
perature glass/epoxy cured systems and are
designed to be light in weight with a thickness
of 3.1-3.8 mm (0.125-0.150 in).
Because some templates may be quite large,
provisions must be made where possible to
Bibliography 575
lighten the template to assist in handling.
Lightening holes can be placed by removal of
sections of the template not serving a specific
function. However, as material is removed to
reduce weight, stiffeners must be added to
prevent warpage that may affect dimensional
stability.
BIBLIOGRAPHY
Mallik, P.K., Fiber Reinforced Composites, New York
Marcel Dekker, 1968.
Fiberite Manufacturing Procedures, Toolrite Tooling
Materials System.
United States Gypsum, Tooling Techniques.
Morena, J.J., Advanced Composite Mold Making, New
York: Van Nostrand Reinhold.

CONTROL
26.1 INTRODUCTION
Consolidation is an important step that occurs
in almost every process used to make an
advanced composite article. Consolidation is
usually brought about by the application of
pressure at a boundary which squeezesair and
resin out of the composite thereby changing
both its microstructure and dimensions.
Improper consolidation can lead to voids,
residual stresses,warping and other unwanted
effects which could ultimately lead to the rejec-
tion of the part. A comprehensive discussion of
consolidation in composites would include
many complex phenomena. Simultaneously,
there is heat, momentum and mass transfer,
accompanied by the chemical curing reaction
of the resin and the deformation and motion of
fibers.
Consolidation techniques have been used in
the fabrication of both thermoset and thermo-
plastic composite parts, but are more crucial
steps in thermoset composite processing. The
traditional composite manufacturing process
for aerospaceindustry products usually starts
with the B-stage impregnated prepregs con-
sisting of fiber preforms and staged resin
matrix. Usually the resin content is relatively
high. In order to achieve the required compos-
ite material properties which are dominated
by the fibers, consolidation is used as an
important processing step.
Figure 26.1 shows a setup of the prepreg
Handbook of Composites. Edited by S.T. Peters.Published
in 1998by O1apman & Hall, London. ISBN 0412 540207
26
Fig. 26.1 Schematic of the prepreg lay-up used in
autoclave cure (Springer, 1986).
lay-up used in autoclave cure. In a traditional
lay-up process, prepregs with different fiber
orientation and architecture are placed in cer-
tain order forming a near-net-shape composite
structure. During the lay-up operation,
whether it is done manually or using a robot,
the trapping of air pockets within the structure
is unavoidable. Thus a consolidation step after
the lay-up operation is necessary.Prepregs are
usually provided with relatively low fiber vol-
ume fraction. With the consolidation step, the
fiber volume fraction of the composite product
can be increased and excessive resin can be
removed.
The basic mechanisms involved in a consol-
idation process are the fiber deformation and
resin flow, which are coupled with thermal
effects and the resin cure reaction. A similar
consolidation process can also be seen in soil
mechanics such as the settlement of a founda-
tion. However, the deformation behavior of
fibrous materials is substantially different
from that of granular structures and resin flow
behavior is strongly affected by thermal effects
 Introduction 577

and chemical reaction of the resin. Thus, the surface roughness. Metals are widely used as
study of the consolidation process of fibrous tooling materials for composite processing.
composite materials involves many disciplines. However, their heavy weight and high cost of
To effectively control a consolidation machining become disadvantages when com-
process, the selection of the equipment and plex geometry is involved. Composite tooling
tooling materials is crucial. Major process materials have been used as alternatives in
parameters for a consolidation process include various consolidation processes.
pressure and temperature and both are func- Another tooling component for the consoli-
tions of time and are usually set as operation dation process is the bleeder, which is usually
cycles. Thus the system setup should be able a nonstructural layer of porous cloth or paper
to effectively control the pressure and temper- which allows the escape or bleed out of exces-
ature profile and transfer heat and pressure to sive gas and resin during the consolidation
composite parts. Figure 26.2 illustrates the process. Sometimes the process is called
process variables applied during autoclave migration. The bleeder cloth or paper is
consolidation and cure. removed after the curing process and is not
part of the final composite.
TEMPER ATU RE Breather material is used to provide a vac-
PRESSURE uum path over the surface of the part. Typical
materials are glass and mat. They can be
stretched over the part contours to ensure an
effective vacuum path and sometime also to
provide a cushion effect to matched metal tools.
Bagging and sealing are crucial to the qual-
ity of the composite parts. General
requirements for the bag are: (1)the bag must
apply curing pressure uniformly; (2) the bag
must not leak under molding conditions; and
t t i t t (3) a good vacuum path must be provided in
bagging. Silicone rubber vacuum bags are
Fig. 26.2 Illustration of the process variables (tem- widely used because of their long service life.
perature, pressure) applied during autoclave Moreover, they are repairable and self-healing
consolidation and cure (Springer,1986). with respect to pinholes. The initial cost of fab-
rication is relatively higher. Nylon is an
One of the commonly used facilities is an auto- alternative bag material for up to 193°C
clave, which is a closed pressure vessel with (380°F) and is usually discarded after use.
means for heating and applying pressure and The commonly used form of resin matrix
vacuum to its contents. The dimensions of the prepreg has a resin content beyond 40% and
composite parts are limited by the size of auto- requires a significant amount of resin bleedout
claves. Thus, for large size composite during cure to achieve a cured laminate resin
structures, alternative processing techniques content of 28-32%0.Low resin content prepregs
have been used, such as vacuum bag molding. have been developed which can be used with-
In addition to the equipment, tooling mate- out resin bleedout processes. Since there is no
rial has direct influence on the composite part bleedout process, less resin and less bleeder
surface quality, dimensional accuracy and material are needed for a consolidation and
residual stress. The main considerations for cure process. However, the removal of
tooling material include strength, stiffness, entrapped air becomes a more critical aspect of
thermal expansion coefficient, hardness and process control.
578 Consolidation techniques and cure control

26.2 CONSOLIDATION MODELS portion of the load, then Gutowski’s and

Kardos’ models are applicable.
As composite applications were expanded In the following discussions, both
rapidly in the late 1970s and early 1980s, stud- Springer’s model and Gutowski’s model will
ies on the process science of composite be presented. Kardos’ model is equivalent to
materials became very active, especially in the Gutowski’s model but different process vari-
areas of consolidation and cure (Lindt, 1982, ables are used in the modeling.
1986; Springer, 1982,1986; Loos and Springer,
1983a,b; Halpin, Kardos and Dudukovic, 1983;
26.2.1 RESIN FLOW
Loos and Freeman, 1985; Gutowski et al.,
1987a,b; Gutowski and Cai, 1988; Dave, The problem of resin flow in composite pro-
Kardos and Dudukovic, 1987a,b; Tang, Lee cessing can be treated as flow through fibrous
and Springer, 1987; Batch and Macosko, 1988; porous media. In general it can be handled by
Kim et al., 1988 and 1989; Connor et al., 1993). Darcy’s law which states that the flow rate is
The purpose of these studies has been to find proportional to the pressure gradient applied
out the most suitable process parameters and and is related to the porous medium perme-
then through scientific process modeling to ability and fluid viscosity. The general form of
achieve the optimized composite product Darcy’s law in a one-dimensional case is:
quality.
Pioneering work in composite consolida- (26.1)
tion and cure modeling was led by Springer
(Springer, 1982; Loos and Springer, 1983a). where q is the average resin flow rate, K is the
Laminated composite structure was consid- preform permeability with the units of length
ered with bleeder layers placed on top of the squared, p is the resin viscosity and dp/dx is
composite laminates. When pressure was the imposed pressure gradient. In the case of
applied transversely to the laminate plate, resin flow into the bleeder, the consolidation
excessive resin material which was in a fluid pressure is established between the advancing
state was squeezed out from the laminate. flow front and the tool or mold surface.
Similar consolidation models have also The main issue involved in using Darcy’s
been developed by Gutowski’s group and law in the consolidation process is that neither
Kardos’ group (Gutowski, Morigaki and Cai the fiber preform permeability nor the resin vis-
1987a; Gutowski et al., 1987b; Dave, Kardos cosity is constant over the process. The preform
and Dudukovic, 1987a,b). In these models, permeability is a function of the porosity or
both the fiber material deformation which is fiber volume fraction, fiber diameter, fiber ori-
highly nonlinear and the outgoing flow of the entation and fiber architecture. Among them
resin are considered. the fiber volume fraction changes substantially
As can be seen from the discussion pre- during a consolidation process. Resin viscosity
sented later, both approaches are valid within is related to temperature, the cure status and
the ranges of parameters considered. cure time and changes dramatically in the
Experimental verification results show good process. Usually at the start of a cure process,
agreement with these model predictions resin is in the semi-solid state. With the rise of
(Gutowski et al., 1987b; Kim et al., 1988; Cai temperature, it becomes fluid. As the degree of
and Gutowski, 1989). When resin content is cure increases, it gels and becomes solid.
relatively high and fiber-to-fiber contact is The permeability of fibrous preforms has
insignificant, Springer’s model can be applied. been studied both analytically and experimen-
On the other hand, if fiber volume fraction is tally (Williams, Morris and Ennis, 1974;
relatively high and fibers carry a substantial Gutowski et al., 1987b; Lam and Kardos, 1988,
 Consolidation models 579

1989; Van Den Brekel and De Long, 1989)

using the well-known Kozeny-Carman equa- 0 20 ply somple (0.002in/min.carn oill
tion. The estimation formula using the fiber x 20 ply sample (0.005 in/rnin.com oill

structural variables can be written as:

r; (1- VJ3
K = -~ (26.2)
4k0 v; Carman- Kozeny Eq, kxx=0.7
where rf is the fiber radius, V, is the fiber vol-
ume fraction so that (1- VJ is the porosity and x 5
k, is an empirical constant, called the Kozeny
constant, which is usually determined experi-
mentally. For different textile architecture and
orientation, the value of k, will be different.
Reported experimental data show that for an
aligned fiber bundle, k,,= 0.5-0.7 for the longi-
tudinal flow and k, = 11.0 for the transverse
flow. For f 45" cross plies, k, = 2.70. For woven
Fiber Volume Fraction (Vf)
type textile preforms, ko = 5.5. It should be
pointed out that many experimental results
Fig. 26.3 Comparison of measured axial permeabil-
have been reported and the variation of the
ity values for aligned AS-4 fibers with
Kozeny constant in some cases is significant. Carman-Kozeny equation (Gutowski et al., 198%).
Also in the transverse direction, a modified
Kozeny-Carman equation has been proposed
to account for the stop-flow phenomenon
when fiber volume fraction reaches the maxi-
mum packing efficiency (Gutowski ef al.,
198%). Figure 26.3 shows a comparison of
measured axial permeability values for aligned
fibers with the Kozeny-Carman equation.
Resin viscosity can be expressed as an
empirical function of temperature and degree
of cure (Lee, Loos and Springer, 1982). The
expression can be written as:
p = p-exp (U/RT+Ka) (26.3)
where p- is a constant, U is the activation
energy for viscosity, a is the degree of cure
and K is a constant which is independent of Fig. 26.4 Measured viscosity of 3501-6 resin as a
temperature. function of time (Lee et al., 1982).
Experimental study has been performed for
the Hercules 3501-6 epoxy resin which is at a constant temperature. Thus the value of K
widely used in composite fabrication. Figure *
is found to be 14.1 1.2. The values of p, and
26.4 shows the viscosity measurement as func- U are found to bep- = 7.93 x Pa s, U = 9.08
tions of temperature and time. To match the x 104J mol-'.
model predictions and experimental data, the The degree of cure a and the rate of degree
constant K is found by fitting a linear least of cure da/dt were determined from the
square curve to the p versus a data generated results of 'isothermal scanning experiments.
580 Consolidation techniques and cure control
Efforts were made to describe the d a l d t ver-
sus a data with a modified Arrhenius type
equation. The proposed empirical equations
are
d a l d t = ( K , + K,a) (1- a ) ( B - a) (26.4) tional. Thus 2-D or 3-D flow equations have to
a 10.3
da/dt = K3 (1- a )
a > 0.3
where
K , = A, exp (-AE,/RT)
K2 = A, exp (-AE,/RT)
K, = A, exp (-AE,/RT)
A,, A, and A, are the pre-exponential factors,
AE,, AE, and AE, are the activation energies, R
is the universal gas constant, and T is the
absolute temperature. The constants in the
expression are found as:
B = 0.47
A, = 2.101 x lo9 min-'
A, = - 2 . 0 1 4 ~ l O ~ r n i n - ~
A, = 1.960 x lo5 min-l
AE, = 8.07 x lo4J mol-'
AE, = 7.78 x 104 J mol-'
AE, = 5.66 x lo4J mol-'
As can be seen from the discussion, all the con-
stants involved in the model are determined
experimentally through a specified process.
Similar treatment can be used for other types of
resin systems, and experimental investigation
results have been reported, including Hercules
HBRF-55 Resin (Bhiet aI., 1987)and Fiberite 976
Resin (Dusiet al., 1987).A similar process model
has also been discussed by Roylance (1988).
When the permeability and the resin viscos-
ity are known, with the imposed applied
pressure condition, the rate of the outgoing
resin flow can be calculated using the Darcy
equation. In general, flow may be multi-direc-
be solved. In practice, resin flow in one partic-
ular direction may be dominant, and the
(26.5) analysis can be handled as 1-D permeable
flow.
26.2.2 FIBER DEFORMATION
The main contribution from Gutowski's model
is the description of fiber deformation behav-
ior. Instead of treating fibers as separate layers,
a network concept is introduced. In other
words, fiber-to-fiber contact is assumed within
a fiber assembly, even in the case of aligned
fiber bundles. Thus a fiber filament span
between the neighboring contact points
becomes a small bending beam. During a con-
solidation process when fibers are pushed
closer, more and more fiber-to-fiber contacts
take place, and the span length reduces. Thus
the bending stiffness of these small fiber
beams increases rapidly, resulting in nonlinear
elastic deformation response. The nonlinear
elastic response of a fiber assembly under a
compressive load has been also studied in the
textile field, and an empirical formula was
proposed (van Wyk, 1946).
A proposed fiber deformation model for
aligned fiber bundles considers the deforma-
tion status variable, the fiber volume fraction
V f ,as a function of the consolidation pressure
(Gutowski, 1985).The expression is
where V , is the maximum obtainable fiber vol-
ume fraction for a given fiber network
configuration, and V , is the fiber volume frac-
tion below which the fiber network carries no
load. The empirical constant As is obtained
from curve fitting on available measurement
data. A typical fiber deformation curve for

well aligned graphite fibers is shown in Fig.
26.5 with the- co-mparison of measured data
points.
In
,Q 700
b
In
v)
? 500 Data Point-
al
-1 300
e
:200
.c
100
n-
0.4 0.5 0.6 0.7 0.8 0.9
Fiber Volume Fraction ( V f )
Fig. 26.5 Typical fiber deformation curve for well-
aligned XA-S and A S 4 graphite fibers (Gutowski et
al., 198%).
The proposed relationship between the com-
pressive fiber stress ofand fiber volume fraction
V , provides a tool to estimate the finished con-
solidation status of the composite products. If
the time window for the consolidation is long
enough, and excessive resin is completely
squeezed out from the structure, the consolida-
tion pressure is then balanced by the fiber
stress. However, because of the dramatic
change of the resin viscosity and preform per-
meability during a consolidation process, resin
flow may not be complete. Thus, developed
consolidation simulation models are needed for
the process analysis and improvement.
During the compression of fibrous pre-
forms, structural relaxation has been observed
(Gutowski, 198%). Thus the deformation to
some extent is not elastic but viscoelastic. This
issue has been addressed by using a Maxwell
type model (Kim, McCarthy and Fanucci,
1991).
Consolidation models 581
26.2.3 CONSOLIDATIONMODELS
As discussed above, in Springer’s model, it is
assumed that there is no fiber-to-fiber contact.
Thus a dynamic fluid pressure exists between
the consolidated layers. The consolidation
time, which is crucial to the cure process, is
related to the permeability of the fibrous pre-
forms, resin viscosity, and the applied
consolidation pressure. In Gutowski’s model,
the fiber reinforcement and the fluid state
resin are considered as a system. Both fiber
network deformation and fluid resin flow are
solved together. Both models are presented
here with a laminated composite structure as
the example.
The example for Springer’s model is the
laminate consolidation with flow in the lami-
nate transverse direction, or z direction. A
bleeder ply is assumed to be placed on top of
the composite. Figure 26.6 shows the setup for
the model. At any instant of time the liquid
velocities in the bleeder Vb and in the compos-
ite V care given by Darcy’s law. For a constant
viscosity liquid, the integrated forms are:
K c (Po - P,)
9, = 7 (26.7)
hC
where p , and pb are the pressures at the com-
posite-bleeder interface and in the bleeder
respectively, po is the consolidation pressure
and is related to the applied force or pressure,
is the instantaneous thickness of the liquid
in the bleeder, and hc is the thickness of the
resin starved layer, or the thickness of the lay-
ers through which resin flow takes place, and
K, and Kb are the permeability of the compos-
ite layer and bleeder respectively. If the
compacted composite layer thickness is h,,
then
hc = nh, (26.9)
where n is the number of layers or plies
already compacted.
582 Consolidation techniques and cure control

L Resin Flow

Fig. 26.6 Illustration of the consolidationmodel proposed by Springer (1982).

The equation of continuity gives the rate of layers. The final status of the composite is
change of volume of the composite as: dependent on the compaction of each individ-
ual layer.
-~ d(hA) = Aq, = Aq, (26.10) As a comparison, Gutowski’s consolidation
dt model combines the flow of resin through
where A is the surface area of the composite porous media and the fiber deformation
laminate, and h is the total thickness of the behavior. Similar treatment has been pre-
composite laminate. The second equation sented in studies of other fields including soil
expresses the fact that at any instant of time, mechanics (Biot, 1941,1955,1956; Gibson and
the flow out of the composite is equal to the Hussey, 1967).In general, consolidation occurs
flow into the bleeder. The pressure po is related in only one direction, but flow may take place
to the applied force as: in all three directions. Thus an element is
deformable in the z direction. A new variable 6
f
(26.11) is used to represent the deformation, and 6 = z
= + pa + w where w is the local displacement of the
where F is the applied force and pa is the fiber network. The laminate setup for the
atmospheric pressure. By combining these model is illustrated in Fig. 26.7. If the initial
equations, the consolidation equation fiber volume fraction for the composite is V,
becomes: and the fiber volume fraction at any instant is
Vf, the fiber continuity condition states
vo=-v,
36 (26.13)
aZ
Therefore for each individual layer, the consol-
idation time can be calculated. The total Resin flow continuity condition requires:
consolidation time is the summation for these
 Consolidation models 583

Here it is assumed that the inertial effects in

the process are small. Therefore the applied
pressure is balanced by a combination of the
average resin pressure and the fiber stress. In
(26.14) other words, any load which is carried by the
fibers is then unavailable for pressurizing the
With the application of Darcy's law, a consoli- resin.
dation equation using the fluid pressure p , and Since both the permeability and the fiber
fiber volume fraction Vf as variables can be stress are expressed as functions of fiber vol-
written as ume fraction V , with the given initial and
boundary conditions, the variables V ,and p , as
a function of time and location can be solved.
In general numerical calculation procedures
have to be developed for solving the partial
differential equations. In some simplified
cases, analytical solutions are possible.
This equation gives a relationship between the
spatial and time-varying nature of the pres-
Example problem 1: One-dimensional flow
sure in the resin and the fiber volume fraction
in compression molding
of the composite. The equilibrium statement
for the consolidation is: A simplified example of composite consolida-
tion is the compression molding of a flat
(26.16) rectangular laminate. The composite part is
A pressed between two solid dies. Therefore
only in-plane flow is possible. In other words,
flow components are in the x and y directions
only. If the initial fiber volume fraction is uni-
form, the equation of the resin flow and fiber
deformation becomes:

P av, = 0 (26.17)
J2Pr + K - a2pr + -~
K X ~y ay2 v, at
ho Here it is also assumed that there is no signifi-
cant pressure gradient in the z direction, and
the viscosity p does not vary spatially.
In some cases, K Z / a 2>> Ky/b2 where a and b
are the dimensions of the laminate in x and y
directions respectively. The compression
molding results in primarily one-dimensional
a€ flow in the x direction. Then the equation can
be solved analytically. With the assumed
boundary conditions of p , = 0 at x = M and
ap,/ax = 0 at x = 0, the result is a parabolic
pressure distribution as

Fig. 26.7 Illustration of the consolidation model

proposed by Gutowski et al. (1987a).
584 Consolidation techniques and cure control

The solution for the fiber volume fraction Vf as Example problem 2 Compression molding
a function of time is: with two-dimensional flow
Here the case of compression molding of a rec-
Po = Of(Vf) 3 pa'
+ K _ Vdvf
,T (26.19)
* L
tangular laminate with an isotropic in-plane
permeability is considered. In other words, Kx
This expression shows how the applied pres-
= Ky = K. This may correspond to a quasi-
sure p, is carried by the fiber stress G~ and the
isotropic lay-up. The flow equation becomes
average pressure in the resin. The load sharing
Poisson's equation, which can be solved by the
in a composite is directly analogous to how the
separation of variables technique. The solution
load is shared in a parallel spring and damper
for the pressure distribution in a laminate with
set. For example, initially if Vf is less than V,,
zero pressure at the boundaries is:
then there is no deformation in the spring
(fibers) and the entire load is carried by the
resin. On the other hand, at long times and
finite viscosity, if the rate of change of Vf is
close to zero, then the pressure in the damper
(resin) goes to zero and the total load must be
carried by the fibers. Figure 26.8 shows an
example of the one-dimensional flow in com-
With the applied load balance condition, the
pression molding with the comparison of
final result is:
computer simulation results.

It can be seen that the result is analogous to the

previous case except for a geometry effect
term which is shown in the bracket.

600
- PR,Theory Example problem 3: Bleeder ply molding

- 400 0 PR,Measured This has been presented with the Springer's

-
'3
0
model. In this case, a porous bleeder ply is
placed on top of the composite, and flow is
principally in the z direction. With the intro-
duction of a new variable, the void ratio
e = (1- Vf)/V, one may obtain the nonlinear
one-dimensional consolidation equation. An
equation similar to this was first derived by
Gibson et al. (1967) for the consolidation of sat-
Time ( m i d
urated clays. The expression is:
Fig. 26.8 Example of one-dimensional flow in com-
pression molding and computer simulation results
(Gutowski, et al., 198%).
-
at
(
de = (e, + 1)2- a - Kz 'Of ")
3.z p ( l + e ) ' e az
(26.22)
 Consolidation models 585

The void ratio e or the fiber volume fraction V,

is a function of both time and location. An
equivalent equation using variables Vf and p ,
can be written as

With similar pressure equilibrium conditions,

the distribution and time history of Vf or e can
be solved numerically. Figure 26.9 shows an DT
example of the bleeder ply molding measure-
ment setup, and the comparison of the TRANSDUCER
computer simulation results with the mea-
sured data.
It is interesting to see that, with Gutowski’s
600
consolidation model, the final status of the /Applied Pressure
composite in terms of the average fiber volume o doto
500 - -theory
fraction can be estimated from the proposed Modified
fiber deformation model if the consolidation
process is complete. The consolidation time for -.-
v)
400-
Cormon-Kozemy

a particular setup can be solved through a

v
300 -
numerical simulation.
3
As can be seen from the analysis, the total
consolidation time for a composite structure is L

strongly dependent on the dimension in the a \o

resin flow direction. For laminated composite IO0 \O

structures, usually the dimensions in x and y P

directions (directions within the laminate
structure) are much larger than that in the z
direction (direction transverse to the laminate
plane). For example, many aerospace struc-
tural parts range from a few inches to several
feet in x or y direction, but only have a thick-
ness of a fraction of an inch in the z direction.
Thus the bleeder ply molding process is pre-
ferred and is widely used in many part
fabrication processes. However, for the so-
called thick composites, for example with
lay-up of 64 or 96 plies, the consolidation time
required increases dramatically in the bleeder
ply molding cases. With the selected cure cycle
for thin composites, complete consolidation
may not be achieved for thick composites.
Thus the final fiber volume fraction of the thick
composite tends to be relatively lower. This has
been observed in experiments involving thick
0
0 10 20 30 40 50 60
Time (rnin)
Fig. 26.9 Example of bleeder molding and com-
puter simulation results (Gutowskiet al., 198%).
composites (Kim, Jun and Lee, 1989).
It can also be seen from the comparison of
the two models that with relatively low fiber
volume fraction, fibers carry almost no load.
Thus the consolidation process is dominated
by the resin flow through the fiber network.
Then the difference between the two models is
very minor. Springer assumes the consolida-
tion is done layer by layer, while Gutowski
treats the fiber network as a whole system.
However, in both cases the top layers are con-
solidated first. When the fiber volume fraction
becomes high, then the predictions from the
586 Consolidation techniques and cure control
two models show significant different results.
On the other hand, the numerical schemes of
the two models are different. Springer’s model
requires only the solutions of a series algebraic
equations, while in Gutowski’s model nonlin-
ear partial differential equations have to be
solved. A comparison study has been pre-
sented by Smith and Poursartip (1993).
26.3 CURE CONTROL
Fiber reinforced thermosetting resin compos-
ites manufactured in autoclaves are made by
forming the uncured fiber-resin mixture into
the desired shape and then curing the mater-
ial. Curing requires the application of heat and
pressure. Heat is used to facilitate and control
the chemical reactions of the resin, and pres-
sure is used to consolidate the composite,
squeeze out the excess resin, and minimize the
void content. A cure cycle usually means the
magnitude, duration, and profile of the tem-
perature and pressure applied during a curing
process. Selection of the cure cycle directly
affects the quality of the finished composite
product, such as fiber content, fiber distribu-
tion, and void percentage.
Viscosity
/
Reaction kinetics
\ Heat transfer
Fig. 26.10 Schematic of overall cure process model (Dave et al., 1990).
Specifically, a selected cure cycle must
ensure that:
the temperature inside the material does
not exceed a preset value at any time during
the cure;
2. at the end of the cure the resin content is
uniform and has the desired value;
3. the material is cured uniformly and com-
pletely;
4. the cured composite has the lowest possible
void content;
5. the cured composite has the desired ther-
mal and mechanical properties;
6. the curing is achieved in the shortest time.
Figure 26.10 shows schematically the overall
cure process model structure. In an early study,
Loos and Springer (1983a)proposed a thermo-
chemical model. Heat transfer from the
environment to the composite material deter-
mines the temperature distribution, the degree
of cure of the resin, and the resin viscosity
within the composite structure. The tempera-
ture inside the composite can be calculated
using the law of conservation of energy. By
neglecting the energy transfer by convection,
the energy equation can be expressed as:
b Flow
Residual stress
 Cure control 587

resin viscosity, the degree of cure a and the

rate of the cure da/dt can be characterized
using a modified Arrhenius type equation,
with relevant constants in the model deter-
-k-
i ~zE)
(
+p-
dH
dt
(26.24) mined experimentally (Lee, Loos and
Springer, 1982; Bhi et al., 1987; Dusi et al., 1987;
where p and Cv are the density and specific Roylance, 1988).Figure 26.11 show an example
heat of the composite, kx, k and k, are the ther- of the rate of heat generation and rate of
mal conductivities, and ?is temperature. In degree of cure of the 3501-6 resin system as
the case of relatively thin composite structure, functions of time and temperature.
conduction heat transfer is mainly in the z It is noted that the densityp, specific heat Cy,
direction. Thus terms in the x and y directions heat of reaction Hr, and thermal conductivity k
can be dropped. The rate of heat generation are all dependent on the instantaneous and
dH/dt is defined as: local resin and fiber contents of each ply, and

(26.25)
01
c3501-6 400K 1 05 450K 1
where H, is the total heat of reaction depend-
ing on the resin type. The rate of the cure
reaction is a function of temperature and the
cure status, and can be expressed symbolically
as:
da
- = f(T,
dt
4 (26.26)

The degree of cure is then determined as:

)$(:I
a =

It is assumed that for an uncured material, a =

0, and for a completely cured material, a
dt (26.27)

o f \ , , Iojo\J
approaches unity. As discussed earlier the 0
0 02 04 06 0 02 04 06
DEGREE OF C U R E , a

TEMPERATURE ( K l

I I 1 1 I I

3501 - 6
-

-1 0 5 r n coI/sec

s\ Fig. 26.11 Rate of heat generation

and rate of degree of cure of the
I , , , , ~ , , l , l l l l
588 Consolidation techniques and cure control

can be handled using rule of mixtures (Loos pressure early in the cure cycle and the initial
and Springer, 1983c) or proposed approximate resin moisture are crucial considerations in
formulas (Springer and Tsai, 1967). producing void-free laminates (Kardos et al.,
The solution to these equations can be 1983, 1988). Since the driving force for diffu-
obtained once the initial and boundary condi- sion rises with temperature, in order to
tions are specified. The initial conditions prevent the potential for pure water void
require that the temperature and degree of growth by moisture diffusion in a laminate at
cure inside the composite be given before the all times and temperatures during the curing
start of the cure. The boundary condition cycle, the resin pressure at any point within
requires that the temperatures on composite the curing laminate must be higher than the
surfaces in contact with the tool be known as a minimum resin pressure required, which is a
function of time during cure. Therefore the function of the relative humidity and temper-
boundary condition is related to the specified ature (Dave et al., 1990).Figure 26.12 shows a
cure cycle and the equipment setup. void stability map for pure water void forma-
The objective for the cure control scheme is tion in epoxy matrices. A similar pressure
to achieve the desired composite quality. Some requirement also holds for small air/water
of the main targets are reasonable temperature voids after an initial growth period. It has also
distribution, complete consolidation, mini- been observed that the void content is reduced
mum thermal stress and minimum void
content.
(1 ATM I 101 kPI)
With a developed numerical scheme, the
temperature distribution inside the laminate is
calculated as a function of position and time. A
(RH), = 1ooO/o (RH),= 50%
good cure scheme should realize the two main
targets: (a) the temperature is reasonably uni-
form inside the material and (b) the
temperature does not exceed a preselected
maximum at any time.
For a given cure temperature and cure pres-
sure, the time window for the consolidation is
then specified. From the consolidation models,
the compaction status of the consolidated
composite can be obtained. In Springer’s
model, the result is the total number of com-
pacted plies, while in Gutowski’s model the
result is the V ,distribution across the layers. If
the consolidation cannot be completed with
the selected cure cycle, proper modifications
are then made. The compaction issue becomes
crucial to the cure process of the thick com-
posite structure. A multiple stage heating
process may be designed to defer the cure
reaction of the resin and thus prolong the con- 300 400 500
solidation time window. 1,K
Voids within the composite material are
harmful to its mechanical Performance. Fig. 26.12 Void stability map for pure water void
Experimental study shows that the resin formation in epoxy matrices (Dave et al., 1990).
 Efects of tooling and part shape 589

significantlywhen the applied pressure is suf- heated to a specified temperature at a speci-

ficiently high to collapse the vapor bubble fied rate under controlled conditions in the
before the gel point is reached. Therefore, after autoclave.
the time-temperature cycle is determined, it is Tooling materials may be metal (steel,
possible to obtain a profile of the minimum nickel, nickel alloys, and aluminum),
pressure versus cure time. The boundary pres- graphite-epoxy and elastomer, depending on
sure is then maintained greater than the different composite part shape, size, volume of
minimum pressure throughout the cure cycle. production and curing method. Selection of
During the cooling stage after the cure of the tooling material often reflects a compro-
the composites, residual thermal stress is mise among these considerations. Thermal
related to the difference between the cure tem- behavior of the tooling material is also crucial
perature and ambient temperature, and the in the design and fabrication. Table 26.1 lists
thermal expansion behavior of the composite the coefficient of thermal expansion of differ-
material. For a laminated structure, calcula- ent composite and tooling materials. The
tion of the thermal stress has been discussed values for the composites are dependent on
and formulated by Tsai and Hahn (1980). the ply orientation and fiber volume fraction,
Since the material shows viscoelastic behav- and typical values are shown there.
ior, stress relaxation has been observed over
time. A post-cure process is usually applied to
the structure to relieve the induced thermal
stress. Table 26.1 Coefficient of thermal expansion (CTE)
For large complex-shaped composite struc- for various materials (Borstell and Turner, 1987)
tures, non-autoclave curing methods are used.
Compared with traditional autoclave curing Material CTE ( I P / K )
methods, the component size restrictions are Structural composite material
eliminated, energy consumption is reduced, Boron-poxy 3.6-10.8
and capital equipment cost can be cut down. Aramid+poxy -2.0-5.8
The non-autoclave processes use an oven, inte- Graphiteepoxy 1.8-9.0
grally reinforced tools, and presses. Major Fiberglass-epoxy 7.2-9.0
issues related to non-autoclave curing are the Tooling material
effective compaction of the composite plies, Graphiteepoxy 4.1-9.0
and the elimination of the trapped interlami- Cast ceramic 0.81
nar or intraply air. Tool steel 11.3
Iron (electroformed) 11.9
Nickel (electroformed) 12.6
26.4 EFFECTS OF TOOLING AND PART High-temperature cast epoxy 19.8
SHAPE Aluminum 23.2
Silicone rubber 81-360
Properly designed tools that produce accept-
able parts on a reproducible basis are a must
when fabricating composite structures. The
tool design requires the consideration of as
26.4.1 TOOLING FOR AUTOCLAVE MOLDING
many factors as are studied in the design of
the part itself. The main requirement for the The traditional autoclave molding process
tools is to maintain proper geometric dimen- uses a vacuum bag to impose a pressure dif-
sional stability and surface profile during the ference on the composite lay-up. A typical
compression and thermal cycling processes. bagging system consists of the following steps
On the other hand, the tool must also be (Schwartz, 1983).
590 Consolidation techniques and cure control

1. Cover the lay-up with a perforated parting Graphite-epoxy laminate Angle caul plate
film or separator. Then lay up a layer or lay-
ers of bleeder material. The requirement of
the bleeder layers should be such as to
ensure adequate bleeding of air and excess
resin out of the part.
2. Place a strip of jute (vent material) just
beyond the edge of the lay-up and put bag-
sealing compound along the outside
perimeter.
3. Cover the lay-up, jute, and sealing com- Mold form -/ Caul plate stop

-
pound with a flexible-film diaphragm and
seal the diaphragm to the mold with the
{Resin reservoir
seal compound. cdp\
4. Connect the vacuum lines and slowly apply
the vacuum pressure while working the
wrinkles and excess air out of the lay-up,
bleeder material, and vacuum bag.
5. Check system for vacuum leaks. Mold half- .Mold half
6. Keep the part under vacuum while it is
waiting to be cured in the oven or auto-
clave.
To prevent surface irregularities on the bag
side (untooled surface) of the parts, a caul
plate may be used. The sole purpose of caul
plates is to improve the visual appearance of
the parts. They do not control part thickness. A I
flexible caul plate with a thermally stable rub- \Cao
ber such as silicone or a fluoroelastomer is
often used to accommodate the surface geom- Fig. 26.13 Example of autoclave tooling (Borstell
and Turner, 1987).
etry. Figure 26.13 shows examples of autoclave
tooling setups with caul plates.
The three issues related to the tooling introducing a thermal strain. As the part and
design (Borstell and Turner, 1987) are thermal tool cool down from the gel temperature, the
expansion correction, coordinating the loca- tool usually shrinks more than the part. As an
tion of partial plies and use of caul plates. alternative, graphiteepoxy molds are used in
Because of the low coefficients of thermal some applications. Although some data has
expansion of composites when compared with been published, not all composite materials
metal tooling materials, thermal strain or have been measured. One empirical method is
stress must be considered for a curing process. to cure a representative panel on a plate of the
In the autoclave, the temperature at which the specified tooling material using the specified
resin solidifies is the gel temperature. At that cure cycle. Corrections can be estimated by
specific temperature, the part is the same size comparing the difference between the mold
as the thermally expanded mold. At a temper- and part dimensions. Another recommended
ature above the gel temperature, the tool empirical correction method is to correct steel
expands more than the partially cured part or nickel tools by making the tool 0.999 of the
 Effects of tooling and part shape 591

engineering dimension, and to correct alu- aluminum. During autoclave curing of com-
minum tools by 0.998. For example, a 2540 mm posite parts, the thermal uniformity is
(100 in) dimension is tooled to be 2537 mm excellent with rapid heat-up and cool-down
(99.9 in) for the steel tool. These corrections are
rates. It is easy to handle and transport
needed to ensure an acceptable fit of mating because of its light weight. It also offers out-
composite parts. standing durability because the mold surface
Most parts contain partial plies to accom- resists cutting or impact damage and is not
modate local areas of increased stress. Several thermally degraded. When damaged, it is easy
techniques are used to control the location of to repair by welding, soldering, silver-solder-
partial plies, including polyester film tem- ing, or selective plating. It can provide
plates, slotted templates, and rails and complex contours without expensive machin-
banking surfaces. These tools serve as supple- ing. With most resin systems, it shows good
mental guidance to position the partial plies inrelease properties.
the lay-up process. Figure 26.14 shows the procedures of mak-
Typical cases of applying a caul plate are toing an electroformed nickel tool. As in some
control the edge of a panel or the flanges of other types of tooling, constructing a model of
channels. The design of the metal caul plates the part surface is the first step in creating an
must take into account the fact that the matrix electroformed mold. The models are the same
resin melts in the autoclave to a very low vis- net dimensions as the required nickel mold.
cosity. The caul plate performs by pushing Compensation may be required when the coef-
excess resin sideways. Thus the rigid metal ficient of thermal expansion of the composite
caul plates must have high rigidity so that part differs greatly from that of the nickel
they do not deflect under autoclave pressure mold. Models are made from plaster, epoxy-
at curing temperature. The thickness of the faced plaster, fiberglass, fiberglass-epoxy,
caul plates can be calculated by use of the wood or other materials. From the model a
equations for unsupported bending beam reverse mandrel 'splash' is generally fabri-
analysis. The deflection of the caul plate can be
cated from epoxy-faced fiberglass or plaster.
estimated using the balance condition of resin The mandrel to be used in electroforming is
pressure and applied force (Gutowski and Cai, then copied from the 'splash', although the
1988).The caul plate deflections should be lim- model can be used as the mandrel if it is pre-
ited to half the tolerance permitted in the part.
pared correctly. The comers of the mandrel
should be designed to have radii in excess of
0.76 mm (0.030 in) to avoid thin spots in the
26.4.2 ELECTROFORMED NICKEL TOOLING
deposit. Draft and taper should be designed
An electroformed nickel tool consists of a into the mandrel to facilitate its removal from
4.6-6.4 mm (0.18-0.25 in) thick electrode- the electroform. Sharp corners or narrow, deep
posited mold surface that is supported by a grooves should be avoided if possible. The
simple steel substructure. The mold surface is mandrel can be fabricated from epoxy-faced
produced by the electroplating process fiberglass, rubber, or other materials. The sur-
(Sheldon, 1987). face of the mandrel is made conductive by
The electroformed tooling concept offers proper coatings. The back of the mandrel must
numerous advantages. The size of the mold is be reinforced to keep the mandrel from dis-
restricted only by the size of the electroform- torting during the electroforming process.
ing tank. The cost of producing duplicated Electroforming is the process of producing
tools is low. The mold surface is very smooth an article by electrodeposition of a metal onto
and scratch resistant. The coefficient of ther- a conductive mandrel surface. An anode sus-
mal expansion is approximately 40% less than pended in an aqueous electrolyte is connected
592 Consolidation techniques and cure control

---t -
Model Splash Fiberglass plating mandrel Mold electroformed
I
I
i

Plated mold and tool Mold and structure Plating mandrel

upport structure joined removed

Fig. 26.14 Example of electroformed nickel tooling (Sheldon, 1987).

to the positive pole of a DC electric source, and parts. These include low coefficient of thermal
the mandrel (cathode) is connected to its neg- expansion, ease of preparation, low density,
ative pole. The flow of electricity or electrons and thermal stability (Harmon, 1987). Their
results in the oxidation of a nickel anode to disadvantage is that they are less durable than
nickel ions and the reduction of nickel ions to metal tools.
nickel metal at the cathode (mandrel). The Composite tool making starts with a master
typical rate of growth is approximately model, usually built with plaster or hard-
0.013-0.025 mm (0.0005-0.001 in) per hour. wood. The master models require proper
When the electroform is removed from the drying, sealing, and coating with mold release.
mandrel, its surface is a mirror image of the Then lay-up can be done directly on the plaster
surface of the mandrel. A natural physical or wood master. Liquid gel coats are required
characteristic of electrodeposition is that elec- to obtain a high fidelity surface on tools cured
tric current will tend to localize the deposit on by the vacuum bag process which does not
all edges and corners, causing an uneven generate enough pressure to ensure a void-free
thickness on the electroform. However, there surface, but may not be required on tools
are a variety of techniques to offset this effect. cured by the autoclave process which does
After the desired mold thickness is provide sufficient positive pressure. Prepregs
obtained, the mold is removed from the tank, with light weight fabrics are used directly
cleaned and the steel back-up structure is against the tool surface, while prepregs with
attached. The nickel mold is then polished to heavier fabrics are used to build up the thick-
the required finish, and ready for use. ness. During the lay-up, care should be taken
to work each ply into all radii and corners and
to remove all entrapped air. Debulking is
26.4.3 GRAPHITE-EPOXY TOOLING
applied after the lay-up, either with a vacuum
Composite tools have definite advantages bag setup or with -assistance of an autoclave
over metal molds for large or highly contoured for a pressure debulk, to consolidate the plies
 Eflects of tooling and part shape 593

and remove all entrapped air. The curing
process is done with a vacuum bagging sys-
tem or with an autoclave. With the tool still on
the model, the support structure, either a solid
laminate or an ’egg-crate’ panel is attached to
the tool by means of locally applied fabrics,
room-temperature curing, and high-tempera-
ture resistant resins. Once the support
structure is cured to the laminate shell, it is
removed from the master. Care should be
taken to avoid damaging either the tool or the
master. Figure 26.15 illustrates the
graphite-epoxy tooling making process.
Compositetools are being used successfully
throughout the aerospace industry to produce
parts that are structurally reliable, repro-
ducible, and dimensionally accurate.
Teflon separator film Breather cloth
In thermal expansion molding, two basic
methods are employed: the trapped or fixed-
volume rubber method and the
variable-volume rubber method. Figure 26.16
shows the setup for both methods. The fixed-
volume method exploits the large difference
between the coefficient of thermal expansion
of the elastomer and that of metals. The elas-
tomer is confined within a closed metal tool
Rubber tool sized to fill
the cavih, in the pan
,Pan

/ Vacuum bag

.--- Floating-plate
pressure control

’ Rubber tool projects above the

-
pan 30 excess pressure is vented
by forcing the floating plate
to the bag.

‘PFP master

Fig. 26.15 Example of graphite-epoxy tooling

(Harmon, 1987).

26.4.4 ELASTOMERIC TOOLING

M ,Outer box

Elastomeric tooling or rubber tooling can be

used to generate molding pressure or to act as
a pressure intensifier. In thermal expansion
molding, elastomeric tooling is constrained
within a rigid frame to generate consolidation
w
Fig. 26.16 Example of elastomeric tooling (Foston
pressure by thermal expansion during the cur- and Adams, 1987) (a) fixed volume method;
ing cycle (Foston and Adams, 1987). (b) variable volume method.
594 Consolidation techniques and cure control

cavity. When heated, it expands into the cavity, Impregnated Composites, Proc. 9th Int. Cod.
exerting the pressure required to compact a Composite Mater. (ICCM-9), 1993, 3,575-583.
composite laminate. The variable-volume Dave, R.S., Kardos, J.L. and Dudukovic, M.P., A
Model for Resin Flow During Composite
method offers more flexibility and control than Processing, Part 1: General Mathematical
the fixed-volume method because a precisely Development, Poly. Composites, 1987, 8(1),
calculated volume of rubber is not normally 29-38.
required. In most applications, the rubber is Dave, R.S., Kardos, J.L. and Dudukovic, M.P., A
simply 'set back' to allow for the bulk factor of Model for Resin Flow During Composite
the molding material during assembly of the Processing, Part 2: Numerical Analysis for
tooling details. A floating plate is used for the Unidirectional Graphite/Epoxy Laminates,
Poly. Composites, 1987,8(2), 123-132.
pressure control. Dave, R.S., Mallow, A., Kardos, J.L. and Dudukovic,
Thermal expansion molding with elas- M.P., Science-based Guidelines for the
tomeric tooling has been successfully used on Autoclave Process for Composites
commercial aircraft parts such as rudders and Manufacturing, SAMPE I., 1990,26(3),31-38.
spoilers (Schneider and Carroll, 1987). This Dusi, M.R., Lee, W.I., Ciriscioli, P.R., and Springer,
reduces the number of detail parts fabricated G.S., Cure Kinetics and Viscosity of Fiberite 976
and the need for bonding and mechanical fas- Resin, J. Composite Mater., 1987,21(3),243-261.
Foston, M. and Adams, R.C., Elastomeric Tooling,
tening on assembly, thereby effecting in Engineered Materials Handbook, Vol. 1:
significant reductions in production time and Composites, ASM International, 1987, pp.
cost. 590-594.
Gibson, R.E. and Hussey, M.J.L., The Theory of
One-Dimensional Consolidation of Saturated
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(ANTEC'89), SPE, New York, 1989, pp.
1408-1412.
Lee, W.I., Loos, A.C., and Springer, G.S., Heat of
Reaction, Degree of Cure, and Viscosity of
Hercules 3501-6 Resin, J. Composite Mater.,
November 1982,16, pp. 510-520.
Lee, S.Y. and Springer, G.S., Effects of Cure on the
Mechanical Properties of Composites, J.
Composite Mater., 1988,22(1), 15-29.
Lindt, J.T., Engineering Principles of the Formation
of Epoxy Resin Composites, SAMPE Quarterly,
October, 1982.
Lindt, J.T., Consolidation of Circular Cylinders in a
Newtonian Fluid, I. Simple Cubic
Configuration, J. Rheology, 1986,30.
Loos, A.C. and Freeman, Jr., W.T., Resin Flow
During Autoclave Cure of Graphite-Epoxy
Composites, High Modulus Fiber Composites in
Ground Transportation and High Volume
Applications, ASTh4 STP 873, (ed D.W. Wilson),
1985, pp. 119-130.
Loos, A.C. and Springer, G.S., Curing of Epoxy
Matrix Composites, J. Composite Mater., 1983,17,
135-1 69.
Loos, A.C. and Springer, G.S., Calculation of Cure
Process Variables During Cure of
Graphite/Epoxy Composites, Composite
Materials: Quality Assurance and Processing,
ASTM STP 797, (Ed. C.E. Browning), 1983, pp.
References 595
110-118.
Loos, A.C. and Springer, G.S., Curing of
Graphite/Epoxy Composites, Air Force
Materials Laboratory Report AFWAL-TR-83-
4040, Wright Aeronautical Laboratories, Wright
Patterson Air Force Base, Dayton, OH, 1983.
Roylance, D., Reaction Kinetics for Thermoset
Resins, in The Manufacturing Science of
Composites, Proc. Manufacturing
International'88, Vol. IV, (ed T.G. Gutowski),
1988, pp. 7-11.
Schneider, C.W. and Carroll, H.E., Elastomeric
Tooling Application, in Engineered Materials
Handbook, Vol. 1: Composites, ASM International,
1987, pp. 595-601.
Schwartz, M.M., Composite Materials Handbook,
McGraw-Hill, 1983.
Sheldon, D.L., Electroformed Nickel Tooling, in
Engineered Materials Handbook, Vol. 1: Composites,
ASM International, 1987, pp. 582-585.
Smith, G.D. and Poursartip, A., Comparison of Two
Resin Flow Models for Laminate Processing, J.
Composite Mater., 1993,27(17),16951711.
Springer, G.S. and Tsai, S.W., Thermal
Conductivities of Unidirectional Materials, J.
Composite Mater., 1967,1, 166-173.
Springer, G.S., Resin Flow during the Cure of Fiber
Reinforced Composites, J. Composite Mater.,
1982,16,400410.
Springer, G.S., Modeling of the Cure Process of
Composites, SAMPE J., September/October
1986, pp. 22-27.
Tang, J.M., Lee, W.I. and Springer, G.S., Effects of
Cure Pressure on Resin Flow, Voids, and
Mechanical Properties, J. Composite Mater., 1987,
21,421440.
Tsal, S.W. and Hahn, H.T., Introduction to Composite
Materials, Technomic Publishing, 1980.
Van Den Brekel, L.D., and De Long, E.J.,
Hydrodynamics in Packed Textile Beds, Textile
Research J., August, 1989, pp. 433-440.
van Wyk, C.M., Note on the Compressibility of
Wool, J. Textile lnst., 1946, 37, T285-T292.
Williams, J.G., Morris, C.E.M. and E d s , B.C.,
Liquid Flow through Aligned Fiber Beds, Polym.
Engng Sci., 1974,14 (6), 413-419.
COMPOSITE MACHINING 27
Kent E. Kokkonen and Nitin Potdar

27.1 INTRODUCTION 27.2 CONVENTIONAL MILLING

The processes used to manufacture composite When milling graphite-epoxy with polycrys-
structures generally require that trimming and talline diamond (PCD) the chips are formed as
other machining operations be performed small particles of powder dust and fumes. The
prior to assembly. Machining processes are surface roughness is a function of fiber orien-
required to produce accurate surfaces and tation, cutting direction and the angle between
holes to allow precision fitting of components cutting direction and fiber direction. The sur-
into an assembly. Due to shrinkage during the face may sometimes exhibit many small holes
curing stage of the composite structure it is not due to fiber pull out. When taking heavy
practicable to place holes in the part during milling cuts there is a greater tendency to
the molding stage, therefore milling, cutting, break comers as the tool exits the material so it
drilling etc. are considered a post cure opera- is advisable to first machine a step on the edge
tion. perpendicular to the final pass. A four fluted
Due to the toughness and abrasive nature of end mill will reduce cutting pressure on the
modern composites, there is a need for harder laminate and keep it cooler. Climb milling
and longer lasting cutting tools. A large data- helps prevent the fibers from separating from
base of machining information for various the matrix bond material.
high speed steel and carbide cutting tool Advantages of machining composites are:
materials exists for machining metal, wood
and some thermoplastics. However, much of 0 improved surface finish unless part surface
this data cannot be applied to machining mod- was directly in contact with the mold sur-
ern composites. Modern composites like face;
0 machined surfaces provide accurate mating
graphite-epoxy, aramid-epoxy and carbon-
carbon each have their own machining charac- surfaces for parts to be assembled;
0 eliminates the majority of the problems
teristics. Composites are not homogeneous or
isotropic, therefore the machining characteris- associated with part shrinkage and insert
tics are dependent on the tool path in relation movement during the fabrication processes.
to the direction of the reinforcing fibers. Tool life factors are:
Metals or metal alloys have nearly homoge-
neous properties throughout the workpiece, 0 PCD end milling cutters will perform sixty
but each material in a composite retains its to one hundred times longer than carbide;
individual properties. 0 cutting speed does not have a great effect
on the flank wear of PCD cutting tools.
With increased cutting speeds, the feedrates
Handbook of Composites. Edited by S.T. Peters. Published can be increased and machining time
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 decreased;

cutting speeds range from 244 surface
m/min (800 surface ft/min) to 762 surface
m/min (2500 surface ft/min) with PCD end
mills;
when cutting parallel to the fiber direction,
the wear ratio on the cutting tool increases
compared with cutting perpendicularly to
the fiber direction;
surface finish remains below 20Ra [arith-
metical average roughness (see IS0 R488)]
when cutting with PCD end mills and the
flank wear is approximately 0.127 mm
(0.005in);
0 the surface finish deteriorates above 150 Ra
when cutting with a carbide end mill and the
flank wear has reached 0.127 mm (0.005in);
0 roughing feedrates range from
0.23 mm/rev (0.007 in/rev) to 0.38 mm/rev
(0.012 in/rev) and finish feedrates range
from 0.076 mm/rev (0.002 in/rev) to
0.13 mm/rev (0.005 in/rev);
0 the depth of cuts should range from one
quarter to one half of the diameter of the
end mill cutter. Depth of cut will vary
depending on the rigidity of machine ways,
spindle and workholding devices.
The disadvantages associated with milling
of composites include controlling the graphite
chips (dust particles), confining them to a small
area and having an adequate collection system.
A second problem is controlling the outer lay-
ers of the composite so that the fibers will shear
instead of lifting up under the force of the cut-
ting action and leaving extended fibers beyond
the cut surface. Also when cutting perpendicu-
lar to the lay of composite fibers, edge
break-out can occur. This can be controlled by
designing a backup structure in the tooling.
27.3 CONVENTIONAL TURNING
The turning of graphite composite is utilized
to produce round surfaces that need to mate
with either metal of graphite parts. The cutting
speeds can be over 305 m/min (1000 ft/min) if
the part can be held securely and PCD tool
inserts are utilized.
Mechanical drilling of composite materials 597
Depth of cut will vary depending on the
thickness of the part and the amount of mate-
rial to be removed.
27.3.1 ADVANTAGES
Computer numerical controlled lathes (CNC)
can be used to machine simple to very complex
rotational parts. CNC machining produces
accurate parts at a high production rate.
27.3.2 DISADVANTAGES
Delamination can also occur on a lathe (Fig.
27.1), therefore the part may require a finish
cut moving from the largest diameter to the
smaller diameter. Graphite chips are a serious
problem. The spinning chuck creates a fan
effect on the graphite particles. The exhaust
system must be adequate to control the
graphite chips. Also, the machine ways and
the ball screws on the machine must have
sealed protection to minimize wear. The com-
puter control requires protection from the
graphite chip particles.
27.4 MECHANICAL DRILLING OF
COMPOSITE MATERIALS
Drilling holes in composites can cause failures
that are different from those encountered
when drilling metals. Delamination, fracture,
break-out and separation are some of the most
common failures. Delamination (surface and
internal) is the major concern during drilling
composite laminates as it reduces the struc-
tural integrity, results in poor assembly
tolerance, adds a potential for long term per-
formance deterioration and may occur at both
the entrance and exit plane. Delamination can
be overcome by finding optimal thrust force
(minimum force above which delamination is
initiated). Figure 27.2 shows push out delami-
nation at exit because at a certain point
loading exceeds the interlaminar bond
strength and delamination occurs. Figure 27.3
shows peel-up delamination at entrance
598 Composite machining

Fig. 27.2 Drill bit showing push-out delamination

at exit.

graphite reinforcement materials. Each of

I these materials requires individual attention
I in the selection of cutting tool parameters. The
composite materials with metal backup panels
require separate drills with different geome-
tries. Cutting speeds and feedrates vary in
each of the various combinations of materials.
Secondary drilling or reaming operations are
required to hold tight tolerances or smooth
surface finishes on the holes. Table 27.1 shows
Fig. 27.1 Machining direction for turning compos- the drilling results when using four styles of
ite parts on a lathe. drills.'
PCD tooling offers increased tool life, better
because the drill first abraded the laminate hole quality, consistent hole size and higher
and then pulled the abraded material away machining rates. Drilling and countersinking
along the flute causing the material to spiral
up before being machined completely. This
type of delamination decreases as drilling pro-
ceeds since the thickness resisting the lamina
bending becomes greater.
Among the variables to be considered for
tool selection include the thickness of material,
diameter of hole, tolerance requirements, hole
finish requirements and the composite mater-
Peeling
ial being drilled. Tungsten carbide, micrograin Action
tungsten carbide and drill tool materials are
used for drilling composite materials. 4
I
Some commonly used composites are I
I
I
glass-epoxy, glass-graphite-epoxy, graphite-
epoxy, graphite-epoxy with aluminum
backup and graphite-epoxy with titanium
backup. Other materials include the aramids Fig. 27.3 Drill bit showing peel-up delaminationat
(Kevlar@) with combinations of glass or entrance.
 Mechanical drilling of composite materials 599

Table 27.1 Summary of drill performance: mean hole quality measures as a function of point angle.
Maximum recorded values of response parameters are shown in box brackets, [I (Reproduced from Ref 1
by permission of ASM Materials Week)

Criterion/drill Dagger 8-Facet 4-Facet Master NAS 907-1HSS

Exit breakout 1 2 3 4
(Rank least = 1)
Panel damage, D, 1.96 (3.34) 2.37 (3.18) 2.75 (3.62) 3.63 (5.54)
Microcrack density 1 2 3 4
(Rank: lowest = 1)
Thrust force, 114 [166] 201 [378] 263 [428] 593 [969]
N (1bf) (25.6 [37.4]) (45.3 [85.2]) (59.3 [96.3]) (133.5 [218])
Torque, 1.29 [2.18] 1.15 [2.0] 0.7 [1.64] 1.53 [2.2]
Nm (ft lbs) (0.95 [1.61]) (0.85 [1.5]) (0.50 [1.21]) (1.13[1.61])
Surface finish, R,, 0.4 [1.6] 0.95 [2.2] 1.6 [3.0] 2.4 [4.12]
Pm (Pin.) (26 [641) (38 [88l) (64L1.221) (96 11651)
Hole diameter, 6.354 [6.379] 6.356 [6.369] 6.367 [6.395] 6.375 [6.397]
mm (in) (0.25016 (0.25022 (0.25067 (0.2510

-
[0.25115]) [0.25075]) [0.251751) [0.25185])
Hole out-of-roundness,
(in) 0.0061 [0.025] 0.003 [0.005] 0.0043 [0.018] 0.013 [0.03]
(0.00024 [0.00101) (0.00012 [0.0002]) (0.00017 [0.0007]) (0.00051 [0.0012])
Drill point angle, deg. 30 24,118 140 135

with a combination tool provides better hole
quality. Tool life is normally determined by the
extent of delamination and fiber break out. For
machining graphite composites with or with-
out aluminum backing, PCD tooling is
suggested with the same speeds and feeds
used for machining graphite composites with-
out any backing.
For machining graphite composites with
titanium backing, it is not recommended that
the same drill be used for both the titanium
and graphite sections. Initially a hole should
be drilled up to the titanium layer with a
hydraulic depth sensing device at high speeds
and feed. A second drill with lower speed and
feed for machining titanium should be used.
Finally finish reaming operation and counter-
sinking should be performed for assuring hole
quality.
A study carried out on carbon fiber-epoxy
(CFRP) and glass fiber-epoxy (GFRP) lami-
nates using HSS and carbide tipped drills
made the following observations. Both chisel
edge and flank wear increased on the carbide
drill with a higher ratio of wear between 200
and 400 holes (test sample 400 holes). The tool
wear was greater in the CFRP laminates due to
the abrasive nature of carbon fibers. Flank
wear is more pronounced in GFRP when the
feed was increased and the same effect is
noted when speed is increased. The HSS drills
lasted for ten holes in the graphite and twenty
holes in the glass.
27.4.1 DFULL GEOMETRY
Drill point geometries influence the torque
requirements. Lip relief and rake angles are
determined by the application. The dagger
drill is ideal to machine graphite composites
600 Composite machining

as it eliminates breakout when exiting the be processed.

workpiece. The dagger drill has 35" included The grinding of polymer matrix compos-
point angle and a 121" chisel edge angle. Twist ites (PMC) has a number problems. For
drills with flute configuration to control metal example in the case of thermoplastic matrix,
chips are also used. Fully fluted drills with the surface of grinder becomes covered with
PCD tips brazed on a solid carbide shaft pro- melted thermoplastic. In the case of aramid
vide the strength of carbide and hardness of fiber it is hard to get a clean cut surface
diamond. Drill geometries are continuing to because the grains cannot abrade the aramid
be experimented with to find ways to elimi- fibers cleanly. Abrasive belts have been used
nate the problems associated with the hole on aramids with some success but dust collec-
making process in composites. tion has been a major problem.
Drill cutting parameters are:
0 feedrates range from 0.025 mm/rev 27.6 MACHINING O F KEVLAR
(0.001 in/rev) to 0.063 (0.0025 in/rev);
0 cutting speeds range from 30 surface Cutting, Trimming, Turning and Milling of
m/min (100 surface ft/min) to 460 surface Kevlar
m/min (1500 surface ft/min); Because of its inherent toughness, Kevlar is dif-
0 high cutting speeds can burn the matrix ficult to cut, so sharp, heavy duty upholstery
material and reduce bond strength between scissors will cut up to 170 g/m2 (5 oz/yd2)fab-
the composite material and the matrix ric of Kevlar. Woven roving and heavier fabrics
material. can be cut using specially designed serrated
scissors. An overview of cutting and trimming
techniques and applications is shown in Table
27.4.2 COOLANTS
27.2. For more information on cutting and
A water soluble coolant forced through a cold machining of Kevlar refer to DuPont's
air blast unit is recommended when machin- Machining Handbook2.
ing most composite materials. However if the
composite is hydrophilic in nature then a cold
air blast unit in combination with dust or vac- 27.7 ABRASIVE WATER JET MACHINING
uum collection system should be used. Abrasive water jet (AWJ)is used for linear pro-
file cutting, turning, milling and drilling
operations in composite materials.
27.5 GRINDING COMPOSITE MATERIALS
Conventional tool machining is affected by
The grinding process has been used exten- fiber or particle reinforcements rather than the
sively for finishing composite golf shafts and matrix material while AWJ machining is not.
fishing rods. Five hundred parts per hour can To make a circular hole 6.35mm (0.25in) in
be produced on centerless grinders. Silicon diameter in aramid 3.18 mm (0.125in) thick, it
carbide wheels are used with an open grain to takes about the same time for both conven-
reduce wheel galling. Surface speeds between tional as well as AWJ machining. The cutting
1219 surface m/min (4000 surface ft/min) and process parameters for AWJ include water jet
1829 surface m/min (6500 surface ft/min) can pressure, velocity, abrasive grain size, abrasive
be achieved. This equipment is specially material, standoff distance and jet impinge-
designed for grinding and finishing compos- ment angle. and some additional parameters.
ites. Grinding accuraces within 0.0127 mm Water jets without abrasive are also used for
(0.0005 in) can be achieved with centerless cutting soft composites. Figure 27.4 shows the
grinding. Both straight and tapered shafts can AWJ processes and machining parameters3.
 Abrasive water jet machining 601
h h h
I X
w
I I X
w
X
w
I
h
X
w
I I
h
5 5
7
W
h h h n
I X X
w
X
w 5 X
W
n
I X
W
I X X
h h n
X
v
X
v
X
W
X X
X X X X X
0 I I 0
rn 0 rn I
I rn rn 0
0 0 0 0
0 0 0 0 I
Y
.-W
M
Y
3"
2 .O I
602 Composite machining
h
e
-T z
u?
+I
i
U
3
2 a
a,
c,
a,
€
(d
 Abrasive water jet machining 603

27.7.1 LINEAR CUTTING WITH AWJ 27.7.2 TURNING

Linear cutting is used to trim composite parts
and to cut profile shapes on the inside of a
part. The cut surface is normally smoother
near the entrance surface then becomes wavy
in the lower half of the cut toward the exit sur-
face. In general, the composite material is
sheared away by a high velocity abrasive
grain. The width of cut (kerf) decreases as the
feedrate increases and the waviness increases
as the feedrate increases3.
Table 27.3 shows some of the observations
made by Hashish3.The maximum cutting tra-
verse rate is primarily controlled by the matrix
material.
Table 27.4 shows results for some compos-
ites with different speeds.
In turning with AWJ, a workpiece is usually
rotated while the jet is fed along all three axes.
The material encountered by the jet is abraded
away in the form of a very fine debris. Higher
jet pressure produces a smoother surface with
a higher material removal rate. Higher tra-
verse rates combined with multiple passes are
more efficient than deeper cuts with lower tra-
verse rates. Surface finish is affected by
unsteadiness in traverse rate or abrasive flow
rate. The repeatability and accuracy of the
AWJ turning process depends on control and
steadiness. A 10% variation in rotational speed
does not affect the surface waviness but a tra-
verse rate variation over 4% will significantly
affect the surface waviness. Some methods to
improve surface finish are:

Table 27.3 Typical through-cutting traverse rates (in mm/s) with AWJs for different composites3

Material Thickness (mm)

0.79 1.60 3.18 6.36 12.7 19.1 50.8
Organic matrix composites:
Plastic and composites 53 38 29 21 15 10 2.5
Carbon-carbon composites 42 32 22 13 7.5 4 0.85
Epoxy-glass composites 105 95 76 42 17 12 15
Graphite-epoxy composites 74 63 52 40 15 10 4.2
Kevlar (steel reinforced) 42 25 17 8.5 4.7 2.5 0.63
Cutting conditions: p = 345 MPa, d, = 0.299 mm, d, = 0.762 mm, garnet mesh 80
Sic abrasives

Table 27.4 Surface waviness and corresponding cutting traverse rates (in mm/s) for some composite
materials3

Material Rh4S surface waviness (pm)

1.9 2.5 3.8 5 6 8
A1,OJSiC (20%) 6.35 mm - - 0.29 - - -
Toughened zirconia (6.36 mm) 0.15 0.2 - 0.4 - 0.5
Mg/B,C (15%) 6.36 I T U ~ - 3 - 6 - 8
Graphite+poxy composites (3.18mm thick) - 4 8 12 20 30
Graphite-epoxy composites (18.5 mm thick) 0.6 0.85 1.7 2.5 3.4 4.25
Cutting conditions: p = 370 MPa, dn = 0.299 mm, d, 0.762 mm, garnet mesh 80
604 Composite machining

0 multipassing by traversing the jet without velocity decreases as the depth increases which
lateral feed; can be attributed to the effect of return flow
0 use of finer abrasive and increasing number which reduces particle velocity and interferes
of passes; with the impact process. Pressures of 3040
0 to improve surface roughness, use softer MPa are common for piercing glass. High pres-
abrasives like silica sand, copper slag etc; sures are necessary to pierce brittle or
0 finishing with slurried abrasive yields laminated composites. The higher pressures
improvement in surface roughness. may cause the following problems: fracture
due to shock loading of water; hydrocracking
due to hole hydrodynamic pressurization;
27.7.3 MILLING
delamination due to loading.
The main objective of AWJ in milling is to pro- Holes larger than the piercing diameter of
duce a cavity with controlled depth. In this the AWJ are first pierced, then profile cut to the
method, the jet material interaction is the depth finished diameter being offset by the kerf
determining factor. The production of kerf amount. Hole shape variance depends on mix-
irregularity can be reduced by manipulating ing tube length, target material, standoff
one of the factors, such as traverse rate, increas- distance, depth of hole and dwell time in the
ing the stand off distance or angling the jets. cut. Mixing tube length is important when
To mill square pockets the traverse speed drilling materials with high resistance.
can be varied rather than angling the water jet Increasing the mixing tube length improves
head. In this case the nozzle can be manipu- the distribution of the abrasive with the water
lated over the workpiece with an oscillatory jet. This produces holes that are straighter and
drive using a motor and an eccentric. A uni- rounded.
form traverse rate and exposure time can Advantages offered by AWJ are:
produce a uniform depth cavity. A hard mate-
rial pattern with the shape to be milled can be 0 suitable for wide range of composites;
used to mask the target surface. This way the 0 can perform many operations like turning,
mask will allow jetting in the traverse zones drilling and milling;
0 no thermal stresses;
where the traverse rate is uniform. Surface fin-
ish variations can be achieved by using 0 high as well as low material removal rates;
different abrasive materials or grit sizes. 0 no heavy clamping of workpieces required;
Harder abrasives can be used for higher mate- 0 omnidirectional machining;
rial removal rates and softer abrasives for 0 process can be automated;
0 optimal range of parameters available to pre-
finishing operations.
vent delamination, loading and splintering;
0 fine holes of 0.5 mm (0.012 in) can be
27.7.4 DRILLING drilled.
Hole drilling can be performed in any of the Disadvantages:
following ways depending on the diameter
and accuracy of the holes: piercing is suitable 0 dimensional accuracy is low;
for small diameter holes; kerf cutting is suit- 0 temperature rise in cutting region may be
able for large diameter holes; milling is observed;
suitable for blind holes. 0 limited data is available with respect to
Techniques of hole piercing vary for each applications in metal and ceramic compos-
composite material. Piercing glass, acrylic and ites;
polycarbonate show that the general geometri- 0 not suitable for materials that are
cal features of pierced holes are similar. Particle hydrophilic in nature.

27.8 LASER MACHINING OF COMPOSITES
Lasers are used in various industrial applica-
tions such as drilling, cutting, welding and
heat treatment of metals, etc. In composites,
polymer matrix materials are most suited for
laser cutting. Laser cutting is a non-contact
ablation process in which efficiency is deter-
mined by thermal properties of the workpiece
material. Two types of laser have been used in
industry: Nd-YAG solid state laser and CO,
gas laser. The Nd-YAG laser operates in the
near infrared (IR) region of the spectrum while
CO, gas laser operates in the far infrared
region. The Nd-YAG IR region wavelength is
not absorbed by glass and many plastics while
the CO, far IR region wavelength is.
Applications of Nd-YAG solid state lasers
extend from drilling fine holes in jet engines to
welding implant devices for the medical
industry. It has been determined that the Nd-
YAG laser is very effective in cutting
graphite-epoxy composite materials. The high
power short pulses achieved with this laser
vaporizes both the graphite and epoxy matrix
before the epoxy resin can be overheated.
The CO, gas laser applications extend from
drilling holes in baby bottle nipples to welding
automotive components in assembly lines.
CO, lasers operate in either continuous wave
or pulsed mode. Pulsed mode is preferred
because of high powers obtained and cool
down time. Aramid fiber reinforced plastic
(AFRP) has been cut very effectively by the
CO, lasers. The general characteristics of a
laser cut zone in composite materials are
shown in Fig. 27.5.
The charred layer which includes a zone
with fibers protruding from the matrix and as
outer darkened zone in which the matrix has
undergone some degradation4t5.
Figure 27.6 shows the relationship between
kerf width and cutting speed. For three dimen-
sional (3D) machining two laser beams are
directed through an optical assembly to inter-
sect in the plane of work piece to cut shoulders
and vee grooves.
Ultrasonic machining 605
Advantages:
0 superior quality edges due to high temper-
atures;
0 vaporization of the material in cut zone;
0 extremely localized action;
0 sealing of the edge in the cut zone;
0 pulsed CO, has been demonstrated as the
best laser for processing Kevlar composites.
Disadvantages:
0 beam divergence after its focal point;
0 material thickness of about 9.5 mm (36 in) is
the maximum thickness that can be cut with
1500 W;
0 heat affected zone of varying dimensions.
27.9 ELECTRIC DISCHARGE MACHINING
(EDMI
Advanced composites can be cut by EDM as
there is no physical contact between the elec-
trodes or workpiece and the tool. In order to
EDM a composite, it should have an electrical
resistivity of less than 1-3 ohm/m. Polymer
matrix composite manufacturers can add a
small amount of copper in the matrix of the
product to allow shaping by EDM. EDM can
be used with conductive silicides, borides, car-
bides, etc. The EDM process is more accurate
than AWJ machining. Small holes of 0.25 mm
(0.01 in) diameter can be drilled in SiC/TiB,
composites. The EDM process is found to be
slow for many production applications.
27.10 ULTRASONIC MACHINING
Ultrasonic machining (USM) incorporates a
tool vibrating at 20 kHz and abrasive in a
slurry to perform impact grinding of brittle
materials. This technique is particularly useful
for machining of ceramic matrix composites
that are difficult to process by conventional
methods. USM is a mechanical material
removal process best suited for machining
brittle materials like glass, ceramics, graphite
and ceramic matrix composites. The process is
limited to workpieces of size below 1OOmm
606 Composite machining

\
I \

I CHARRED LAYER
PROTRUDING FIBRES \
I
i

\ ,
,i 'I
I ICROSS SECTION 1
4
0
L- beam exit side
Fig. 27.5 Schematic of FRP laser cut. (Reproduced
by permission of Marcel Dekker Ltd.) W,: kerf
width at the beam entry side; W,: kerf width at the

02 -

-
Fig. 27.6 Kerf width as a function of cutting speed
for (0/90), laminates. (Reproduced by permission '.'a
'
m u
'
) Bo 80 Irn 120 1

of Marcel Dekker Ltd.) Cutting speed (mm/s)


(3.94 in) because of the limitation on the size of
the tool. Some of the variables that influence
USM for close tolerances are as follows:
Abrasive type and size
Abrasives contained in the slurry do the actual
machining so they must be selected on the
basis of the workpiece material and the surface
quality needed. As in the case of AWJ, larger
abrasive grains give higher material removal
rates and rougher surfaces. The grain diameter
cannot be larger than amplitude of the
sonotrode as this would inhibit the injection of
the grains to the machining gap. Common
types of abrasive used are A1,0, oxide, Sic, BC
and diamond.
Table 27.5 shows recommended abrasive
for various materials. The grain diameter
affects surface roughness, overcut and
machining rates. When high removal rates are
necessary with no high surface quality
required, 180-280 mesh abrasive do the job.
For finer surface finish 320-600 mesh abrasive
is recommended. Table 27.6 shows surface
roughnesses for different workpiece materials.
Table 27.5 Recommended abrasive for various materials6
Material
Graphite
Zirconia
Ceramic matric composites
Metal matrix composites
Table 27.6 Surface roughness for various materials6
Workpiece material
Graphite
Zirconia
Ceramic matrix composites
Metal matrix composites
Ultrasonic machining 607
Sonotrode (tool) material
Tools with diamond tips have good material
removal characteristics and very low wear but
are difficult to machine. Table 27.7 shows accu-
racy results of using a non-rotating steel
sonotrode.
Ultrasonic vibrations
The ideal condition would be the amplitude of
ultrasonic vibration to be equal to the grain
mean diameter. If the amplitude is too small
the abrasive cannot enter the machining gap, if
too large it causes the grains to be incorrectly
projected. A mixture of both the types of abra-
sive may be used and a suitable amplitude
selected to determine which size grain enters
the machining gap.
Surface area
This factor influences removal rates and tool
wear. With a small diameter, higher feed rate
is obtained but also higher tool wear is
noticed. This can be overcome by using a dia-
mond tool or with a closed loop force sensitive
Recommended abrasive
Silicon carbide
Silicon carbide or boron carbide
Silicon carbide
Boron carbide
Surface roughness Ra
@ m)
1-2
0.75
0.70
0.90
608 Composite machining

servo system maintaining accurate machining on prepreg materials like glass fiber, carbon
pressures. Table 27.8 shows typical ultrasonic fiber and Kevlar with reduced fiber damage.
machining rates for a variety of materials6. Advantages:
USM is used in applications like drilling
aerospace cooling holes in ceramic matrix 0 conductive and nonconductive materials
composite turbine blades, slotting, irregular can be machined;
0 material hardness is not so important;
configurations in ceramics and composites,
machining of phased array radar components, 0 there are no chemical or electrical alter-
cutting tool inserts, superconductors, wire ations in the workpiece;
0 3D and complex shapes can be machined
draw dies and extrusion dies. A CNC USM can
cut through 6mm (0.24in) thick composite easily and quickly;
0 no heat affected zone.
layers and produce a controlled depth up to
50mm (1.97in). The latter is important, as Disadvantages:
many composites have backing sheets that
should not be damaged. The ultrasonic action 0 amplitude of ultrasonic vibrations are very
reduces the amount of force required to sever important for proper machining;
the hard materials. This results in a better cut 0 limited sizes can be machined.

Table 27.7 Accuracy results with a non-rotating steel sonotrode6

Material Inlet diameter Outlet diameter Taper Roundness

(mm) (mm) (Yo) (mm)
Graphite 10.23-10.25 10.07-10.10 3.00 0.03"
10.26-10.29 10.02-10.05 2.70 0.03b
Metal matrix composite 10.20-10.24 8.87-9.92 9.00 0.04b
10.09-10.12 8.85-9.90 6.60 0.05b
Ceramic matrix composite 10.11-10.15 10.00 3.50 0.04b
5.04 4.99 1.25 -c
Zirconia 5.05 4.85 5.50 -C
a Tool 1: Exponential,Diameter = 10 mm
Tool 2: Exponential,Tube D = 10 mm, ID = 7 mm
' Tool 3: Exponential,Diameter = 5 mm

Table 27.8 Typical ultrasonic machining rates for a variety materials7

Drilling diameter = 5 mm Drilling diameter = 10 mm

Material Time Removal rate Time Removal rate

(min) (mm3/min) (rnin) (mm3/min)
Graphite 1 164 1.25 224
Ceramic matrix composite 3.5 39 5.6 50
Metal matrix composite 10 7.6 14 9.3
Zirconia 210 0.65 90 3.1

REFERENCES
1. Mehat, M., Reinhart, T.J. and Soni, A-H., Effect
of fastener hole drilling anomalies on structural
integrity of PMR-l5/GR composite laminates,
Proc. Machining of Composite Materials Symp.,
ASM Materials Week, Chicago, Ill, 1-5 Nov.
1992.
2. Kevlar Cutting and Machining Handbook, E.I. Du
Pont de Nemours and Co.
3. Hashish, M. State of the art of abrasive waterjet
machining operations for composites. Proc.
Machining of Composite Materials Symp., ASM
Materials Week, Chicago, Illinois, 1-5
November 1992.
4. Di Ilio, A., Tagliaferri, V. and Veniali, F.
Machining parameters and cut quality in laser
cutting of aramid fibre reinforced plastics.
Materials and Manufacturing Processes, 1990,5(4),
591-608.
5. Lemma, S. and Sheehan, B. Laser Machining of
Composite Materials. Proc. Machining of
Composite Materials Symp., ASM Materials Week,
Chicago, Illinois, 1-5 November 1992.
6. Gilmore, R. Ultrasonic machining of composite
materials, Proc. Machining of Composite Materials
Symp., ASM Materials Week, Chicago, Ill. 1-5
November, 1992.
FURTHER READING
Bhattacharyya, D., Allen, M.N. and Mander, S.J.
Cryogenic Machining of Kevlar Composites.
Materials and Manufacturing Processes, 1993,8(6),
631,651
References 609
Bhatnagar, N., Naik, N.K. and Ramakrishnan, N.
Experimental investigations of drilling on CFRP
composites. Materials & Manufacturing Processes,
1990, 5(4), 591-608
Geskin, E.S., Tisminetski, L., Verbitsky, D.,
Ossikou,V., Scotton, T. and Schmitt, T.
Investigation of waterjet machining of compos-
ites. Proc. Machining of Composite Materials
Symy., ASM Materials Week, Chicago, Illinois,
1-5 November 1992.
Hochegn, H., Puw, H.Y. and Yao, K.C. Experimental
aspects of drilling of some fiber-reinforced plas-
tics. Proc. Machining of Composite Materials
Symp., ASM Materials Week, Chicago, Illinois,
1-5 November 1992.
Krishnamurthy, R., Santhanakrishnan, G. and
Malhotra, S.K. Machining of polymeric compos-
ites. Proc. Machining of Composite Materials
Symp., ASM Materials Week, Chicago, Illinois,
1-5 November 1992.
Lubin, G., ed., Handbook of Composites, 1982, New
York: Van Nostrand Reinholt.
Ramulu, M., Faridnia, M., Gargini, J. L. and
Jorgensen, J. E. Machining of graphite/epoxy
composite materials with polycrystalline dia-
mond (PCD) tools. Trans. ASME, J. Engng Mater.
and Tech., 1991,113, October .
Zaring, K., Erichsen, G. and Burnham, C. Procedure
optimization and hardware improvements in
abrasive waterjet cutting systems. PYOC.
Machining of Comr?osite Materials Svmp., ASM
Materials" Week, Chicago, Ill., 1-5 "November
1992.
MECHANICAL FASTENING AND ADHESIVE
BONDING
D. W. Oplinger
28.1 INTRODUCTION
It would be difficult to conceive of a structure
that did not involve some type of joint. Joints
often occur at a transition between a major
composite part, where most of the structural
performance is generated, and a metal feature,
which is introduced to allow for very high
localized bearing contact for which the com-
posite has inadequate strength or durability. In
aircraft such a situation is represented by artic-
ulated fittings on control surfaces as well as on
wing and tail components which require the
ability to pivot the element during various
stages of operation. Tubular elements such as
power shafting often use metal end fittings for
connections to power sources or for articulation
at points where changes in direction are
needed. In addition, assembly of the structure
from its constituent parts will involve either
bonded or mechanically fastened joints or both.
Joints represent one of the greatest chal-
lenges in the design of structures in general
and in composite structures in particular. The
reason for this is that joints entail interruptions
of the geometry of the structure and often
material discontinuities, which almost always
produce local highly stressed areas, except for
certain idealized types of adhesive joint such
as scarf joints between similar materials. Stress
concentrations in mechanically fastened joints
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
28
are particularly severe because the load trans-
fer between elements of the joint have to take
place over a fraction of the available area. For
mechanically fastened joints in metal struc-
tures, local yielding, which has the effect of
eliminating stress peaks as the load increases,
can usually be depended on; such joints can be
designed to some extent by the 'P over A'
approach, i.e. by assuming that the load is
evenly distributed over load bearing sections
so that the total load (the 'I") divided by the
available area (the 'A') represents the stress
that controls the strength of the joint. In
organic matrix composites, such a stress
reduction effect is realized only to a minor
extent, and stress peaks predicted to occur by
elastic stress analysis have to be accounted for,
especially for one-time monotonic loading.
28.2 MECHANICALLY FASTENED JOINTS
COMPARED WITH ADHESIVE JOINTS
In principle, adhesive joints are structurally
more efficient than mechanically fastened
joints because they provide better opportuni-
ties for eliminating stress concentrations; for
example, advantage can be taken of ductile
response of the adhesive to reduce stress peaks.
Mechanically fastened joints tend to use the
available material inefficiently and are charac-
terized by sizeable regions where the material
near the fastener is nearly unloaded, which
must be compensated for by regions where
high stresses occur to achieve a particular
 Mechanically fastened joints 611

required average load capacity. As mentioned

composites first came into use. It was found
above, certain types of adhesive joint, namely
early in this period that the behavior of com-
scarf joints between components of similarposites in bolted joints differs considerably
stiffness, can achieve a nearly uniform stress
from that which occurs with metals, primarily
state throughout the region of the joint. because stress concentrations are much more
In many cases, however, mechanically fas-
of a factor in joint behavior of composite struc-
tened joints cannot be avoided because of tures, and stress analysis to quantify the level
requirements for disassembly of the joint, for
of various stress peaks is more important. It
replacement of damaged structure, or to was fortunate that significant computing
achieve access to underlying structure. In addi-
power became available in this period to keep
tion, adhesive joints tend to lack structural
up with the need for the intimate details of
redundancy, and are highly sensitive to manu-
stress conditions around mechanical fasteners.
facturing deficiencies, including poor bonding The current approach to the design of
mechanically fastened joints in composite
technique, poor fit of mating parts and sensitiv-
ity of the adhesive to temperature and structures evolved mainly out of a number of
environmental effects such as moisture. DoD, NASA and associated university pro-
Assurance of bond quality has been a continu-
grams aimed at providing a methodology
ing problem in adhesive joints, primarily which could be applied routinely to aircraft and
because, while ultrasonic and X-ray inspection
other applications. Numerous stress analysis
may reveal gaps in the bond, there is no present
approaches to the mechanics of fastened joints
technique which can guarantee that a bond have been conducted over the years since the
which appears to be intact by ultrasonic or X-
introduction of 'advanced' composites in the
ray inspection does not lack load transfer mid-1960s. These have included: the work of
Waszczak and Cruse' based on the boundary
capability, because of such factors as poor sur-
face preparation. Surface preparation and integral method; the use of two-dimensional
complex variable elasticity solutions which
bonding techniques have been well developed,
treated the problem of variable contact around
but the possibility that lack of attention to detail
the fa~tenel-2-~;
in the bonding operation may lead to such defi- as well as recent work reported
by Madenci and Illeri7; and a number of finite
ciencies needs constant alertness on the part of
those responsible for the bonding. Thus element approaches, especially the work of
Crews and Naik8 which featured an inverse
mechanical fastening tends to be preferred over
bonded construction in highly critical and method for dealing with the contact problem.
Hart-Smith9 developed an analytic approach
safety rated applications such as primary air-
based on the use of available solutions for
craft structural components, especially in large
isotropic plates with bolt-loaded holes as well
commercial transports, since assurance of the
as unloaded holes in plates under tension or
required level of structural integrity is easier to
compression which came out of classical efforts
guarantee in mechanically fastened assemblies.
Bonded construction tends to be more preva-such as those reported in Petersonlo.The latter
lent in smaller aircraft however and for provided simple functional descriptions of the
effect of joint geometry on peak stresses which,
non-aircraft applications as well as in non-flight
critical aircraft components. with various empirically derived correction fac-
tors introduced by Hart-Smith9, provided
valuable insight into a number of trends in joint
28.3 MECHANICALLY FASTENED JOINTS
behavior.
Mechanically fastened joints for composite In addition to the analytic efforts, several
structures have been under study since the fairly extensive programs aimed at the devel-
mid 1960s when high modulus, high strength opment of design approaches for structural
612 Mechanical fastening and adhesive bonding

systems have been supported by DoD and
NASA4r6.Numerous papers have been pre-
~~
sented Over the years in a series Of
DoD/NASA/FAA 'Onferences On Fibrous
Composites in Structural De~ign~,'~-'~. Many of
the design principles which have been devel-
'ped to take into account the
characteristics of bolted composite structures
have been described4,6, 13.
It is not possible within the scope Of this
discussion to describe all the details and
Processes that are necessary for achieving the
design of specific joints. The objective is rather
to give the reader Some insight into the
factors that control the behavior of mechani-
fastened joints in structures'
The behavior of mechanically fastened
joints is governed by types Of information:
(l)the features that the behavior Of the
joint around individual fasteners and; (2) the
behavior of multiple arrays of fasteners. The
behavior of individual fasteners can be consid-
ered in terms of a generic rectangular element
surrounding each fastener (Fig. 28.1), whose
length and width are represented as ratios
wi& respect to the fastener diameter. The
effects of the geometry of this element together
with effects of the reinforcement arrangement
used in the laminate for the element determine
the structural conditions under which the ele-
ment will fail. Once the characteristics of the
rectangular element are selected, its deforma-
tion characteristics can be combined with
those of other rectangular elements making up
the joint to obtain the performance of the joint
28.3.1 KEY FEATURES OF MECHANICALLY
FASTENED JOINTS
Figure 28.1 represents a generic single fastener
joint, while Fig. 28.2 depicts a multiple fas-
tener configuration. Many of the most
important features of joints are illus-
trated in the single fastener case s h o r n in Fig.
28.1. Key dimensions are D, the fastener diam-
eter, t, the thickness of the joint structural
elements, e, the edge distance (distance from
the fastener center to the edge of the
upper plate) and W, the width of the part of
the upper plate to the left of the fastener.
Similar featups apply to the lower plate ele-
ment. Note that the Same load, p, is passed
successively through various sections of the
joint, including the bearing section in front of
the fastener of area Dt which is in compres-
sion, the b o shearout sections of total area 2et
which are loaded in primarily in shear, the net
section,(w - D)t which is in tension, the
gross section wt which is also in tension.
The average stresses associated with these
sections are:
average bearing stress, ab= P / D t ;
average shearout stress, a,, = P/2et;
average net section stress, aN= P/(W - D)t;
average gross section stress, aG= P / Wt.
(28.1)
LOAD PATH
P
t

as a whole. This discussion is organized in

terms of these two aspects of joint design.
In addition to a preliminary discussion of
general features of mechanically fastened I ' \ bearid section
goss net sectiqn
joints, the discussion which follows also con- section section Dt I
siders: (1) single fastener joints, including wt (W-O)t I
I
I I
effects of joint geometry together with those of I
,/-7-. I
composite material behavior; (2) multi-fas- c I ! : I J
tener joints; (3) fastener effects, and (4) a
discussion of test methods which provide
empirically-based data needed for completing
the joint design. Fig. 28.1 Single fastener joint.
 Mechanically fastened joints 613

Axit!
tit h
Lateral
Pitch
w
eff
* Lateral Pitch

Fig. 28.2 Multi-fastener joint.

From the standpoint of the designer, the gross

section strength is of primary interest since the
objective of good design is to stress the gross
section to its highest level. Structural perfor-
mance of the joint can be rated in terms of joint
efficiency, which refers to the ratio of average
-8-1
gross section stress at failure of the joint to the
strength of the laminate in the gross section, G

essentially the strength achieved in coupon

tests for tensile or compressive loading of
unnotched specimens. For organic matrix
composites, single fastener joints achieve joint Fig. 28.3 Peak stresses around fastener.
efficiencies of less than 50%, while for multi-
fastener joints the maximum achievable
efficiency is of the order of 60%. In contrast, gross section:
metallic joints can reach efficiencies of close to
KGt = O,&JO~ (28.2)
80% because of the opportunity for taking
advantage of local yielding around points of or
high stress, though even in metallic joints,
design for avoidance of crack initiation in qt= q J m x / o G
cases where long life under cyclic loading is where a )
, is the maximum axial stress on
required may force the joint efficiency to be the net section. Predictions of the peak stresses
lower than for single cycle loading. in the joint can be made using continuum elas-
ticity analysis1", 7, 12, photoelastic measure-
ments'O or finite element methodsE.
28.3.2 EFFECTS OF JOINT GEOMETRY
The behavior of K$ as a function of D / W
The peak value of axial stress on the net sec- for isotropic joint elements is given in Fig. 28.4
tion on,),,, (Fig. 28.3) is one of the key which was obtained from photoelastic mea-
controlling parameters on joint performance. surements of KNnt against D / W (note that Kgt =
It is convenient to express this as a stress con- KNnt/(l - D / W ) ) given by Petersenlo. Similar
centration factor, i.e. a ratio with respect to curves for orthotropic plates were obtained by
either the mean stress in the net section or the elasticity analysis2,3, 12.
614 Mechanical fastening and adhesive bonding

There is obviously a competition for space
between the bearing section and the net sec-
tion. Increasing the fastener diameter, D, to
lower abhas to decrease (W - D)t, the net sec-
tion, thereby increasing uN, and vice versa.
Furthermore, if D / W is much less than 1, the
case is similar to that of a fastener in an infi-
nitely wide plate; in such a case all the peak
stresses become a constant multiplier of the
bearing stress ab, which becomes large for
D/W<<l. If D is large enough to fill most of
the available width, the net section becomes
small, oNbecomes large, and the peak net sec-
tion and shear stresses become proportional to
uNfor this case. As seen in Fig. 28.4, is large
for small D / W as well as for D / W approach-
ing 1, leading to a minimum around D / W =
0.59J2. The quantity 0.89ub/uG + 1.8 uN/uG
which is plotted in Fig. 28.4 gives a reasonable
approximation to the curve of KGt against
D / W, so that the use of eqn (28.1) to express ob
and uNin terms of D / W, shows:
Kgt 0.89W/D + 1.8/(1 - D/W) (28.3)
The behavior of this approximation empha-
sizes the tradeoff between the effect of the
bearing section and the net section on the peak
net section stress. A similar functional fit to the
curve of KNt (the stress concentration based on
a,) against D / W was given for isotropic plates
by Hart-Smith9, based on photoelasticity
results reported in the literature; when stated
in terms of Kgt, the Hart-Smith approximation
leads to
K;t (bolt loaded hole) = W/D + 2/(1- D/W)
- 1.5/ (1+ D / W ) (28.4)
He also gave an expression for KNt for open,
unloaded holes (i.e. with no load transfer
between the fastener and plate) in isotropic
plates; when the stress concentration is
expressed as a ratio with respect to ac rather
than uN the Hart-Smith open hole expression
reduces to:
Kgt (open hole) = 2/(1- D / W )
+ (1 - D/W)* (28.5)

'T Functional Fit,

0.89%+ 1.8oN

\
Y
4 --

3 -- elastic measurements)

01 I

0.1s 028 0.4 0.53 0.65

DIW ---31.-

Fig. 28.4 Predicted net section stress concentration against D /W.

 Mechanically fastened joints 615

This is of interest in later discussions of com- delamination and fiber-separation around

bined bearing-bypass loads on bolted joints.
As a means of predicting joint strength, we can
equate the peak stress CTJ,,,~~ to F'", the
strength of the orthotropic laminate used in
the joint. If the joint material acts purely elasti-
cally, then the elasticity prediction of K$ gives
F; which denotes the value of C T when~ net sec-
tion failure occurs, as F," = F'"/K,"'. The
minimum in the KGntagainst D/W curve of
Fig. 28.4 will result in a maximum in the rela-
tionship between F," and DIW at D / W = 0.5.
However, joint strength is usually found to
be considerably greater than that based on
purely elastic behavior of the composite to fail-
ure, and it is appropriate to use the method
developed by Whitney and NuismerI4 to cor-
rect strength predictions based on linear elastic
response to failure. The Whitney-Nuismer
approach was developed for strength predic-
tion of composite plates in the presence of
circular holes, crack-like slits and other types of
notches, and is meant to take into account the
softening effect of local damage such as
regions of peak stress. The method is applied
by averaging the stresses predicted by two-
dimensional elasticity analysis over a selected
length a,, along a path lying normal to the load
direction, in the vicinity of the peak stress. The
failure load is obtained by equating the aver-
aged stress to the laminate strength P, and u,
is determined by an empirical fit of the mea-
sured strength data. In an alternative version of
the Whitney-Nuismer analysis, F'" is equated
to the stress at a point spaced an empirically fit-
ted distance do from the location of the stress
peak. The latter approach has frequently been
used for joint strength predi~tion'~, although
the averaging and point stress versions of the
Whitney-Nuismer analysis are equivalent.
Figure 28.5 illustrates the prediction of F;
for net section tension failure as a function of
D / W . The curves here were obtained from
stresses given by elasticity analysis of 0/90°
glass epoxy joint elementsI2,by averaging the
predicted axial stress distribution uxin the net
section (usingthe definition of x and y indicated

D = 0.63 cm (0.25 ") Laminate Tensile Strength 110 ksi (0.76 GPa)
45 ,-0.31 GPa Compressive Strength 100 ksi ( 0.69 GPa)

0-
40
35
vi
30
c
25
C
50 20

$ 15
v)
g L
10

a 5
0
0.13 0.25 0.33 0.5 0.63
DIW
Fig. 28.5 Maximum gross section stress against D/ W.
616 Mechanical fasfening and adhesive bonding

by the coordinate axes centred at the hole in

Fig. 28.3 from the edge of the hole to a point a
distance u, from the hole, using the a, values
listed in Fig. 28.5. The lowest curve of Fig. 28.5
which corresponds to a, = 0 represents purely
elastic behavior of the joint material. It is clear
that increasing the value of a, causes an
upward shift of the predicted strength curve.
Experimental joint strength datal2 gave an a,
value of about 3.8 * 1.3 mm (0.15 & 0.05 in) for
quasi-isotropic carbon epoxy laminates, for

-
net section failure. Nuismer and W h i t n e ~ ' ~
suggested that a, and the corresponding d, are
relatively constant for composite materials in
general, although this is not always true.
However, for a given material and stacking
sequence, a, is independent of hole size; this
M
has the effect that for large fastener diameters,
the averaging effect is less important, and Fig. 28.6 Experimental results on strength against
D/W2.
strength values tend toward those predicted
by the elasticity analysis.
All the net section failure curves of Fig. 28.5 'bearing failure', corresponding to compressive
have the peak in the vicinity of D/W = 0.5 failure in front of the pin. Except for joints with
which was predicted by the linear elastic short edge distance or multi-fastener joints
response analysis. This suggests that the joint where high bypass loads are present, the peak
strength is a maximum for bolt diameters near compressive stress in front of the fasteneP is
half of the plate width. For multi-fastener found to be about 1.3 times ab,and uGfor bear-
joints such as the one shown in Fig. 28.2, the ing failure can be estimated by setting abequal
length corresponding to W for the single fas- to F" (compressive strength of the laminate)
tener joint is replaced by WeE, the spacing of from which uG)max = F'" D/1.3W, a linear func-
the dashed lines, which are lines of lateral tion of D / W. Although this result implies that
symmetry; note that We* is also equal to the the laminate compressive strength is the same
lateral s cing of the fasteners (the lateral as the bearing strength as is approximately true

\
pitch), so t t the peak strength value occurs in some cases, the actual value of Fb" = ub)mm
at a lateral pi ch of about twice the fastener depends on the stacking sequence of the lami-
diameter. The experimental data of Fig. 28.612 nate as well as a number of details of the joint
confirms the occurrence of a strength maxi- such as the type of fastener and whether the
mum for D / W = 0.5 in single fastener joints. joint is in single or double shear (Section
For multi-row joints (see Section 28.3.4) in 28.3.5); thus Fbu has to be empirically deter-
which bypass load is present, the net section mined for a given fastener, joint configuration
strength peak occurs for smaller values of and joint material selection by appropriate
D / W. High bypass loads give results similar bearing strength tests (Section 28.3.6). Hart-
to those for plates with unloaded holes, in Smith9J3introduced a method of comparing
which case large values of W / D correspond- bearing and net section tension failure similar
ing to large fastener pitch are desirable. to that given in Fig. 28.5 to show the trade off
In addition to the solid curves in Fig. 28.5 for in failure modes for various values of D/W,
net section failure is the dashed line designated and recommended selecting D/ W for the
 Mechanically fastened joints 617

design of the joint as the point at the intersec- strength will not be achieved unless e is at least
tion of the bearing and tension failure as great at W. This is shown schematically in
envelopes. However, it was also pointed out in Fig. 28.8, which indicates that the minimum e
Nelson, Bunin and Hart-Smith13 that in multi- for full joint strength over a wide range of fas-
row joints in which the bearing load is tener diameters remains equal to W. It is true
distributed over several fasteners in a given that there is a tendency for bending failures to
column, the bearing stress is smaller than for occur at the unloaded end of the joint (Fig.
the single fastener case and bearing failure may 28.9) for edge distances as small as 1-2 times
not occur in practical joint designs. D, which were shown in Op1ingerl2, in fact, to
The value of the edge distance, e, is another be a function of e / D; however, this type of fail-
critical parameter for bolted joints. While it ure is eliminated for e / D greater than about 2.
has become customary to present joint
strength as a function of e / D , in fact9,12it is
more a function of e/ W if e / D is much greater
than 1, and plotting data on the effect of edge
distance as a function of e / D is somewhat mis-
leading even though it persists as accepted
practice. Both stress analysis9,l2 and experi-
mental results (Fig. 28.7) indicate that full joint

Fig. 28.8 Minimum edge distance is equal to W

(independent of D).

y / I
high bending
stress 0
Y

I I I
b .W
I
1 4

Fig. 28.7 Effect of edge distance on joint strength Fig. 28.9 Tendency for bending failure with small
W / D = 212. e/ D.
618 Mechanical fastening and adhesive bonding
28.3.3 EFFECTS OF JOINT MATERIAL
Typical failure modes for mechanically fas-
tened joints are shown in Fig. 28.10. Figure
28.11 indicates that shear-related failures may
include what are usually 'shearout' failures
such as the upper figure for 0,&5 reinforce-
ments, which tend to lie along straight lines
tangent to the bolt hole and to run to the end
of the joint, as opposed to those for 0/90° lam-
inates which originate at about 45" points
around the bolt hole and run along curving
lines to the joint end. Hart-Smith9 shows
examples of 'shearout' type failures while the
second type are demonstrated by experimen-
tal results for 0/90" glass epoxies12.Since the
90" points around the bolt hole are traction
free, shear stresses cannot exist there, and
'shearout' failures are probably associated
with fiber separation failures resulting from to
a deficiency of 90" fibers in 0,&5 laminate,
while failures originating at the 45" points in
0/90° laminates appear to be true shear fail-
ures. Chang and Hun@ provided an
analytical approach which modelled progres-
sive damage in 0/90° laminates that predicted
the types of shear failures that are depicted in
Fig. 28.11.
l€NSlON FAIUIIL
Fig. 28.10 Typical failure modes in composite joints13.
Fig. 28.11 Shear failures in bolted joints.
In addition to modelling shear failures, Chang
and Hung16 also reported results related to
bearing failure which show that these failures
result from high out-of-plane shear stresses;
the associated failure surfaces are oriented
along planes at 45" to the x-y plane. In addi-
tion to clarifying the bearing failure modes,
these results verified the importance of clamp-
ing pressure as a factor in achieving maximum
bearing strengths. This is discussed further in
Section 28.3.5.
It should be mentioned that the term 'bear-
ing' strength, which is usually associated with
the maximum achieved value of ab,does not
necessarily imply that the joint fails by bearing
failure, since, depending on the joint geometry
-
BO11 PULLING lHlOUGn U M I W T E

and reinforcement, failure may take the form
of shearout or net tension rather than bearing
failure; bearing strength only identifies the
value of abthat occurs when the joint fails. The
value of abfor the bearing failure mode can be
looked on as a laminate material parameter,
however, and can be obtained from appropri-
ate single fastener strength tests, to be
discussed in Section 28.3.6, in which e/ W (usu-
ally specified in terms of e / D ) and W / D are
large enough to guarantee a bearing failure
mode. The effect of the reinforcement configu-
ration on the maximum achieved ab is an
important factor in joint design. Note that for
design purposes, the normal reinforcement
arrangement includes only plies in the 0", 45"
and 90" directions with respect to the load
axis, implying that other orientations are not
encountered; in addition, the 45" reinforce-
ment is arranged symmetrically as double
plies of k45" reinforcement. The notation com-
monly used to describe the stacking sequence
is condensed to reflect percentages of plies in
the three customary directions, 25/50/25 rep-
resenting 25% 0", 50% 45", and 25% 90", or
quasi-isotropic, reinforcement, for example.
The effects of reinforcement percentages on
maximum achieved bearing stress are shown
in Fig. 28.12, a three-parameter 'carpet plot'
which is used to show the effect of percentage
of reinforcement in the 0", 90" and 4 5 " direc-
tions on maximum achieved bearing stress for
a fixed joint geometry. The contours of con-
stant bearing strength indicate that maximum
joint strength is achieved within a broad
plateau lying between 3040% 0" and 1040%
+45" reinforcement. To avoid low strength
against shearout failure, it is generally agreed
that a minimum number of 90" plies, at least
lo%, should be included in the laminate.
Laminates reinforced in fewer than three
directions, i.e. 0/90° and k45" reinforcement,
should be avoided if possible, since they
respond ductiley with excessively low yield
strengths. These recommendations may be dif-
ficult to follow if considerations other than
maximum joint structural performance govern
Mechanicallyfastened joints 619
PEICfNTAGf W-DEGIEE PLIES
BEARING STRESS CONTOURS 6 5 1 )
WLT DIUETER = 0.25 IN.
(10RQUED WLW
O M Z O 3 D ~ S O ~ M ~ W l W
RKfNlAGE f4S-DEGltE PLIES
Fig. 28.12 'Carpet' plot of maximum bearing stress
vs. percentage of reinforcement in key directions4.
the reinforcement arrangement in the vicinity
of the joint.
28.3.4
Single fastener joints cannot generally achieve
anything close to the strength of the laminate
being loaded and are not usually encountered
in structural joints. Single fastener coupons
do, however, serve as building blocks for
design of multi-fastener joints (Fig. 28.2) since
stress analysis and strength test results on sin-
gle fastener geometries provide data which
translate directly to multi-fastener arrays in
structures. There are two principal features
that affect multi-fastener arrays; that of bear-
ing-bypass load is illustrated in Fig. 28.13. The
bypass load, Pb , can be considered as a load
added at the d o a d e d (right) end of the upper
element in the single fastener joint in Fig. 28.1.
In the case of a multi-fastener array (Figs. 28.2,
28.14), Pbpfor a given fastener is equivalent to
the sum of the loads developed by the fasten-
ers lying to the right of (i.e. those lying in the
direction of the load from) the one under con-
sideration. For each fastener, the load P, in
620 Mechanical fastening and adhesive bonding
pN
Pf +pbp
Fig. 28.13 Definition of bypass load.
Fig. 28.13 (see also Fig. 28.14) is the load
passed through the net section associated with
that fastener and is the sum of P , the fastener
load, and Pb ;P, is also equivalent to the total
load at the feft end of the joint in Fig. 28.13.
The situation in Fig. 28.14(b) shows the
buildup of P, along a joint containing five fas-
teners for the hypothetical case of equal P, for
each fastener, while Fig. 28.14(c) shows the
distribution of Pb /PNfor that case. It is impor-
tant to realize that the net section stresses
build up along with P,. If the joint design is
such as to distribute the fastener loads P,
evenly as in Fig. 28.14, the load on each fas-
tener is then the total load divided by the
number of fasteners, a fraction of 1/5 in Fig.
28.14, so that the bearing stress at each fastener
is much smaller than for a single fastener joint.
Fig. 28.14 Bypass against bearing load.
On the other hand, the net section load on the
last fastener is the sum of all fastener loads and
is therefore the same as in a single fastener joint
carrying the same total load. The benefit of
multi-rowed fastener configurations is primar-
ily because the stress concentration factor
associated with pure bypass load (eqn (28.4))is
smaller than that associated with pure bearing
load (eqns (28.7), (28.3)),and the load ratio for
the most highly loaded net section (the left most
in Fig. 28.14) tends toward the case of pure
bypass loading for large numbers of fasteners.
Stress analyses for combined bearing-bypass
loading have been discussed7,*, 12, 17, la.
Figure 28.1512 gives the elasticity predic-
tions of KEt for various ratios of Pbpto P,,
indicating the KEt is a nonlinear function of
P,/P . (The results in Fig. 28.15 are for a per-
bF
fect fit fastener and for a joint under tension.)
This nonlinearity is caused by the variation of
angle of contact between the fastener and the
plate with the load ratio; Fig. 28.16 illustrates
the difference in the contact region for the
extreme cases of pure bearing and pure bypass
load. In the latter case the plate stretches in
opposite directions along a line parallel to the
load direction and contact splits into two
regions centered about +90" and -90" with
respect to the load direction, while for pure
bearing load, a single contact region occurs
ranging from about -100" to +loo" about the
load axis for perfect-fit fasteners. (For clear-
ance fits in the case of pure bearing load the
Fig. 28.15 Net section SCF against bearing/bypass
load ratio.

contact
[AI
WWS
- -
ce)
-
BEARING
Fig. 28.16 Contact angles for pure bearing load and
pure bypass load.
contact region varies with load and is smaller
than that of exact-fit fasteners. Crews and
Naik8 treated the case of 1.2% clearance, i.e. a
hole diameter 1.2% greater than the fastener
diameter, for which contact between the fas-
tener and hole occurs from about -60" to +60°
for typical loads.)
For intermediate bearing/bypass ratios, the
contact region is a mix of the two situations.
Oplinger12gave the variation of the radial pres-
sure distributions for exact fit fasteners, for
joints in tension, which showed how the con-
tact region is modified as the bearing/bypass
ratio varies, while Naik and Crewss treated
cases of both exact and clearance fits for both
tension and compression loaded joints; in addi-
tion, Madenci7 gave comparable results for
cases of shear loaded joints. A number of
efforts have treated the contact problem for
pure bearing by assuming a radial pressure
distribution which varies around the hole as
the cosine of the angle with respect to the load
axis; in addition, for combined bearing and
bypass loading (following industry practice)
Hart-Smith9 and others have, as a matter of
expediency, superposed the peak stresses pre-
dicted for pure bearing and pure bypass (i.e.
the values of Kt: predicted by eqns (28.4) and
Mechanically fastened joints 621
(28.5)). The results, given in Oplinger12,indi-
cated that this will result in inaccurate
predictions, not only for the general bearing-
bypass situation but also for the case of pure
bearing load with small edge distances (Fig.
28.9). Currently available analytical and finite
element tools are sophisticated enough to treat
the contact problem routinely, and the 'cos 8'
radial pressure distribution should be avoided,
although the superposition method gives some
useful insight into the situation if analytical
tools for dealing with the contact problem are
not available. Crews and Naiks obtained
results which showed that the hoop stresses
around the bolt hole are predicted with reason-
able accuracy by the superposition method, so
that with judicious use of N~ismer-Whitney'~
correction factors, net section failure stresses
can be reasonably well predicted by superposi-
tion; bearing failures cannot.
Naik and CrewsIs described test methods
for joint strength under combined bearing-
bypass loading, with compressive as well as
tensile bypass loads. Typical results are given
in Fig. 28.17 for a 1.2% clearance fit fastener in
a quasi-isotropic carbon epoxy laminate.
Failure modes here are designated 'TRB' ('ten-
sion reacted bearing', i.e. bearing failure with
tension bypass loading), 'TRC' (bearing 'fail-
ure with compression bypass loading), 'NT'
(net section tension), 'NC' (net section com-
pression) and 'OSC' or 'offset compression'
which refers to the failure mode illustrated in
Fig. 28.18 for compression bypass load.
Although the load distribution for the five-
fastener joint shown in Fig. 28.12 is
represented as having the same P, for each fas-
tener, this condition cannot be achieved for
joints in general. As shown in Fig. 28.1913,
there is usually considerable variation of fas-
tener loads along the joint. In a two-fastener
joint such as that shown in Fig. 28.20, the
upper and lower plate elements ('U' and 'L')
have to stretch equally under load if there are
no fastener deflection effects (no fastener tilt-
ing or bending).
622 Mechanical fastening and adhesive bonding

Bearing stress, Sb, Wa

Bypass stress, S Wa
nP'

Fig. 28.17 Laminate strengths under combined bearing/bypass loading17.

and
EGL = gGL/EL,
the elongations are:
6,= kGu and 6 , = ZE,,.
The condition that 6, = 6, requires that:
I(P - P,,)/E,t,W = lPf,/E,f,W.

Since Pp = P - P,, this is equivalent to:

Fig. 28.18 'OSC' failures for combined bearing Pf, = (E,f,/E,t,)Pf,,

bypass loading17. If E,>>E, or tL>>t,, the resulting P,, will be
small compared with P,, so that the second fas-
With the average gross section stresses and tener will be nearly unloaded. In such a case
strains for the two plate elements in Fig. 28.20 the joint will be equivalent to a single fastener
give by: joint containing an unloaded hole at the loca-
tion of the second fastener. On the other hand,
OGU= ( P - P, )/tuW; the last equation showsthat if the stiffnesses of
the upper and lower plates are equal, the two
fasteners will be loaded equally. In general,
fastener loads will be highly variable in a way
that depends on the relative thicknesses and
 Mechanically fastened joints 623

moduli of adjacent plate elements in the

regions around each fastener; fastener deflec-
tions due to beam-bending of the fasteners as
well as clearance effects will add other compli-
cations to the situation. In Fig. 28.19,
configuration A illustrates the behavior of
joints with both elements tapered (i.e. scarf
joints); due to load transfer between the ele-
ments by fastener load, the net section load P,
decreases from the loaded (thick) end of each
plate to its unloaded (thin)end, while the cor-
responding thicknesses decrease keeps the Fig. 28.20 Two fastener joint.
gross section stresses and strains and therefore
the stretching deflections uniform along each listed under each configuration), it is noted
element, providing for nearly equal load trans- that the scarfed configuration gives the lowest
fer at each fastener. For configuration B of Fig. strength of the four, and is about 9% weaker
28.19, the case of uniform element thickness, than the uniform thickness configuration, B. It
the interior fastener loads are smaller than is usually expected that scarfing will lead to a
those at the joint ends, which is typical of this way of keeping the bearing load minimized at
situation. Since the configurations shown at the joint ends where the highest P,s are
the right in Fig. 28.19 are arranged in order of encountered, but other factors having to do
increasing load capability (see the strains with the balance between the effects of local

BOLT LOAD DISTRIBUTIONS

4-ROW BOLTED NINT

E, -
CONFIGURATION D
O11(#lNIIN.

CONFIGURATIONC

-
E- = 0A)OMINIIN.

CONFIQURATION A
O----QCONFIQURATION B
0- 4 CONFIGURATIONC
-1n CONFIGURATION D
-
CONFIGURATION B
0#)46INIIN.

1 2 3
BOLT NUMBER
4
Ob0IN.

1 A 112. 112. 112

1 2
!
3 4 0251N.
i I - .'-
I

I'
-
E
, -
CONFIGURATION A
O m 1 INAN.

Fig. 28.19 Effectof joint configuration on fastener load di~tribution'~.

624 Mechanical fastening and adhesive bonding

element thickness and local bearing load pre-
dominates here. Note that configuration D, the
strongest, uses a combination of variable fas-
tener diameter and element tapering to
achieve a maximum thickness of the outer ele-
ments which is greater than that in
configuration C, to obtain maximum joint
strength. Thus, judicious use of element taper-
ing and variation of fastener diameters as well
as other joint parameters can improve joint
performance. With untapered joints, the maxi-
mum benefit of additional rows of fasteners is
not much more than 20% greater than that for
single row joints. Joint tapering will provide
28.3.5 FASTENER EFFECTS
Joint strengths for local areas (Fig. 28.13)
around individual fasteners are affected by a
number of parameters associated with the fas-
teners. Some of these include: whether the
joint is in single or double shear (Fig. 28.21);
the use of countersunk (flush head) compared
with protruding head fasteners (Fig. 28.22);
effects of fastener diameter; effects of fastener
clamping; fastener clearance effects, and effect
of fastener deflections on fastener load distrib-
ution. Bearing strengths are significantly
affected by the use of single compared with

p7=g=7p2p
some improvement over that figure, although
the benefit is limited; it should be kept in mind
that the net section load at the loaded end of a P
given element will be the same for single fas-
tener and multi-fastener joints, so that the
benefit of adding more than a few rows may (A ) Double Shear Configuration
not be great. The interaction of the effects
encountered in multi-fastener joints is fairly
complicated and requires the use of analyses ~

which can take into account the stresses and

P
strains in single fastener configurations with
bypass loading present (Fig. 28.13), represent- I'2
ing 'unit cells' of the joint configuration, (B) Single Shear configuration
together with finite element calculations
which evaluate the interactions among the Fig. 28.21 Single shear and double shear configura-
various unit cells to provide the overall fas- tions.
tener load distribution. Computer codes have
been developed under DoD and NASA spon-
sorship to provide for this type of integrated
joint design. For example, Nelson, Bunin and
Hart-Smith13 discuss the application of the
+f-
well-known 'A4EJ' codeI9in conjunction with P
the code 'BJSFM' (Bolted Joint Stress Field 3
Model15)which were developed by McDonnell (A) Protruding Head Fastener
Douglas under NASA and Air Force sponsor-
ship for this type of joint design analysis.
Northrop similarly developed codes 'SASCJ' P
(Stress Analysis of Single Fastener Composite P
Joints) and 'SAMCJ' (Stress Analysis of
Multifastener Composite Joints) under Air (B) Countersunk Fastener
Force Contract6,20. For information on the the-
ory and application of these codes, the reader Fig. 28.22 Countersunk and protruding head fas-
is directed to the references. teners.

double shear configurations,bearing strengths
for single shear joints tending to run consider-
ably below those for double shear because of
greater through-the-thickness variation of fas-
tener-plate contact pressure. Bearing strength
tests referenced in Section 28.3.6 include sepa-
rate test configurations for the two situations.
In addition, as indicated in Fig. 28.22(a),bend-
ing moments tend to occur in single shear
joints which are not present with double shear
arrangements. Fastener head pull through
(Fig. 28.10) can be a problem in the presence of
such bending effects, and special test methods
for fastener pull-through strength are
described in Section 28.3.6. Countersunk, or
flush head, fasteners (Fig. 28.22(b)) are fre-
quently encountered in exterior surfaces of
aircraft components where avoidance of air
flow disturbance is required. Countersunk fas-
teners for composites include (Fig. 28.23)
'tension head' fasteners having the larger head
depths and therefore wider heads, and 'shear
head' fasteners having smaller head depths,
with head angles ranging from 100" to 130".
Countersunk fasteners tend to bear against the
surrounding element more unevenly through
the thickness than protruding head fasteners
do. Tension head fasteners are generally pre-
ferred over shear head fasteners because of
greater strength against head pull-through;
however, if the joint element is so thin that the
countersunk depth is greater than 70% of the
element thickness, the tendency toward
uneven bearing pressure in tension head fas-
teners is too great and shear head fasteners are
recommended in this case.
Fig. 28.23 Tension head and shear head fasteners.
Mechanicallyfastened joints 625
The fastener diameter should be on the
order of the thickness of the thicker of the
plate elements making up the joint, or greater,
( D / t 2 1) to avoid excessive fastener bending.
As in Fig. 28.10 (lower right-hand sketch)
excessive bending can lead to failure of the fas-
teners, which is intolerable. In addition,
fastener bending causes uneven distribution
of bearing pressure through the plate element
thicknesses, so that the full bearing strength is
not available in such cases. The effect of large
fastener deflections on the clamping pressure
provided by the fastener is another adverse
effect of fastener bending deflections. Figure
28.2413 illustrates the fact that bending defor-
mations reduce the clamping pressure
provided by fastener head, causing a reduc-
tion of bearing strength which is in addition to
that caused by uneven bearing pressure
through the thickness.
The beneficial effect of clamping pressure
on bearing strength, discussed earlier, has
been well established. Required clamping lev-
els are usually described in terms of bolt
torques, 'finger tightened' being the lightest
level, and installation requirements specify
torque levels which supposedly represent par-
ticular bolt tensions (and therefore clamping
-
-
TENSION JOINT
HlQH BEARING LOAD SIDE
LOELAMINATIONS
DUE TO BEARING LOAD AND REDUCED
HlQH BEARINQ LOAD SIDE
-
COMPRESSION JOINT w-
Fig. 28.24 Effects of fastener bending on joint fail-
ureI3.
626 Mechanical fastening and adhesive bonding
pressures) that can be calculated in terms of
the pitch of the fastener threads from machine
design formulas. Bolt tensions for a given
torque level are notoriously variable because
of friction effects in the bolt threads, but spec-
ified torque levels which have been
determined empirically probably represent
minimum clamping levels necessary to insure
maximum bearing strengths that can be
achieved when variations in service condi-
tions are taken into account. Steps should be
taken to avoid loss of clamping pressure due
to through-the-thickness viscoelastic deforma-
tion of the laminatez1”at elevated temperature
and humidity.
Fastener clearances are typically on the
order of 0.075 mm (0.003 in) or less for typical
0.635 mm (0.25 in) aircraft fasteners. Analytical
studies have shown that bearing stresses
increase significantly for such relatively small
clearances since the angle of contract decreases
rapidly as the clearance increases. Clearances
also have a significant effect on the fastener
load distribution since the last in a series of
fasteners cannot take up load until all the
clearances have been taken up.
In addition to the effect of clearances on fas-
tener load distribution, effects of fastener
bending deflections must be taken into
account in load distribution calculations such
as those provided by the A4EJ, SASCJ and
SAMCJ codes described above. In the case of
the two-fastener joint shown in Fig. 28.20,
bending and rotational deflections of the fas-
teners will modify the load distribution
described in the discussion of that figure for
zero fastener deflection. For E,t,>>E,t,, in Fig.
28.20 for example, fastener deflections will
allow some load to be transferred to the sec-
ond fastener, as opposed to the case of no
fastener deflections discussed earlier which
led to Pf2= 0. Fastener deflection effects can be
inferred from bolt bearing tests which provide
for deflection measurements. Alternatively,
analytical approaches based on beam models
for the fastener which include both bending
and shear deformations have been used13.
Complications, such as the way in which the
fastener head and nut/washer combination
bears on the surfaces of the plate element will
influence the outcome of such calculations and
must be taken into account. In addition, the
through-thickness distribution of bearing
pressure between the fastener and the sur-
rounding the plate element should be
included in the calculations. The method of
Harris, qalvo and Hoosonz3which treats the
bore of the fastener hole as an elastic founda-
tion for the beam used to model the fastener
has been applied6for such calculations.
28.3.6 TEST METHODS
Joint strength tests are needed to establish cer-
tain key parameters of the joint as inputs to
design analyses. Such data as failure stresses
for pure bearing load as obtained from single
fastener coupons, and open hole coupon
strengths for both tension and compression
loading, are needed to establish joint perfor-
mance for pure bearing and bypass loads.
Intermediate combinations of bearing and
bypass load must also be considered to pro-
vide empirical curves for dealing with the
general situation. Because of differences in the
way the fastener contacts the surrounding
plate materials, bearing tests have to be con-
ducted to treat both single and double lap
(single and double shear) configurations. In
single lap joints in particular, tests are needed
to establish the effect of fastener rotation and
bending deflection. Fastener deflections must
be determined in tests of the type just
described for providing fastener response data
in connection with predictions of load distrib-
ution in multifastener joints. In addition,
fastener head pull-through strength tests have
to be performed to allow for joint configura-
tions in which overall bending takes place, in
which case out-of-plane forces between the
fastener and joint plates tend to be sigruficant.
The details of test methods for mechanically
fastened joints are described by Shyprykevichz4
and in Mn-HDBK-1725.

28.4 ADHESIVE JOINTS
28.4.1 INTRODUCTION
Adhesive joints are capable of high structural
efficiency and constitute a resource for struc-
tural weight saving because of the potential
for elimination of stress concentrations which
cannot be achieved with mechanically fas-
tened joints. Unfortunately, because of a lack
of reliable inspection methods and a require-
ment for close dimensional tolerances in
fabrication, aircraft designers have generally
avoided bonded construction in primary
structure. Some notable exceptions include:
bonded step lap joints used in attachments for
the F-14 and F-15 horizontal stabilizers as well
as the F-18 wing root fitting, and a majority of
the airframe components of the Lear Fan and
the Beech Starship.
While a number of issues related to adhe-
sive joint design were considered in the earlier
literaturezG3, much of the methodology cur-
rently used in the design and analysis of
adhesive joints in composite structures is
based on the approaches evolved by L.J. Hart-
Smith in a series of NASA/Langley-sponsored
contracts of the early 1 9 7 0 as~ well
~ ~as~from
the Air Force’s Primary Adhesively Bonded
Structures Technology (PABST) programw3 of
the mid-1970s. The most recent such work
developed three computer codes for bonded
and bolted joints, designated ‘A4EG’, ’A4EI’
and ’A4EKW under Air Force Contract . The
results of these efforts have also appeared in a
number of open literature publi~ations~’-~. In
addition, such approaches found application
in some of the efforts taking place under the
NASA Advanced Composite Energy Efficient
Aircraft (ACEE) program of the early to mid-
198Os5O,51.
Some of the key principles on which these
efforts were based include: (1)the use of simple
one-dimensionalstress analyses of generic com-
posite joints wherever possible; ( 2 ) the need to
select the joint design so as to ensure failure in
the adherend rather than the adhesive, so that
Adhesive joints 627
the adhesive is never the weak link;(3) recog-
nition that the ductility of aerospace adhesives
is beneficial in reducing stress peaks in the
adhesive; (4) careful use of such factors as
adherend tapering to reduce or eliminate peel
stresses from the joint; (5) recognition of slow
cyclic loading, corresponding to such phenom-
ena as cabin pressurization in aircraft, as a
major factor controlling durability of adhesive
joints, and the need to avoid the worst effects
of this type of loading by providing sufficient
overlap length to ensure that some of the adhe-
sive is so lightly loaded that creep cannot occur
there, under the most severe extremes of
humidity and temperature for which the com-
ponent is to be used.
Much of the discussion to follow will retain
the analysis philosophy of Hart-Smith, since it
is considered to represent a major contribution
to practical bonded joint design in both com-
posite and metallic structures. On the other
hand, some modifications are introduced here.
For example, the revisions of the
Goland-Reissner single lap joint analysis36
have been re-revised according to the
approach presented in Refs. 53,54.
Certain issues which are specific to compos-
ite adherends but were not dealt with in the
Hart-Smith efforts will be addressed. The most
important of these is the effect of transverse
shear deformations in organic composite
adherends.
28.4.2 SUMMARY OF JOINT DESIGN
CONSIDERATIONS
28.4.2.1 Effects of adherend thickness:
adherend failures versus bond failures
Figure 28.25 shows a series of typical bonded
joint configurations. Adhesive joints in general
are characterized by high stress concentrations
in the adhesive layer. These originate, in the
case of shear stresses, because of unequal axial
straining of the adherends, and in the case of
peel stresses, because of eccentricity in the
load path. Considerable ductility is associated
 628 Mechanical fastening and adhesive bonding

illustrate this point, shows a progression of

joint types which represent increasing strength
capability from the lowest to the highest in the
figure. In each type of joint, the adherend
thickness may be increased as an approach to
achieving higher load capacity. When the
1
adherends are relatively thin, results of stress
- - (0)
- 4 analyses show that for all of the joint types in
TAPERED SINGLE-UP JOINT
Fig. 28.26, the stresses in the bond will be small
enough to guarantee that the adherends will
DOUBLE-UPJOINT reach their load capacity before failure can
occur in the bond. As the adherend thicknesses
(F) 1 DUJBLE-STRAP JOINT
increase, the bond stresses become relatively
larger until a point is reached at which bond
(0) 4 n f failure occurs at a lower load than that for
&
which the adherends fail. This leads to the gen-
TAPERED STRAP JOINT
eral principle that for a given joint type, the
Fig. 28.25 Adhesive joint types”, 55. adherend thicknesses should be restricted to an
appropriate range relative to the bond layer
with shear response of typical adhesives, thickness. Because of processing considera-
which is beneficial in minimizing the effect of tions and defect sensitivity of the bond
shear stress joint strength. The response of typ- material, bond layer thicknesses are generally
ical adhesives to peel stresses tends to be limited to a range of 0.125-0.39 mm
much more brittle than that to shear stresses, (0.005-0.015 in). As a result, each of the joint
and reduction of peel stresses is desirable for
achieving good joint performance.
From the standpoint of joint reliability, it is
vital to avoid the condition where the adhesive
layer is the weak link in the joint, i.e. that the
joint be designed to ensure that the adherends
fail before the bond layer whenever possible.
T ~ isE because failure in the adherends may be
controlled, while failure in the adhesive is resin
dominated, and thus subject to effects of voids
and other defects, thickness variations, envi-
ronmental effects, processing variations,
deficiencies in surface preparation and other
factors that are not always adequately con-
trolled. This is a significant challenge, since
adhesives are inherently much weaker than the
composite or metallic elements being joined.
However, the objective can be accomplished by
recognizing the limitations of the joint geome-
try being considered and placing appropriate
restrictions on the thicknesses the adherends ADHEREND THICKNESS
for any given geometry. Figure 28.26, which
has frequently been used by Hart-Smith39, 55 to Fig. 28.26 Joint geometry effects39.

types in Figs. 28.25 and 28.26 corresponds to a
specific range of adherend thicknesses and
therefore of load capacity, and as the need for
greater load capacity arises, it is preferable to
change the joint configuration to one of higher
efficiency rather than to increasing the
adherend thickness indefinitely.
28.4.2.2 Joint geometry effects
Single and double lap joints with uniformly
thick adherends (Fig. 28.25(b), (e) and ( f ) ) are
the least efficient joint type and are suitable
primarily for thin structures with low running
loads (load per unit width, i.e. stress times ele-
ment thickness). Of these, single lap joints are
the least capable because the eccentricity of
this type of geometry generates significant
bending of the adherends that magnifies the
peel stresses. Peel stresses are also present in
the case of symmetric double lap and double
strap joints, and become a limiting factor on
joint performance when the adherends are rel-
atively thick.
Tapering of the adherends (Figs. 28.25(d)
and (g)) can be used to eliminate peel stresses
in areas of the joint where the peel stresses are
tensile, which is the case of primary concern.
For joints between adherends of identical stiff-
ness, scarf joints (Fig. 28.25(i))are theoretically
the most efficient, having the potential for
complete elimination of stress concentrations.
(In practice, some minimum thickness corre-
sponding to one or two ply thicknesses must
be incorporated at the thin end of the scarfed
adherend leading to the occurrence of stress
concentrations in these areas.) In theory, any
desirable load capability can be achieved in
the scarf joint by making the joint long enough
and thick enough. However, practical scarf
joints may be less durable because of a ten-
dency toward creep failure associated with a
uniform distribution of shear stress along the
length of the joint unless care is taken to avoid
letting the adhesive be stressed into the non-
linear range. As a result, scarf joints tend to be
used only for repairs of very thin structures.
Adhesive joints 629
Scarfjoints with unbalanced stiffnessesbetween
the adherends do not achieve the uniform shear
stress condition of those with balanced
adherends, and are somewhat less structurally
efficient because of rapid buildup of load near
the thin end of the thicker adherend.
Step lap joints (Fig. 28.25(h)) represent a
practical solution to the challenge of bonding
thick members. This type of joint provides
manufacturing convenience by accommodat-
ing the layered structure of composite
laminates. In addition, high loads can be trans-
ferred if sufficiently many short steps of
sufficiently small ’rise’ (i.e. thickness incre-
ment) in each step are used, while maintaining
sufficient overall length of the joint.
28.4.2.3 Effects of adherend stiffness
unbalance
All types of joint geometry are adversely
affected by unequal adherend stiffnesses,
where stiffness is defined as axial or in-plane
shear modulus times adherend thickness.
Where possible, the stiffnesses should be kept
approximately equal. For example, for step lap
and scarf joints between quasi-isotropic car-
bon epoxy (Young’s modulus = 55 GPa = 8 x
lo6 lb/in2) and titanium (Young’s modulus =
110 GPa = 16 x lo6 lb/in2) ideally, the ratio of
the maximum thickness (the thickness just
beyond the end of the joint) of the composite
adherend to that of the titanium should be
110/55 = 2.0.
28.4.2.4 Effects of ductile adhesive
response
Adhesive ductility is an important factor in
minimizing the adverse effects of shear and
peel stress peaks in the bond layer. If peel
stresses can be eliminated from consideration
by such approaches as adherend tapering,
strain energy to failure of the adhesive in shear
has been shown by Ha~?-Smith~~ to be the key
parameter controlling joint strength; thus the
square root of the adhesive strain energy
630 Mechanical fastening and adhesive bonding

density to failure determines the maximum sta- transverse tension, as a result of which the
tic load that can be applied to the joint. The limiting element in the joint may be the inter-
work of Hart-Smith has also shown that for pre- laminar shear and transverse tensile strengths
dicting mechanical response of the joint, the of the adherend rather than the bond strength.
detailed stress-strain curve of the adhesive can Ductile behavior of the adherend matrix can
be replaced by an equivalent curve consisting be expected to have an effect similar to that of
of a linear rise followed by a constant stress ductility in the adhesive in terms of response
plateau (i.e. elastic-perfectly plastic response) if of the adherends to transverse shear stresses,
the latter is adjusted to provide the same strain although the presence of the fibers probably
energy density to failure as the actual limits this effect to some extent, particularly in
stress-strain curve gives. Test methods for regard to peel stresses.
adhesives should be aimed at providing data The effect of the stacking sequence of the
on this parameter. Once the equivalent elastic- laminates making up the adherends in compos-
perfectly plastic stress-strain curve has been ite joints is sigruficant. For example, 90” layers
identified for the selected adhesive for the most placed adjacent to the bond layer theoretically
severe environmental conditions (temperature act largely as additional thicknesses of bond
and humidity) of interest, the joint design can material, leading to lower peak stresses, while
proceed through the use of relatively simple 0” layers next to the bond layer give stiffer
one-dimensional stress analysis, thus avoiding adherend response with higher stress peaks. In
the need for elaborate finite element calcula- practice it has been observed that 90” layers
tions. Even the most complicated of joints, the next to the bond layer tend to seriously weaken
step lap joints designed for root-end wing and the joint because of transverse cracking which
tail connections for the F-18 and other aircraft, develops in those layers, and advantage cannot
have been successfully d e ~ i g n e d ~ and ~ , ~ ”be
~ taken of the reduced stresses.
experimentally demonstrated using such Large disparity of thermal expansion char-
approaches. Design procedures for such analy- acteristics between metal and composite
ses which were developed on Government adherends can pose severe problems.
contract have been incorporated into public Adhesives with high curing temperatures may
domain in the form of the ’A4EG’, ‘A4EI’ and be unsuitable for some uses below room tem-
‘A4EK computer codes- mentioned previ- perature because of large thermal stresses
ously in Section 28.4.1.Note that the A4EK code which develop as the joint cools below the fab-
permits analysis of bonded joints in which local rication temperature.
disbonds are repaired by mechanical fasteners. Composite adherends are relatively pervi-
ous to moisture, which is not true of metal
adherends. As a result, moisture is more likely
28.4.2.5 Behavior of composite adherends
to be found over wide regions of the adhesive
Organic matrix composite adherends are con- layer, as opposed to confinement near the
siderably more affected by interlaminar shear exposed edges of the joint in the case of metal
and tensile stresses than metals, so that there is adherends, and response of the adhesive to
a significant need to account for such effects in moisture may be an even more significant
stress analyses of joints. Transverse shear and issue for composite joints than for joints
thickness-normal deformations of the between metallic adherends.
adherends have an effect analogous to thick-
ening of the bond layer, corresponding to a
28.4.2.6 Effects of bond defects
lowering of both shear and peel stress peaks.
On the other hand, the adherend matrix is Defects in adhesive joints which are of concern
often weaker than the adhesive in shear and include surface preparation deficiencies, voids
 Adhesive joints 631

and porosity, and thickness variations in the adherends, porosity may grow catastrophi-
bond layer. cally and lead to non-damage tolerant joint
Of the various defects which are of interest, performance.
surface preparation deficiencies are probably Bond thickness variations'jl usually take the
the greatest concern. These are particularly form of thinning due to excess resin bleed at
troublesome because there are no current non- the joint edges, leading to overstressing of the
destructive evaluation techniques which can adhesive in the vicinity of the edges. Inside
detect low interfacial strength between the tapering of the adherends at the joint edges
bond and the adherends. Most joint design will compensate for this condition; other com-
principles are academic if the adhesion pensating techniques are also discussed'jl.
between the adherends and bond layer is poor. Bond thicknesses, per se, should be limited to
The principles for achieving good adhesion of ranges of 0.12-0.24 mm (0.005-0.01 in) to pre-
the bond to the adherends (see Chapter 29) are vent significant porosity from developing
well established for adherend and adhesive although greater thicknesses may be accept-
combinations of interest. Hart-Smith, Brown able if full periphery damming or high
and Won$ give an account of the most crucial minimum viscosity paste adhesives are used.
features of the surface preparation process. Common practice involves the use of film
Results shown in that reference suggest that adhesives containing scrim cloth, some forms
surface preparation which is limited to of which help to maintain bond thicknesses. It
removal of the peel ply from the adherends is also common practice to use mat carriers of
may be suspect, since some peel plies leave a chopped fibers to prevent a direct path for
residue on the bonding surfaces that makes access by moisture to the interior of the bond.
adhesion poor. (However, some manufactur-
ers have reported satisfactory results from
28.4.2.7 Durability of adhesive joints
surface preparation consisting only of peel ply
removal.) Low pressure grit b l a ~ t i n g ~ is ~ ,Hart-Smith45
~~ discusses differences in durabil-
preferable over hand sanding as a means of ity assessment of adhesive joints between
eliminating such residues and mechanically concepts related to creep failure under cyclic
conditioning the bonding surfaces. loading and those related to crack initiation
For joints which are designed to ensure that and propagation which require fracture
the adherends rather than the bond layer are mechanics approaches for their interpretation.
the critical elements, tolerance to the presence In summary, Hart-Smith suggests that if peel
of porosity and other types of defect is consid- stresses are eliminated by adherend tapering
erable45.Porosity'jOis usually associated with or other means, and if the principle discussed
overthickened areas of the bond, which tend in Section 28.4.2.1 of limiting the adherend
to occur away from the edges of the joint thickness to ensure failure of the adherends
where most of the load transfer takes place, rather than the adhesive is followed, crack-
and thus is a relatively benign effect, espe- type failures will not be observed under
cially if peel stresses are minimized by time-varying loading, failures being related
adherend tapering. In such cases6", porosity primarily to creep fatigue at hot wet condi-
can be represented by a modification of the tions, in joints with short overlaps which are
assumed stress-strain properties of the adhe- subject to relatively uniform distributions of
sive as determined from thick-adherend tests, shear stress along the joint length. Additional
allowing a straightforward analysis of the discussion of viscoelastic response of bonded
effect of such porosity on joint strength, as in joints is
the A4EI computer code. If peel stresses are There is an extensive body of literature6571
significant, as in the case of over-thick on fracture mechanics approaches to joint
632 Mechanical fastening and adhesive bonding
durability, based on measurement of energy
release rates for various adhesives together
with analytical efforts aimed at applying them
to joint configurations of interest. In particular,
Johnson and Malln report fatigue crack initia-
tion in bonded specimen configurations with
adherend tapering aimed at reduction of peel
stresses in varying degrees, in some cases prac-
tically eliminating them; data in Ref. 92
indicate that crack initiation will occur even
with the adhesive in pure shear, for cycling to
lo6cycles above loading levels which are prob-
ably considerably below static failure loads.
The results given” suggest that for combina-
tions of peel and shear stressing, total (mode 1
+ mode 2) cyclic energy release rate can be
used to determine whether or not cracking will
occur. However, Hart-Smith reportedfi that in
’thick adherend‘ test specimens that provide a
relatively uniform shear stress distribution in
the adhesive (see MIL-HDBK-17, Vol. 1,
Chapter 7, Section 7.3) which were subjected to
fatigue tests in the PABST programM,cycling to
more than lo7 cycles applied at high cycling
rates (30 Hz) were achieved without failure of
the adhesive, although in certain cases, namely
those involving 6.27 mm (0.25 in) adherend
thicknesses, fatigue failures of the metal
adherends did result. More study is needed to
resolve some of the apparently contradictory
results which have come out of various studies.
28.4.3 STRESSES IN ADHESIVE JOINTS
28.4.3.1 General
Stress analyses of adhesive joints have ranged
from very simplistic ‘P over A’ formulations in
which only average shear stresses in the bond
layer are considered, to extremely elegant elas-
ticity approaches that consider fine details, e.g.
the calculation of stress singularities for appli-
cation of fracture mechanics concepts. A
compromise between these two extremes is
desirable, since the design of structural joints
does not usually depend on the fine details of
the stress distributions. Since practical consid-
erations force bonded joints to incorporate
adherends which are thin relative to their
dimensions in the load direction, stress varia-
tions through the thickness of the adherend and
the adhesive layer tend to be moderate. Such
variations do tend to be more sigruficant for
organic composite adherends because of their
relative softness with respect to transverse
shear and thickness normal stresses. However,
a considerable body of design procedure has
been developed based on ignoring thickness-
wise adherend stress variations. Such
approaches involve using one-dimensional
models in which only variations in the axial
direction are accounted for. Accordingly, the
bulk of the material to be covered here is based
on simplified one-dimensional approaches
characterized by the work of Hart-Smith. The
Hart-Smith approach makes extensive use of
closed form and classical series solutions since
these are ideally suited for making parametric
studies of joint designs. The most prominent of
these have involved modification of Volkersen26
and Goland-ReissnerZ7solutions to deal with
ductile response of adhesives in joints with uni-
form adherend thicknesses along their lengths,
together with classical series expressions to
deal with variable adherend thicknesses
encountered with tapered adherends, and scarf
joints. Simple lap joint solutions described
below calculate shear stresses in the adhesive
for various stiffnesses and applied loadings.
For the more practical step lap joints, the
described expressions can be adapted to treat
the joint as a series of separate joints, each hav-
ing uniform adherend thickness.
28.4.3.2 Adhesive shear stresses
Figure 28.27 shows a joint with ideally rigid
adherends in which neighboring points on the
upper and lower adherends slide horizontally
with respect to each other when the joint is
loaded to cause a displacement difference 6 =
uu - uLrelated to the bond layer shear strain by
yb = 6 / f b .The corresponding shear stress, zb, is
given by zb = Gbyb. The rigid adherend
 Adhesive joints 633

assumption implies that 6, y, and t, are uni- one for which E,tL >> E&), stretching elonga-
form along the joint. Furthermore, the tions in the upper adherend lead to a shear
equilibrium relationship indicated in Fig. strain increase at the right end of the bond
layer. The case in which both adherends are
28.27(c),which requires that the shear stress be
related to the resultant distribution in the equally deformable, shown in Fig. 28.29(b),
upper adherend by indicates a bond shear strain increase at both
ends due to the increased axial strain in
dTU/dx= zb (28.6) whichever adherend is stressed at the end
leads to a linear distribution of Tu and TL under consideration. For both cases, the varia-
(upper and lower adherend resultants) as well tion of shear strain along the bond results in an
as the adherend axial stresses uxuand ax,indi- accompanying increase in shear stress which,
cated in Fig. 28.28. These distributions are when inserted into the equilibrium eqn (28.6)
described by the following expressions: leads to a nonlinear variation of stresses. The
Volkersen shear lag analysisz6provides the
simplest calculation of adhesive shear stresses
for the case of deformable adherends. This
involves the solution of the following differen-
tial equation:

where ax = T/t. In actual joints, adherend

deformations will cause shear strain variations
in the bond layer which are illustrated in Fig.
28.29. For the case of a deformable upper B, = E&; B, = E,t, (28.8)
adherend in combination with a rigid lower
adherend shown in Fig. 28.29(a) (in practice, which applies to the geometry of Fig. 28.30

I I

[a RIGID KkU

f-

Fig. 28.27 Elementary joint analysis (rigid adherend model).

634 Mechanical fastening and adhesive bonding

(A) AXIAL RESULTANT DISTRIBUTION (a) AXIAL STRESS DISTRIBUTXOH

Fig. 28.28 Axial stresses in joint with rigid adherends.

[A) RIGID UIIW

AaEml

--f
T-

Fig. 28.29 Adherend deformations in idealized joints.

-
below. The solution for this equation which TL = T - T U (28.9)
provides zero traction conditions at the left
where
end of the upper adherend and the right end
of the lower adherend, together with the
applied load T at the loaded ends gives the
resultants as:
- tu + tL
t=- 2 ; PB = BL/B"

Using eqn (28.6) to obtain an expression for

+- the shear stress distribution leads to:
1 +PB SinhPZ/t
 Adhesive joints 635

I
0-
I X

+- PB
1 + pB tanhpZ/T
) (28.11)

where
Gx= T/t
Fig. 28.30 Geometry for Volkersen solution.
Also of interest in the discussion which fol-
lows is the minimum shear stress in the joint.
This occurs approximately at x = 1/2, leading
to:

B, 2 B,; to be discussed subskquently. Figure 28.31

I 0 44 &4 a6 Q1 t
IS
1.2 1.4 1s 1 1 2

I 1

.-.
4 U a.4
. .
OS
.
a.0
.
1
:
IS!
:
1.4
.
IJ
.
1.8 2
b . . . . . . . . . .
o) a4 w os 1 IZ 11) i g t i 2
#- I---
I
636 Mechanicalfastening and adhesive bonding
Fig. 28.32 Comparison of average and maximum shear stress vs. l / t .
shows the distribution of axial adherend
stresses and bond layer shear stress for two
cases corresponding to E, = E , and E, = 10Eu
with tu = t,, p = 0.387 and l / t = 20 for both
cases (giving p l / t = 7.74) and a nominal
adherend stress 0, = 10. As in the approximate
analysis given earlier, the shear stresses given
by eqn (28.10) are maximum at both ends for
equally deformable adherends (B, = B,); for
dissimilar adherends with the lower adherend
more rigid (B, > E$,), the maximum shear stress
obtained from eqn (28.10) occurs at the right
end of the joint where x = I , again as it did for
the approximate analysis.
Figure 28.32 compares the behavior of the
maximum shear stress with the average shear
stress as a function of the dimensionless joint
length, l / t , for equal adherend stiffnesses. The
point illustrated here is the fact that although
the average shear stress continuously
decreases as the joint length increases, for the
maximum shear stress which controls the load
that can be applied without failure of the
adhesive, there is a diminishing effect of
increased joint length when q = p l / t is much
greater than about 2.
An additional point of interest is a typical
feature of bonded joints illustrated in
Fig. 28.31(d) which gives the shear stress dis-
tribution for equal adherend stiffness, namely,
the fact that high adhesive shear stresses are
concentrated near the ends of the joint. Much
of the joint length is subjected to relatively low
levels of shear stress, which implies in a sense
that that region of the joint is structurally inef-
ficient since it does not provide much load
transfer. However, the region of low stress
helps to improve damage tolerance of the joint
since defects such as voids and weak bond
strength may be tolerated in regions where the
shear stresses are low, and in joints with long
overlaps this may include most of the joint. In
addition, Hart-Smith has suggested51 that
when ductility and creep are taken into
account, it is a good idea to have a minimum
shear stress level no more than 10% of the
yield strength of the adhesive, which requires
some minimum value of overlap length.
Equation (28.12) can be used to satisfy this
requirement for the case of equal stiffness
adherends. The two special cases of interest
again are for equal adherend stiffness and a
 Adhesive joints 637

rigid lower adherend, since these bound the relatively obvious due to the offset of the two
range of behavior of the shear stresses. As a adherends which leads to bending deflection
practical consideration, we will be interested as in Fig. 28.33@).In the case of double lap
primarily in long joints for which pZ/t >> 1. joints, as exemplified by the configuration
For these cases eqn (28.11) reduces to: shown in Fig. 28.34, the load path eccentricity
is not as obvious, and there may be a tendency
p1/t >> 1;
to assume that peel stresses are not present for
this type of joint because, as a result of the lat-
eral symmetry, there is no overall bending
deflection. However, a little reflection brings
to mind the fact that while the load in the sym-
1
B, = B,; zJrnaX=-pax (28.13) metric lap joint flows axially through the
2
central adherend prior to reaching the overlap
Thus, for long overlaps, the maximum shear region, there it splits in two directions, flowing
stress for the rigid adherend case tends to be laterally through the action of bond shear
twice as great as that for the case of equally stresses to the two outer adherends. Thus
deformable adherends, again illustrating the eccentricity of the load path is also present in
adverse effect of adherend unbalance on shear this type of joint. As seen in Fig. 28.34(c), the
stress peaks. shear force, designated as F,, which repre-
sents the accumulated effect of zb for one end
of the joint, produces a component of the total
28.4.3.3 Peel stresses
moment about the neutral axis of the upper
Peel stresses, i.e. through-the-thickness exten- adherend equal to FsHz/2. (Note that F , is
sional stresses in the bond, are present because equivalent to T/2, since the shear stresses react
the load path in most adhesive joint geome- this amount of load at each end.) The peel
tries is eccentric. It is useful to compare the stresses, which are equivalent to the forces in
effect of peel stresses in single and double lap the restraining springs shown in Fig. 28.34(b)
joints with uniform adherend thickness, since
peel stresses are most severe for joints with
uniform adherend thickness. The load path
eccentricity in the single lap joint (Fig. 28.33) is

, \

Fig. 28.33 Peel stress development in single lap Fig. 28.34 Peel stress development in double lap
ioints. ioints.
J
638 Mechanical fastening and adhesive bonding

and (c) have to be present to react the moment It is important to understand that peel
produced by the offset of FsHabout the neutral stresses are unavoidable in most bonded joint
axis of the outer adhered. Peel stresses are configurations However, they can often be
highly objectionable. Later discussion will reduced to acceptable levels by selecting the
indicate that effects of ductility significantly adherend geometry appropriately.
reduce the tendency for failure associated with
shear stresses in the adhesive. On the other 28.4.3.4 Effects of joint geometry
hand, the adherends tend to prevent lateral
contraction in the in-plane direction when the In this section the behavior of joints is consid-
bond is strained in the thickness direction, ered with linear response of the adhesive in
which minimizes the availability of ductility shear assumed. Effects of ductility will be con-
effects that could provide the same reduction sidered later.
of adverse effects for the peel stresses. This is
illustrated by the butt tensile test shown in Fig.
28.4.3.4.1 Single and double lap joints with
28.35 in which the two adherend surfaces adja-
uniform adherend thickness
cent to the bond are pulled away from each
other uniformly. Here the shear stresses asso- Double lap joints will be considered first since
ciated with yielding are restricted to a small they are somewhat simpler to discuss than sin-
region whose width is about equal to the gle lap joints because of deflection effects in the
thickness of the bond layer, near the outer latter. Shear and peel stresses in double lap
edges of the system; in most of the bond, rela- joints with uniform adherend thickness were
tively little yielding can take place. For organic treated by Hart-Smith%.For the shear stresses,
matrix composite adherends, the adherends the type of analysis discussed in Section 28.4.3.2
may fail at a lower peel stress level than that at can be applied with suitable changes in nota-
which the bond fails, which makes the peel tion, i.e. the expressions for the shear stresses
stresses even more undesirable. given in eqns (28.11)and (28.12)can be applied
with subscripts 'i' and '0' ('inner' and 'outer')

P t P substituted here for 'L' and ' U ('lower' and

'upper') used in eqns (28.6-28.11); in addition,
the outer adherend thickness in the earlier
equations is now equivalent to half the thick-
ness of inner adherend because of vertical
symmetry of the double lap joint. However, we
will also introduce the effects of thermal mis-
match effects in the following expressions for
Bond later reference. The notation used here is:
Bo = toEo; Bi = tiEi;
E@e Region
(Distornal
Strains)

B B.
pB = Bi/Bo; Tth = (ao- a,)AT;
Bo + Bi L
A -

Fig. 28.35 Shear stresses near outer edges of butt ax = T / t ; &* =T,/t (28.14)
tensile test.
 Adhesive joints 639
h

where a,, a, are thermal expansion coefficients
and AT is the temperature change.
Note that is related to the resultants (axial
adherend stress times thickness) at the ends of
the joint as shown in Fig. 28.36. The shear
stresses are then given by:
In the absence of thermal effects ( Tth = 0) and
assuming that Bi 1 Bo, the maximum value of
the shear stresses occurs at the right end of the
joint as noted earlier (Fig. 28.31). With thermal
effects present, the situation is complicated by
the sign of &* which is positive if (a, - a,)and

Zb =/35
[ ~
1 coshp(x - I)/: AT have the same sign and negative otherwise.
The peel stresses in the double lap joint are
+pB sinhBl/t described by a beam-on-elastic foundation

**--
type differential equation of the form:
d40 ?d
b + 4 - 0 =-f- dzb (28.18a)
- coshp(Z - x ) / t ] dP t4 2 O dx

sinh pz /t
(28.15)
yd = (3x)
Ebto 114
(28.18b)

(A) DOUBLE STRAP JOINT The solution to eqn (28.18) depends on

whether a strap joint or a lap joint is consid-
2Tt 2t ered. The exact form of the solution contains
products of hyperbolic and trigonometric
functions but for the practical situation of
joints longer than one-or-two adherend thick-
nesses and B << yd, are given by:
Double lap joint,
1*’
1 (E) WUBLE LAP JOINT

Fig. 28.36 Symmetric double strap/double lap

joints. Double strap joint,
For the usual situation in which the overlap is
long enough so that p l / t is greater than about
3, the peak shear stresses at the ends of the
joint are given by: (28.19)
For the case of identical adherends, the maxi-
x = 0; Zb, = B(& 5,- &&
mum peel stresses, which occur at x = 0, are
given by:
Ob)max = ‘b)max yd (28.20)

and for the special case of equal adherend stiff- ‘b)-x = P ax/2 - p
nesses (Bi = Bo) we have: (identical adherends)
Here z ~is taken
) ~to be~ the peak stress at the
Bi = BJp, = 1);
left end of the joint, corresponding to the
expression for x = 0 in eqn (28.16), since the
1 out-of-plane normal stresses are compressive
‘b)-x = T p ax “* (28*17) at the other end of the joint for a tensile load.
640 Mechanicalfastening and adhesive bonding

For compressive loading, the situation would

reverse for the double lap joint (Fig. 28.36(b)),
Quarter Plane Symmetry
with the positive out-of-plane stresses occur-
ring at the right end of the joint ( x = l), in the
case of the double snap joint (Fig. 28.27(a)),the t /t b t
peak out-of-plane stresses would be compres-
sive at the left end of the joint and would not
occur at x = 1, since the inner adherends butt
against each other there and act as a continu-
ous element. t p-' I 4
Effects of thermally induced stresses will be
discussed in a later section. Figure 28.37 com-
pares the peel and shear stress distributions 2.00 3

i
for 8, = 0, in a typical joint having balanced
adherend stiffnesses (the sum of the outer
adherend stiffnesses equal to the inner
adherend stiffness) whose parameters are
listed in Fig. 28.37(b). The diagram at the top
indicates the origin of x at the left end of the
overlap. The distribution of peel stresses is
~x-,-,,A-
somewhat more concentrated near the ends 0.00. : : : : : :
0.00 0.200.400.60 0.801 .OO 1.20 1.40 1.601.80 2.00
than that of the shear stresses and the peel
(a) X-
stresses at the right end of the joint are nega-
tive. In addition, the compressive peak at the
right end is half as great for the strap joint as
for the lap joint, which is the result of the
restraint of bending rotations in the strap joint m v)

for a gap which is essentially zero. If the load- g o v)

ing were compressive rather than tensile, the
%-0.5 X-
inner adherends would bear directly on each
other and no shear or peel stress peak would Double strap joint
occur at the gap, whereas in the lap joint the
-1.5
right end of the overlap would experience the
same peak stresses for compressive loading as (b)
the left end does for tensile loading. Fig. 28.37 Bond stresses in double lap/strap joints;
The situation for the single lap joint (Fig. (a) bond shear stress distribution; (b) bond peel
28.38) is complicated by the effects of lateral stress distribution.
deflection which are indicated in Fig. 28.39.
Literature for the following discussion on the The effects of lateral deflections on the bond
single lap joint is given53,51,7*78. stresses were first evaluated by
The deflection effect is dependent on the Goland-ReissnerZ7 for the case of equal
joint load, given in terms of the quantity adherend thicknesses, so that tu and t, can be
LIl/2(8)1/2tu,where denoted by t in the following. The lateral

LI = tud( c){( E 12%); D, = EEutA

1
deflections can then be stated in terms of a
(28.21) dimensionless ratio, k, with respect to the
adherend thickness, and are of the following
form:
 Adhesive joints 641

- I --
E

wL"
DI PLACEMENTS

Fig. 28.38 Single lap joint geometry.

effects. The most accurate expression (given in

Ref. 74) is fairly elaborate and will not be
repeated here; an expression of intermediate
accuracygiven in Ref. 74 retains the essential
form of the GR result but gives considerable
improvement over the GR expression for thin
adherends:
tanhLUo
k = (28.23a)
Fig. 28.39 Effects of bending deflections in single tanhLUo+ d8C,tanh(LU/2Cp)
lap joints. where
t" = t, = t;

U/.IS(X - L M ]
l o ~ x < l + l o ;=
w w,sinh[
sinh[Ulfl8t]
+ -tu
---
t
+ tb x ; W, = -(1 - k)
2 2 L 2
The Goland and Reissner (GR) expression for
the parameter k has been re-examined by
Hart-Smith%and more recently by Oplinger",
based on the discussion in Ref. 74, the
Goland-Reissner expression appears to pro-
vide adequate accuracy unless the adherends
are excessively thin,not more that one or two
times the bond layer thickness, in which case
the expressions given in Refs. 73, 74 and pro-
vide corrections for bond layer thickness
The original GR expression for k is recovered if
Cpis set equal to 1corresponding to tu >> t, (i.e.
relatively thick adherends) and tanh LUo is like-
(28.22) wise set to 1 corresponding to very long outer
adherend lengths. A plot of k against the
adherend loading stress is is given in Fig. 28.40
for two different values of adherend thickness
corresponding to bond thickness-to-adherend
thickness ratios (p, in eqn (28.23b)) of 0.5 and
0.1. This plot suggests that k is fairly constant at
a value of about 0.25 for a wide range of
applied stress values once the initial drop has
occurred. The effect of bond-to-adherend thick-
ness ratio is not particularly great and can
perhaps be ignored for the most part.
642 Mechanical fastening and adhesive bonding

a9

ae

a7

I 0.6

* a5
0.4

a3

0.2

ai
0

Fig. 28.40 k parameter vs. adherend loading stress.

The lateral deflections of the joint have a x-lo-l

significant influence on the stresses in the + ucos y,
bond layer, which show this through the pres-
ence of the k parameter in expressions for x - lo
them. The shear stress is given by:

Zb = 0, B(l + 3k) cash [@(x - L ) / t ]

cos y , t - sin y
"-")
, t

I4 sinh @A/) x - lo lo - x

+ mu('
3
k, - 'Osh iu(' - ')/.lst1
sinh ( d / 2 & ) where y, = (6 Ebt/Extb)1/4 (28.26)
where B and U are given in eqns (28.14) and
(28.21). Equation 28.24, which represents a The maximum stresses in the bond layer are
slight modification of the GR expression, given by:
reduces to the latter for small values of LIl/t. In Maximum bond shear stress,
addition, the peel stresses, for joints in which
the overlap length is more than one or two zb)- = 0;
adherend thicknesses (essentiallythe only case
of practical interest) are given by

ab =a,-
- b
-
L
s (28.25)
+ mU(l - k)/tanh ($)I (28.27)

Maximum bond peel stress,

lo+l-x lo+l-x
B ([YS(COS Y, t + sin y, t 1

Figure 28.41 gives a comparison of the maxi-
mum bond stresses as functions of the loading
stress ax for two different adherend thick-
nesses in a joint with a bond layer thickness of
0.01. It is interesting to note that the peel and
shear stresses take on quite similar values.
Since the maximum peel stress varies approx-
imately as y i according to eqn (28.27) (the
contribution of U being relatively minor), the
relationship for ys given in eqn (28.26) sug-
gests that the peel stresses should be expected
to vary as (t/tb)1/2, while the same variation is
seen from eqn (28.27) for the maximum shear
stresses since p also contains (t/t,)'/* as a fac-
tor. Thus both stresses should vary with the
thickness ratio by the same factor. The fact that
they are numerically close together for all
stresses is partly due to the effect of other
parameters that enter into eqns (28.27) and
(28.28) and partly due to the fact that k does
not vary much with load for axgreater than 5.
A slight nonlinearity can be observed in the
curves of Fig. 28.41 for the lower loading
stresses.
Figure 28.42 gives a comparison of maxi-
mum bond stresses in single and double lap
joints for a fixed value of the loading stress ax.
For loading stresses above this value the bond
&=looOO, Gb=150,%=SO0
'4 I M.02; (52,
12
4
E "
si3
lo
0 10 20
Fig. 28.41 Maximum bond stresses in single lap joint, bond thickness = 0.01.
Adhesive joints 643
stresses vary essentially in proportion to the
load even in the single lap joint, as just dis-
cussed. The stresses are plotted in this figure
as a function of adherend thickness with the
adherend axial modulus as a parameter. The
trend toward higher bond stresses and there-
fore a greater tendency toward bond failure
with increasing adherend thickness which was
discussed in Section 28.4.2 is clearly borne out
in these curves. Note also that reduction of the
adherend modulus tends to aggravate the
bond stresses. In addition it is apparent that
there is considerable separation between the
peel and shear stresses in the case of the dou-
ble lap joint, the peel stresses for the latter case
being smaller. This reflects the fact that the
peel stresses vary linearly as yd defined in eqn
(28.18b) and therefore vary as (t/tb)1/4 rather
than as (t/tb)l/*as in the single lap case. Thus,
peel stresses for double lap joints are not as
much of a factor in joint failure as they are in
single lap joints, although they are still large
enough relative to the shear stresses that they
can not be ignored.
Failure characteristics of single and double
lap joints will be discussed below. If the
adherends are thin enough, failure in double
lap joints should be in the form of adherend
g=10
/
-
=* - 30 40
644 Mechanical fastening and adhesive bonding

Single Lap Joint Double Lap Joint

peel strau Shear Stress

4 -
Ex = 10,OOO
3.5 -.
Ex = 5,wO
3-
2.5 -
2-
-------

'
1.5 -
O
-0

1
0.5
Ex I20,oOo

-
0
0'5 0.08 0.1 0
0.02 0.04 0.06 0.02 0.04 0.06 0.08 0.1
AdherendThickness AdherendThickness +

CTx= 10 Gb= 150 E,= 500

l,,= 50 1 = 10

Fig. 28.42 Maximum bond stresses in single and double lap joints, fixed vx = 10.

axial (tensile or compressive) failure. For sin-
gle lap joints, adherend bending stresses are
significant at the ends of the overlap as indi-
cated in Fig. 28.39; using standard beam
formulas, the maximum axial stress for com-
bined bending and stretching (the latter stress
corresponding to the single lap joint in tension
loading) for the bending deflection given in
eqn (28.22) can be expressed as
- length, but in this case the stresses reach mini-
QJrnax
= OX3(1+ t,/t)k
The maximum adherend axial stress is
largest for adherends which are particularly
thin with respect to the bond thickness; these
will be prone to brittle bending failures for
composite adherends or to yielding associated
with bending for metal adherends. Hart-Smith
discusses difficulties with the use of standard
single lap shear test specimens50.The problem
is that adherent bending failures are likely to
occur with such specimens rather than bond
failures and test results obtained in such cases
tend to be irrelevant and misleading.
One additional characteristic difference
between single and double lap joints should
be discussed. The effect of lateral deflections
on single lap joint performance is quite long
range. Figure 28.43 shows that for a joint with
an adherend thickness of 2.54 mm (0.1 in) the
bond stresses do not reduce to their minimum
values until the overlap length reaches a value
in the range of 10-12.7 cm (4-5 in), for a load-
ing stress of 69 MPa (10 ksi). Double lap joints
also require some minimum length before
stresses settle out as a function of overlap
(28.29) mum values with respect to overlap length for
lengths on the order of 5 to 10 adherend thick-
nesses, in the present case amounting to
1.3-2.5 cm (0.5-1 in).
28.4.3.4.2 Effects of adherend tapering
In this section we will consider joints with
adherend thicknesses which vary along the
joint length. These include the configurations
shown in Figs. 28.44 and 28.45, namely, double
strap joints with tapered outer adherends and
scarf joints as well as step lap joints. As dis-
cussed in Section 28.4.2.2, tapering the outer
adherends of strap joints as in Fig. 28.44(a) is
beneficial mainly for reducing or eliminating
 Adhesive joints 645

m 1.6
t m e w 0.7 -
Signmba--lO
1 .'
Gb--160 Eb--500 Er--S.OOO
0.5 ..
-
tb- 0.01 M call-
~ ht@h -- 20

Fig. 28.43 Effects of overlap length in single lap joints.

(A) PARTIALLY TAPERED STRAP JOINT Qf-

I am i nat e meta 1
I
I
Triangular Elewnt
Fig. 28.45 Generic step lap joint.

I +B * (E) SCARF JOIN1

I I
Bond
Fig. 28.44 Tapered double strap and scarf joints.
peel stresses, while scarf and step lap joints
(Figs. 28.44@), 28.45) can eliminate shear stress
peaks as well as peel stresses.
With both tapered outer adherends and
scarf joints, it can be shown that the bond
stresses can be related to the ratio of taper
length to thickness by
zb= axt/Z ;ab=axt 2 / P
This relationship is quite accurate for scarf
joints having the same maximum stiffness
(axial modulus times maximum thickness) in
each adherend. For tapered portions of strap
joints it is fairly accurate for the peel stresses,
and holds approximately for the shear stresses
if the tapered portion is not too long. Note that
eqn (28.30) implies that the bond stresses are
constant along the length of the joint and can be
reduced to any arbitrary level by making t/Z
small enough, i.e. making the joint long enough
with respect to the adherend thickness.
Moreover, the effect of t/Z on the peel
stresses is quite strong, being governed by the
square of the thickness-to-length ratio. This is
especially important in the case of outer
adherend tapering in strap and lap joints as a
means of reducing peel stresses to a manage-
(28.30)
able level.
Step lap joints (Fig. 28.45) represent a com-
promise version of the scarf joint which can
646 Mechanical fastening and adhesive bonding
take advantage of the layered structure of the
composite adherend. The average slope of the
region represented by the line through the
steps in Fig. 28.45 tends to control the average
shear stresses developed in the bond. Within
each horizontal section, equivalent to the tread
of a staircase, the behavior is analogous to a
joint with constant adherend thickness, and
the differential equation given in eqn (28.10)
(Section 28.4.3.2)applies locally when tu and tL
are adjusted to match the local situation. An
expression similar to eqn (28.12), i.e. for thejth
step,
PB
+-
gives the maximum shear stresses within each
step, and the overall solution is a chain of such
expressions with allowance for continuity of
the shear strain and resultants, Tuj and TLjat
the points where neighboring steps join. In
each step of the joint the shear stresses will
have a distribution similar to that of Fig. 28.36,
the size of the peaks being governed primarily
by the length of the step through the parame-
ter P.Z./t.The aspect ratio for the step, Zj/t,
can
11
in prmciple be kept small enough to almost
completely avoid any peaking by using a large
number of steps and keeping the length of
each one small. In practice, the number of
steps is governed by the number of plies in the
laminate. In addition, if the joint is used to
connect a composite adherend to a metal com-
ponent, machining tolerance requirements
and cost considerations for the metal part
enter into the selection of the number of steps.
The following discussion will address the
specific benefits of adherend tapering in
tapered double strap joints, scarf joints and
step lap joints. The overall approach is to aim
for a highly efficient joint which reduces the
effects of shear and peel stress concentrations
at the ends of the joint. Ideally we would like
to achieve the joint strength provided by the 'P
over A' concept obtained with the case dis-
cussed in Section 28.4.3.2 for perfectly rigid
adherends (Fig. 28.27), in which increasing the
joint length indefinitely brings the shear stress
in the bond down to any required level regard-
less of the magnitude of load being supported
by the joint. While tapering does reduce the
peel stresses markedly in the tapered strap
joint as will be seen below, shear stress peaks
can not be avoided, and the law of diminish-
ing returns continues to prevail with regard to
increasing the joint length to obtain greater
load capacity; however, adhesive ductility will
enhance the strength beyond what elastic
analysis suggests.
Double strap joints with tapered outer
adherends are considered in Figs. 28.46 to
28.48. Figure 28.46 indicates the tapered con-
figurations that are considered. Figure 28.47
gives some shear stress predictions for joints
with uniform adherend thickness for compari-
son with the tapered cases which are
considered in Fig. 28.48.
Figure 28.46 defines the notation used in
Fig. 28.45 in terms of 'fully tapered' outer
adherends (Fig. 28.46(a)), partially tapered
adherends in which the taper extends only
part of the length of the joint (Fig. 28.46@))and
fully tapered adherends with an 'initial rise',
i.e. in which the thin end of the adherend does
not come to zero thickness. (The term '% initial
rise' implies that the rise is expressed as a per-
centage of the maximum adherend thickness.)
The three cases considered in Fig. 28.48 can
be compared with the case for uniform
adherends with equal upper and lower
adherends modulus (E, = EL)in Fig. 28.47. For
the situation of no initial rise, two cases are
considered in Fig 28.48, the case of 50% taper
and that of full taper. There is an appreciable
difference in the shear stress distribution at the
 Adhesive joints 647

(A) F u l l y tapered - - no i n i t i a l r i s e left end of the joint for these two cases, but the
peel stress distribution is essentially unaf-
fected. For both the full taper and 50% taper
cases, a minor tensile secondary peel stress
peak is present at the right end of the region
under consideration (near the midpoint of the
strap joint). The peel stress expression in eqn
(28.30) gives a good estimate of the peel stress
level at the left end of the joint, and the result
of the estimate is so small for both cases that
the difference is not distinguishable in Fig.
28.48. However, in the case of an initial rise of
(@ 5G% tapered j o i n t only 1 / 4 of the maximum outer adherend
thickness (25% initial rise), significant peel
---I 1.0 I.c I
stresses arise at the left end of the joint, in fact,
---- I
about 80% of the level occurring for the case of
no tapering. The initial rise also causes a
greater increase in shear stress at the left end
of the joint than in the case of 50% taper. Thus,
tapering is advantageous mainly as a way of
(C] F u l l taper - - 25% i n i t i a l r i s e
eliminating the effects of peel stresses in dou-
ble strap joints. Once this is accomplished, the
/ 0.05 initial rise
effects of peel stress peaks can be controlled to
a significant extent by taking advantage of
adhesive ductility. Tapered strap joints can not
\'T achieve the ideal behavior which is possible
with scarf or step lap joints, but they provide a
simpler solution to good joint performance if

-==E==- I
the adherends are thin enough.
Shear stress distributions in scarf joints (Fig.
28.49) are given in Fig. 28.50. Practical scarf
Fig. 28.46 Tapered strap joints under consideration.

Shear strws - - Uniform Adhemd l h l c k m u

eT
:I
:I

0 0.2 0.4 b.r 0.8 1 1.2 1.4 1d 1.8 2

Fig. 28.47 Shear stresses in unta-
X
pered strap joints.
648 Mechanical fastening and adhesive bonding
5 T
(A) Shear stresb
Fig. 28.48 Stresses in tapered double strap joints.
joints are arranged in a symmetric double lap
configuration which avoids bending effects.
Figure 28.49 represents a balanced stiffness
design for dissimilar materials, by achieving a
continuous thickness change over the length
of the joint. The most important parameter for
- -
/
0.2, 0.4
TI, E.16 ffii QI graphite epoxy
E.8 msi
Fig. 28.49 Stiffness-balanced scarf joint configura-
tion.
- - Double Strap Tapered Adherends
the scarf joint is the effect of adherend stiffness
unbalance ( E , # Ei; ’0’ and ‘i’ refer to the outer
and inner adherends as in Fig. 28.36). The
results given in Fig. 28.50 represent the effect
of varying degrees of stiffness unbalance. The
ratio of peak-to-average shear stresses com-
pare well with the values given by
Hart-Smith37,although the latter did not give
--Es
the distribution of stresses along the length of
the joint. For fairly sizeable unbalances, up to
4:1, the maximum shear stress peak is not as
great as that observed in Fig. 28.47 for the uni-
form adherend case. However, it is clear that a
stiffness unbalance will increase the shear
stress peak and weaken the joint. For the equal
stiffness case the shear stress is constant and
equal to the average stress at all points.

EU = 8,000 tu = n = .2
G b = l 6 0 Eb-600 t b = O . O l
-
Sigma x = 10
0 0.2 0.4 0.6 0.8
Fig. 28.50 Shear stresses in scarf joints.
If there is no reason why the joint cannot be
configured as in Fig. 28.49 for dissimilar mate-
rials so as to take advantage of the benefits of
the balanced stiffness case, then in principle,
the scarf joint provides a near ideal solution to
achieving as much load capacity as is required
in any situation without overstressing the
bond layer. However, the dimensions of the
joint may grow too large to be practical for
high joint load. In addition, an extremely good
fit, for example, to tolerances on the order of
the bond thickness over large lengths, has to
be maintained to ensure that the joint can
maintain uniform load capacity over its
length. Thermal stresses will also be a factor in
various combinations of dissimilar materials
which will prevent the ideal form of behavior
from being achieved. In terms of the Hart-
Smith approach to avoiding creep failure
under slow cyclic loading, the balanced scarf
joint is at a disadvantage in not providing a
shear stress minimum. For this situation the
allowed load would have to be limited to pre-
vent environmental conditions corresponding
to hot wet exposures; thus the advantage of
the scarf joint in eliminating stress peaks
Adhesive joints 649
EL I EU = 4
2
1 1.2 1.4 1.6 1.8 2
X
might be lost if performance in hot wet envi-
ronments is required.
Step lap joints798oare treated in Figs. 28.51
to 28.53. Figure 28.51 shows a generic joint
configuration that is introduced to illustrate
some of the effects of design parameters on
stresses in the joint. The results presented in
Figs. 28.52 and 28.53 were generated for this
discussion using a linear elastic response
model for the adhesive; in practice, consider-
able strength capability of the adhesive is
unused if elastic response of the adhesive is
assumed; Fig. 28.54 taken from the discussion
by Hart-Smithsois an example of joint design
using elastic-plastic response for the adhesive.
The elastic adhesive model used in Figs. 28.52
and 28.53 is adequate for illustrate some of the
controlling parameters on joint design. These
results are based on the classical Volkersen-
type analysis with provision for resultant and
shear strain continuity at the interfaces
between neighboring steps, as discussed pre-
viously. The 5-step design in Fig. 28.52 and the
10-step design in Fig. 28.53 were chosen with
the following characteristics:
650 Mechanical fastening and adhesive bonding

I I / / V I

Quasi-Isotropic Carbon @OXY, Fig. 28.51 Step lap joint

E =8nsi
X configuration.
Except for the first and last steps, the As discussed above, the joint design shown in
adherend thickness was equal for each step. Fig. 28.5437represents a practical joint design
The first and last thickness increments were which accounts for several considerations that
half those of the generic steps. the simplified elastic analysis approach used
The lengths of each step were chosen with-a for Figs. 28.52 and 28.53 neglects. The neglect
fixed value of the parameter qs, = pirj/fj, of ductility effects has already been men-
where lj is the length of step j . tioned. In addition, the use of as large a
The half-incremented end steps gave a more
uniform shear stress distribution than main-
taining the same increment for all steps. The
symmetric joint configuration shown in Figs.
28.51 and 28.54, the thickness increment for
the outer adherend (composite) was greater
than that for the inner adherend by the inverse
of the modulus ratio, to achieve the desired
stiffness balance for the dissimilar adherends.
The parameter ETA listed in Figs. 28.52 and
28.53 is equivalent to qs, defined above. This
parameter essentially controls the length of the
joint; both Figs. 28.52 and 28.53 show an
increase in joint length with qsl ('ETA' in the
two figures). Note further that the load capac-
ity of the joint in terms of the allowed
resultant, 5, listed as "BAR in Figs. 28.52 and
28.53, which provides for the required bond
shear stress limitation of 5 (ksi for the units
mentioned earlier) shows a general increase
with joint length, but with diminishing
increase when vsl gets much beyond 3. Table
28.1 gives a summary of the results shown in
the two figures. Fig. 28.52 Shear stresses in 5-stepjoint.
 Adhesive joints 651

presented by Corvelli and Saleme79;this was

later enhanced by Hart-%~ith~~, under NASA
funding, to provide for elastic-plastic
response, culminating in the A4EG and A4EI
programs-, to allow for variations in thick-
ness, porosity, flaw content and moisture
content in the bond layer. Hart-SmithsoI8lnotes
that in mathematical treatments of step joints,
all properties have to be constant within each
step; however, in an actual joint such as that
shown in Fig. 28.54, artificial breaks may be
inserted to permit changes in porosity of bond
thickness.

28.4.4 MECHANICAL PERFORMANCE OF

ADHESIVES

28.4.4.1 Ductile response of adhesives

C L : : : : : : : : : : : : : : : :
0 uyaa1mkL11unuuur
I dependence and strain rate dependence of the
Fig. 28.53 Shear stresses in 10-step joint.
number of steps as 10 in Fig. 28.53 may not be
practical. The joint design shown in Fig. 28.54
represents the evolution of steplap joint design
over many years. Early analytical work was
Table 28.1 Summary of step lap joint results (Figs. 28.52 and 28.53)
Figure 28.55 taken from the 1983 edition of the
DoD/NASA Advanced Composites Design
Guides1 show shear stress-strain response
characteristics of typical aerostructural adhe-
sives. Figure 28.55(a) represents a relatively
ductile film adhesive, FM73, under various
environmental conditions, while Fig. 28.55@)
represents a more brittle adhesive (FM400)
under the same conditions. Similar curves can
be found in other sources62. Temperature
stress-strain characteristics are important
characteristics; these are also addressed in the
results shown in Ref. 62. Even for the less duc-
tile material such as that represented in Fig.
28.55@),ductility has a pronounced influence
on mechanical response of bonded joints, and
design only for elastic response deprives the

No. of steps 10 10 10 5 5
V7sl 1 2 3 3 6
Joint length, cm 4.44 8.89 13.33 6.05 12.5
(in) (1.75) (3.5) (5.25) (2.47) (4.93)
Allowed resultant, kN/cm 12.03 18.78 22.05 12.35 13.43
(103 lb/in) (6.87) (10.72) (12.59) (7.05) (7.67)
652 Mechanical fastening and adhesive bonding

3
2

- 0 0
1 2 3 4 5 6I 1 2 3 4 6 6

Fig. 28.54 Practical step lap joint designs0.

( A ) FM78 NON P O R O U S

0 0.2 0.4 0.8 0.8 1 1 .z f.4

S h e s r 8 traln

6o LT = -55 d q C
46 RT = Room Temp
H T M = 60 degC1100%RH
$
-aa
I:2 16 I$ F m o o ~ a m u r b m d
5 10
6
0
o om om 001 om ai a12 0.14
Mr-

Fig. 28.55 Typical stress-strain characteristics of aerospace adhesivess1.

 Adhesive joints 653

application of a significant amount of avail- zp, which can be obtained by solving for zp
able structural capability. from eqn (28.32), leading to
The work of H a r t - S ~ n i t h
emphasized
~~~ the
importance of ductile adhesive response and 'p = Gb$max - d[(GbOYmax)2 - 2GboSEl
introduced the relationship between the strain
energy to failure of the adhesive and the load (28.33)
capacity of the joint. As a means of simplifying Hart-Smith has also used an equivalent
the stress analysis of the joint in the presence bilinear representation in which the horizontal
of ductile adhesive response, Hart-Smith part of the curve is set equal to zmax,the maxi-
showed that any bilinear stress-strain curve mum shear stress of the actual stress-strain
which has the same ultimate shear strain and curve, and the initial modulus Gboadjusted to
maximum strain energy as that of the actual give the strain energy match, using the expres-
stress-strain curve will produce the same total sion:
load in the joint. Figure 28.5681gives an exam-
ple of the method for fitting a bilinear curve to Gbo = 'ma:('maxYmax - /2 (28'34)
the actual stress-strain curve of the adhesive which is also obtained from eqn (28.32) when
in shear. With the strain energy of the adhesive rmax is substituted for zp. In either case the use
given by of a bilinear representation of the stress-strain
SE = rJmax- zp2/2Gb0 (28.32) curve for the response of the adhesive in shear
makes it straightforward to obtain one dimen-
where GbO! yma, and SE are the initial modulus sional stress distributions in various types of
of the stress-strain curve, the maximum strain joint geometry with adhesive ductility
and the strain energy of the adhesive at ymaX accounted for; solutions are given for single
respectively, then the equivalent bilinear curve and double lap joints with uniform and
consists of an initial straight line of slope Gbo tapered adherends, as well as more sophisti-
together with a horizontal part at an abscissa cated joint designs such as scarf and step lap

Fig. 28.56 Elastic-perfectly plastic adhesive response model (Fh473)*'.

654 Mechanicalfastening and adhesive bonding

geometries ( H a r t - S ~ n i t h ~These
~ ~ ) . have sub-
sequently been incorporated in the 'A4Ex'
series of computer programs- mentioned
previously.
Figure 28.57 (see notation of Fig. 28.36)
shows an example of the use of the bilinear
stressstrain curve approximation, in this case
for predicting the stresses in a symmetrical
double lap joint with equal adherend stiff-
nesses (i.e. Eo = Ei; to = fi/2). Figure 28.57(a)
gives the distribution of upper adherend axial
stress resultant while Fig. 28.57@) gives the
shear stress distribution in the bond layer. The
linear portions at the ends of the resultant dis-
tribution in Fig. 28.57(a)correspond to the ends
of the shear stress distribution in Fig. 28.57@)

4.5 (A) Upper adherend resultant distribution

f 4 ( 1 k-lblln = l.762 kNlom)

Axial load 310 MPa (46 ksl)

0
0 0.6 1 1.I 2
K

le

(6)Shear stress distribution

(1 ksi= 6.896 MPa)

Axial k a d 310 MPa (45 ksi)

0.5 --
o i I
0 0.c z 1.Q 2

Fig. 28.57 Stress distributions in double lap joint - ductile adhesive response.

where the shear stress is a constant because of
the plateau in the bilinear representation of the
stress-strain curve, in agreement with the equi-
librium relation given in eqn (28.6). Following
the analysis developed by Hart-Smith, the
lengths of the plastic zones designated in Fig.
28.57(b) as Ip are given by
lp = (aX/2zp- l/pbd)to;p,, = [2Gbflto/EotbI’/*
(28.35)
Here p,, (subscript ’bd’ denoting balanced
double lap) is equivalent to p given in eqn
(28.14) when the latter is specified for the case
of equal-stiffness adherends, while 5, is the
nominal loading stress at either end of the
overlap. The expression for Ip given in eqn
(28.33)is valid only if greater than 0, of course, The Hart-Smith analysis based on the equiva-
negative values of plastic zone length not hav-
ing any meaning. Thus if /33,/2 < zp, no plastic
zone is present and the behavior of the joint
can be considered to be purely elastic. The
maximum value of 5, for this case can be
expressed by inverting the shear stress expres-
sion in eqn (28.17) with oth= 0, for the case of
equal adherend stiffnesses and setting zb)max to is determined, the same types of solution
zp. For the case of pax/2 2 zp which corre-
sponds to ductile response of the adhesive (the
plateau of the bilinear stress-strain curve), the stress distributions, together with linear resul-
Hart-Smith analysis35provides the required
expression for 0, The two cases are summa-
rized as follows:
< zp (elastic response):
pbdSX/2
‘x)max = 2zp/pbd E (28.36a)
PbdCx/22 zp (ductile response):
(28.36b)
If y, = zp/GbO,which is the maximum strain
in the elastic part of the bilinear representation,
Adhesive joints 655
then eqns (28.36a, b) give the same value. The
factor (2GbOymax/zp- 1)1/2in eqn (28.36b)acts as
a load enhancement factor and represents the
increase of joint load capacity due to ductile
adhesive response over the maximum load
allowed by elastic response of the adhesive.
Note that eqn (28.36b) can be rearranged to
express 5x)ma,in terms of the maximum strain
energy of the adhesive:
where ye = zp/Gb, (28.37)
then eqn (28.3613)can be written:
2
-
= p’(2Gb()SE) (28.38)
lent bilinear stress-strain law was shown in
Ref. 35 to give the same joint load capacity as
the solution for the problem using the actual
stress-strain curve of the adhesive. The conve-
nience of the bilinear stress-strain description
is in the simplicity of the solutions it allows;
once the length of the plastic zone at each end
apply for the elastic zone as were given in eqns
(28.9) and (28.10) for the resultant and shear
tant and constant shear stress distributions in
the plastic zones.
The most obvious effect of ductility in the
adhesive behavior is the reduction of peak
shear stresses. In addition, there is a beneficial
effect on reduction of peel stresses. For the
double lap joint considered in Fig. 28.57, the
maximum peel stresses denoted by ob),ax
which occur at the ends of the joint, are given39
by:
Ob)max = Fb)max ; (28.39)
(
y = 3- i’” ;
E, = peel modulus of adhesive
656 Mechanical fastening and adhesive bonding

where z ~ is )the ~maximum~ ~ shear stress, leads to high shear and peel stresses at the
either /?OX/2 for the elastic case or zp for the ends of the joint, and may inhibit desirable
case of ductile response. The maximum peel flow characteristics of the adhesive. On the
stresses are thus reduced by the same ratio as other hand, thick bond lines tend to generate
the maximum shear stresses in the case of duc- porosity which weakens the bond. Data pre-
tile response of the adhesive. sented in Ref. 83 show a fairly persistent
Even though ductile response of the adhe- tendency for lap shear strength to drop off
sive provides additional load capacity of the somewhat as the bond thickness is increased
joint over what is provided by purely elastic above 0.12 mm (0.005 in).
response, it is advisable to keep the load In addition to effects of bond thickness per
capacity of the joint low enough to ensure se, Hart-Smith60 discusses the effect of bond
purely elastic response for most practical situ- thinning at the ends of the joint which is
ations where time-varying loading is caused by resin flow during curing. Figure
encountered. Some damage to the adhesive 28.58 illustrates the tendency toward bond
probably occurs in the ductile regime which thinning at joint edges together with some
would degrade the long-term response. The manufacturing techniques for avoiding the sit-
main benefit of ductile behavior is to provide uation. Loss of bond thickness may cause
increased capacity for peak loads and damage considerable elevation of shear and peel
tolerance with regard to flaws - voids, poros- stresses in the bond. In addition to the
ity and the like - in the adhesive layer. In approaches shown in Fig. 28.58, tapering of
addition, calculations of the plastic zone the adherends near the ends will help to alle-
length play a part in the avoidance of creep viate the situation; tapering from the inside
failures which can constitute a major consider- surface of the adherend will also provide a
ation for slow cyclic loading in hot wet local thickening of the bond line to compen-
environments. sate for thinning due to resin loss.
Effects of porosity in the bond layer are
illustrated in Fig. 28.59(j1which compares the
response of FM73 for porous and non porous
28.4.4.2 Effects of bond layer defects
bond layers for various environmental condi-
Defects in adhesive joints include surface tions. The data6' indicate that porosity is
preparation deficiencies leading to low mainly a characteristic of thickness of the bond
strength interfaces between the adhesive and layer. There is some loss of structural capabil-
adherends, voids and porosity, and lack of ity in the presence of porosity in the bond, but
bond thickness control. Surface preparation there may still be adequate strength for the
effects were discussed in Section 28.4.2.6 and bond to function as required if the joint is
will be treated in considerable detail in designed adequately. Since porosity is associ-
Chapter 29. However, it should be kept in ated with thickened regions of the bond which
mind that adhesive joints will not succeed in tend to occur away from the edges, porosity
providing dependable performance if good tends to be confined to the interior of the joint
surface preparation procedures are not main- where the stresses are relatively small, and
tained. may not be objectionable in many cases. The
Bond layer thicknesses of 0.12-0.25 mm main focus in Ref. 61 is the effect of adherend
(0.005-0.010 in) are typical of structural thickness with regard to damage tolerance in
bonded joints. There appears to be a tradeoff the presence of bond layer defects. The issue
between negative effects which occur when has to do with the design principle discussed
the bond is too thin and those occurring for in Section 28.4.2.1 of keeping adherend thick-
too thick bond layers. Thinness in bond layers nesses within limits which ensure that the
 Adhesive joints 657

4. NIIOIQFfCERVVACVUWMQ

Fig. 28.58 Manufacturing techniques to relieve bond pinch-off 51,

60

2
50 I rLT /Stress VQ. Strain -- FM731
I 40
Y
67
67

E5 30
20
LT -
-
- -55dqC
RT -room temp.
H/w - - 60 degC/lOo% rh
5 10
2.
o $ I

0 0.5 1 1.5 2
S h e a r Strain

Fig. 28.59 Effect of porosity on adhesive stress-strain characteristicss1x : porous; : non porous bond layers.

adherends fail rather than the bond. Ductile tJc,which ensures adherend failure can be
response of the adhesive has an important expressed by restating eqn (8) of Ref. 52 as fol-
influence on the situation. By making use of lows:
eqn (28.36b) above, together with the defini-
tion of p,, given in eqn (28.35), the adherend -
thickness limit for a double lap joint,
658 Mechanical fastening and adhesive bonding

which is equivalent to: damage, while tests conducted at one cycle per
hour produced failures within a few hundred
t, = 4 {Maxadhesive strain energy]/ cycles. On the other hand, specimens repre-
{Maxadherend (elastic) strain energy] (28.41)
sentative of structural joints which have the
Hart-Smith states that for to not greater than characteristic shear stress trough seen in Figs.
to),, given in eqn (28.40),joint performance will 28.37 and 28.57 are able to sustain hot wet con-
be relatively insensitive to bond flaws pro- ditions even at low cycling rates if the length
vided there is adequate ductility in the of the elastic region (Ie in Fig. 28.57) is long
adhesive response. Problems may arise with enough. Based on experience of the PABST
high temperature adhesives such as the FM program, the Hart-Smith criterion for avoid-
400 considered in Fig. 28.55(b), since these ance of creep failure requires that t,),, be no
tend to have limited ductility. As indicated in greater than t p / l O . But the stress analysis for
eqn (28.36b), limited ultimate strain capability the elastic-plastic case using the bilinear adhe-
(y,,,) will reduce margin of ultimate strength sive response model leads to an expression for
over elastic response of the joint. the minimum shear stress equivalent to eqn
(28.12)with 2 replaced by Ze:
28.4.4.3 Durability of bonded joints
,
I
'
-

- P (28.42)
*b)& sinh PbdZe/2fo
Two major considerations in the joint design
philosophy of Hart-Smith are: (1)either limit- do,, - see eqn (28.35)).Since sinh (3) = 10, this
ing the adherend thickness or making use of amounts to a requirement that PbdZe/2tobe at
more sophisticated joint configurations, such least 3, i.e. that the elastic zone length be
as scarf and step lap joints, to ensure that determined by Ze 2 6to/Pbd.Since le is equiva-
adherend failure takes precedence over bond lent to the total overlap length, 1, minus the
failure; (2) designing to minimize peel stresses, sum of the plastic zone lengths, i.e. 21, then
P
either by keeping the adherends excessively making use of the expression for ZP m eqn
thin or, for intermediate adherend thicknesses, (28.33), the criterion for elastic zone length
by tapering the adherend. In addition, it is reduces to a criterion for total overlap length
essential that good surface treatment practices corresponding to a lower bound on 1 which
be maintained to ensure that the bond can be stated as
between the adhesive and adherends does not - 4
fail. When these conditions are met, reliable
performance of the joint can be expected for (
1 2 -+-to
pbd ) (28.43)

the most part, except for environmental
extremes, i.e. hot wet conditions. The Hart-
Smith approach focuses primarily on creep
failure associated with slow cyclic loading (i.e.
one cycle in several minutes to an hour) under
hot wet conditions, this corresponds, for
example, to cyclic pressurization of aircraft
fuselages. In the PABST program4143,18 test
specimens used for characterizing adhesives
(so-called 'thick adherend' specimens) which
are designed to produce essentially uniform
shear stress along the bond were tested at high
cycling rates (30 Hz) and were able to sustain
more than 10 million loading cycles without
Equation 28.43 for the joint overlap length is
the heart of the Hart-Smith approach to dura-
bility of bonded joints for cases where
adherend failure is ensured over bond failure
for static loading and in which peel stresses are
eliminated from the joint design. This type of
requirement has been used in several contexts.
For example60,it becomes part of the require-
ment for acceptable void volume in the bond
layer, since in t h s case the voids, acting essen-
tially as gaps in the bond layer, reduce the
effective length of the overlap. The criterion
has to be modified numerically for joints other
than symmetric double lap joints with equal

stiffness adherends and uniform thickness. For
more sophisticatedjoint configurations such as
step lap joints, the A4EI computer code pro-
vides for a step length requirement equivalent
to that of eqn (28.43) for simple double lap
joints.
In addition to creep failures under hot-wet
conditions, the joint may fail due to cracking
in the bond layer. Johnson and Mall7*pre-
sented the data in Fig. 28.60 which shows the
effect of adherend taper angle on development
of cracks at ends of test specimens consisting
of composite plates with bonded composite
doublers, at lo6 cycles of fatigue loading; here
the open symbols represent the highest load
levels at which cracks fail to appear while the
solid symbols are for slightly higher loads at
which cracks just begin to appear. It is noted
that even for outer adherend taper angles as
low as 10” (left-most experimental points in
Fig. 28.60) for which peel stresses are essen-
tially nonexistent for static loading, crack
initiation was observed when the alternating
load was raised to a sufficient level. A number
of factors need to be clarified before the impli-
cations of these results are clear. In particular it
is of interest to establish the occurrence of
bond cracking at shorter cycling times, say less
than 3 x lo5 cycles corresponding to expected
lifetimes of aircraft. Effects of cycling rate and
environmental exposure are also of interest.
Nevertheless, the data presented in Ref. 65
FM-XII
D NO MBOND
APPLIED
CYCLIC PREDlClED
S I A E S S , IM
~ 5 MPa
,
,,.*
--
0 M
TAPER ANGLE. 0.
60
deg
Po
Fig. 28.60 Crack development in bonds of tapered
composite doublers at lo6loading cycles7*.
Adhesive joints 659
suggest the need for consideration of crack
growth phenomena in bonded composite
joints. Indeed, a major part of the technical
effort that has been conducted on the subject
of durability of adhesive joints6”” has been
based on the application of fracture mechanics
based concepts. The issue of whether or not a
fracture mechanics approach is valid needs
further examination.Apparently, no crack-like
failures occurred in the PABST program,
which was a metal bonding program, even
when brittle adhesives were examined at low
temperatures. The amount of effort which has
been expended by a number of respected
workers on development of energy release
rate calculations for bonded joints certainly
suggests that there is some justification for
that approach, and the results obtained by
Johnson and Mall appear to substantiate their
need for composite joints in particular.
28.4.5 MECHANICAL BEHAVIOR OF
COMPOSITE ADHERENDS
28.4.5.1 Joint failure characteristics
Typical failure modes in structural joints are
illustrated in Fig. 28.61 which are indicative of
adherend rather than bond failures. In the case
of single lap joints (Fig. 28.61(a))bending fail-
ures of the adherends will occur because of
high moments at the ends of the overlap. For
metal adherends, bending failures take the
form of plastic bending and hinge formation,
MBOND while for composite adherends the bending
failures are brittle in nature. In the case of dou-
ble lap joints, peel stresses build up for thicker
adherends causing the types of interlaminar
failures in the adherends illustrated in Fig.
28.61(b).
28.4.5.2 Thermal stress effects
Thermal stresses are a concern in joints with
adherends having dissimilar thermal expan-
sion coefficients. Figure 28.62 illustrates the
660 Mechanical fastening and adhesive bonding

A. c

A 0. AND C INDICATE FAUURh I - E

(B) Double Lap hints

Fig. 28.61 Failure modes in composite adherends49,

50.

E; = E, 68.97GPa (10000 ksi); G,

= 1.04 GPa (150 ksi); f1/2 = f, =
2.54 mm (0.1 in); fb = 0.254 mm
(0.01 in); a, = 23.4 x lo4 "C-'(13 x
1O4 OF-'); a. = 1.8x 1O4"C (1 x
10-6°F-1
).
Cure temperature 121.1"C
(250°F);
Application temperature 23.9%
(75°F)
Loading stress 68.97MPa
(10 ksi).

Fig. 28.62 Thermal shear stresses in double lap joints: outer adherend 0 / 9 0 carbon epoxy; inner adherend
aluminum.
 Adhesive joints 661

effect of thermal stresses in a double lap joint
consisting of an aluminum inner adherend
and a 0/90° carbon epoxy outer adherend. The
stresses due to thermal mismatch between the
aluminum and composite arise if the cure tem-
perature of the bond is substantially different
from the temperature at which the joint is
used. The case considered here represents a
121°C (250°F) cure temperature for the adhe-
sive and a room temperature application, a
temperature difference of -79°C (-175"F),
which (see Tables 28.2 and 28.3) would result in
a strain difference of 0.002 between the alu-
minum and composite if no bond were present.
(The material combination considered here,
aluminum and carbon epoxy, represents the
greatest extreme in terms of thermal mismatch
between materials normally encountered in
joints in composite structures.) Thermal
stresses in bond layers of double lap joints can
be determined from the expressions given in
eqns (28.14-28.20). (These calculations are all
based on an assumed elastic response of the
adhesive.)
Hart-Smith3"39 provides corrections for
ductile response in the presence of thermal
effects. Figure 28.62 illustrates how the ther-
mal stresses combine with the stresses due to
structural load to determine the actual stress
distribution in the adhesive. The thermal
stresses in themselves develop an appreciable
fraction of the ultimate stress in the adhesive,
and although they oppose the stresses due to
structural loading at the left end, they add at
the right end and give a total shear stress that
is somewhat beyond the yield stress of typical
adhesives, even with as small a structural
loading stress as 69 MPa (10 ksi). Similar
effects occur with the peel stresses, although
the peel stresses due to thermal mismatch
alone have the same sign at both ends of the
joint; with a composite outer adherend the
thermally induced peel stresses are negative,
which is beneficial to joint performance.
Peak peel and shear stresses obtained from
these relationships for various combinations
of metal and composite adherends whose
properties are given in Tables 28.2 and 28.3 are
shown in Table 28.4. For joints with an alu-
minum inner adherend, the difference in
thermal expansion between the adherends is
relatively large, giving considerably higher
thermal stresses for the most part. In addition,
carbon epoxy has a particularly low thermal
expansion, which tends to produce higher
thermal stresses with carbon epoxy adherends
in combination with metals than do other
composites. Note that boron epoxy in combi-
nation with titanium gives particularly small
thermal stresses because of similarity of the
thermal expansion coefficients shown in
Tables 28.2 and 28.3 for these materials. As
Table 28.3 Generic metal properties (MIL-HDBK-5
1983)
Ti6-Al4-4V 1025 2014
Steel Aluminum
Young's 110.3 206.9 69.0
modulus,
GPa
Poisson 0.3 0.3 0.3
ratio
a, 10" OC-1 8.82 10.26 23.4

Table 28.2 Generic mechanical properties of composites (C.C. Chamis NASA Lewis Research Center,
NASA TM-86909,1985)

Unidirectional lamina 0/90 Laminate

Composite E,, GPa E , GPa vLT aL,10-6 "C-' aT,1 P OC-l E x GPa ax1 k6O C - I
Boron epoxy 201 20.1 0.17 11.7 30.4 113.8 8.6
S-glass epoxy 60.7 24.8 0.23 3.78 16.7 43.72 7.92
Carbon epoxy 137.9 6.90 0.25 0.72 29.5 72.6 2.34
662 Mechanical fastening and adhesive bonding

Table 28.4 Bond layer thermal stress in double lap joints (0/90 composite outer adhered, metal inner
adherend)

Boron epoxy Glass epoxy Carbon epoxy

-
Titanium
Shear stress, MPa 0.419 2.33 15.64
(ksi) 0.061 0.338 2.27
Peel stress, MPa -0.465 -3.73 -19.43
(ksi) -0.067 -0.541 -2.817
Steel
Shear stress, MPa 5.44 7.99 26.22
(ksi) 0.789 1.16 3.80
Peel stress, MPa -6.30 -15.0 -38.1
(ksi) -0.914 -2.17 -5.52
Aluminium
Shear stress, MPa 27.7 28.2 40.47
(ksi) 4.02 4.08 5.86
Peel stress, MPa -24.4 40.1 -44.6
(ksi) -3.54 -5.82 -6.47
t, = 5.08 mm (0.2 in); to adjusted for equal adherend stiffnesses;t, = 0.253 nun (0.1 in). Adhesive properties: shear mod-
ulus, 1.03 GPa (150 ksi); peel modulus, 3.49 GPa (500 ksi). Give temperature, 121°C (250°F).Application temperature,
24°C (75°F).

discussed earlier, the 'peel' stresses shown in tion for metal adherends which are relatively
Table 28.4 are all negative (i.e. compressive) stiff with respect to transverse shear deforma-
because of the location of the composite on the tion, but for polymer matrix composite
outside of the joint, although the shear stresses adherends which have low transverse shear
are unaffected by this aspect of the joint. moduli, transverse shear deformations are
Composite repair patches on aluminum air- more significant and can have an important
craft structures benefit from this type of influence on bond layer shear stresses. A use-
behavior, in that peel stresses are not a prob- ful correction to the classical Volkersen
lem for temperatures below the cure solution which allows for transverse shear
temperature. Placing the metal rather than the deformations in the adherends can be
composite on the outside of a double lap joint obtained by modifying the shear modulus of
would reverse the signs of the peel stresses the adhesive from its actual value, Gb, to an
making them tensile and aggravating the effective value, Gb)eff,given by
effects of differential thermal expansion of the
adherends. (28.44)

28.4.5.3 Transverse shear and stacking

sequence effects in composite adherends
Classical analyses such as the Volkersen shear
lag model for shear stresses in the bond layer
(Sections 28.4.3.3 and 28.4.3.4.1) are based on
the assumption that the only significant defor-
mations in the adherends are axial, and that
they are uniformly distributed through the
adherend thicknesses. This is a good assump-
where Ksh = 1 +
Here GUo and Gxzi are the transverse shear
moduli of the adherends. For the double lap
joint, the parameter /?appearing in eqn (28.14)
(see the third equation of the top row of eqn
(28.14)) is then modified by replacing Gb by
Gb/K,,, using the value for Ksh given in eqn
(28.44), and all the expressions in eqns

(28.15-20) for stresses in the bond layer are
modified by the resulting alteration of p. The
correction given here amounts to treating 1/ 3
the thickness of each adherend as an extension
of the bond layer, and assigning the shear stiff-
ness of the adherend for that part of the
effective bond layer. The factor 1/3 corre-
sponds to a linear distribution of shear stress
through the adherend thicknesses, which is
consistent with the assumption that the axial
deformations are approximately uniform
through the adherend thickness.
As an example, consider joint with a 0/90
carbon epoxy outer adherend joined to an alu-
minum inner adherend, with adherend
thicknesses of 2.53 mm (0.1 in) and 5.06 mm
(0.2 in), respectively, and a 0.253 mm (0.01 in)
bond thickness. Assume a shear modulus of
the bond layer of 1.06 GPa (150 ksi) and trans-
verse shear moduli of 4.82 GPa (700 ksi) for the
composite adherend and 26.5 GPa (3800 ksi)
for the aluminum. A value of 1.839 is then
obtained for Ksh, and the value of p and the
maximum shear and peel stresses which
depend on it are reduced by a factor of (Ksh)1/2
or 1.36 for this case. The shear and peel
stresses are therefore approximately 30%
lower than the values predicted with the
unmodified bond shear modulus. This type of
correction can be shown to give relatively
good predictions of the adhesive stresses in
comparison with finite element analyses. In 11. Lenoe, E., Oplinger, D.W. and Burke, J,J.,
addition, the departure of Ksh given in eqn
(28.44) from 1 gives a good indication of the
range of joint parameters for which adherend
shear deformations are important.
REFERENCES
1. Waszczak, J.P. and Cruse, T.A., A synthesis proce-
dure of mechanically fastened joints in advanced
materialsJ Air Force
Laboratory Report AFML-TR-73-145 (1973).
2. Oplinger, D.W. and Gandhi, K.R., Stresses in
mechanically fastened orthotropic laminates. In
Proc. Zst Con5 Fibrous Composites in Flight Vehicle
Design, Air Force Flight Dynamics Laboratory
Report AFFDL-TR-74-103 (1974).
References 663
3. Oplinger, D.W. and Gandhi, K.R., Analytical
studies of structural performance in mechani-
cally fastened fiber-reinforced plates. In Proc.
A r m y Solid Mechanics Conf. 1974, Army
Materials and Mechanics Research Center
Manuscript Report AMMRC MS 74-8 (1974).
4. Garbo, S.P., Ogonowski, J.M. and Reiling, H.E.,
Jr, Effect of variances and manufacturing tolerances
on the design strength and life of mechanically fas-
tened composite joints. v2 Air Force Wright
Aeronautical Laboratories Report AFWAL-TR-
81-3041 (1981).
5. Hyer, M.W. and Klang, E.C., Contact stresses in
pin-loaded orthotropic plates, Virginia Tech Center
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CCMS-84-02 (1984).
6. Ramkumar, R.L., Saether, E.S. and Appa, K.,
Strength analysis of laminated and metallic plates
bolted together by many fasteners, Air Force Flight
Dynamics Laboratory Report AFWAL-TR-86-
3034 (1986).
7. Madenci, E. and Illeri, L., Analytical determina-
tion of contact stresses in mechanically fastened
composite laminates with finite boundaries.
Intern. J. Solids Sfructures 30, pp. 2469-2484
(1993).
8. Crews, J.H. and Naik, R.A., Combined bearing
and bypass loading on a graphite/epoxy lami-
nate. Composite Structures, 6, pp. 2148 (1986).
9. Hart-Smith, L.J., Mechanically-fastened joints
for advanced composites - phenomenological
considerations and simple analyses. In Fibrous
Composites in Structural Design. New York:
Plenum Press (1980)pp. 543-574.
10. Petersen, R.L., Stress Concentration Factors. New
York: John Wiley and Sons (1974)p. 135.
Fibrous Composites in Structural Design. In
Proc. 4 f h Con& Fibrous Composites in Structural
Design, New York: Plenum Press (1980).
12. Oplinger, D.W., On the Structural Behavior of
Mechanically Fastened Joints in Composite
Structures. In Fibrous Composites in Structural
Design, New York Plenum Press (1980) pp.
575-602.
13. Nelson, W.D., Bunin, B.L. and Hart-Smith, L.J.,
Critical Joints in Large Composite Aircraft
Structure. In pyoc. 6th Con$ Fibrous Composites in
Structural Design, Army Materials and
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AMMRC MS 83-2 (1983), pp. u-2to II-38.
14. whitney, J.M. and Nuismer, R., stress fracture
criteria for composites containing
664 Mechanical fastening and adhesive bonding

stress concentrations. J. Composite Materials, 8, (1944).

pp. 253-265d (1974). 28. Kutscha, D. and Hofer, K., Feasibility of joining
15. Garbo, S.P. and Ogonowski, J.M., Efect of vari- advanced composite Fight vehicle structures, Air
ances and manufacturing tolerances on the design Force Materials Laboratory Report AFML-TR-
strength and life of mechanically fastened composite 68-391 (1968).
joints, Air Force Flight Dynamics Laboratory 29. Dickson, J.N., Hsu, T.N. and McSkinney, J.N.,
Report AFFDL-TR-78- 179 (1978). Development of an understanding of the fatigue phe-
16. Chang, EK. and Hung, Chang-Li, Response of nomena of bonded and bolted joints in advanced
double shear-lap bolted composite joints under mul- filamentary composite materials. Vol. 1, Analysis
tiple bypass loads. Standford University Dept. of Methods, Lockheed Georgia Aircraft Company,
Aeronautics and Astronautics Report, Doctoral USAF Contract Report AFFDL-TR 72-64, vol I
dissertation of Chang-Li Hung. (1993). (June 1972).
17. Garbo, S.P., Efjrects of bearingbypass load interac- 30. Grimes, G.C., Wah, T. et al., The development of
tion on laminate strength, Air Force Flight non-linear analysis methods for bonded joints in
Dynamics Laboratory Report AFWAL-TR-81- advanced filamentary composite structures, South-
3114 (1981). West Research Institute, USAF Contract Report
18. Naik, R.A. and Crews, J.H., Jr., Ply-level failure AFML-TR-72-97 (September 1972).
analysis of a graphitelepoxy laminate under bear- 31. Renton, W.J., The analysis and design of composite
ing/bypass loading, NASA Technical materials bonded joints under static and fatigue
Memorandum 100578 (1988). loadings, PhD Thesis, University of Delaware
19. Hart-Smith, L.J., Design methodology for bonded- (1973).
bolted composite joints. v l Air Force Wright 32. Renton, W.J. and Vinson, J.R., The analysis and
Aeronautical Laboratories Report AFWAL-TR- design of composite materials bonded joints under
81-3154 (1982). static and fatigue loadings, Air Force Office of
20. Ramkumar, R.L., Saether, E. and Cheng, D., Scientific Research Report TR-73-1627 (1973).
Design guide for bolted joint in composite struc- 33. Oplinger, D.W,. Stress analysis of composite
tures, Air Force Wright Aeronautical joints. In Proc. 4th Army Materials Technology
Laboratories Report AFWAL-TR-88-3035 (1986). Con$, Newton, MA: Brook Hill Publishing Co.
21. Shivakumar, K.N. and Crews, J.H., Jr., Bolt (1975), pp. 405-451.
clamp-up relaxation in a graphitelepoxy laminate, 34. Hart-Smith, L.J., AFFDL-TR-72-130, pp.
NASA Technical Memorandum 83268 (1982). 813-856.
22. Slepetz, J.M, Oplinger, D.W. and Andrews, B. 35. Hart-Smith, L.J, Adhesive bonded double lap joints,
O., Bolt tension relaxation in composite friction NASA Langley Contractor Report, NASA CR-
joints. In Proc. 7th Con$ Fibrous Composites in 112235 (1973).
Structural Design, Wright Patterson 36. Hart-Smith, L.J., Adhesive bonded single lap joints,
Aeronautical Laboratories Report AFWAL-TR- NASA Langley Contractor Report, NASA CR-
85-3094 (1985). 112236 (1973).
23. Harris, H.G., qalvo, I. and Hooson, R.E., Stress 37. Hart-Smith, L.J., Adhesive bonded scarf and
agd deflection analysis of mechanically fastened stepped-lap joints, NASA Langley Contractor
joints, Air Force Flight Dynamics Laboratory Report, NASA CR-112237 (1973).
Report AFFDL-TR-70-49 (1970). 38. Hart-Smith, L.J., Analysis and design of advanced
24. Shyprykevich, P., Characterization of bolted joints composite bonded joints, NASA Langley
behavior, MIL-HDBK-17 Accomplishments at Contractor Report, NASA CR-2218 (1973).
Standardization ASTM J. Composite Technical 39. Hart-Smith, L.J., Advances in the analysis and
Research, 17(3),pp. 260-270 (1995). design of adhesive-bonded joints in composite
25. Military Handbook MIL-HDBK-17: Polymer aerospace structures. In SAMPE Process
Matrix Composites (1992). Engineering Series, 19, pp. 722-737 Asuza:
26. Volkersen, O., Die Nietkraftverteilung in SAMPE, (1974).
Zugbeanspruchten Nietverbindungen mit 40. Primary adhesively bonded structure (PABST) tech-
Konstanten Laschenquerschnitten. nology, Air Force Contract F33615-75-C-3016
Lufffahnforschung, 15, pp. 4-47 (1938). (1975).
27. Goland, M. and Reissner, E., Stresses in 41. Thrall, E.W., Primary adhesively bonded structure
cemented joints. J. Appl. Mech., 11, A17-27 technology (PABST) Phase 7 b: Preliminary Design,

Air Force Flight Dynamics Laboratory Report
AFFDL-1R-76-141 (1976).
42. Shannon, R. W. et al., Primary adhesively bonded
structure technology (PABST): General Material
Property Data, Air Force Flight Dynamics
Laboratory Report AFFDL-TR-77-101 (1977).
43. Land, K.L., Lennert, F.B. et a/., Prima ry adhesively
bonded structure technology (PABST): Tooling,
Fabrication and Quality Assurance Report, USAF
Technical Report AFFDL-TR-79.3154 (October,
1979).
44. Hart-Smith, L.J., Adhesive bond stresses and
strains at discontinuities and cracks in bonded
structures. Trans. J. Engng Mater. Tech., 100, pp.
128-144 (1978).
45. Hart-Smith, L.J., Differences between adhesive
behavior in test coupons and structural joints,
Douglas Aircraft Company Paper 7066.
Presented to ASTM Adhesives Committee D- 14
Meeting, Phoenix, Arizona, 1981.
46. Hart-Smith, L.J., Design methodology for bonded-
bolted composite joints, Douglas Aircraft
Company, USAF Contract Report AfWAL-TR-
81-3154, Vol I and I1 (February 1982).
47. Thrall, E.W., Jr., Failures in adhesively bonded
Structures, AGARD-NATO Lecture Series No.
102, ‘Bonded Joints and Preparation for
Bonding’, Oslo, Norway and The Hague,
Netherlands, April 1979 and Dayton, Ohio,
October 1979.
48. Hart-Smith, L.J., Further developments in the
design and analysis of adhesive-bonded structural
joints, Douglas Aircraft Company Paper 6922.
Presented at the ASTM Symp. Joining of
Composite Materials, Minneapolis, MN, April
1980.
49. Hart-Smith, L.J., Adhesive bonding of aircraft pri-
mary structures, Douglas Aircraft Company
Paper 6979. Presented to SAE Aerospace
Congress and Exposition, Los Angeles,
California, October 1980.
50. Hart-Smith L.J., Stress analysis: a continuum
analysis approach. In Developments in Adhesives
- 2 (ed. A. J. Kinloch), London: Applied Science
Publishers, pp. 1-44(1981).
51. Hart-Smith, L.J. and Bunin, B.L., Selection of
taper angles for doublers, splices and thickness
transition in fibrous composite structures. In
Proc. 6th Conf. Fibrous Composites in Structural
Design, Army Materials and Mechanics
Research Center Manuscript Report AMMRC
MS 83-8 (1983).
52. Nelson, W.D., Bunin, B.L. and Hart-Smith, L.J.,
References 665
Critical joints in large composite aircraft struc-
ture. In Proc. 6th Conf. Fibrous Composites in
Structural Design, Army Materials and
Mechanics Research Center Manuscript Report
AMMRC MS 83-8 (1983).
53. Oplinger, D.W., A layered beam theory for single
lap joints, US Army Materials Technology
Laboratory Report MTL TR 91-23 (1991).
54. Oplinger, D.W., Effects of adherend deflections
on single lap joints. Int. J. Solids Structures, 31
(18), pp. 2565-2587 (1994).
55. Hart-Smith, L.J., Adhesively bonded joints in
fibrous composite structures, Douglas Aircraft
Paper 7740. Presented to the Intern. Symp.
Joining and Repair of Fibre-Reinforced Plastics,
Imperial College, London (1986).
56. Hart-Smith, L.J., Induced peel stresses in adhesive-
bonded joints, Douglas Aircraft Company,
Technical Report MDC-J9422A, August 1982.
(see also USAF Report AFWAL TR-82-4172,
(1982).)
57. Hart-Smith, L.J., Brown, D. and Wong, S.,
Surface preparations for ensuring that the glue will
stick in bonded composite structures, 10th
DoD/NASA/FAA Conf. Fibrous Composites in
Structural Design, Hilton Head Is, SC (1993).
58. Hart-Smith, L.J., Ochsner, W. and Radeckv, R.
L., Surface preparation of fibrous composites
for adhesive bonding or painting. Douglas
Service Magazine, 1, pp. 12-22 (first quarter
1984).
59. Hart-Smith, L.J., Ochsner, W. and Radecky, R.
L., Surface preparation of fibrous composites
for adhesive bonding or painting. Canadair
Service News, 2, pp. 2-8 (1985).
60. Hart-Smith, L.J., Effects of adhesive layer edge
thickness on strength of adhesive-bonded joints,
Quarterly Progress Report No. 3, Air Force
Contract F33615-80-C-5092 (1981).
61. Hart-Smith, L.J., Effects of flaws and porosity on
strength of adhesive-bonded joints, Quarterly
Progress Report No. 5, Air Force Contract
F33615-80-C-SO92 (1981).
62. Frazier, T.B. and Lajoie, A.D., Durability of adhe-
sive joints, Air Force Materials Laboratory
Report AFML TR-74-26, Bell Helicopter
Company (1974).
63. Becker, E.B. et al., Viscoelastic stress analysis
including moisture difision for adhesively bonded
joints, Air Force Materials Laboratory Report
AFWAL-TR-84-4057 (1984).
64. Jurf, R. and Vinson, J., Efects of moisture on the
static and viscoelastic shear properties of adhesive
666 Mechanical fastening and adhesive bonding
joints, Dept. of Mechanical and Aerospace
Engineering Report MAE TR 257, University of
Delaware (1984).
65. Mostovoy, S., Ripling, E.J. and Bersch, C.F.,
Fracture toughness of adhesive joints. J.
Adhesion, 3, pp. 125-144. (1971).
66. DeVries, K.L., Williams, M.L. and Chang, M.D.,
Adhesive fracture of a lap shear joint.
Experimental Mechanics, 14, pp. 89-97 (1966).
67. Trantina, G.G., Fracture mechanics approach to
adhesive joints, University of Illinois Dept. of
Theoretical and Applied Mechanics Report
T&AM 350, Contract N00019-71-0323 (1971).
68. Trantina, G.G., Combined mode crack extension in
adhesive joints, University of Illinois Dept. of
Theoretical and Applied Mechanics Report
T&AM 350, Contract N00019-71-C-0323 (1971).
69. Keer, L.M., Stress analysis of bond layers. Trans.
ASME J. Appl. Mech. E., 41, pp. 79-83 (1974).
70. Knauss, J.F., Fatigue life prediction of bonded pri-
mary joints, NASA Contractor Report
NASACR-159049 (1979).
71. Wang, S.S. and Yau, J.F., Analysis of interface
cracks in adhesively bonded lap shear joints, NASA
Contractor Report NASA-CR- 165438 (1981).
72. Johnson, W.S. and Mall, S., A fracture mechanics
approach for designing adhesively bonded
joints. In Delaminafion and Debonding of
Materials, ASTM Special Technical Publication
STP 876, American Society for Testing and
Materials, pp. 189-199 (1985).
73. Tsai, M.Y. and Morton, J., On numerical and
analytical solutions to the single lap joint.
Intern. J. Solids and Structures (1994).
74. Benson, N.K., Influence of stress distribution on
strength of bonded joints. In Adhesion,
Fundamentals and Practice, New York: Gordon
and Breach, (1969), pp. 191-205.
75. Adams, R.D. and Wake, W.C., Structural
Adhesive Joints in Engineering, Amsterdam:
Elsevier Applied Science Publishers (1984).
76. Kuenzi, E. and Stevens, G., Determination of
mechanical properties of adhesives for use in the
design of bonded joints, Forest Products
Laboratory Note FPL-011 (1963).
77. Snedon, I., The distribution of stress in adhesive
joints. In Adhesion, (ed. D.D. Eeley), Ch. 9,
Oxford: Oxford University Press (1962).
78. Carpenter, W., Goland and Reissner were cor-
rect. J. Strain Analysis, 24(3), pp. 185-187 (1989).
79. Hart-Smith, L.J., Further developments in the
design and analysis of adhesive-bonded struc-
tural joints. In Joining of Composite Materials,
American Society for Testing of Materials
Special Technical Publication ASTM STP 749
(1981).
80. Hart-Smith, L.J., In Fiber Composite Analysis and
Design, Federal Aviation Administration
Technical Center Report DOT/FAA/CT-88/18,
Vol. 2, Ch. 3 (1988).
81. DoD/NASA Advanced Composites Design
Guide, 1983.
SURFACE PREPARATIONS FOR ENSURING 29
THAT THE GLUE WILL STICK IN BONDED
COMPOSITE STRUCTURES
L.J. Hart-Smith, D. Brown and S. Wong

29.1 INTRODUCTION 29.2 HISTORICAL BACKGROUND

Adhesively bonded joints can be no stronger During the late 1970s and early 1980s, the
than the interface between the adhesive and Douglas Aircraft Company at Long Beach,
the members being bonded together. In-ser- California, was the site of one of the techni-
vice bond failures have always been cally most successful research contracts ever
associated with weak interfaces, for both metal funded by the Wright-Patterson Air Force
and composite adherends. While most people Laboratories - the Primary Adhesively
acknowledge that adhesive bonding of metal- Bonded Structure Technology (PABST) pro-
lic structures requires strict adherence to gram. This research was directed at
proper processes, many people unthinkingly well-known problems concerning the adhe-
accept the notion that it is easy to make epoxy sive bonding of metallic aircraft structures.
stick to epoxy, for example, and pay no atten- These problems were the need to change con-
tion to the need for proper processing for the temporary processing from etching to
adhesive bonding of composite structures. anodizing, and the need to select adhesives
This chapter begins with a historical review and primers on the basis of long-term dura-
of the need for appropriate surface treatment to bility rather than short-term strength. These
ensure that the glue will stick to composite sur- failings had been made very clear by wide-
faces. It then focuses on photomicrographs of spread in-service problems experienced for
different surfaces, to which the adhesive will or many years by both commercial and military
will not stick, as a basis for inspections prior to operators. A successful outcome to the
bonding. Such prebond inspections are vital research was assured because of the success
because of the inability to detect weak bonds of the Redux bonding developed in England
after manufacture, until they have fallen apart. during WWII and since employed exten-
The characterization of the surfaces prepared sively by Fokker. The PABST program
by different techniques can assist in formulat- succeeded in all of its objectives, bar one. It
ing process specifications that will ensure omitted a large-scale flight demonstration
reliable adhesive bonding and in identifying program, because it would have solved no
past practices that should be discontinued. problem that had not already been solved by
the successful ground testing of panels and a
Handbook of Composites.Edited by S.T. Peters. Published complete wide-body fuselage barrel with
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 simulated wing center section. However, in
668 Suface preparationsfor ensuring that the glue will stick in bonded composite structures
retrospect, such a demonstration was neces-
sary as a public relations exercise to convince
the decision makers to apply the technology,
where appropriate, on the primary structure
of large aircraft. Nevertheless, the technology
did not die. The combination of phosphoric
acid anodizing for aluminum alloys, a pheno-
lic-based corrosion-inhibiting primer and
adhesives formulated to resist the absorption
of water has since been applied very exten-
sively on the primary structures (wings,
fuselages, and tails) of Cessna and SAAB air-
craft with excellent results.
The composites bonding industry could be
described today as being in the same state that
metal bonding was in 25 years ago, but with
one big difference. The need to properly pre-
pare the surfaces of composite laminates prior
to bonding is acknowledged only by those
who have suffered a major problem from hav-
ing failed to do so on some previous occasion.
Ironically, there are many researchers and pro-
duction engineers worldwide who are aware
of the problems and their causes. However,
there is no highly visible activity like the
PABST program to draw attention to the
issues. This chapter cannot be expected to
solve these problems, but it is hoped that it
will raise the level of awareness of the subject
and that its content will help achieve better
bonded composite structures by providing
standards for inspecting the surfaces before
bonding, rather than creating the impossible
situation of trying to detect weak bonds after
bonding. What is needed is a method that will
ensure a reliable bond every time, using pro-
cedures to which all manufacturers of
composite structures will be willing to adhere.
The first part of this challenge has already
been accomplished: light grit-blasting or thor-
ough mechanical abrasion has been shown to
work. Unfortunately, more often than not,
films of adhesive are applied to the surfaces
left by the removal of a peel ply without any
surface treatment. Most, and possibly all, peel
plies are known not to create a suitable surface
for bonding, at least when used with laminat-
ing resins or adhesives. They create a weak
interface, with failure occurring at only a frac-
tion of the strength that would have been
developed by grit-blasting. However, the
resulting weak bonds cannot be detected by
conventional ultrasonic nondestructive
inspection. Also, most bonded composite
structures are so thin that they will not fall
apart even if the bond has as little as one-tenth
of the strength of a properly processed bond.
Consequently, little has been done about the
problem, in the mistaken belief that doing so
would incur an unnecessary expense.
On the contrary, even if local bond failures
can be tolerated structurally, once they become
detectable in service they cause expensive
inspection programs and possibly rework, not
necessarily to add to the strength of the parts,
but to prevent the flaws from being detected
and repaired again on subsequent inspections.
Failing to ensure that the glue sticks properly
in the first place is definitely a false economy.
The delay in solving the corresponding prob-
lems on bonded metal structure gave the
technology such a bad name in the USA that it
was the direct cause of the extensive use of riv-
eted structure when bonding would have been
lighter, less expensive, and more durable, with
better than a twentyfold reduction in the inci-
dence of fatigue cracks and a dramatic
improvement in damage tolerance. Lest the
same preference for mechanical fastening
rather than bonding continue to be followed
for thin composite structures, it should be
noted that the typical fasteners cost about a
hundred times as much as the simple rivets
used with aluminum structures. Worse, the
minimum diameter of the specialty fasteners
for composites is 50% larger than the diameter
of comparable rivets. Conventional aluminum
rivets are not used for carbon composite struc-
tures because of concern about galvanic
corrosion, between the rivets and the carbon
fibers, so composite structures that could have
been bonded must be locally reinforced to be
mechanically fastened instead, adding to both
the cost and weight.

There are, then, very great incentives for
reliable processing of adhesive bonds in com-
posite structures. There is also no hstory of
properly processed composite bonds failing in
service. (This is also true of metal bonding. All
in-service failures are the result of environ-
mental attack, at load levels far too low to
have initiated mechanical failure of the bonds.
Testing during the PABST program of coupons
cut from retired aircraft stored at Davis-
Monthan, Arizona, showed that there was no
structural deterioration after 20 years.)
There are others that call for improvements
in surface preparation for bonding of compos-
ites. Robert Schliekelmann, the famous pioneer
of Redux bonding at Fokker, was sufficiently
concerned about the failure to recognize the
need for proper surface treatment of compos-
ites as well as metals to make a plea’ for more
attention to this issue. Almost a decade ago,
Douglas engineers prepared an article on the
subject2to help the airlines until the repair man-
uals could be updated. The article was judged
to be of sufficient importance to be reprinted in
the Canadair house journal3.Every experiment
had to be repeated to create new photographs
and every phenomenon was duplicated,
thereby verifying that the problems discussed
in the original article really existed. A similar
concern was expressed in England, where
Parker and Waghom4 reported on a far more
comprehensive test program on the effects of
surface preparation on adhesive bond strength
for carbon-epoxy laminates. They also con-
cluded that ‘composite surfaces must be
abraded to achieve strong adhesive-bonded
joints.’ Pocius and Wentz advocated the use of
Scotchbrite pads with embedded abrasive par-
ticles as an effective and reliable technique for
achieving good composite bonds5. A recent
research program6 addressed both thermoset
and thermoplastic composites. Reference 6 also
cites other English research. The problems still
exist, on both sides of the Atlantic Ocean.
A more recent article on this subject7,voiced
concerns because of the reintroduction of infe-
rior techniques throughout much of the
Historical background 669
aerospace industry. It seems significant that,
today, some factories prohibit the use of bond-
ing directly to a composite surface created by
the mere removal of a peel ply and that the
automotive racing industry has experienced
the same kind of premature failures with peel-
ply treatments that the aerospace industry has
suffered. If what may be called the peel-ply
bonded joints were twice as strong as they
actually are, there would be little concern.
Conversely, if they were only half as strong,
the problem would have been more widely
recognized long ago and far more done about
it. The real problem with peel-ply bonded
joints is that, while quite unreliable in the eyes
of those closest to the subject, they usually
have sufficient strength to pass ultrasonic
inspections (because there are no gaps) and are
sufficiently strong some of the time that the
joints do not fail prior to delivery of the com-
ponent. This makes it difficult to present a
convincing case to non-technically minded
participants in the industry that there is a real
problem. One non-failure tends to be inter-
preted as complete success.
This chapter cannot possibly provide all the
answers on the subject of surface preparations
for composite bonding. It took a $20 million
5 year program to solve the corresponding
problems for metal bonding. It should also be
acknowledged that the concerns expressed
here are based exclusively on consistently bad
experiences with 180°C (350°F) cured epoxy
composites. (The problem may be associated
with the curing of the laminate and the peel
ply as much as with the adhesive.) It may also
be significant that most, if not all, of these
problems were associated with nylon peel
plies, whose use with a 180°C (350°F) cured-
laminate is believed by some polymer
chemists to be undesirable, because the nylon
may break down and transfer a thin film of
low-molecular weight material to the compos-
ite surface. Photographic evidence of this
phenomenon is included here. Such a surface
would be very difficult for an epoxy adhesive
to wet, because of too low a surface energy.
670 Surface preparationsfor ensuring that the glue will stick in bonded composite structures
The polymer chemists express less concern
about the use of nylon at 120°C (250"F), but
some adhesion failures of glued joints have
occurred with those materials also. The domi-
nant factor may be the low surface energy
level of the composite cured against a slick
peel ply, or one contaminated by a release
agent to ensure that it can be removed easily
without fracturing (damaging) the composite
laminate.
It is certain that the criteria by which manu-
facturers evaluate their peel plies are precisely
the opposite of those that someone else trying
to promote adhesion in a bonded joint would
follow. Some peel plies are even coated with
release agents to ensure that they can be
removed easily without damaging the basic
laminate. Silicone transfer has been observed
with some peel plies supposedly totally free of
contamination. What is needed to create a
bondable surface is a tear ply that will remove
a small amount of surface resin over the entire
area to be bonded. However, peel plies known
to be capable of achieving this are almost
invariably shunned because they are so hard
to peel off, because they break and inevitably
lead to local contamination as the process is
restarted, or because there is concern that the
interior of the laminate will be damaged.
It cannot be asserted on purely technical
grounds that there are no circumstances under
which some peel plies will produce an ade-
quate surface for adhesive bonding. It stands
to reason that some users of this approach
have been spared the problems Douglas and
others have encountered, or the products
would have all been removed from the mar-
ketplace. However, it is likely that still others
have also suffered, but are unaware of the
cause of their problems. Nevertheless, the
argument against peel plies is irrefutable on
economic grounds. The cost of investigating
weak bonds has been far, far greater than
would have been incurred if Douglas had
insisted that all suppliers and subcontractors
lightly grit-blast or thoroughly hand-sand
composite surfaces following removal of the
peel plies. Not one in-service delamination has
occurred in those composite structures pre-
pared for bonding by the grit-blast technique.
It is hoped that this chapter will inspire
those who believe that their structural adhe-
sive bonds are both strong and reliable to
assess composite surfaces prior to bonding. (A
request for information from a major US aero-
space manufacturer about a peel ply different
from those used at Douglas resulted in their
switching to another peel ply. Microscopic
examination of the surface to be bonded made
it clear to them that one of their problems
could be tied directly to the choice of a new
peel ply. Once alerted, they checked all related
procedures and even changed one of their old
and trusted peel plies once its true capabilities
had been exposed.)
This chapter concentrates exclusively on the
issue of surface preparation. Obviously, one
must also follow correct thermal and pressure
profiles during cure to achieve a properly
cross-linked adhesive that has a chance to flow
and wet the surface to which it is to be
bonded. Prebond moisture, in both laminates
and adhesives, is also known to be a major
cause of weak bonds. These and other impor-
tant issues are discussed in References 7 and 8.
This does not imply that they are any less
important.
We now present electron-micrographs of
glue that failed to stick to the composite, com-
posite surfaces to which the adhesive did not
stick, similar surfaces to which the glue will
not stick, surfaces to which adhesive is known
to have stuck in the past, and surfaces to
which it is hoped it will stick. The effectiveness
of light grit-blasting as a reliable surface treat-
ment has already been established. It was used
on all bonded joints of the Lear Fan all-com-
posite aircraft9, creating bonds stronger than
the surrounding structure even when half the
overlapping area was disbanded because of
inappropriate solid-rubber tooling used for
the fuselage skin splices. The bond to the grit-
blasted surface was so strong, where the
mating surfaces were brought properly into
 The problem - weak bonds 671

contact, that 100%bonding was not necessary. area with a different texture is part of the sur-
Grit-blasting is used today on some of the face ply of unidirectional carbon-epoxy left
most trouble-free composite components on when the remainder separated. The reason
the MD-11 aircraft; specifically, the compo- why this very small segment adhered is
nents made in Japan. However, some unknown. It is almost as if there were one
manufacturers of bonded composite structures small drop of chemical acting like a wetting
will prefer to continue to use peel-ply-only agent on the composite when it was bonded.
surface preparations, no matter how weak or If this should prove to be the case, and
unreliable the resulting bonds are. One must research can identify an agent capable of pro-
find different peel plies that do not release moting the wettability of cured epoxy in a
cleanly, but which take some of the surface laminate by uncured epoxy in an adhesive
resin with them, without damaging the layer, it would be a giant contribution to com-
remainder of the matrix, or find a coupling posites technology. The idea of a coupling
agent to improve the behavior of what are agent, equivalent to the silanes used for
known today to be unsatisfactory peel plies no epoxy-bonding of aluminum alloys during
matter how widely they may be used, or trans- repairs, is apparently feasible for composites
fer the production to factories in which reliable also - at least when the peel ply has not been
surface-treatment practices are followed. coated with a release agent. Coupling agents
would be more likely to work if the basic lam-
inate were not fully cured prior to bonding.
29.3 THE PROBLEM - WEAK BONDS
One would prefer an incomplete initial cure in
No more convincing proof of the existence of order to leave some active chains in the mole-
weak bonds created on peel-ply composite cular structure of the composite to which the
surfaces can be found than in Fig. 29.1. This is glue could bond. The bond cycle would then
a scanning electron microscope (SEM) pho- be relied upon to complete the cure of the
tomicrograph not of a composite surface after laminate and this process might affect the
the peel ply was lifted off, but of the cured choice of adhesive. However, such an out-
adhesive, showing the imprint left by the com- come must be preceded by an
posite laminate after it peeled off! The small acknowledgment that the remainder of
Fig. 29.1 and the large similar surrounding
area imply the existence of a problem.
Figure 29.2 shows the same lack of adhesion
evident in Fig. 29.1 at a small magnification
over a very much larger area, to show how
widespread this phenomenon can be. The tex-
ture of the peel ply is clearly imprinted in the
glue over almost the entire area. The different
texture visible on the left side of the figure is
the peel-ply imprint on the underlying com-
posite laminate. In this area, the adhesive
failed to bond to the lower surface.
Throughout everywhere else shown in Fig.
29.2, the adhesive failed to bond to the other
composite part, the peel-ply imprint of which
is embossed on the adhesive. Figure 29.3
Fig. 29.1 Imprint of peel ply, in background, on shows an adjacent area on the same-part. The
cured adhesive film that failed to adhere (mag x30). thick glue layer (shiny area) at the bottom left
672 Surface preparations for ensuring that the g2ue will stick in bonded composite structures
Fig. 29.2 Large area of adhesive that failed to bond,
showing imprint of peel-ply surface (mag X5).
of Fig. 29.3 shows the unmistakable imprint of
the fine-weave peel ply left by the other com-
posite part where it did not stick. Immediately
above it, there is a small area of cohesive frac-
ture of the bond. (The reason for bonding in
just that small area is not known.) The dark
area in the lower right of Fig. 29.3 shows the
imprint of the peel ply in the composite under-
neath the adhesive layer. The small vertical
white lines define the fine weave of the peel
ply. The more widely spaced larger white
blotches, with some sharply defined edges,
reveal the very small extent of the sanding car-
ried out on this sample. The white blotches are
the high points in the coarser weave of the
plain-weave cloth in the basic laminate. These
are evident on the surface opposite from that
cured against the lay-up tool.
These large white blotches in Fig. 29.3 illus-
trate one unavoidable problem with sanding
as a surface preparation. How can one sand
down to the bottom of every depression in the
fine-weave texture left by the peel ply without
sanding into the fibers at the top of every
raised bump in the texture of the composite
material itself? This problem is aggravated by
the use of woven fabrics rather than unidirec-
tional tape and is unavoidable on the bag side
of the laminate, unless a caul plate is used on
both sides. The customary use of dry (nonim-
pregnated) peel plies, which absorb resin from
the surface plies of the laminate, results in
such an ultrathin layer of surface resin that it is
Fig. 29.3 Adhesive that failed to bond, also show-
ing sanding confined to high spots of the composite
weave (mag ~ 5 ) .
virtually impossible to sand the surface with-
out breaking the fibers. One needs to use
preimpregnated peel plies or to include a layer
of resin (or adhesive) film between the basic
lay-up and any dry peel ply to create what
amounts to a gel coat sufficiently thick to sand
as the surface for bonding or painting. It is also
impossible to completely sand a surface con-
taining ply drop-offs or local buildups. Only
light grit-blasting would work in such a case.
It should be noted that, at the time when the
bond shown in Figs. 29.1 to 29.3 was manufac-
tured, conventional ultrasonic inspection
failed to find any evidence of a defect. The gap
had not yet opened up even though an after-
the-fact inspection revealed almost no
adhesion throughout most of the area meant to
have been bonded. This is very significant.
Weak bonds cannot be detected by inspection
before they have failed. They can be prevented
only by adhering to process specifications that
ensure they will not occur.
Figure 29.4 shows the typical composite
surface left by removal of the same type of
peel ply (in this case, a corona-treated nylon
peel ply). A comparison with Fig. 29.1 will
leave no doubt about the origin of the surface
embossed into the cured adhesive layer.
(Scientific testing of this particular piece of
adhesive revealed nothing untoward about
the way it was cured, although there are

Fig. 29.4 Imprint of nylon peel ply in epoxy surface
of composite laminate (mag x65).
unconfirmable suspicions that prebond mois-
ture may have exacerbated the problem.)
An examination of the surface of the nylon
peel ply itself after removal from the laminate
revealed no resin adhering to the peel ply (Fig.
29.5). [Regrettably, this is not from the same
sample, even though it is nominally the same
peel ply cured in the same laminating resin, at
180°C (350"F).]Significantly, the other side on
the peel ply was covered by a considerable
amount of resin bled from the surface plies of
the laminate. This is most undesirable,
because most composite specifications call for
unreasonable resin starvation as the norm.
(The purpose of minimizing the resin content
is to boost the easily measured in-plane ten-
sion strength. Resin-dominated strengths are
both more difficult to measure and more diffi-
cult to analyze, so few such considerations are
included in the design process.) There is usu-
ally barely enough resin to hold the fibers
together. Removing surface resin makes it
more difficult to transfer loads through
bonded joints. It also makes the surface more
prone to impact damage and more difficult to
prepare for repainting in service. This is
acknowledged by the way in which some
Boeing components are now made with
preimpregnated peel plies despite the added
cost and storage and handling problems with
respect to dry ones.
The problem - weak bonds 673
Fig. 29.5 Enlargement of nylon peel ply after strip-
ping off composite laminate cured at 180°C (350°F)
(mag X41).
Higher resin contents in aerospace composite
structures do not necessitate no-bleed cure
cycles. They retain a higher resin content, but
they also prevent the removal of any volatiles
absorbed and trapped before cure or gener-
ated during the cure. The lack of volatile
removal introduces a whole new family of
processing problems and structurally inferior
laminates.
Figure 29.6 shows a greatly magnified view
of the same peel ply shown in Fig. 29.5. The
peeling motion was from right to left. (The cor-
responding picture to the left of the vertical
bundle of peel-ply fibers shows far less fractur-
ing of the matrix.) Noteworthy features shown
in Fig. 29.6 include (1) the tendrils of resin
around the vertical filament on the extreme
left, (2) the way the resin has pulled away
cleanly from the horizontal filaments on the
right of the adjacent vertical fiber, (3) striations
in the fracture surface of the resin between the
second and third horizontal filaments from the
top, (4)the loose piece of resin between the first
674 Surface preparationsfor ensuring that the glue will stick in bonded composite structures

in thick test coupons with impractically short

bonded overlaps, provided that the surface
treatment and cure are carried out properly.
The resulting fracture surface is shown greatly
magnified in Fig. 29.7. The randomly oriented
fibers are the carrier in the adhesive layer and
quite distinct from the regular patterns of
woven composite laminate and peel plies.
There is no possibility of mistaking this cohe-
sive fracture surface for either the interfacial or
interlaminar failures shown in Fig. 29.1.
I Apart from the grossly dissimilar surface
textures, most adhesives are distinctively col-
!
ored. Carbon-epoxy is invariably black. It is
very easy to distinguish between:
1. Cohesive failure of the adhesive with com-
plete coverage of both surfaces by the
adhesive layer.
2. Adhesion failure with all of the adhesive on
Fig. 29.6 Highly magnified view of peel ply one surface, although the adhesive may
removed from carbon-epoxy laminate cured at fracture and end up as small segments
180°C (350°F) (mag x41).
adhering to both surfaces, but only to one in
any given area (Fig. 29.8). The figure shows
and second horizontal filaments from the bot-
predominantly the surface of the adhesive
tom, and (5) the white markings on the nylon
to which the overlaying piece of composite
filaments themselves. At still higher magnifica-
tion, these markings appear to be crazing that
occurs within the nylon filaments as they were
bent while the peel ply was being stripped off.
The marks do not appear to be resin extracted
from the surface of the laminate. There was no
indication of any matching roughness in the
grooves left in the laminate for the samples that
did match this particular piece of peel ply,
although, as discussed later, there is some indi-
cation at very high magnification that ultrathin
layers of nylon transferred to some areas (but
not all) of the composite laminate as it cured.
(There was also no evidence of nylon transfer
when nominally the same peel ply was used
with a different resin matrix and cured at
120°C (250°F).
Had the adhesive in Fig. 29.1 stuck properly,
failure would have occurred interlaminarly
within the thin carbon-epoxy composite lami-
nate, with no adhesive visible anywhere. One Fig. 29.7 Cohesive fracture within adhesive bond
can enforce a cohesive failure of adhesive layers (mag x83).
 Samples of diferently prepared surfaces for bonding 675
Fig. 29.8 Predominantly adhesion failures in peel-
ply bonded joint (mag ~ 5 ) .
failed to adhere and local dark exposed
areas of the underlaying composite with the
peel-ply imprint made clearly visible as
those portions of the adhesive lifted off
with the upper piece of composite.
3. Interlaminar failure of the composite lami-
nate, with fibers on both surfaces. (Failure
close to the surface of the composite may
leave a transparent layer of resin matrix
covering the adhesive, but microscopic
examination will reveal a very different
fracture surface from that associated with
the adhesion failure shown in Fig. 29.1.)
Naturally, there can be no photograph equiva-
lent to Fig. 29.1 for a grit-blasted surface
because the interface will not fail unless it was
deliberately contaminated prior to bonding.
29.4 SAMPLES OF DIFFERENTLY PREPARED
SURFACES FOR BONDING
The remainder of this chapter will provide a
comparison between photomicrographs of dif-
ferent surface preparations, good and bad.
Figure 29.9 shows the surface left by light
grit-blasting with alumina grit at 140 kPa
(20 psi). Although resin has been removed
from the entire surface, so little has been
removed that the texture of the peel ply is still
evident. The uniformity of the surface treat-
ment, prepared under less than ideal
conditions with no handling aids, is impres-
sive and suggests that the procedure is not
unreasonably demanding, particularly when
done with suitable equipment. A very highly
magnified photo (Fig. 29.10) confirms that no
damage was done to the fibers in the car-
bon-epoxy laminate. The grooves in this
figure are not carbon fibers; they are the fur-
rows left by removing the peel ply.
The same grit-blast machine used to pro-
duce the sample illustrated in Figs. 29.9 and
29.10 had many years earlier burnt holes in
6.3mm (0.25 in)-thick laminates in only 20 s
when operated at 698 kPa (100 psi). Restricting
the blast pressure is critical when using this
technique. Because the negatives of the photos
used in the earlier article2 had been lost, the
blast pressure was turned up to provide a
comparative illustration of what happens
when the blasting is overdone. Despite these
676 Surface preparations for ensuring that the glue will stick in bonded composite structures

Fig. 29.9 Lightly grit blasted composite surface, Fig. 29.10 Highly magnified grit-blasted epoxy sur-
retaining imprint of peel ply (mag X50). face, showing no damage to underlying fibers (mag
x1000).

explicit instructions, the process did not seri-

ously damage the laminate. The new
overblasted surface is shown in Figs. 29.11 and
29.12 at low and high magnifications. The
greatest difference with respect to Figs. 29.9
and 29.11 is that the texture visible in Fig. 29.11
is that of the weave of the carbon fabric. The
imprint of the peel ply has been totally
removed. (Figure 29.11 is at a far lower magni-
fication than Fig. 29.9.) The vertical bands in
Fig. 29.12 are the fibers. Only a tiny fraction of
the surface fibers is damaged and the surface
is rough enough for the adhesive to stick.
The difference in size between the weaves
of peel plies and typical composite fabrics is
made very clear in the peculiar failure surfaces
shown in Fig. 29.13. The uppermost areas are
of the imprint of the fine-weave peel ply, to
which the adhesive refused to bond. The lower
coarser weave shows exposed carbon fibers Fig. 29.11 Deliberately over-blasted epoxy compos-
ite surface, showing weave of carbon fibers with no
left after very local interlaminar failures in the
trace of the fine-weave peel-ply surface (mag x9).
uppermost ply. The reason for such rapidly
alternating failure modes is unknown,
although it is probably significantly related to since the exposed carbon fibers are all oriented
the direction of propagation of the disbond in the same direction.
 Samples of diflerently prepared surfaces for bonding 677

The lightly done and deliberately overdone

grit-blasted surfaces in Figs. 29.9 to 29.12 are
consistent with the ease and reliability with
which the grit-blasting was carried out on the
Lear Fan all-composite aircraft. A portable
low-pressure machine (Fig. 29.14) was used
then. It had a vacuum collector to minimize
the spread of debris, and the central nozzle
was surrounded by a bristle comb, which
ensured that the nozzle was always held at the
same distance from the surfaces. The samples
shown in Figs. 29.9 to 29.12 were made under
far more difficult circumstances - with cum-
bersome gloves to hold the part and the nozzle
inside a chamber. Production parts as good as
those in Figs. 29.9 and 29.10 should be far eas-
ier to produce.
Figures 29.15 to 29.17 show low, intermedi-
ate, and high magnifications of the surface left
Fig. 29.12 Highly magnified over-blasted compos- by removal of a nylon peel ply from a car-
ite surface still showing minimal damage to fibers bon-epoxy laminate cured at 180°C (350°F)
(mag X500). The imprint is consistent with the intermedi-
ate magnification shown in Fig. 29.4. The
imprint left by each fiber in the peel ply is so
smooth and slick that the adhesive will not

Fig. 29.13 Disbonded surface, showing peel-ply

imprint where adhesive failed to bond and local
interlaminar failures in underlying composite (mag Fig. 29.14 Portable low-pressure grit-blasting
X15). machine.
678 Surface preparationsfor ensuring that the glue will stick in bonded composite structures
Fig. 29.15 Peel-ply imprint on epoxy surface to
which the glue will not adhere (mag X38).
Fig. 29.16 Magmfied peel-ply imprints showing
transfer of ultra-thin layer of nylon to otherwise sanding. Unfortunately, many specifications
smooth furrows in composite surface (mag x225).
I
Fig. 29.17 Same sample at higher magnification
(mag x750).
adhere there. It can adhere only to the exceed-
ingly narrow strips of fractured resin between
each fiber depression. The adhesive can
adhere to the entire composite surface shown
in Fig. 29.9, a bondable area that is an order of
magnitude greater, at least.
Figure 29.17 shows something not evident
in the companion photo of the peel ply surface
itself (Fig. 29.6). At a magnification of ~750,
some of the furrows appear to be coated in
places by ultrathin coatings of nylon from the
peel ply. The lesser magnification of x215 (Fig.
29.16) of the same area on the surface indicates
that some but not all other areas are similarly
coated.
Figure 29.18 shows what some regard as
adequate sanding. Yet, on close examination, it
is evident that the peel-ply imprint is clearly
visible except for a miniscule fraction of the
total area. The sanded area lies outside the
area meant to be bonded, on the left, but there
is no reason to suspect any different degree of
call for light (or scuff) sanding because of
 Samples of diflerently prepared surfaces for bonding 679
Fig. 29.18 Inadequate abrasion achieved by scuff
sanding (mag ~ 1 2 ) .
greater concern that the fibers in the compos-
ite laminate not be damaged than for the need
for sufficient mechanical abrasion to ensure
that the adhesive will stick properly. As long
as fifteen years ago, the McDonnell (St. Louis)
specifications explicitly called for sufficient
sanding to eliminate the imprint of the peel
ply. In other words, the entire surface of the
composite laminate was to be stripped back,
just as in Fig. 29.9. (One wonders what moti-
vated such a precise specification. Something
taught them a lesson they planned not to for-
get.) The results of the inadequate level of
sanding are evident in Fig. 29.18. The imprint Fig. 29.19 Slight fiber damage caused by thorough
of the peel ply is just as clear to the left of the sanding of unidirectional carbon-epoxy laminate
broken glue fillet at the edge of the disbonded (mag X460).
stiffener as in the unbonded area to the right.
Figure 29.19 shows slight damage to the
uppermost fibers as the result of thorough
sanding of another sample, this time a unidi-
rectional carbon-poxy laminate, prepared at
a different facility. In this case, sanding paral-
lel to the surface fibers would minimize any
damage. However, that option would not be
available for woven fabrics because the sur-
face fibers do not all run in the same direction.
The number of fibers damaged in Fig. 29.19 is
an extremely small fraction of even the surface
ply. Carbon fibers are so small that each tow
contains 3000-12 000 individual fibers in a
layer 0.13 mm-0.33 mm (0.005-0.013 in) thick.
The loss of strength from damaging a few sur-
face fibers through too energetic sanding is far
less than from a bonded structure coming
apart in service because of inadequate sand-
ing.
Figures 29.20 and 29.21 show sanded Sam-
ples. The woven texture is that of the peel ply,
not the carbon fabric. The matt sanded areas in
the figure are the high spots in the laminate
surface. The peel-ply imprints still visible are
in depressions. Clearly, the operator never
came close to damaging the carbon fibers.
Sanding should have continued for far longer
or a more abrasive grade of emery paper
should have been used. It is clear that some
30% of the bond area was sanded, a huge
680 Surface preparations for ensuring that the glue will stick in bonded composite structures

Fig. 29.20 Moderately sanded peel-ply imprint on Fig. 29.21 Highly magnified surface, showing how
surface of woven composite laminate, showing how most of the peel-ply imprint remains after hand
sanding does not abrade the entire surface (mag sanding (mag ~1000).
x100).
improvement over the few percent removed in
the sample shown in Fig. 29.18.
While it must be acknowledged that both
grit-blasting and hand-sanding can be over-
done, doing so takes time and effort if one is
using the right abrasives and equipment. A
significant loss of strength from such actions is
far less likely than from either simply remov-
ing a peel ply or sanding the composite
surfaces far too lightly.
To cover the possibility that the bad experi-
ences with peel plies at Douglas might have
been associated exclusively with the break-
down of nylon at too high a curing
temperature, samples were obtained from
Oxford Brookes University, which used a dif-
ferent laminating resin and both a polyester
peel ply and what is probably the same nylon
peel ply. The polyester peel ply was noticeably
more difficult to remove than the nylon peel
ply, but far easier than what were referred to
as tear plies in Reference 2. The surface created Fig. 29.22 Imprint of polyester peel-ply, showing
by removing the polyester peel ply from a more fractured resin than with nylon peel-plies
120°C (250°F) cured carbon-poxy laminate (mag ~ 5 0 ) .
 Samples of diferently prepared surfaces for bonding 681

(Fig. 29.22 mag x37.5) is generally very similar

to the surface shown in Fig. 29.4 after a nylon
peel ply had been removed, except for the ran-
domly oriented tendrils, which appear to be
lengths of attached polyester filaments. The
university’s nylon peel ply left slick imprints
almost exactly like the one used at Douglas. A
comparison of the SEM photographs suggests
that the polyester peel ply performed better
because the filaments were smaller and there
was proportionately a greater length of the
very fine strips of fractured resin between the
filaments. The improvement in strength from
this source alone should be about 25%.
However, there was another possible differ-
ence: the higher magnification of the polyester
peel-ply imprint (Fig. 29.23) shows faint
streaks in the grooves left by removal of the
peel ply. If these could be traced to surface
roughness in the resin, rather than to smooth Fig. 29.24 Highly magnified image of polyester
irregularities in the polyester filaments, it peel-ply after removal from 120°C (250°F) cured
would be an indication that the peel ply carbon-epoxy laminate (mag X830).
stripped off some surface resin and promoted
adhesion of the glue. Unfortunately, a microscopic examination of
the removed peel ply itself suggests that the
imprint remains smooth at the molecular level.
The polyester peel ply seems to be better than
the nylon one but not in the same class as the
surface created by light grit-blasting. Figure
29.24 shows a x830 enlargement of the surface
of the removed polyester peel ply. The fibers
are generally smooth and, where they are not,
the visible strands represent tearing of the
fibers rather than a buildup on the surface as
the result of tearing the matrix resin.
Nevertheless, it should be noted that the tear-
ing shown could not have occurred if there
were no adhesion at all between the peel ply
and the resin matrix. The interface definitely
seems more bondable than the much smoother
one associated with nylon peel plies.
What may be a far more sigruficant differ-
ence is that the surface created from peeling off
a nylon peel ply from the carbon-poxy lami-
nate cured at 120°C (250°F) shows no sign of
Fig. 29.23 Highly magnified imprint of polyester nylon on the surface at either low or high mag-
peel-ply in epoxy composite (mag X500). nification (Figs. 29.25 and 29.26). Nevertheless,
682 Surface preparationsfor ensuring that the glue will stick in bonded composite structures

the surfaces are so slick that one would have no

confidence that a reliable bond could be made
other than to the thin strips of fractured resin
between the grooves left by the peel ply.
However, it might well be far less weak than
would result from trying to bond to a nylon
interface and, indeed, lap-shear testing of such
bonded joints has been reported in Reference 6
as resulting in cohesive failures at the expected
bond strength. The fractured surfaces look
excessively porous, but so do the companion
coupons made with grit-blasted surfaces,
which developed essentially the same strength.
These bonds definitely do not look as strong as
that shown in Fig. 29.7, but they are ever so
much stronger than that shown in Fig. 29.1.
Figure 29.27 shows the fractured surface of
an interlaminar failure within the
carbon-epoxy composite. The fibers shown
Fig. 29.25 Slick surface left by removal of nylon are carbon and are noteworthy for the failure
peel-ply from 120°C (250°F) cured carbon-epoxy of the resin to adhere to them over most of
laminate (mag X46). their surface. The fractured surface is that of
the resin matrix. One would expect that the
same kind of surface would be created by the
1

I 1

--- -1

Fig. 29.26 Highly magnified image of nylon

peel-ply imprint taken from 120°C (250°F) cured Fig. 29.27 Extreme enlargement of interlaminar
laminate, showing slick surface with no transfer of fracture in top layer of carbon-epoxy laminate (mag
nylon (mag X450). x1100).

removal of a tear ply that adhered to the
matrix as tenaciously as conventional peel
plies refuse to adhere. This, in turn, raises
questions about the feasibility of tear plies as a
surface-preparation technique since the lami-
nate is damaged far more than by light
grit-blasting, as a comparison between Figs.
29.10 and 29.27 will attest.
29.5 COMMENTARY
In the mid-l980s, a major effort was aimed at
the resolution of a problem associated with
adhesive bonding of aluminum alloy struc-
tures. In that case, as in the problem discussed
here, the glue failed to stick and interfacial fail-
ures resulted. However, there remains a very
great difference between the two cases. In the
earlier case, every factor associated with the
weak bonds that passed all ultrasonic inspec-
tions was identified in a matter of weeks. The
conditions had been replicated in a laboratory
and the investigation closed within a few
months. Significantly, there were no loose
ends and the problem has not recurred. The
primary cause of the problem was condensate
on adhesive film that had been removed from
storage before it had thawed out.
However, there was a second factor
involved as well. The first violation of proper
processing procedures would not cause a
defective bond unless the moisture was
trapped at the interface between the details.
This condition happened consistently with
one kind of bonding tool, while similar parts
made concurrently on a different kind of tool
showed no such problems. The second kind of
tool permitted complete ventilation of any
trapped volatiles as well as of any generated
during the cure. There were no large area
defective bonds. Both tools produced local
bond defects where a tool or the parts were out
of contour. These problems were eliminated
by correcting the tools and by better straight-
ening of the stiffeners. This problem was
resolved very quickly, whereas the present
problem with peel plies has not been solved at
Commentary 683
the production level in over 20 years. Because
the metal-bond problem was resolved so
quickly, very few panels were involved. There
were no in-service failures because every
affected panel was identified before delivery
and reinforced by rivets.
Peel-ply ’surface preparation’ for bonding
of composites has not been as thoroughly
explained. There have been many instances of
such weak bonds not being detected until they
had split apart in service, even though there is
no reason to believe that the bonds wore out
under mechanical loads. The observed modes
of failure are consistent with a manufacturing
problem. There is little doubt that gentle grit-
blasting is the most reliable method of
preparing thermoset composite surfaces for
bonding. Sanding can work only on fairly fine-
weave cloths in composite laminates.
Otherwise, it is not possible to sand to the bot-
tom of all depressions left by the peel ply
without also sanding significantly into the
structural fibers. A few other manufacturers
have used tear plies, which leave a completely
fractured resin surface, rather than the more
commonly used easily removed peel plies dis-
cussed here. More use should be made of tear
plies. However, if a tear ply were used on a
lightweight honeycomb or foam sandwich
panel, there is a good chance that the core
would fail instead.
There can also be no doubt that when prob-
lems have occurred as a result of bonding
directly to the surface left by removal of a peel
ply, or one with totally inadequate sanding,
they are widespread and serious. These prob-
lems have been experienced at many places.
Yet, if they happened as repeatedly as the
defects caused by the combination of the two
factors cited above, one would have expected
such a backlash against the procedure that
every unreliable peel ply would have been
withdrawn from the marketplace, preventing
any recurrence of the problems. That has not
happened so, presumably some organizations
are able to bond successfully to composite
structures by simply removing a peel ply.
684 Surface prqarations for ensuring that the glue will stick in bonded composite structures
Regrettably it seems as if anyone doing this
process successfully has no reason to investi-
gate why he is successful, so the differences
between his techniques and those that lead to
trouble have remained unidentified.
It seems that there is something else
involved as well possibly prebond moisture or
something associated with venting during the
cure or possibly the breakdown and transfer of
nylon peel plies cured at too high a tempera-
ture or the transfer of a release agent on some
peel plies. Weak interfacial bonds between the
adhesive layer and both composite adherends
should never have been strong enough to rip a
properly cured adhesive back and forth from
one interface to the other in the manner that is
so evident in Fig. 29.8. And, more significantly,
attempts to replicate the weak bonds in the
laboratory have been inconclusive and, at
times, inconsistent. This merely reinforces the
assumption that the problem is not yet fully
understood without, in any degree, diminish-
ing the conviction that the problem is serious
and needs to be resolved.
It would be helpful if there were a reliable
a peel-dominated quality-control test for com-
posite surface preparation that was
equivalent to the wedge-crack test used for
metal bonding. Unfortunately, the experi-
ments performed to date have been
bedevilled with extraneous influences that are
not yet understood but have a much greater
effect on the strength of the coupon than the
variations in surface treatment. Neverless the
goal remains.
29.6 CONCLUSIONS
As acknowledged above, more technical infor-
mation needs to be uncovered about adhesive
bonding to fiber-polymer composite surfaces
created by simply removing a peel ply. The
weak bonds associated with this technique are
a financial burden that is both serious and easy
to avoid.
The use of low-pressure grit-blasting as the
final step in the preparation of these surfaces
for bonding has been found to be extremely
reliable in service. While one needs to buy
appropriate equipment, the cost of doing so is
a small fraction of the typical cost of even one
composite detail. With the right equipment,
training of technicians is straightforward.
There can be no valid argument in favor of
not mastering the art of grit-blasting. While
there may be choices for the surface prepara-
tion during initial fabrication, peel plies
cannot possibly be stripped off a second time
to create a new 'clean' surface during repairs.
It may be that some manufacturers make
successful bonds to peel-ply composite sur-
faces already. It may also be possible that
coupling agents may be found to enable others
to do the same. However, it is undeniably true
that, for at least two decades, some manufac-
turers of composite components who have
relied on peel plies alone as surface prepara-
tion for bonding have created weak bonds that
have fallen apart in service. The cost of unan-
ticipated repairs and investigations has greatly
exceeded any expected initial cost savings.
Given the widespread nature of these prob-
lems, it is appropriate to recommend that the
use of peel-ply surface preparation alone be
discontinued unless it can be shown that its
use never results in interfacial failures
between the composite and adhesive layers. It
is quite clear, from experience, that the cost of
even one in-service bond separation exceeds
by far the savings derived during an entire
production run by not thoroughly abrading
the surface.
Scanning electron microscope images,
such as those presented here, show easily dis-
tinguishable differences between the matt
rough surface created by mechanical abrasion
and the microscopically smooth furrows
associated with peel-ply removal alone. It is
not difficult to ensure that the surface prepa-
ration is adequate for bonding or painting
before the bond has been made. Conversely, it
is extremely difficult to detect a weak bond
nondestructively once the error has been
made.

REFERENCES
1. Schliekelmann, R.J., Adhesive bonding and
composites, Progress in Science and Engineering of
Composites. In Vol. 1, Proc. 4th Intl Conf.
Composite Materials (Tokyo), 22-28 Oct., 1982.
Japan Society for Composite Materials and The
Metallurgical Society (TMS) of AIME; (T.
Hayashi, K. Kawata and S. Umekawa, eds)
Amsterdam: North-Holland, 1982, pp. 53-78.
2. Hart-Smith, L.J., Ochsner, R.W. and Radecky,
R.L., Surface preparation of fibrous composites
for adhesive bonding or painting, Douglas
Service Magazine, 1984, First Quarter, pp. 12-22.
3. Hart-Smith, L.J., Ochsner, R.W. and Radecky,
R.L., Surface preparation of fibrous composites
for adhesive bonding or painting, Canadair
Service News, 1958,14(2), 2-8.
4. Parker, B.M. and Waghom, R.M., Surface pre-
treatment of carbon fibre-reinforced composites
for adhesive bonding, Composites, 1982, 13,
280-288.
References 685
5 . Pocius, A.V. and Wenz, R.P., Mechanical surface
preparation of graphitepoxy composite for
adhesive bonding, SAMPE J., 1985, Sept/Oct,
50-58.
6. Wingfield, J.R.J., Treatment of composite sur-
faces for adhesive bonding, Int. J. Adhesion and
Adhesives, 1993,13(3),151-156.
7. Hart-Smith, L.J., Joining of organic-matrix com-
posites. In A S M Handbook, Vol. 6: Welding,
Brazing, and Soldering, Ohio: ASM Intl, Dec.
1993, pp. 1026-1036.
8. Mahoney, C.L., Fundamental factors influenc-
ing the performance of structural adhesives,
Internal Report, Dexter Adhesives & Structural
Materials Division, The Dexter Corporation.
9. Hart-Smith, L.J., Design and development of
the first Lear Fan all-composite aircraft,
Douglas Paper 8184, presented to Institution of
Mechanical Engineers Conference on Advanced
Composites, London, England, March 7-8,
1989.
LAMINATE DESIGN 30
Jocelyn M . Seng

30.1 INTRODUCTION birch or spruce, laid over balsa core or fir

stringers to form a sandwich structure1. This
An early example of laminated composite
successful production aircraft (7781 units built)
materials is the de Havilland Mosquito
was designed without the analytical techniques
fighter/bomber used by the British Royal Air
described in this chapter and without fancy
Force during World War I1 (Fig. 30.1). This air-
computer tools. With current laminate design
craft was built entirely out of wood because of
and analysis techniques, today’s higher-perfor-
limited metal supplies and the need for quick
mance composite aircraft are made possible;
delivery. The wings, for example, were made as
with the increase in speed and accuracy of com-
three-ply skins (each 1.5 mm (0.060 in) thick) of
putation results, designer confidence in

Fig. 30.1 The de Havilland Mosquito, an all-wood

Handbook of Composites. Edited by S.T. Peters. Published WWII Production aircraft.Printed With Permission,
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 Zokeisha Publications, Inc.

composites structures is increased. This chapter
presents the basic mathematical tools used to
design laminates and provides insight on the
many options for optimizing the material for
particular needs.
Three distinct levels of benefit can be
derived when using composites and laminate
design. With equal fiber distribution in multi-
ple directions, rendering an effectively
quasi-isotropic material, composites can
approximate metals while providing a weight
savings due to the difference in material den-
sities. In addition, however, designers opting
to use composite parts enjoy the advantage of
being able to tailor the properties of their
material by orienting load-carrying fibers in
the directions that there are loads. The result is
an anisotropic material, which by definition is a
material with different properties in different
directions. Ultimately, the composites industry
is finally beginning to see the development of
unique structures that have never before been
attempted and with material behavior that is
only possible with distinct laminate designs.
This is a result of coupled behavior, for exam-
ple, an extensional load on an anisotropic
material can yield extension coupled with
bending and twisting deformations.
The objective of this chapter is to outline a
method to design ply layouts which achieve
structural design goals for composite parts.
This method is based on laminated plate the-
ory used with the quadratic failure criterion2.
This general discussion, which assumes famil-
iarity with undergraduate mechanical
engineering fundamentals, shows how the
principles for isotropic materials (such as met-
als) are extended to the analysis of advanced
composites. The basic equations are presented
and the analysis procedure is outlined.
Simplifying concepts are introduced and dis-
cussed. Simple computer codes that embody
these equations are now widely available,
making it unnecessary to ever have to solve
these equations by hand. Examples and sam-
ple problems are included to demonstrate
concepts.
Laminated plate theory 687
30.2 LAMINATED PLATE THEORY
30.2.1 LAMINA
Advanced composite materials are typically
supplied as a thin layer, called a ply or lamina,
which is subsequently stacked into a thin
plate, called a laminate. A unidirectional ply or
lamina is a flat or curved layer of fibers ori-
ented in one direction and held together by
matrix material that serves to support the
fibers. The stresses perpendicular to the planar
surface are assumed to be zero.
While the behavior of isotropic materials can
be described with two elastic constants (typi-
cally the Young’s modulus and the Poisson’s
ratio) and one strength value, a composite ply
that is transversely isotropic is characterized by
four elastic (stiffness) constants and five
strength parameters in two-dimensional analy-
sis. The material properties are defined along
the fiber (x-direction ) and perpendicular to the
fiber (y-direction ). For each unidirectional ply
in its own axes, the four orthotropic elastic con-
stants are the longitudinal tensile modulus, Ex;
the transverse tensile modulus, EY;the major
Poisson’s ratio, vx; and the shear modulus, Es.
Only one Poisson’s ratio is necessary since Y,,=
vx(€,,/Ex). The five strength parameters for each
unidirectional ply are the longitudinal tensile
strength, X; the longitudinal compressive
strength, X’; the transverse tensile strength, Y;
the transverse compressivestrength, Y’; and the
shear strength, S.
The five initial coupon tests to experimen-
tally determine the nine material constants are
shown in Fig. 30.2. In the stress, o, versus
strain, E , plot, the material is characterized by
the slope of the line, which represents material
stiffness, and by the failure point, which
defines the maximum stress that the material
can sustain, i.e. its strength, and by the corre-
sponding maximum strain. Use of the strength
parameters is discussed in the section on fail-
ure criteria.
During three of the coupon tests, the
nonzero strains are monitored and the rela-
tionships in eqn (30.1) are determined. The
688 Laminate design

Longitudinal Transverse

EX j

" =-- EY

......

Longitudinal Transverse
Compression Compression

Fig. 30.2 Coupon tests to determine the nine material constants used to characterize an anisotropic material.

material is assumed to be linear and elastic; If a unidirectional specimen was simultane-

thus, the stiffness of a material is the same in
tension as in compression. Based on the four
elastic constants, infinitely different lami-
nates can be designed using laminated plate
theory.
ously tested under the three load cases,
longitudinal tension, transverse tension, and
shear, then superposition of the strains results
in

Longitudinal tension test

1
E = -0 --0VX
3 Y EY Y Ex
E = - 0 (30.1)
Ex
1
ES = -0,
E S

Written conveniently in matrix notation,

Transverse tension test

1
E = - 0
y E,, y

0 0

Shear test
(30.3)
1
E =-a,
E,
 Laminated plate theory 689

Defining the plane stress stiffness matrix [QJ =
[SI-', another form of eqn (30.3) is
laminate, x, y, s and 1,2,6 are interchangeable.
Material properties are specified with
respect to the on-axis coordinates. The proper-
ties of an off-axis ply, anything other than 0
degrees, can be calculated by transforming the
properties of the 0-degree ply. The angle of
transformation, 8, is equal to the ply angle
shown in Fig. 30.3, where 1 and 2 are the lam-
inate axes and x and y are the rotated ply axes.
8 is positive counterclockwise from the 1-axis
to 90°, and negative clockwise to -90".

Y
l o 0 E, J
This calculation of the plane stress stiffness
matrix [Q]for a single ply is the starting point
of laminated plate theory, once the engineer- 1
ing constants have been experimentally
determined.

30.2.2 COORDINATE TRANSFORMATIONS

Two coordinate systems are used in laminated
plate theory. The local, or on-axis, coordinate
frame is defined by x and y, also referred to as
the ply axes. The x-axis is along the longitudi-
nal direction of the ply (along the fiber); the
y-axis is in the same plane, but in the trans-
verse direction (perpendicular to the fiber
direction). The subscripts is used with expres-
sions for shear, and is a contraction for the
subscript xy. The ply's material properties are
Fig. 30.3 Definition of ply axes (x,y) and laminate
axes (1,2), where the lines indicate the fiber direc-
tion.
The laminate off-axis stiffness matrix is com-
puted from the ply on-axis stiffness matrix by
using the following ransformation relation:
Q1ll
Q22

defined in this axis system. Since not all plies

are aligned in the same direction along the
principal loading axis in a laminate, a second
set of coordinates is necessary to analyze com-
posite laminates. The global, or off-axis,
coordinate frame is defined by 1 and 2, also m4 n4 2rn2n' 4m2n2
referred to as the laminate axes. The 1 direc-
n4 m4 2m2n2 4m2n2
tion is along the principal orientation of the
laminate; the 2 direction is perpendicular to it. m2n2 m2n2 m4+n4 -4m2n2
The subscript 6 is used with expressions for m2n2 m2n2 --2m2n2 (m' -n2)'
shear, and is a contraction for the subscript 12. m3n -mn3 mn3 - m3n 2(mn3- m3n:
The loads on the laminate and the boundary
mn3 -m3n m3n- mn3 2(m3n- mn3:
conditions are usually defined in the global
svstem.
, In the case of a 0-degree
" unidirectional (30.5)
690 Laminate design
where rn = cos 8, n = sin 8. A summary of some
other useful transformation relations is given
in Section 30.7. It is clear from these relations
that when 8 = 0, then Q,, = Q,, = 0, which
means shear and extension are uncoupled, i.e.
shear loading only causes shear deformation,
and extensional loading causes extensional
deformation with Poisson’s effect but no shear
deformation.
Using the off-axis plane stress stiffness coef-
ficients, the constitutive relations of eqns (30.4)
and (30.3) can be generalized to a ply of any
orientation:
and inversely
For example, a physical interpretation is
shown in Fig. 30.4. In general, the terms on the
diagonal (S,,, S,, S,) reflect the amount of
deformation in the direction of loading. As
Fig. 30.4 Extensional loading of (a) a unidirectionalply and (b) an off-axis ply and their associated off-axis
stiffness matrix.
with the [Q] matrix, the S12(and SJ, terms
reflect the deformation in the direction per-
pendicular to the direction of loading, and are
commonly referred to as the ‘component due
to Poisson’s effect’ (implying the major
Poisson’s ratio). The S,, and S2, (and S,, and
S62)terms reflect the amount of shear deforma-
tion under extensional loading, and are
commonly referred to as ’coupling terms’.
Unlike the off-axis unidirectional ply shown in
Fig. 30.4@), the 0-degree unidirectional ply
shown in Fig. 30.4(a) does not exhibit any
shear deformation under extensional loading.
30.2.3 KINEMATICS
Kinematics is the study of movement and
depends solely on geometry, not on material
properties. Since composite laminates are
often thin two-dimensional structures, plate
theory is used to simplify the three-dimen-
sional behavior. Plate theory tries to account
for stretching and bending behavior relative to
the midplane of the laminate.
The key assumption of plate theory is that
normals remain normal, straight and
unstretched. In practical terms, the plies in the
laminate are assumed to be completely
bonded to each other, allowing no interlami-
nar shear. Some other assumptions are that the
 Laminated plate theory 691

material exhibits perfectly linear elastic behav-

ior and that there is a perfect bond between
the fiber and matrix. The out-of-plane dis-
placement, w, can be described by a function
of the in-plane coordinates such that E: -I-ZK1

w = wo(x,y) (30.7)
Based on the Kirchhoff assumptions, Fig. 30.5
shows the deformation of a cross section of the
plate in the x-z plane, relative to the x-direc-
tion

u = uo-z-
aw0
ax (30.8) 30.2.4 STRESS RESULTANTS
Similarly, the displacement along the y-axis is Just as beam theory defines net tensile force,
shear force, and moment, relating everything
Y = Y,-Z-
awo (30.9) to the neutral axis, plate theory defines stress
aY resultants and moment resultants to eliminate
Based on the definition of strains, any z-direction dependence and to relate
au auo azw, everything to the midplane, as shown in Fig.
& =-=--z- (30.10) 30.6. Ply stresses along each loading direction
1 ax ax a x 2 are summed for the laminate:

(30.12)

2
M-
Undeformed Deformed
Cross Section Cross Section
Fig. 30.6 Force and moment resultants acting on a
Fig. 30.5 Extension and bending deformation. plate.
692 Laminate design

These resultants can be rewritten in terms of A,, indicates the relationship between longi-
strain by substituting in the constitutive rela- tudinal in-plane load, N,, and the
tions. Putting the two-part expression for longitudinal extension, E;;
strains, eqn (30.11), into the constitutive rela- A,, indicates the coupling between longitu-
tions, eqn (30.6), and substituting the resulting dinal in-plane load, N,, and the extension
stress expression into the definitions for the in the transverse direction, E;, (the tradi-
resultants, eqn (30.12), tional Poisson's effect);
A,, indicates the coupling between longitudi-
{N] = [A] (E'} + [B](K) (30.13) nal in-plane load, N,, and the in-plane
shear, E;;
A, indicates the relationship between in-
plane shear load, N,, and the in-plane
All Bll 1' 2 B16 shear distortion, E;;
'21 2'2 B26 B,, indicates the coupling between transverse
'61 '62 '66
in-plane load, N,, and the twist, K ~ ;
B, indicates the relationship between in-
1
'1 1' 2 1
'6 Dll D12 D16
plane shear load, N6, and the twist, K ~ ;
B21 '22 B26 D21 D26 D12 indicates the coupling between longitudi-
6
'1 B62 '66 D61 D62 D645 nal bending load, MI, and the transverse
bending curvature, K,;
(30.14) D, indicates the relationship between twisting
moment load, M6, and the twist angle, K ~ .
The ply stacking sequence has no effect on the
[AI = IIQldz (30.15) A matrix coefficients, which reflect in-plane
behavior. However, since the B and D matrix
coefficients are a function of z, they are depen-
dent on the stacking sequence.
There are two unique physical situations
that deserve mention. When the laminate is
symmetric about its midplane, the B coeffi-
cients are zero, which means that there is no
It can be shown that A,, = A,,, B,, = BZ1, D,,= coupling between in-plane loads and curva-
DZ1,etc. Equation (30.14)represents the funda- tures, nor between bending loads and
mental relationships in laminated plate theory. in-plane deformations. Another common sit-
The 6 x 6 matrix is the laminate stiffness uation is when the A,, and A,, coefficients are
matrix. zero (usually in the presence also of all the €3
A composite with unidirectional plies lami- coefficients being zero): this arises when a
nated in different directions (a generally laminate is balanced, i.e. there are an equal
anisotropic material) under an inplane load number of off-axis plies in the +8 and 4
may stretch, bend and twist, as a result of directions and they have equal thickness. In
extensional/ shear coupling. By comparison, a this case, there is no coupling between exten-
metal structure will stretch only under an sion loads and shear strain. If, in addition,
inplane load, bend only under flexure, and those +8 and 4 plies are effectively the same
twist only under torque. Each matrix coeffi- distance from the midplane, then the corre-
cient in eqn (30.14) relates a particular sponding B and D matrix coefficients tend
resultant to a strain expression. For example, toward zero.
 Laminated plate theory 693

Most laminates used today are symmetric a flexural contribution, then it must be added
to eliminate or reduce any tendency of the
structure to warp unexpectedly. Most lami-
nates are also balanced, often because it is
erroneously thought to be necessary to pre-
vent the structure from warping. A balanced
laminate is really only necessary in situations
with reversible shear loading conditions. The off-axisply strains can be transformed to
on-axis ply strains for each ply and their signif-
icance can be evaluated per a failure criterion
30.2.5 RESULTING STRAIN STATE (refer to the relations given in Section 30.7).
Knowing the laminate stiffness matrix and the
applied loads, the resulting strains can be
computed. The strains are obtained by invert-
ing the stiffness matrix and multiplying by the
input load. Instead of inverting the 6 x 6 stiff-
[Et
Es I
=.
i
m2
n2
n2
m2
-mn
mn
2mn -2mn m2-n2
f:
., I (30.19)

ness matrix, however, it is sometimes possible
to simplify the analysis even further. If the
laminate is symmetric about the midplane so
that the B coefficients are identically zero, then
the in-plane (described by N, [A], E ) and bend-
ing problems (described by M I [D], IC)become
uncoupled. In this case, it is much easier to
invert two 3 x 3 stiffness matrices to get the
compliance matrices (see also Section 30.7 for
the explicit terms to invert a matrix)
[a] = [AI-’
where, as before, m = cos 8, n = sin 8. One step
further, the on-axis ply stresses can be obtained
by multiplying the on-axis ply strains by the
ply stiffness matrix [Q] as shown in eqn (30.6).
The laminate engineering constants, which
have meaning with symmetric laminates only,
are calculated from the compliance matrix and
are useful for comparison to the properties of
other materials, such as metals

[d] = [Dl-’ (30.16)

Then, the compliance matrix is multiplied
by the appropriate input load conditions to
compute the laminate strains
where the compliance terms have been nor-
malized to have the necessary units of
[length2/ force]

I
‘EP ‘11 ‘12 ‘16 ‘IN, ’
= a12 aZ a26 N2 (30.17) [a*] = [a]h (30.21)
E;
\E: ‘16 ‘26 ‘66. tN6 ,

In summary, the mathematical process of ana-

lyzing composite laminates is indicated in Fig.
30.7. A laminate’s stiffness is calculated as the
summation of its individual ply properties.
Load on the laminate is described in terms of
Since all the plies are bonded together, the the laminate coordinates. Calculated from the
strains in each ply, in the laminate axes, (1,2), applied load and the known material stiffness
are equivalent to the laminate strain. If there is properties, the response of the laminate is
694 Laminate design

expressed as laminate strain. In order to apply 30.3.2 HYGROTHERMAL EFFECTS

a failure criterion, the laminate strain is com-
Most structure is exposed to a variety of envi-
monly transformed into ply strains and each
ronmental effects. Of particular concern are
ply is individually evaluated. heat and moisture. The design must account
for the hygrothermal effects (hygrothermal
30.3 ENHANCEMENTS TO THE BASIC means water and temperature). A laminate
LAMINATED PLATE EQUATIONS that is stress-free when curing at an elevated
temperature will have residual stresses when
30.3.1 SANDWICH CONSTRUCTION brought back to room temperature. It has been
thought that some of the apparent improve-
In composite structures, sandwich construc-
ment in toughness of 250°F resins over 350°F
tions are commonly used. By increasing the
resins is simply due to the reduction in resid-
distance between the load-carrying laminate
ual stresses (AT = 75 - 250 = -175°F versus AT
skins, a core can provide increased bending
= 75 - 350 = -275°F). In addition, moisture is
stiffness without a significant weight penalty.
absorbed by the laminate, usually into the
The core is often idealized in laminate design:
resin. The negative effect on the mechanical
it is assumed that the core does not contribute
properties is particularly pronounced at both
to laminate strength or in-plane stiffness, and
high temperature and high humidity.
that the shear bonds between the skins and
Assuming that the primary effect on resid-
core are perfect. The parallel axis theorem can
ual stresses is due to different thermal
be used to account for the increased moment
expansions and moisture expansions along
of inertia that the core creates by offsetting the
and transverse to the fiber direction, two addi-
laminate load-carrying skins from the mid-
tional strains on the laminate result:
plane. Once the skin laminates have been
sized, further calculations can be performed to {E) = {a)AT+@)Ac (30.22)
confirm that the core assumptions are valid3.

Measured Plane Laminate Inverted Given Loads;

Ply Stress Stiffness Stiffness Resulting Ply
Stiffnesses Coeff. Matrix Matrix Laminate Strains
Strains
Fig. 30.7 Logical flow of calculations involved in analyzing a symmetric composite laminate that is loaded
axially and/or in bending.

The summation process can be used to deter-
mine the effective laminate expansion
coefficients.
The hygrothermal load, sometimes called
non-mechanical load, can be computed by
multiplying the laminate stiffness by the
hygrothermal strain (i.e. laminate thermal
expansion coefficients multiplied by the
change in temperature). The stress induced by
moisture absorption can be accounted for sim-
ilarly by using PAC in place of aAT. Thus, the
non-mechanical loading in the laminate can be
expressed as
The mechanical and non-mechanical loads, N
and W , can be added together to determine
the total load experienced by the laminate.
30.4 FAILURE CRITERIA
The ultimate objective in any structural design
is to create a structure able to withstand
deflections or loads without failing. The initial
concern is to remain below a prescribed deflec-
tion as part of stiffness criteria. Once these
criteria are satisfied, the focus shifts to a
strength criterion, such that applied stress
must not exceed laminate strength.
Composite materials normally possess dif-
ferent strengths when loaded in either tension
or compression. The following represent the
minimum number of strength properties nec-
essary to characterize a unidirectional or fabric
ply. They are determined using material
coupon tests, previously outlined in Fig. 30.2.
X = longitudinal tensile strength,
Failure criteria 695
X' = transverse tensile strength,
Y = longitudinal compressive strength,
Y' = transverse compressive strength,
S = shear strength. (30.24)
The maximum ply strain values can be inter-
preted by dividing the above strengths by the
appropriate ply stiffness coefficient.
cx* = max longitudinal tensile strain,
E ~ ' *= max longitudinal compressive strength,
E * = max transverse tensile strength,
Eyf* =
Y
max transverse compressive strength,
E,* = max shear strength. (30.25)
Laminate strength is function of material (ply)
strength and the constraints on the ply within
the laminate. Thus, failure is best assessed at
the ply level. The proper interpretation, how-
ever, of the significance of the applied stress
relative to the material strength is still
debated. Maximum stress and maximum
strain failure criteria are common wherein the
applied stress or strain value is compared
directly to the strength value. A review of fail-
ure criteria has been published4.
Early laminate failure theories fail to
account for Poisson's effects and interaction
between loads in orthogonal directions (a
complex load condition). For example, the
major weakness of both the maximum stress
and the maximum strain failure criteria are
their inability to couple stress, or strain, com-
ponents in determining the ultimate failure of
a ply. It is important to understand that the
longitudinal tensile failure of a ply is affected
not only by the longitudinal load, but also by
the magnitude of applied transverse loads. As
a result, stress interaction criteria are widely
used throughout the industry to determine ply
failure in a laminate.
30.4.1 QUADRATIC FAILURE CRITERION
Tsai developed a two-dimensional stress inter-
action failure criterion and predicted the
strength of an orthotropic ply subjected to
combined stresses or strains. This analysis
696 Laminate design
takes into account the effects of other stress
components on the strength in any one direc-
tion. Tsai postulated a criterion in stress space
consisting of the sum of linear and quadratic
scalar products as follows:
F ‘1DOI
1
+ Ftp1I 1 i, j = x, y, s
or, in expanded form,
+ ( F p x + Fyuy)I1
Note that Fxs = Fys= F, = 0, and the six strength
parameters are interpreted from the ply
strength values (reviewed in Section 30.8):
1
F = -
s
2
1 1 1 1
F = -- - F = -- -
x x y Y Y’
The stress interaction term, Fx,*, can have a
value of -1 I Fx; < 1although is recommended
to be -1/2. When F,; = -1/2, the quadratic fail-
ure criterion is a general case of the von Mises
criterion (Section 30.8.2).
Instead of simply evaluating the failure cri-
terion to determine if the laminate failed, it is
useful to consider a nondimensional ratio to
provide a perspective of the significance of the
applied stress relative to material strength.
Tsai defines the strength ratio, R, such that
The strength ratio is always a positive number
with the following physical implications:
X = 1 failure occurs (at the applied stress or
strain level);
R > 1 failure has not occurred and R repre-
sents a factor of safety (e.g. if R = 2, then
the applied stress can be safely doubled
before failure occurs);
R < l failure has already occurred (i.e. occurs
prematurely at some point below the
applied stress or strain) and the applied
stress or strain level can not be attained
(e.g. if R = 0.5, then only half the
(30.26)
applied stress can be sustained).
Equation (30.28) is substituted into eqn (30.26)
and the solution of this quadratic equation can
be obtained.
[ F I , ~ l ~ ~+][F,u,]
R‘ R -1 = 0 (30.29)
i, j = x, y, s
The positive and negative roots of the qua-
dratic equation can be found and represent
failure of the laminate in tension and compres-
sion (where the absolute value of the negative
root is used), respectively.
Failure envelopes can be plotted to show
laminate strength for any combination of
(30.27) loads. Instead of the stress space representa-
tion, however, the examination of failure
envelopes in strain space is a useful alterna-
tive. The representation of failure envelopes in
strain space is preferred because strain is usu-
ally specified in laminated plate theory. Strain,
unlike stress, is at most a linear function of the
thickness. Furthermore, failure envelopes are
fixed in strain space, and are independent of
other plies with different angles which may
exist in a laminate. Thus, they can be regarded
as material properties. Another additional
advantage of strain space is that the axes are
dimensionless.
30.4.2 STRENGTH OF LAMINATES
(30.28)
Traditional failure criteria based on strength of
materials are limited to the prediction of the
FPF, the point beyond which the continuous
and homogeneous material assumptions are
no longer valid. The use of a simple method
for modeling of degraded plies is recom-
mended, from which the FPF can be estimated.
The load-carrying capability of a laminate
 Laminate design 697

beyond the FPF can be formulated using a ply of the preselected orientations results in a
degradation model. Two possible methods are quasi-isotropic laminate. This is the perfor-
recommended: first, the simplified microme- mance baseline, because load-carrying fiber is
chanics model based on the modified in effectively all directions. Laminate perfor-
rule-of-mixtures relations can be used. Plies mance can only be improved beyond that of a
with transverse cracks are replaced by plies quasi-isotropic laminate as fiber is biased into
with reduced matrix modulus, Em. load directions, since, of course, fiber would
Micromechanics translates the effect of the never be put in unnecessary directions.
altered constituent material properties to the Heretofore, quasi-isotropic laminates have
ply level, e.g. how a change in the matrix mod- been used because they give properties like
ulus affects the shear and transverse modulus those of metals, and predictable responses that
of the unidirectional ply. Degraded plies are are familiar, although they are not optimal in
modeled by quasi-homogeneous plies so that strength-to-weight or stiffness-to-weight
laminated plate theory can be reapplied to ratios. Many laminates used today on aircraft
determine the ply stresses and ply strains. structures tend to be of this type. In general,
Another approach for the prediction of however, the more directional the loading, the
post-FPF strength can be based on macrome- bigger the payoff possible with anisotropic tai-
chanics, without resorting to micromechanics. loring.
The degradation factor (DF) is applied directly To improve on the performance obtained
to the transverse and shear modulus, as well with a quasi-isotropic laminate, the cost to
as the major Poisson's ratio. The exact value design and analyze the anisotropic part (using
for the degradation factor must be determined the tools like those discussed in this chapter) is
empirically.A value between 0.1 and 0.3 is rec- unfortunately often thought not to be worth
ommended. If the degradation factor is given the additional weight savings. This attitude is
a value close to zero, the quadratic failure cri- commonly rationalized by worry about holes,
terion can be made to resemble the maximum increase in work associated with more compli-
strain criterion and results in a generally con- cated fiber placement (preform assembly), etc.
servative estimation of laminate strength. In practice, laminate designs, if not quasi-
isotropic, are certainly still symmetric about
30.5 LAMINATE DESIGN
the midplane, balanced (equal quantity of -8
and +8 plies), and orthotropic. Capitalizing on
To simplify the analysis, it is commonly initially the benefits of anisotropy will probably occur
specified that a laminate will be constructed of in other industries first before being adopted
plies oriented with fibers in a few preselected by the more conservative aircraft industry.
directions, where only the percentage distribu- An exception to traditional aircraft laminate
tion in each orientation must then be design is the X-29 experimental aircraft, which
determined. Laminates with plies distributed demonstrated a unique attribute of anisotropy
every 45" are called n/4 laminates (plies can be (Fig. 30.8). The basis for this design lies in the
in the 0, 45, 90 or 4 5 directions. Ply orienta- important assumption that the 1,2,6 axes are
tions are usually specified as a value between usually the primary load directions for the
-90 and 90". For example, instead of identifying laminate. With the coordinate system for load-
the orientation as 135, the laminate orientation ing changed to be 20" off a designated
is more commonly called 45", although they laminate system, it can be shown that the lam-
are the same). Another class of laminates are inate behavior in flexure and torsion is
called n/3, where plies are placed every 60" coupled. In fact, twisting will result with flex-
(plies can be in the 0, 60 or -60 directions). In ural loading, even though the material would
both cases, an equal percentage of plies in each normally behave as most metals. This is the
698 Laminate design
principle used on the X-296. The normal ten-
dency for forward swept wings to diverge at
increasing speeds was counteracted by this
laminate design: the increase in lift creates a
decrease in angle of attack, as the laminate
twists in the direction opposing the forces.
It is conceivable that in the future the
graphite golf shafts currently gaining in popu-
larity could be tailored to the individual golfer.
The same coupling principle could be applied.
A golfer’s tendency to consistently slice the
ball might allow the designer to customize a
golf shaft which not only bends, but also
twists slightly under the bending load of the
bad swing.
30.5.1 UMQUE BEHAVIOR
The most unique features of composite materi-
als are the highly direction-dependent
properties. Highly coupled deformation and
load-carrying capability can be designed into
Fig. 30.8 Top view of the Grumman X-29 aircraft with wings that twist under flexure to counteract the
detrimental aerodynamic effects.@ NASA)
the laminate. Composite materials are not
merely a light-weight substitute for heavy-
weight metals. Structural performances which
are not possible with metals are easily achiev-
able. Examples of such unique properties
include Poisson’s ratios greater than unity or
even negative, bending-twisting coupling, and
zero or negative coefficients of thermal expan-
sion (CTE). The problems and examples below
illustrate the engineering constants of angle-
ply and related laminates. Examples of large
and negative Poisson’s ratios and examples of
bend-twist coupling are also given.
30.5.2 UNUSUAL POISSON’S RATIOS
Personal computer software based on a com-
puter spreadsheet allows rapid sensitivity
studies and parametric analysis of the behav-
ior of laminates. Laminated plate theory with
micromechanics is programmed into ’Mic-
Mac/In-Plane’2. A companion charting tool,
 Laminate design 699

'Chart-quick', can be used to plot variation of Table 30.1 Material property data for three differ-
CTE as a function of independent variables (0, ent carbon fiber systems: IM6/Epoxy, T300/5208
E,,, E,, vf, etc.). For the following problems and M40J/F584
and examples, the carbon fiber reinforced
polymer material data used are shown in lM6/ T300/ M40J/
Epoxy 5208 F854
Table 30.1.
Figure 30.9(a) shows the engineering con- Longitudinal tensile
stants for a unidirectional laminate as it is modulus, E x (Msi) 29.44 26.27 32.8
rotated from the on-axis. The Poisson's ratio, vx, Transverse modulus,
of a 0" laminate is approximately 0.3. With EY(Msi) 1.62 1.49 1.2
increasing angle of the off-axis laminate, the Poisson's ratio 0.32 0.28 0.26
Poisson's ratio decreases. The Poisson's ratio of
a 90" laminate is effectively zero, because con- Shear modulus, Es (Msi) 1.22 1.04 0.66
traction in the transverse direction is Longitudinal CTE, a1 -0.14
constrained by the fibers. Transverse CTE, a2 15
Figure 30.9(b) shows the engineering con-
stants for an angle-ply laminate. It is interesting Volume fraction V,(%) 66 70 62
to observe the very large Poisson's ratio of 1.32
for a [ S O ] laminate. A value of greater than one
implies that the transverse dimensional change image' of the longitudinal modulus, Ex.
is more than in the dimensional change in the Figure 30.10(a) shows the engineering con-
longitudinal direction of loading. stants for cross-ply laminates. For any given
When the ply angle is either 0 or 90", the laminate, the longitudinal modulus, Ex, and
laminates (and consequently the values for the the transverse modulus, E , are equal. The
engineering constants) in Figs. 30.9(a) and Poisson's ratio, vx, of a [d/90] laminate is
30.9(b) are the same. In both Figs. 30.9(a) and approximately zero, because of the presence of
30.9(b), the transverse modulus, E,, is a 'mirror fibers in the transverse direction. The largest

Modulus Poisson's Modulus Poisson's

(Msi) Ratio (Msi) Ratio
30 00 2 30.00 2

22.50 1.5 22.50 1.5

15.00 1 15.00 1

'
7.50 0.5 7.50 0.5

0.00 0 0.00 0
15 30 45 60 75

Ply Angle, 8 (degrees)

f -0.5
Ply Angle, 8 (degrees)
(4 (b)

Fig. 30.9 Engineering constants of IM6/epoxy laminates as a function of 6 for (a) off-axis unidirectional [e],;
and (b) mgle-ply [+el,.
700 Laminate design
LO7 (6 + 90>1,,
Modulus
(Msi)
30.00
22.50
15.00
7.50
0.00
15 30 45 60 75
Ply Angle, 8 (degrees)
(4
Fig. 30.10 Engineering constants of IMG/epoxy laminates as a function of 19for (a) cross-ply [I9,(0+ 90)],,;
and @) LO,, * qs.
Poisson's ratio is 0.55 for a [*45] laminate. The
shear modulus, E , is a maximum, of course,
for the [*45] laminate.
Figure 30.10(b) shows the engineering con-
stants for laminates with 50% 0" plies and 50%
angle-plies. With the exception of the trans-
verse modulus, the results are similar to those
for the angle-ply laminate shown in Fig.
30.9(b).When the ply angle is 90", the values
for the engineering constants in Figs. 30.10(a)
and 30.10(b)are the same.
Figures 30.11(a) and 30.11(b)show the engi-
neering constants for some unusual laminates.
When the ply angle, 8, is 15", Fig. 30.11(a)
shows an off-axisunidirectional laminate and
Fig. 30.11(b)shows an angle-ply. For all other
ply angles, the laminates are unbalanced.
From Fig. 30.11(a),it can be observed that the
[15/60Is laminate exhibits an extremely large
negative Poisson's ratio of -0.32, meaning the
laminate will expand in the transverse direc-
tion under longitudinal tension loading and
compress in the transverse direction under
longitudinal compressive loading. From Fig.
30.11(b), it can be observed that the [-15/30Is
LO, f 6,Is
Poisson's
15 30 45 60 75
Ply Angle, 8 (degrees)
(b)
laminate exhibits a very large Poisson's ratio
of 1.32, when compared with that of an
isotropic material (0.3). Besides the unique
Poisson's ratio behavior, it is also important to
examine the values of the other coupling coef-
ficients.
EXAMPLE
Table 30.2 considers the resulting deforma-
tions on coupon specimens under load, and
Fig. 30.12 indicates the relative magnitude of
deformation due to large and negative
Poisson's ratios.
30.5.3 STIFFNESS AND COUPLING
It is useful to look at the A, B, D stiffness matri-
ces of some simple laminates. For ease of
comparison, the stiffness matrices can be nor-
malized to have units of [force/length2]by
defining
[A*]= [ A ] / h , [B*] = 2[B]/h2,
 Laminate design 701

Poisson‘s [-I 5/9 14s Poisson‘s

,r”
Modulus
Ratio (Msi) Ratio
30.00 T ’ T 2
30’00 T
22.50 22.50 1.5
1
15.00 15.00 1

7.50 0.5 7.50 0.5

0.00 0 0.00 0

1 Ply Angle, 6 (degrees) 1 -0.5 Ply Angle, 8 (degrees) -0.5

(4 (b)

Fig. 30.11 Engineering constants of IM6/epoxy laminates as a function of 8 for (a) [15/8],s; and (b)
[-w~I,.

Table 30.2 Strains, deformations and strength ratio (based on first-ply-failure) of 10 in x 1 in x 0.1 in spec-
imens under 1000 lb longitudinal load, N,

Longitudinal Transverse Longitudinal Transverse Strength

strain strain displacement displacement ratio
El E2 A1 A2
R
Material (1C3in/in) in/in) (1C3in) (10-3 in)
.-
40ksi Steel 0.34 -0.10 3.4 -1.0 3.9
IM6/Epoxy 0.34 -0.11 3.4 -1.1 50.0
IM6/Ep 0.65 -0.02 6.5 -0.2 7.9
IM6/Ep 0.95 -1.29 9.5 -12.9 6.8
30ksi Aluminum 1.02 -0.30 10.2 -3.0 2.9
IM6/Ep 1.09 0.35 10.9 3.5 3.1
IM6/Ep 2.40 -1.77 24.0 -17.7 2.7
E-glass/Ep 3.20 -2.07 32.0 -20.7 4.5
IM6/Ep 6.25 -0.11 62.5 -1.1 0.8

Fig. 30.12 Relative deformation of 10 x 1 x 0.1 in specimens under 1000 lb load along the centerline (lami-
nates are IM6/epoxy, unless otherwise indicated).
702 Laminate design

A four-ply laminate consisting of two 0" and
two 90" plies can be combined into four differ-
ent laminates. From Table 30.3 it can be
observed that while the A* matrix remains
unchanged through varied ply stacking
sequences, large differences arise in the B* and
D*matrices.
From Table 30.4 it can be observed that only
the fourth laminate is unsymmetric and has a
B* matrix with nonzero terms. The first and
fourth laminates are balanced and so the A*16
and A*26coefficients are zero. For the second
and third laminates which differ by the sign of
the off-axis plies, the stiffness behavior differs
only in that the A*16,A*26,D*,6 and D*26coeffi-
cients are of opposite signs.
Table 30.5 displays different quasi-isotropic
laminates. Note that the normalized A* matrix

Table 30.3 Normalized stiffness coefficients for four IM6/epoxy laminates, in units of Msi

Layup 10/90/90/01 190/0/0/901 ~0/90/0/901 f 0/0/90/901

' 15.624 0.525
.15.624 0.525 0 '
'
15.624 0.525 15.624 0.525
[A*] 0.525 35.634 0 0.525 15.634 0 0.525 15.634 0 0.525 15.634 0
~ 0 0 1.220 0 0 1.220, , 0 0 1.220 0 0 1.220

- 6.997
:]I0
' 0 0 0 ' ' 0 0 3.499 0 0 - 0 0 '
[B*] 0 0 0 0 0 0 -3.499 0 0 -6.997 0
, o 0 o , , 0 0 0 0 o * , 0 0 0 .

26.129 0.525 0 . ' 5.138 0.525 0 ' ' 15.634 0.525 0 . .15.634 0.525 0 '
0.525 5.138 0 0.525 26.129 0 0.525 15.634 0 0.525 15.634 0
0 0 1.220. . 0 0 1.220, , 0 0 1.220, 0 0 1.220,

Table 30.4 Normalized stiffness coefficients for four IM6/epoxy laminates, in units of Msi

Layup [0/0/+45/-451$ 10/0/+45/+451+ [0/0/-45/-45Is f+45,/45,1

I
' 19.463 3.692 0 ' ' 19.463 3.692 3.499 19.463 3.692 -3.499- 9.297 6.859 0
[A*] 3.692 5.469 0 3.692 5.469 3.499 3.692 5.469 -3.499 6.859 9.297 0
, o 0 4.387. , 3.499 3.499 4.387 .-3.499 -3.499 4.387 . , 0 0 7.555 *

IB"1
* o
0
, o
0
0
0
:I
0 J
0
0
o
0
0
0 :ll!
0
0
0
0
: [:
0
0
0
3.499 3.499
3.499
3.499
0 I
II
27.087 1.316 0.656 27.087 1.316 0.875 27.087 1.316 -0.875 9.297 6.859 0
1.316 2.597 0.656 1.316 2.597 0.875 1.316 2.597 -0.875 6.859 9.297 0
0.656 0.656 2.012 0.875 0.875 2.012 -0.875 -0.875 2.012 0 0 7.555
 Laminate design 703

Table 30.5 Normalized stiffness coefficients for four IM6/epoxy laminates, in units of Msi

1[
I
12.466 3.692 0 12.466 3.692 0 12.466 3.692 0 12.466 3.692 0
3.692 12.466 0 3.692 12.466 0 3.692 12.466 0 3.692 12.466 0
0 0 4.387 0 0 4.387 0 0 4.387 I O 0 4.387

I
20.932 3.098 1.312 20.2115 2.504 1.968 18.194 2.782 3.735 22.001 1.932 0.737
3.098 5.188 1.312 2.504 7.094 1.968 2.782 8.558 2.208 1.932 6.451 1.956
1.312 1.312 3.793 1.968 1.968 3.200 3.735 2.208 3.477 0.737 1.956 2.628

terms are equivalent for all quasi-isotropic Multiplying out the strains, = a , , ~ , , E2 =
laminates. This means all have the same stiff-
a12N2/ ‘6 = a16N1
ness to weight ratio. (iii) Evaluate the displacements by integrating
The differences between these laminates the strains. (Note that for the tube,
thus manifests themselves only in how they
dd)
behave in bending. E =r-.)
dx
PROBLEM
Find the amount that an anisotropic 20-layer
[0/30], T300/5208, 3 in diameter, 12 in tube
1 Eldx = l:$dx = l:llNldx - u = allNIL

tube will extend, change in circumference, and

twist under an in-plane load, N, = 100 lb/in. I E2dy=$$dC =[a12NldC ---t z, = ul2N12nR

SOLUTION
1 L
(i) Compute the laminate stiffness matrix and -
+@ = a , 6 ~ l R
invert to get the compliance matrix: R

21.159 2.567 3.935

2.567 2.476 1.458 ,
3.935 1.458 3.195 I (iv) Evaluate the displacements numerically:
=-a*ll N L = - 62.563 x 100 x 12
h 0.1
= 0.75 x 10-3in

I
62.563 -26.647 -64.893
[a*] = -26.647 563.836 -224.518
-64.893 -224.518 495.374

(ii) Evaluate the strains:

I v = -Nl2nR
a*,,
h
26*M7 x 100 x 2 x 3.14 x 1.5
= -___
0.1
= -0.25 x 10-3 in

@ = -U*16
N- L = x 100 x 12/1.5
64 893L
-
h ‘R 0.1
= -0.52 x radian = -0.03 degree
704 Laminate design

30.5.4 CTE BEHAVIOR the a1 is -2 to -2.5 (versus -0.14 for a1 of the

The following four figures show the coefficient unidirectional tape, as shown in Fig. 30.13(a)).
of thermal expansion (CTE) in two principal As the number of ply angles increases, the
directions (referred to as a , and a,) for CTE behavior becomes less intuitive. Figure
M40J/F584 carbon fiber laminates. Figure 30.14(a) shows the CTE of a laminate with 50%
30.13(a)shows the CTE of an off-axis unidirec- 0 plies and 50% angle-ply; Fig. 30.1303) shows
tional ply; Fig. 30.1303) shows the CTE of an the CTE of a laminate with 25% 0 plies, 25% 90
angle-ply laminate. From Fig. 30.13@), it can plies and 50% angle-ply. Note that when &
be observed that, due to the Poisson coupling equals 45", the resulting laminate is quasi-
effect, laminate CTE values less than that of a isotropic [0, 90, &45] as confirmed by a ,
unidirectional material are possible for specific equaling a*. Examination of the fundamental
ply angles. In Fig. 30.13(b), for 0 of GO to do", trends in Figs. 30.13 and 30.14 indicates

16.00 16.00 -r
14.00 14.00
12.00 1200
10.00 10.00
8.00 am
6.00 600

-0
c
4.00

200
4.00
200
C
a,
._
0 0.00 0.00

0 -200
p 10 20 30 40 SO 60 70 80 90
-200
0 Ply Angle, 0 (degrees) -4.00
(b)

Fig. 30.13 Coefficient of thermal expansion of M40J/F584 laminates as a function of 8 for (a) off-axis undi-
rectional [e,],; and (b) angle-ply [&J,.

0
4.00 --
c
c 200 --

Ply Angle, 0 (degrees) Ply Angle, B (degrees)

(4 (b)
Fig. 30.14 Coefficient of thermal expansion M40J/F584 laminates as a function of 0 in the following lami-
nates (a>[o,, and (b) IO, ,90,, 4 1 , .

potential near-zero CTE laminates, particu-
larly useful in spacecraft applications to
minimize deformation due to the large cyclic
thermal loading.
EXAMPLE
To remove a composite shaft from a metal
mandrel after elevated temperature cure, the
laminate CTE in the hoop direction of the
cylindrical section has to be less than that of
the mandrel material to prevent lock-on. The
composite is considered to be stress-free at
cure-temperature, and thus the temperature
loading is associated with the temperature
decrease to room-temperature.
Figure 30.15(a) illustrates that it is preferable
to have the metal mandrel contract more than
the composite during cool-down, which
means that the metal CTE must be more than
the composite CTE. For a shaft with fibers pre-
a composite ' aofmandrel
(significantamount fibers
in hoop direction)
comDosite
AT<O
Fig. 30.15 Result of different coefficients of thermal expansion (CTE), a,for metal and composite cylindri-
cal sections under two thermal load cases.
Laminate design 705
dominantly in the longitudinal direction to
accommodate flexural loading (like a mast or
golf club), Fig. 30.14(a) indicates that a [O,,
G0JS with a steel mandrel would be a prob-
lematic choice, resulting in a composite shaft
locked on to the mandrel as shown in Fig.
30.15@).There is a need for sufficient fibers in
the hoop direction (90") to result in a laminate
CTE less than that of the mandrel material.
The CTE of the metal materials given in Table
30.6 indicates that it is easier to remove a com-
posite shaft from an aluminum mandrel than
from a steel mandrel.
Table 30.6 Average coefficients of linear thermal
expansion of selected materials
Aluminum alloy 12.8
Concrete 6.7
Invar 0.39
Steel
Titanium alloy 6.5
4.9
a composite ' a mandrel
(predominantly longitudinalfibers)
706 Laminate design
EXAMPLE
Carbon fiber room temperature curing materi-
als are often used for composite bicycle
frames. To prevent a metal-composite joint
from coming apart under in-service thermal
loading, the metal lug is generally on the
inside. Ideally, under an in-service tempera-
ture increase due to sun shining on a part
(which can be up to 82"C(18OoF)),or friction,
the lug will expand more than the composites.
REFERENCES
This 'seizing' action will prevent the lug from
breaking loose. If there are mostly longitudinal 1. Harper, R. The Fifth Halford Memorial Lecture,
fibers due to flexural design considerations,
2. Tsai, S.W. 1990 Composites Design, 4th Edn.,
the CTE in the hoop direction may be greater
than that of the metal; the metal fitting should 3. MIL-HDBK-23A, Military Handbook -
be then on the outside. More commonly, how-
ever, the composite has more fiber wound
around the lug (in the hoop direction) and the 4. Quinn B.J. and Sun, C.T. A critical evaluation of
CTE is less than that of the metal.
These are only two of the challenges in cop-
ing with different thermal expansion
coefficients of dissimilar materials. In general,
because of the low CTE of the fiber, multidirec-
tional laminates typically have a laminate CTE
less than metals. This can cause difficulties in
part manufacture, in cases of elevated cure. It is
generally desirable to match the CTE of a com-
posite part with the tooling to minimize
springback and residual stresses. A tool with
zero CTE results in a dimensionally more
accurate part; a tool with equivalent CTE
results in no chance of lock-on. Composite tool-
ing systems may be used in order to match
CTE; however, such tools usually do not have
the necessary durability over long production
runs.Steel tooling is often preferred over alu-
minum tooling because of the lesser CTE.
30.6 CONCLUSIONS
Composite materials have many well-known
advantages over other structural materials
including increased strength-to-weight ratio,
stiffness-to-weight ratio, increased fatigue life,
corrosion resistance, and the ability to tailor the
properties of the material. The extraordinary
freedom to design the laminated material is at
the price of more complicated analysis. This
chapter presented an explanation of the basic
mathematical tools used to design laminates
including laminated plate theory and the qua-
dratic failure criterion. Some examples were
provided to lend insight on the many options
for optimizing the material to particular needs.
J. Roy. Aeronaut. Soc., Apr 1966,70,477-486.
Think Composites, Dayton, OH, 1988.
Structural Sandwich Composites, Department
of Defense, Washington., 1968.
failure analysis methods for composite lami-
nates, Proceedings of the Ninth
DoD/NASA/FAA Conference on Fibrous
Composites in Structural Design, Lake Tahoe,
Nevada, Nov 67,1991, pp. V21-V37.
5. Tsai, S.W. and Hahn, H.T. Introduction to
Composite Materials. Technomic Publishing Co.,
1980.
6. Hadcock, R.N. X-29 Composite Wing, AIAA
Evaluation of Aircraft/Aerospace Structure and
Materials Symposium, Air Force Museum,
Wright-Patt AFB, Apr 24-25,1985.
7. Popov, E.P. Mechanics of Materials, 2nd Edn.,
Prentice-Hall, Inc., 1976, p. 295.
OTHER READING
MIL-HDBK-17-2C, Military Handbook - Polymer
Matrix Composites, Vol. II: Material Properties,
Department of Defense, Washington D.C., Feb
25, 1994.
MIL-HDBK-17-3D, Military Handbook - Polymer
Matrix Composites, Vol. 111: Utilization of Data,
Department of Defense, Washington DC, Feb
28,1992.
Hyer, M.W. Calculations of the Room-Temperature
Shapes of Unsymmetric Laminates, J. Composite
Materials, 1981,15,296-310.
Hyer, M.W. Some observations on the cured shape
of thin unsymmetric laminates, J. Composite
Materials, 1981,15, 175-194.
 Appendix B 707

Garfinkle, M. Twisting Smartly in the Wind,

Aerospace America, American Institute of m2 -mn n2
Aeronautics and Astronautics, Reston, VA, July = n2 mn m2 (30.A8)
1994, 18-20.
Smith, E.C. Vibration and Flutter of Stiff-Inplane 2mn -2mn m2-n2
Elastically Tailored Composite Rotor Blades,
34th AIAA/ ASME/ ASCE / AHS/ ASC
Structures, Structural Dynamics and Materials
Conferece, La Jolla, CA, AIAA-93-1302-CP, Apr
19-21, 1993, pgs. 26-37.
-2mn 2mn m2- n2
NOTE
MIL-HDBK-23 is obsolete and no longer available.
The data is being included in MIL-HDBK-17, which
can be obtained from DODSSP, BLDG4D, 700 ‘11 ‘12 ‘16’ 1
Robbins Ave., Philadelphia, PA 19111-5094, or ~
‘12 ‘n ‘26 = x (30.A10)
http:/ /www.dodssp.daps.mil.
‘16 ‘26 ‘66 I

30.7 APPENDIX A: TRANSFORMATION

RELATIONS
.A27!A, - A;6 A16A26 - A17!26 -
-
-A1866 -
There are several useful transformation rela- LA17!26 - A27!16 - - A:2
tions (prime refers to the off-axis coordinates
1,2,6 and no prime refers to the on-axis coor- where the determinant is IAl = (A,,A, - A:,)A6,
dinates x, y, s as in Fig. 30.3). + 2Al.$26A16 - A,,A;, - A2,A:,. The flexural stiff-
ness matrix [D] can be inverted similarly to
{a’}= Ullal (30.A1)
obtain the compliance matrix [d].
(4 = Ul-’la’} (30.A2)
30.8 APPENDIX B: MORE DETAILS ON THE
QUADRATIC FAILURE CRITERION5

{&’I = (30.A4) 30.8.1 DETERMINING THE COEFFICIENTS

A useful exercise is to review how the F coeffi-
(Q’} = UIIQIVI (30.A5)
cients in the quadratic failure criterion
where m = cos 6, n = sin 6 .
F,,a: + 2Fqaxay+ FyYai+ FS& + Fxax+ Fyay= 1
m2 n2 2mn (30.B1)
ul= n2 m2 -2mn (30.A6) are mathematically determined from the ply
-mn mn m2--n2 strength properties. During a uniaxial tension
test of a 0 degree unidirectional laminate along
the longitudinal axis (pulling in the direction
m2 n2 -2mn of the fibers), ax = X and ay = os = 0.
n2 m2 2mn (30.A7) Substituting into eqn (3O.B1), the failure crite-
mn -mnm2-n2 rion reduces to
FxxX+ FIX = 1 (30.B2)
708 Laminate design

During a uniaxial compression test of a 0 familiar from isotropic materials. The most
degree unidirectional laminate, a, = X' and a common form of the von Mises criterion is
= as = 0 and the failure criterion in eqn (30.Blf probably the equation written in terms of the
reduces to principal stresses in three dimensions7.
FxxX'-FxX = 1 (30.B3) (a,- a,)' + (a, - a,), + (a,- a,)*= %2yield
Solving the two equations given by eqns
(30.B7)
(30.B2) and (30.B3) for two unknowns, F,, and
F,, yields For plane stress a, = 0, eqn (30.B7) becomes
1 a: - ala2+ a; = a*,,d (30.B8)
Fxx = xx'
Instead of computing the principal stresses,
(30.M)
11 the von Mises criterion in eqn (30.B8) can also
F =--- be written in terms of a general stress state that
x X' includes a shear stress contribution
Similarly for the transverse direction, a 90
- aXay+ 0; + 30: = (30.B9)
degree unidirectional laminate can be experi-
mentally evaulated under uniaxial tension (ay Now, for comparison, the quadratic failure cri-
= Y, a, = as =0) and compression (ay= Y', a, = terion is repeated here
as = 0).
Substituting each test situation into the qua-
FxXa:+ 2Fya,uy + FW$ + Fssa:+ Fp, + Fyay= 1
dratic failure criterion and solving the two
(30.B10)
equations, the resulting two unknown coeffi-
cients, Fw and Fy,would be where
1 1
1
1
1

F =- (30.B5) F = F = - (30.Bll)
Yy' Yy'
~

YY xx XX' YY

1 1 1
F =--- Fss = 7 Fy=F*yd(Fx,FYY)
!I Y Y' S
For a shear test, a, = S and the resulting coeffi- 1 1 1 1
cient is F =--- F =---
X X ' Y Y Y'
1
F ss = -s2 (30.B6) We can recover the von Mises failure criterion
for isotropic materials when F*y = -1/2 and
The sixth coefficient, F ,must be determined by setting the strengths to be the same in all
empirically from biaxiar tests such that directions
FXY= F*&&) X = X' = Y = Y', S = X/d3 (30.B12)
To have a closed failure envelope, Fey must be where the 43 factor is the result of the von
between -1 and 1. Mises invariant. Substituting expressions in
eqn (30.B12) into those of eqn (30.Bll) and
then rewriting eqn (30.B10) results in
30.8.2 RECOVERING VON MISES CRITERION
It may be useful to review the quadratic failure
0; - O ~ O ~+ +ai = x2 (30.B13)
criterion and make it less of a mathematical which matches eqn (30.B9).
abstraction by comparing it with what is
DESIGN OF STRUCTURE WITH COMPOSITES 31
F.J. Schwan

to avoid confusion in this chapter. The term

31.1 INTRODUCTION
'material properties' is used generally to
Composite materials are finding more uses include extensional and compressive moduli
each year across a wide spechum of applica- of elasticity, Poisson ratios, inplane shear mod-
tions. Designers of structural components, in ulus, coefficients of thermal expansion and
particular, continue to find new applications for coefficients of moisture expansion. 'Design
reinforced composite materials. The most suc- allowables' refer to material strengths, specifi-
cessful structural applications are those where cally tension, compression, inplane shear,
the innate advantages of reinforced materials interlaminar shear and bearing. This distinc-
can be translated into performance advantages tion between material properties and strengths
for the manufactured part. These advantages is established because of the significant differ-
include stiffness-to-density ratios, strength-to- ences which exist in our ability to predict and
density ratios, low thermal expansion measure each group, and because of the differ-
characteristics, and occasionally others, such as ent treatment which properties and strengths
resistance to specific environments, thermal receive in all phases of the design process.
conductivity, and fatigue characteristics.
This section focuses on the design of com-
31.2 DESIGN PROCESS
ponents determined by mechanical
performance requirements such as stiffness, A general comment concerning the contents of
durability, or strength. The importance of this section, and the chapter in general, is that
establishing and articulating design require- the perspective represented throughout the
ments cannot be overstated. The extent to chapter is that of a designer within a large
which design requirements are isolated and organization, operating as part of a large
quantified determines the degree of certainty design team, a situation typical of aerospace
associated with trade studies and material projects. However, the process is the same for
selection decisions. Unsuccessful applications all sizes of projects involved with design of
are quite often the result of unclear or poorly composite structure. The primary differences
defined design requirements. are in the formality associated with each step in
Two terms which will be used extensively the process. In large organizations, extensive
throughout this chapter are 'material proper- documentation tends to occur at each step,
ties', and 'design allowables'. Since there are while in one-man teams little informal, and
no universally accepted definitions of each of usually no formal documentation is required.
these terms, it is necessary to adopt definitions The process itself, however, is the same.
A typical conceptualization of the design
Handbook of Composites. Edited by S.T. Peters. Published process is presented in Fig. 31.1. While the
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 process is generically the same for all engineer-
710 Design of structure with composites

Peliminary desian

Preliminary material selection

Detailed desian
Member sizing - laminate design

Material specs

Process specs 7'

-joint design
-tooling design

Manufacturing development
- I
Engineering
development
tests
- materals
- critical elements
- inspection techniques

Design - analyses
verification - prototypes
- testing
Fig. 31.1 The design process. - non-destructive evaluation

ing materials, the content of each box in the Table 31.1 Design requirements for an aircraft sta-
chart varies with many factors, including the bilizer
materials of construction. The intent of this dis- ~~~~~~~~

cussion is to provide some guidelines on what Type of Description

information is required to make key decisions requirement
and eventually converge on a design when Geometric Maximum length
composite materials are under consideration. constraints Maximum root and tip dimensions
The complex series of decisions which we Production Number of units per month
refer to as the design process is commonly rate
considered to comprise two phases: prelimi- Cost/ Maximum weight; $ per kg of
nary design and detailed design. Each phase benefits weight saved
requires a different level of requirements defi- Minimum service life; + $ per
nition and application. additional hour of service life
Figure 31.1 indicates the information and Environmental Service temperature extremes
data required to proceed in each phase. This Chemicals - cleaning solvents,
data typically includes many kinds of infor- fuels, oils
- concentrations
mation about the materials of construction and - exposure periods
the fabrication processes to be considered.
Design characteristics for each material are an Mechanical Stiffness
important subset of this information. - maximum tip deflections
- aeroelastic performance
The objective of the preliminary design Strength
process is to develop a design concept to a - imposed strains acceptable
level that includes configuration, materials, under design loads with factors
and preliminary assessments of performance, of safety included
cost and manufacturing approaches. To sup- - fatigue life derived from
port these determinations, a set of material required service life
characteristics data is required. As an example,
key design requirements and a sample of what
data is required to support preliminary design
 Design process 711

Table 31.2 Preliminarymaterials data for aircraft stabilizer study

Type of data Form of data

Available material forms Prepreg
-tape widths
- thicknesses
Pultruded forms
- shapes
Resin systems
Specification details
- fiber volume
- void content
- density
- etc.
Material availability
Manufacturing characteristics Handling characteristics of material in automated tape laying process
Cure characteristics
- gel time
- resin flow
Prepreg storage conditions
Cost data Material price
Material development tests
Manufacturing hours
Tooling costs
Environmental resistance Service temperature limits
Moisture absorption characteristics
Chemical resistance
Mechanical characteristics Material properties
- extensional and shear modulus
Allowable strains
- tension
- compression
- shear
Fatigue data
- strain against number of cycles to failure

of an aircraft component are shown in Tables
31.1 and 31.2 respectively. The component
selected for this example is a vertical stabilizer.
The design requirements define maximum tol-
erable deflections, imposed loads, a weight
goal, production rate, cost goal, service life
and operating temperature extremes. In real-
ity, the set of preliminary design requirements
would be much larger including, perhaps,
maintenance and inspection characteristics,
descriptions of qualification tests, center of
gravity characteristics, and numerous others.
The data required to support preliminary
design investigations include stiffness, den-
sity, strengths, fatigue characteristics, data at
elevated and low temperature, forms in which
the material is available and associated mater-
ial prices. In addition, some experience with
the material in the fabrication process selected
is required to support decisions concerning
production rates and costs. Generally, reliable
published data can be used for preliminary
design. Only when no data is available is it
necessary to generate data in this phase of the
design.
712 Design of structure with composites
The sequence of decisions in this design
case would typically be to make a preliminary
decision on a manufacturing technique, fol-
lowed by selection of one or more materials
based on cost and availability. Once this has
been done, the component is 'sized' for stiff-
ness, strength and service life in each
candidate material. Material properties and
strengths are used for these calculations.
Material selection may depend on weight
minimization or life cycle cost minimization
or a combination of the two criteria.
The result of this process is a material selec-
tion and a preliminary design. This 'design'
possesses enough detail to support confidence
that (1)the material selection is justified, and
(2) that the design concept is feasible in this
material. The set of mechanical properties and
strengths was, by no means, a complete or final
set of design values, but rather contains those
characteristics needed to support preliminary
design calculations. These values are generally
the 'best available' from material supplier data,
literature publications, data from other projects
and data from material specifications.
While the dominant design goal of aerospace
designers is usually to reduce weight, the dri-
ving requirements vary widely from one
product to another. Table 31.3 provides a syn-
opsis of the diversity of these requirements
across defense and commercial industries. This
table indicates that requirements are numerous
and, therefore, the derived design objectives are
diverse and numerous. Payoffs are achieved in
the form of weight savings or greater service
life. Sometimes, as in the case of carbon-carbon
rocket nozzles, the use of composite materials
results in a new level of performance which is
difficult to quantify due to a lack of economic
alternatives. Table 31.3 shows a very large
range in quantified payoffs. Each of these prod-
ucts reflect a history of successive applications
and successive generations of the same applica-
tion. With each successive development effort,
the industry has become better at understand-
ing and defining requirements, material
characteristics, and payoffs. Since composite
materials incur increased engineering develop-
ment, testing, and increased raw material costs,
data from previous applications is quite valu-
able in performing cost trades and making
preliminary design decisions.
Table 31.3 suggests the ever-increasing
scope of structural applications for reinforced
composites. The requirements identified in
this table are as diverse and varied as the
components. The result of the wide range of
requirements imposed upon composite mate-
rials, compounded by the ingenuity of
material developers, has led to an over-
whelming array of constituent materials.
Many of these materials are very specific sys-
tems with a narrow range of applications.
Some materials are suited to numerous uses.
This multiplicity of materials and features has
produced a plethora of design data. In order
to make material comparisons and selections
on a rational basis, the designer needs to
establish a clear set of requirements for the
material. These requirements are sometimes
captured in a document which governs mate-
rial procurement. The aerospace industry
typically refers to these documents as mater-
ial specifications.
The situation in which the structural
designer usually finds himself at the initiation
of a design includes a broad and usually
incomplete set of requirements and a moun-
tain of literature on a vast array of materials. A
design checklist, such as that contained in
Table 31.4, may be of some help in getting
started in this situation. This checklist offers a
systematic approach to determining what
information is needed at each step and sug-
gests which design team members need to be
involved at various points in the process.
The structural design team will employ a
process which resembles this one in order to
develop a preliminary design which specifies
configuration, materials, manufacturing
process, and establishes a basis of confidence
to proceed with final design. This basis com-
prises having answers or a plan to develop
answers to all key questions.
 Design process 713
c
a,
Y
a
8
.3
4
3
714 Design of structure with coinposites
Table 31.4 Design checklist for composite structures
What do 1 need to proceed with design of a structural component in composites?
1. A clear design objective
2. Some quantitative measure of what
that improvement is worth
3. A manufacturing approach
4. Material properties and allowables
5. Material procurement
6. Joint concepts
7. Design verification
8. Inspection
Fig. 31.2 Design team.
What am I trying to achieve?
Are the tooling concepts feasible?
Are the fabrication processes well defined?
Do I need tool try units?
Which characteristics are critical?
How will I establish and verify these?
Will materials be procured to specifications?
Do all specifications already exist?
Will materials be available in suitable time and quantities?
Is material development or tailoring necessary?
How is the component to be attached to adjacent parts?
Do I need special tests because I am using composites
e.g. exposure to temperature or moisture?
What kind of prototypes do I need?
What tests will I subject the component to?
What am I looking for?
What are my accept/reject criteria?
What techniques will I use?

Figure 31.2 shows the makeup of a typical
design team. For designs with composite mate-
rials, the team may be larger than design teams
using other engineering materials. The focus of
the team is the individual with design responsi-
bility. Essential members are representatives of
manufacturing, tooling, and materials procure-
ment. Others might include materials
suppliers, and specialists in testing and analy-
sis. In some product development activities, the
team includes subcontract managers or mater-
ial procurement specialists who interact both
with other team members and with other com-
panies who also need to be considered as team
members. More important than the list itself, is
the early and continued involvement of all
members. Interaction among these team mem-
bers produces the design. As shown in Fig. 31.1,
preliminary design begins with requirements
definition and produces a design complete to
the point of materials identification, fabrication
approaches, size and shape, and preliminary
lay-ups and joint designs. The development of
this information requires the constant input
and review of all key team members.
One feature of the design team which is
unusual is the inclusion of the material sup-
plier in the design team. There are several
reasons for doing this. Sometimes, existing
materials do not 'fit the bill'. In these instances,
further material development or modification
may become part of the design process. The
material specification can be looked at as a
blueprint for the material supplier to use in
design of the desired material. It is important
to recognize the material supplier as a member
of the design team so that his inputs and
development efforts can be integrated into the
design. Otherwise, some beneficial options
may be excluded, both in terms of existing
materials and near term material development
efforts which may be of value to the project.
31.3 PRELIMINARY DESIGN
The discussions which follow concern the por-
tion of the design process characterized as
Preliminary design 715
preliminary design. The primary assumption
made in this section is that the materials of
construction are laminated composites with
continuous fiber reinforcement. These materi-
als are typical of structural applications.
31.3.1 MATERIALS
The subject of material design data, and the
closely related subjects of material characteri-
zation and specifications, assume greater
importance for composites than for conven-
tional materials. There are several primary
reasons for this: lack of a single, comprehen-
sive design database or source; greater
variability in measured values from one mate-
rial to another and from one lot of the same
material to another; differences between pre-
dicted and measured component performance
introduced by variables associated with
'workmanship' in the manufacture of the part.
The most basic reason, however, is the simple
fact that the engineering development process
encompasses design of both the material and
the structure. For these reasons, the designer
of composite structure needs to focus more
attention, and usually more resources, on the
subject of materials, than his counterpart
using only conventional materials.
Material data is required in order to make
key design decisions, first in the preliminary
design phase and later in detailed design. The
type and extent of the data depends on the
application, but, typically, data on the stiff-
nesses, strengths, and densities of candidate
materials is needed.
Figure 31.3 shows relative ranges of specific
tensile modulus for composites with various
fiber reinforcements. Specific modulus is a
term which refers to the ratio of composite
modulus to composite density. Specificmodu-
lus is a measure of stiffness per kilogram of
material, and is commonly used as an aid in
material comparisons. Figure 31.4 shows the
ranges of material costs for these same families
of materials. Both of these figures were con-
structed considering the entire range of
716 Design of structure with composites
300.00 T
cn 250.00 --
-aa
200.00 --
$g
-‘8 3 150.00 --
8
=a
En
u
z
s2. 100.00 --
u
8
2 50.00 --
0.00 I
I
I
EGLASS ARAMID
FIEF! FlBER
Fig. 31.3 Specific tensile modulus of various composite materials.
properties available from each specific mater-
ial. These ranges are the result of including
different forms of the material and the entire
range of laminate values, including quasi-
isotropic values on one end and unidirectional
values on the other.
Figure 31.4 suggests some general conclu-
sions. First, there are three more or less distinct
regions of composites. The first group is glass-
reinforced composites. The second is
intermediate modulus graphite and aramid
fiber-reinforced composites. The third group
includes high and ultra high modulus graphite
fiber composites. Each of these types is suitable
for a distinct range of applications. A compari-
son of where the common metals fall on this
figure provides a pretty good explanation of
why aramid and graphite have replaced metals
in applications where the market can ’pay for
performance’. Glass has replaced metals in
those applications where some performance
can be sacrificed for lower cost, increased envi-
ronmental resistance or longer life.
The second conclusion suggested by Fig 31.4
is that there is extensive overlap in the price of
aramid and intermediate modulus graphite
fiber composites. Selection from this group of
I
I ,
I
I
T300 M I-M
GRAPHITE GRAPHKE GRAPHITE
FER
Material
materials is usually made on the basis of per-
formance. Figure 31.4 considers only material
cost, which in some applications, is the major
portion of product cost. In other applications,
material cost is completely overwhelmed by
manufacturing costs or other life-cycle costs.
Material cost is typically about 30% of compo-
nent cost in aircraft parts, less than 10% in
satellite components, and generally higher than
30% in most commercial applications. It is
therefore critical that product cost analysis
include all important cost contributors.
Generally, ’you get what you pay for’ or,
more precisely, ’you must pay for what you
need.’ However, the range of properties and
costs within a family of materials is an indica-
tion of the latitude which a structural designer
has when employing reinforced composites.
The upper end of each range of specific
modulus in Fig. 31.3 is established by values
for a unidirectional laminate. While this is one
equitable basis for comparing reinforced mate-
rials to each other, it is not a good basis to use
for design calculations because so many
requirements drive the design towards multi-
directional reinforcement. Foremost among
these is the need for properties in more than
 Preliminary design 717

1000 -

900 --

800 --

P '0°--
600-- W HMSYMBOUZES HIGH MODULUS FIBERS
INCLUDING GY70, M60J, PlOO & P120
500.-
IMSYMBOUZESINERMEDIATEMODULUS
4
EI- 400-
FIBERS INCLUDING T40, T50, T650 AND
M40J

9 300.-

200 --

100 --

3
I-
Fig. 31.4 Costs of composite materials.
140

120

100

h
0
u) 80
3
#
5
t
s 60

40

20

Fig. 31.5 Mechanical properties of M laminates - T300/epoxy (0.60 fiber volumes).

718 Design of structure with composites

one direction. Figure 31.5 shows the relation-
ship of tensile modulus in x and y directions
and inplane shear modulus (xy) for a varying
lay-up angle, 13.The same type of relationship
exists for strengths and thermal expansion
coefficients. A design which maximizes modu-
lus in one direction at the same time
minimizes modulus in the direction transverse
to this and minimizes inplane shear modulus
as well. Strength in the transverse direction
and inplane shear strength will be low in mag-
nitude also. These low properties and
strengths in the 'secondary directions' will
severely limit the ability of the laminate to
resist load and deformation in these direc-
tions. Highly directional laminates are
therefore not appropriate for structures which
act as plates or shells, and for beams with sig-
nificant secondary loads. Highly directional
laminates also present severe design con-
straints in joint regions where loads are
multi-directional in nature.
Multi-directional reinforcement offers a
more robust design because strengths and
properties are dominated by fiber properties
in all inplane directions. Furthermore, lami-
nates with multi-directional reinforcement
offer more desirable cure characteristics and
usually avoid high levels of residual stress,
internal damage or warpage in thin parts,
induced by cooldown from cure temperatures.
Successful instances of unidirectionally rein-
forced parts are nearly non-existent.
Table 31.5 provides a typical list of materials
data required for structural design in rein-
forced composite materials. This table shows
mechanical properties and strengths for four
fiber-reinforced materials. These material
properties and strengths are the basic data
from which laminate values are calculated. As
explained in Chapter 30, lamination theory
simply uses layer values to determine engi-
neering constants and to estimate strengths for
any desired laminate. Materials testing is
therefore conducted primarily at the layer
level. Laminate test coupons are employed to
confirm predictions and 'workmanship'. The
exceptions to this statement are strengths
which are laminate-specific, such as bearing
strength and interlaminar shear strength.
However, these are values which are impor-
tant to only specific regions of the component,
and generally do not enter into material selec-
tion decisions.
For preliminary design, laminate values are
typically predicted from available ply-level
values. Design calculations and trades are con-
ducted with these predicted laminate values.
Later, in detailed design, predictions are con-
firmed with selective tests of design laminates.
Carpet plots
The infinite number of combinations of ply
thickness, ply angle and material reinforce-
ment is both a curse and a blessing in
preliminary design. Once the design require-
ments have been identified and quantified, the
question of how to meet these requirements
with any given material presents itself. An

Table 31.5 Typical materials data for preliminary design

~~ ~~ ~

Material Mechanical properties Strengths

Fiber volume Density Modulus Tensile Compressive
fraction (dcrn3) ,Tong, Trans, Long. Trans. Long. Trans.
(GPa) (GPa) (MPa) (MPa) (MPa) (MPa)
T300 Fabric 0.6 1.55 68.9 68.9 620 620 414 414
M60J Tape 0.6 1.69 248 5.52 993 27.6 496 172
PlOO Tape 0.6 1.74 414 4.14 827 27.6 414 138
Aramid fabric 0.6 1.36 37.2 37.2 827 827 138 138

extremely useful tool in addressing this ques-
tion is the simple carpet plot. This graphical
representation provides a way to present the
entire range of properties, or strengths, avail-
able from a particular family of laminates.
Figure 31.6 shows a carpet plot of tensile mod-
ulus for laminates comprised of layers of
T300-epoxy with orientations of 0,45 and 90".
The plot contains all possible proportions of
the three directions, and is read as the legend
indicates. This type of plot treats laminates as
homogeneous combinations of various per-
centages of layers. Carpet plots do not
recognize lay-up sequence. Generally, this pre-
sents no limitation, but for laminates
composed of very few plies, or laminates
employing significantly unbalanced stacking
sequences, the assumption can lead to incor-
rect strengths.
Carpet plots of material properties are con-
structed directly from a table of values for
many specific laminates. Values of moduli,
Poisson ratios, and expansion coefficients are
calculated from lamination theory for a series
of laminates with varying percentages of rein-
140
120
0 1
0 10 20 30 40 50
PERCENTAGE4M)EGREE LAYERS
Fig 31.6 T300/epoxy x-directionmodulus.
Prelimina y design 719
forcement in each of three specified directions.
While 0, 45 and 90" plies are most commonly
used, the three angles can be any selected val-
ues. Another common combination is
0/30/60. Typically, values are calculated using
a difference of 10%between successive points,
which requires about 1000 data points per set
of curves. For this reason, creation of carpet
plots is done with the aid of computers.
Development of carpet plots of strength
values is less straightforward. The primary
complication is the definition of failure of the
laminate. An extensive discussion of laminate
failure modes is contained in Chapter 30.
Calculation of laminate strength involves con-
sideration of progressive failure of each layer
and construction of strength envelopes for
combined states of loading. Construction of a
carpet plot requires an approximation of ply
strength which is adequate for preliminary
trade studies and initial member sizing. The
recommended approach is to define laminate
strength as the product of allowable fiber
strain and the laminate modulus in the appro-
priate direction. This calculation assumes that
-0- 0% 0 LAYERS
++ 10% 0 LAYERS
-C-20% 0 LAYERS
4 3 0 % OLAYERS
+40% OLAYERS
43- 50% 0 LAYERS
+60% OLAYERS
4 7 0 % 0 LAYERS
+80% OLAYERS
+90% 0 LAYERS
+100% 0 LAYERS
I
60 70 80 90 100
720 Design of structure with composites

the laminate contains fibers oriented in at least
two directions, and further ignores the Poisson
effect in the calculation of strength. While this
approximation tends to overpredict strength,
it has proven to be suitable for preliminary
laminate selection in strength critical struc-
ture. Using this definition of strength, carpet
plots can be directly constructed from allow-
able tensile and compressive strain values,
and predicted modulus values.
Carpet plots provide a quick method for
selecting a candidate laminate for the prelimi-
nary design process. For example, let us
assume that design calculations indicate that a
modulus of about 90 GPa is required. The car-
pet plot of Fig. 31.6 offers a large number of
laminates which meet this single requirement.
One is a laminate comprised of about 55%
0" layers, 35% 45" layers and 10%90" layers. If
tensile strength and inplane shear stiffness
were important to the design, it would be nec-
essary to consider the values associated with
the selected laminate. Related carpet plots pro-
vide ranges of tensile strength (Fig. 31.7) and
shear modulus (Fig. 31.8). These are about
427 MPa and 15.5 GPa, respectively. If this set
of properties were not suitable, the three carpet
plots would be used to iterate to an optimum
set of values and an accompanying laminate.
The use of carpet plots can greatly facilitate
the laminate selection process in the early
stages of design. It should be noted that these
plots are simply visual representations of the
results of lamination theory calculations, using
ply level input values. Carpet plots of all
inplane material properties: elastic moduli,
Poisson ratios, thermal expansion coefficients
and moisture expansion coefficients can be
developed from the appropriate equations.
Design values
Appropriate values for properties and
strengths are required in both of the primary
design phases - preliminary and detailed. For
preliminary design, values are typically
acquired from existing sources. These can
include data published or provided by mater-
ial suppliers in the form of brochures, design
handbooks, data sheets, data published in

'0° T

-D- 0% 0 LAYERS

2- 600
A

X- 10% 0 LAYERS
+20% OLAYERS
I
&w 500 -A- 30% 0 LAYERS
+40% 0 LAYERS
a +50% 0 LAYERS
b
w
400
+60% 0 LAYERS
d -A-70% 0 LAYERS
v)
300 +EO% 0 LAYERS
t-
+90% 0 LAYERS
200 +loo% 0 LAYERS

100

0 1
0 10 20 30 40 50 60 70 80 90 100
PERCEMAGE W E G R E E LAYERS

Fig. 31.7 TSOO/epoxy x-direction strength.


40 T
0 0 0 0 0 0
7 01 r n d In
PERCENTAGE&DEGREE LAYERS
Fig. 31.8 T300/epoxy x-direction shear modulus.
professional society proceedings or publica-
tions, data from textbooks such as this one, or
data developed on previous projects within
the organization. An abbreviated list of
sources of preliminary design data is pre-
sented at the end of this chapter.
As might be expected, this available data
comes in various forms, so comparison of data
from different sources may require some judg-
ment and mathematical manipulation. Fiber
volume fraction usually varies from one
source to another. The data is sometimes nor-
malized to a 'standard' value, typically about
60%. This normalization process is rarely
explained in the literature, but most often con-
sists of simply multiplying measured values
by the ratio of 0.60 to whatever fiber volume
was measured. The values most frequently
normalized include tensile and compressive
modulus, and tensile and compressive
strength. The validity of normalizing compres-
sive strength is debatable because
compression strength of reinforced composites
is dependent, to some extent, on the matrix.
The validity of normalizing values other than
the four mentioned above is dubious.
Preliminay design 721
t
I
0 0 0
(D b 00 : g
F
Test methods also tend to vary from one lab-
oratory to another. In general, it is best to be
wary of specimens other than the standard
ones. Standard coupons and test methods are
defined by the American Society for Testing
and Materials (ASTM), and other organiza-
tions such as Suppliers of Advanced
Composite Materials Association (SACMA).
The primary value of employing standard
coupons and tests is the confidence established
with time and existing databases. While each
standard coupon may possess some shortcom-
ing, it does offer consistency and a basis of
comparison with existing data.
Fiber volume and coupon configuration are
only two variants present among published
data. Others include the resin system, material
form, and method of fabricating panels from
which specimens are taken. These variants
underscore the reasons why existing data can
be useful for preliminary design, but almost
always needs to be augmented or replaced by
data specific to the design application for final
design. Two different approaches are
employed in the development of design val-
ues. The first of these is to buy existing
722 Design of structure with composites
commercial grade composite material, charac-
terize it, and design to those values. The
second is to include the material supplier in the
process by jointly developing a specification to
which the delivered material must comply.
While the second approach may increase mate-
rial costs, it guarantees the suitability of the
material and usually results in the use of
higher or more specific design values.
A material specification typically defines
acceptable values of all critical characteristicsof
the material to be purchased. The specification
may be a simple one page document speclfylng
reinforcement, resin system, and limiting val-
ues of fiber volume, or a multiple page
document including minimum values of mod-
ulus, strengths, cure characteristics, and other
items. Material procurement cost will tend to
follow the number and stringency of the criteria
specified, since the material supplier will need
more quality assurance activity before delivery
and may need to perform additional material
development.The more demanding a specifica-
tion becomes, the greater the need to identify
and work with one (or more) material suppliers
in its development. One reason for this is sim-
ply to ensure the development of a specification
which can be met by at least one supplier. A
good specification needs to recognize the nor-
mal variation in material characteristics from
one manufactured lot of material to another.
Data illustrating this lot-to-lot variation will be
shown and discussed in a later section of this
chapter.
31.3.2 DESIGN EXAMPLE
Key aspects of the preliminary design process
have been described in this chapter. An exam-
ple, consisting of the design of a composite
beam, is included here to illustrate the
methodology typically employed in prelimi-
nary design, and to provide a demonstration
of a trade study performed for the purpose of
material selection.
The structural element selected is a beam of
constant cross section, fixed against
displacement and rotation at both ends, and
loaded by a uniform load along the entire
length, I, as shown in Fig. 31.9. Design require-
ments are summarized below:
w = 2.0 nVmm
A
S h
I = 1500 mm
4
Fig. 31.9 Example: trade study of beam with a uni-
form load.
1. Maximum beam weight is not to exceed
5.0 kg or 3.33 g/mm excluding end fittings.
2. Maximum beam deflection (at midspan)
must be less than 2.5 mm under the load
shown in Fig. 31.9.
3. Maximum stresses in the beam must not
exceed allowables, including a factor of
safety of 2.0.
4. The cross section of the beam must be
closed and rectangular as shown.
Four materials will be considered for this
application: aluminum (7075 alloy), E-
glass/ epoxy composite, T300 graphite / epoxy
composite, and M60J graphite/epoxy compos-
ite. Formulas for deflection, maximum
compressive stress, and beam weight, in
pounds per inch, are presented below:
Deflection: d = (w14/384EI)
where €I = (Ebth2)/2
Max. stress: f, = M c / I
f, = ( M / W
= (wL2/4hbt)
Weight: W = v(2h+2b)t < 3.33 g/mm
One additional constraint must be introduced to
the design. Buckling of one side of the rectangu-
lar section is governed by elastic moduli and by
the width-to-thickness ratio of that side. The
crippling strength of a side can be sigruficantly
lower than the laminate compressive strength or

inplane shear strength. In order to prevent com-
pressive or shear buckling of the sides and
flanges, a rule of thumb is to limit the side
dimension, h, to no more than twenty times the
thickness, and to limit the flange dimension, b,
to no more than fifteen times the thickness.
Using these relations, h and b are eliminated
from the equations and replaced by multiples of
t. The three equations are then solved by itera-
tion for each of the four materials using
properties and strengths shown in Table 31.6.
The summary table presents a comparison of
the calculated design thicknesses and corre-
sponding beam weights for each of the four
candidate materials. The deflection requirement
proved to be the dominant requirement for all
four materials, i.e. the thickness required to sat-
isfy the deflection requirement was greater, in
each case, than that required to limit imposed
stresses to acceptable values. The estimated pre-
liminary design weight of each design is less
than 5 kg, as required.
Several conclusions can be drawn from this
comparison. First, the aluminum and E-glass
designs are comparable on a weight basis due
to the fact that the lower density of fiberglass
offsets its lower stiffness. End fittings have
been ignored, along with numerous other
details, in this preliminary study, but it is
worth noting that the additional weight intro-
duced by metallic end fittings would probably
cause the E-glass detailed design to be heavier
than the aluminum design. The T3OO/epoxy
design offers a significant weight savings over
aluminum and E-glass, deriving primarily
from its higher modulus-to-density ratio.
Table 31.6 Results of design trade study of composite beam
Material" Modulus Compressive strength
(GPa) (MPa)
Alum (7075) 68.9 482
E-glass 34.5 475
T300 99.3 572
M60J 248 379
a Design values for each composite material are developed assuming a laminate with the following proportions: 65% 0"
plies; 25% 45" plies; and 10%90' plies.
Detailed design 723
However, the cost of a beam fabricated in T300-
epoxy may still exceed the cost of an aluminum
beam, despite the fact that less T300 material is
required. The next calculation might be to esti-
mate the fabricated costs, including materials,
of the T300 and aluminum designs, to ascertain
the cost differential. A final comparison can be
made between T300 and M60J fiber reinforced
beams. As presented in Table 31.6, the addi-
tional weight savings associated with an M60J
beam is relatively small. The cost differential is
going to be substantial because M60J prepreg is
over $200 per kilogram while T300 prepreg is
about $20 per kilogram. Only a substantial
payoff in increased component life or overall
system performance would justify the selection
of M60J over T300.
In a real design situation, the trade would
probably be more complex. Perhaps, the load
would be a cyclic load or an intermittent load,
leading to consideration of fatigue allowables.
Or, perhaps the natural frequency of the beam
is another important design consideration in
the structural system. The trade methodology
remains the same, but additional characteris-
tics would need to be considered.
31.4 DETAILED DESIGN
Many of the activities which constitute
detailed design are extensions or iterations of
activities already performed in preliminary
design. However, a few topics require special
attention. This section will focus on three areas
specifically. These include a discussion of the
development and use of material design data,
Density Wall thickness Weight
(g/cm3) hm) (g/mm)
2.68 2.7 1.37
1.93 3.2 1.38
1.50 2.5 0.66
1.69 2.0 0.47
724 Design of structure with composites
the approach to joining and the development
of joining details, and the construction of
drawings.
31.4.1 USE OF MATERIAL DESIGN DATA
The first of these three areas is an extension of
the discussion of material data introduced in
the section on preliminary design. The point
was made in that section that material data
relies heavily on ply-level values. A typical set
of mechanical material data is shown in Table
31.7. The material of interest is T50 graphite
fiber in an epoxy resin system. The material
was ordered in significant quantity to an aero-
space specification and was manufactured in
ten lots. Table 31.7 is subdivided into material
properties and strength values. The values
shown as 'measured' are average for all speci-
mens from all ten lots of material. The table
also includes preliminary design values for the
sake of comparison.
This comparison shows excellent agreement
between measured and preliminary design
material properties. The largest differences are
in coefficient of thermal expansion (CTE) val-
ues, and these are on the order of 20-25%. This
is excellent agreement considering the difficul-
ties and uncertainties associated with the
Table 31.7 Mechanical design values for T50/epoxy tape: preliminary and measured layer properties and
strengths
Material characteristic
Tensile modulus, E,,(GPa)
Tensile modulus, E,,(GPa)
Poisson ratio, v
Inplane shear modulus, GI,, (GPa)
Longitudinal CTE (x l P / " C )
Transverse CTE (x 1O4/'C)
Tensile strength, F;, (MPa)
Tensile strength, FZt,(MPa)
Compressive strength, FIC,(MPa)
Compressive strength, F;, (MPa)
Inplane shear strength, F,,, (MPa)
Subscript 1 denotes fiber direction.
Subscript 2 denotes direction transverse to fiber.
Subscript 12 denotes shear in the plane of the fiber.
measurement of this property, and the
expected variation in this characteristic.
Differences in design values and measured
strengths are larger. However, preliminary
design values are all exceeded by average mea-
sured values, confirming the fact that strength
critical regions are conservatively designed.
There are some differences in values mea-
sured from one lot of material to another. The
kind and amount of variation is described in
more detail in Figs. 31.10 and 31.11. Specified
'acceptance values' are shown on each figure
for reference. In this case, these acceptance val-
ues are lower than those used for preliminary
design. The figures also show results of tests
conducted by the material supplier and by the
receiving company. Differences in these results
provide some insight into the influence of test
methods, facilities, and personnel. The first
figure compares tensile modulus and the sec-
ond tensile strength. Figure 31.10 indicates
that, while values are different from lot to lot,
all lots exceed the specification value for ten-
sile modulus and are therefore acceptable. The
measured ply-level data confirms the design
values of tensile modulus. The measured val-
ues for tensile strength exhibit larger
variations, but are also higher than the speci-
fied value. Once again, all measured values
Prelimina y design value Measured value
209 228.2
6.89 7.03
0.27 0.245
5.52 5.44
- 0.63 - 0.79
28.8 25.0
1034 1136
24.1 28.06
758 821.2
110 171.6
62
 Detailed design 725

300 T
iii 250
n
9
;
v)

-
200
0
I
W LMSC DATA
d 150 HEXCEL DATA
6
I- +LMSCSPEClFlCAl-ION VAI-UE

0
1 2 3 4 5 6 7 8 9 10
LOT NUMBER

Fig. 31.10 Lot-to-lot variation in tensile modulus - T50/F384 unidirectional tape (manufactured by
Hexcel).

1400 1
g 1200
n
3
I
6 1000
E
F 800
HEXCEL DATA
d mLMSC DATA
u)
z 600
+
W +LMSC SPEClFlCPiTlON VAI.LIE

0
1 2 3 4 5 6 7 8 9 10
LOT NUMBER

Fig. 31.11 Lot-to-lot variation in tensile strength - T50/F384 unidirectional tape (manufacturedby Hexcel).
726 Design of structure with composites

exceed specification levels and all lots are
acceptable.
This data is typical of aerospace applica-
tions. The types and amounts of data will, of
course, depend on the specific application.
The major difference between this data and
preliminary design data is that the data sup-
porting final design will be specific to the
material form, resin system, and fiber volume
selected. Final design data is an extension of
data available for preliminary design. It will
generally focus on ply level values since this is
the most cost-effective way to obtain data for
all of the laminates which will be employed in
final design of the part or assembly. These val-
ues now become an important part of the
database for establishing preliminary design
values for the next application.
Table 31.8 contains a further comparison of
predicted and measured laminate values for
T50-epoxy tape, developed in the same appli-
cation. The values in this table correspond to
specific design laminates. Three sets of values
are shown for each of the design laminates -
the first developed from preliminary design
layer values, the second from measured layer
values, and the third directly from tests per-
formed on laminate coupons. Using measured
layer properties produces a better correspon-
dence between predictions and measurements,
but not an exact overlay. The primary differ-
ence is workmanship, i.e. changes introduced

Table 31.8 Comparison of measured and predicted material design values for T50/F584 graphite epoxy
tape laminates

Design value Laminate description

(60/0/-60/0,)~ (45/45/0,)s
Prelimina y Prediction Measurement Prelimina y Prediction Measurement
design design
Tensile modulus, 129.5 141.1 148.9 (60) 115.4 125.2 129.6 (10)
Ex, (GPa)
Tensile modulus, 51.4 55.6 51.1 (60) 28.8 30.8 26.8 (10)
Ey' (GP4
Poisson ratio, v 0.303 0.303 0.289 (60) 0.762 0.776 0.777 (10)
Inplane shear 19.8 21.2 - 29.3 31.8 -
modulus, Gx ,(GPa)
LongitudinaICTE - 0.58 - 0.49 - 0.41 (5) - 0.67 -1.08 -1.17 (3)
(x lOd/OC)
Transverse CTE - 0.29 +1.55 +2.02 (6) - 0.01 +3.51 +4.10 (3)
(x lP/OC)
Tensile strength, 641 703 693 (60) 565 578 781 (10)
F,',
Tensile strength, 324 341 170 (60) 255 284 116 (10)
F t, (MPa)
dbmpressive strength, 469 507 623 (60) 414 446 605 (10)
F;, ( m a )
Compressive strength, 255 278 165 (60) 255 235 128 (10)
F;, (MPa)
Inplane shear strength, 165 134 - 214 209 -
Fm, (MPa)
Number of test specimens shown in parentheses alongside measured values.
Subscript x denotes the 0" direction.
Subscript y denotes the 90"direction.

by handling and fabrication that simply are
not accounted for by theory. These differences
are larger for strengths than for properties,
and account for the knockdown factors nor-
mally used in developing material design
strengths.
One final point to be made concerning these
comparisons is that differences exist, but are
not typically an inhibitor to designing with
composites. These variations must be recog-
nized in the design process, and can be
handled with statistically-derived knockdown
factors, and conservative but realistic design
approaches. Key design values can also be
controlled through development of intelligent
material specifications. In most designs, the
usual variations are easy to accommodate. The
important point is that they need to be quanti-
fied and included in the design process.
This leads to a discussion of the role of test-
ing in the development of design allowables. It
was previously pointed out that normally little
or no testing is performed in support of pre-
liminary design. In fact, the only testing which
is essential is that performed to determine crit-
ical values which are just not available.
In the process of detailed design, however,
the picture changes. Once a material is
selected and a design acquires some maturity,
the values critical to establishing sufficient
confidence in the final design can be identified
and addressed through test. The emphasis is
usually placed upon layer level coupons for
two reasons. The first is that the information
obtained from unidirectional, standard
coupons is the most direct information avail-
able about the material. Failure modes are
predictable and repeatable, and results can be
directly converted to allowables. An addi-
tional benefit deriving from the use of
unidirectional coupons is that direct compar-
isons to other materials and different lots of
the same material can easily be made.
The second reason for allocating the major-
ity of testing resources to ply-level testing is
that this data can be used for prediction of a
wide range of laminate properties and
Detailed design 727
allowables, and so provides maximum lever-
age in terms of applying testing resources to
development of design confidence.
A less extensive series of laminate tests
may be required in addition to the unidirec-
tional coupon testing. The purpose of these
tests would be to provide some selective con-
firmation of key design properties and
strengths for comparison with values pre-
dicted from measured layer values. In
addition, some very specific strength charac-
teristics, such as bearing strength, are specific
to laminates, and cannot be reliably predicted
from layer values. If this allowable is critical
to the design, tests of specific design lami-
nates may be necessary.
31.4.2 JOINING
Joining of composites normally presents some
challenges and tends to influence the configu-
ration of the part. The two recognized
methods for joining composite structure to
other composite or to metallic parts are adhe-
sive bonding and mechanical fastening. The
advantages and disadvantages of each method
will be discussed, followed by some guide-
lines for selection between the two. The
discussion is not an exhaustive one by any
means, but is intended to highlight key con-
siderations which determine joint designs and
provide some initial direction to the designer.
Numerous factors need to be considered in
the selection process. Figure 31.12 offers a list
of the most common requirements. It should
be kept in mind that some of these 'require-
ments' may become design variables in the
course of the process. Geometry of the mem-
bers being joined, for instance, could be
altered locally to facilitate joint design.
Reliability potentially includes an array of
requirements, one of which is the implications
of joint failure on system performance. Is it
catastrophic or benign? Is it easily detectable
prior to failure or insidious?
Determination of this list of requirements
will lead directly to the formulation of key
728 Design of structure with composites

Joint design criteria

1
Temperature
-Static strength range
-Durability (fatigue) Moisture
limits

How important

i
,
is weight?
How critical
is cost?
Reliability

t Service life
Implications of
fai Iure

Fig. 31.12 Joint design.

design questions possibly including, but usu-

ally not limited to the following:
Will the joint be disassembled and reassem- Mechanically fastened
bled? - fatigue life
What is the nature and magnitude of the - insensitive to temperature
- ease of inspection
loads? - reliability
Are the loads cyclic or static or a combina-
tion?
What are the operating temperature and
moisture ranges? 1
What are the cost limitations? Adhesively bonded
- no local reinforcement
Some of the major advantages of bolted joints (load spreading)
and bonded joints are shown in Fig. 31.13. - fewer parts
High tolerance to repeated loads, good resis- - lower cost
- corrosion resistance
tance to most environments, ease of
inspection, and high reliability are primary Fig. 31.13 Advantages of bolted and bonded joints.
advantages offered by mechanical fasteners
in composite structure. Fewer pieces, lower
weight, good load distribution, and lower selection of the adhesive system, and process-
cost are advantages offered by adhesive ing. Extensive information on each of these
joints. subjects is available in other sections of this
The major considerations in design of a text. The following design procedure is offered
bonded joint can be grouped into five cate- as a facilitator to the design process.
gories. These include joint strength, Generally, component configurations are
environmental resistance, joint geometry, predetermined by other design requirements,
 Detailed design 729

and so the joint geometry is established prior other sections, and so this discussion is aimed
to finalization of the adhesive joint design. at providing a brief summary of the process.
Factors including how well the mating parts The process begins with the determination
will 'fit up' to each other after allowances for of a configuration for the joint. Single lap joints
all specified dimensional tolerances, and the are normally adequate for thin laminates (up
quality of the adherend surfaces need to be to about 5 mm (0.2 in) in thickness). Fastener
recognized and defined. bending and initial bearing failure are primary
The first step in the process is to determine concerns. Double lap joints are better for cyclic
a dimensional configuration which minimizes (fatigue) loads, and generally stronger.
tensile and peel stresses in the bonded joint. The next step is to select the type of fastener
Once this is accomplished, the next task is to required. Fastener selection usually raises
select an adhesive system which best satisfies issues requiring decisions concerning laminate
static strength, fatigue life, and environmental reinforcement, hole sizes and locations,
requirements. This selection is sometimes the drilling, fastener installation, and inspection.
result of a simple trade study among several Table 31.9 identifies issues and proven design
candidates. The third step is the development approaches to each issue. The table reveals
of formal or informal process specifications for that the complexity of designing bolted joints
the joint. This specification will include details derives from two primary sources: (1) com-
for surface preparation, curing the joint, and posite laminates cannot redistribute high local
maintaining pressure during cure if necessary. loads by yielding and plasticity; (2) compos-
The joint strength is typically verified analyti- ites are more easily damaged by drilling and
cally or by structural test or both. fastener installation than metals.
Similarly, a design process can be outlined Design of local reinforcement of the lami-
for mechanical joints. The primary design con- nate to resist local stresses is an important step
siderations for bolted joints include joint in the design of bolted joints. If reinforcement
strength, fastener type, local reinforcement, is required, a proven approach is to increase
joint configuration, holes, and preload. All of laminate thickness by the addition of plies
these subjects are discussed extensively in placed at 345 and 90" to the primary load

Table 31.9 Design issues: fasteners in composite laminates

Issue Solution approach

Drilling damage 1. Closely controlled manufacturing operations
2. Inspection of drilled holes
High local stresses 1. Larger fastener diameter
2. Insert (bushing)
3. Increased laminate thickness (locally)
Preload relaxation 1. Large fastener head
2. Washers (one or both sides)
3. Limit on installation torque
Countersunk head 1. Avoid, if possible
2. Increased laminate thickness (locally)
Damage induced by installation of blind fasteners 1. Specially-designedblind fasteners
and drive rivets 2. Development of modified installation techniques
3. Verify joint strength with tests
730 Design of structure with composites
direction. A quasi-isotropic laminate provides
the best bearing strength in any continuous
fiber polymer composite.
Local reinforcement
As in metal structures, local reinforcement is
generally required where any hole or cutout is
placed in a structural part. Analogous to metal
parts, reinforcement can be bonded or fas-
tened to the structure. Reinforcement can often
be incorporated into the design of the part in
the form of additional plies extending across a
limited region of the structure. Local reinforce-
ment may also be required in the vicinity of
joints, either bonded or bolted, and in loca-
tions where concentrated loads are introduced
into the structure.
The design of the reinforced region will
derive primarily from the orientation and
magnitudes of the stresses in the structure,
and so no generalizations can be made con-
cerning laminate design. However, some
generalizations concerning transition in these
regions and the behavior of laminates are
appropriate.
Laminates behave as a series of layers, each
stressed in membrane action, and each capable
of transferring stresses to adjacent layers
through shear. When laminates bend, adjacent
layers remain attached and experience states
of strain which are similar. Therefore, in a rein-
forced region, such as that shown in Fig. 31.14,
load is introduced into the reinforcing plies
through interlaminar shear. Since the level of
interlaminar shear stress required to induce
delamination in any composite will not exceed
70-80MPa, a design must aim to maintain
these stresses to acceptable levels. This is typi-
cally done through the gradual introduction of
reinforcing plies, as shown in Fig. 31.14. This
gradual transition precludes a sudden discon-
tinuity in thickness which would produce
sharp peaks in interlaminar shear stress.
The selection of ply orientation is also a
consideration. Transfer of load from ply to ply
is facilitated by the minimization of differences
4 x 0.25
,
w
(1 .O)
Scale: 118
See view B view
0.10 (reference). .- .K-
, _ f ~ . 2(reference)
~
_f I
I
f' \
'--'
A-A
Scale 1:2
Fig. 31.14 Local reinforcement.
in the stiffnesses of the two plies. Therefore,
load transfer is most effective between two
plies with the same fiber angle and least effi-
cient between two plies with a 90" difference
in fiber angle. The use of 45" plies between 0
and 90" plies is a good compromise for rein-
forcement areas.
Analysis methods are limited by underly-
ing assumptions, and are most reliable for
regions where the assumptions are simple
and few. This is not the case for regions in
which the laminate changes and the stress
gradients are steep. Therefore, complete
reliance on analysis in the regions of joints
and local reinforcement is not prudent. In
addition, these regions sometimes present
manufacturing challenges which raise ques-
tions concerning the quality of the finished
part. Therefore, testing is very often an inte-
gral part of engineering development and of
the design verification process.
31.4.3 DRAWING CONSTRUCTION
A drawing of a component or assembly in
composite materials has the same objective as
this type of drawing in any material: furnish-
ing a blueprint for manufacture of the item.
However, some of the details and the manner
in which information is presented on the
 Detailed design 731

drawing are unique. There are countless varia-
tions on the format of a drawing, so the
discussion will be more or less limited to the
content, with a specific format shown only for
the purpose of providing an example.
A drawing detailing a composite part needs
to specify geometry, materials, sources of
those materials, ply sequence for each unique
laminate, details of transition regions, process-
ing definition, post fabrication instructions for
drilling, sawing, etc. and any inspection
requirements. Other details, such as individ-
ual ply patterns, may be necessary for a
specific part, but this list is suggested as one of
general applicability.
Dimensions are defined in the same manner
as for metal parts with the exception of thick-
nesses. Thickness is really defined by laminate
sequence meaning that the part will be as thick
as the cured laminate dictates. A thickness
dimension is normally shown as a reference
dimension and provided for tooling design. It
should be recognized that specifymg a thick-
ness as a fixed dimension demands
compliance to that dimension. Unless manu-
facturing ‘tool try’ units have been fabricated
to determine cured laminate thickness with
the particular manufacturing process speci-
fied, there is no guarantee that the thickness
can be achieved with the number of plies and
resin content specified.
Dimensional tolerances are generally deter-
mined by tooling design and the amount of
material shrinkage. Experience with the
process and material is the only reliable guide
in setting tolerances.
Material definition can be accomplished in
two ways. The first is to create a note or a
table defining the material: fiber reinforce-
ment, resin system, material form, resin
content, material source or sources, and sur-
face treatments. The second is to invoke a
document, such as a specification, which
defines the material required. If the second
approach is used, it may still be a good idea to
provide a brief identification of the material
on the face of the drawing to facilitate inter-
pretation by analysts, tool designers,
manufacturing and inspection personnel.
Table 31.10 shows an example of material
description employing both methods.
Specifying a fabric requires the designer to be
familiar with all of the variable characteristics
of the material form - weave style, surface
treatment, and end count. This is necessary
because fabrics are available in numerous
weave styles, with various surface treatments,
and can be woven with any of several differ-
ent size yarns.
Each unique laminate in the part requires
definition sufficient to allow a fabricator to lay-
up the part. Figure 31.15 presents a typical
example of the usage of a ply sequence table on
the face of a drawing. The figure identifies the
surface that ply number 1 is placed upon and
then details the ply stacking sequence to be fol-
lowed. It is desirable, but not always practical,
that the first ply shown in the table be the first
ply physically laid up on the tool. The ply table
contains a column identifying the material of
each ply since sometimes a single laminate
contains plies of different materials.
Areas of transition are handled as shown
in Fig. 31.16. The two adjacent regions of
‘constant’ thickness are defined by appropri-
ate tables as shown. The tables, however,

Table 31.10 Format for material definition on drawings

Material designation Characteristics Source

M1 Fabric prepreg, 120 style weave, Company name and address
T300 fiber, 10K bundle size,
934 resin system, sizing
M2 M40J tape Specification number
732 Design of structure with composites

Material Fiber orientation

Ply number designation ("1
1 M1 90
2 M1 0
3 M2 45
4 M1 90
-b 5 M1 0
6 M1 0
7 M1 0
8 M2 45
9 M1 0
10 M1 90

Fig. 31.15 Ply sequence table.

Material -iber angle

(")
90 M2 90
0 M2 0
-45
45 M2 0
M1 M1 45
-45 M1 -45
45 M2 90
0 M2 0
90 M1 45
M1 -45
10 M2 0
11 M2 90
12 M1 -45
M1 45
M2 0
M2 0
M2 90

Fig. 31.16 Specifymg transition regions.

employ a common ply numbering sequence specifications typically include definition of

so that the continued and terminating plies
can be distinguished. The termination details
are specified on the face of the drawing as
shown in Fig. 31.16.
Processing instructions are supplied in one
of two ways, either as notes, or by reference to
a document such as a process specification.
The second alternative is by far the most
common because of the amount of informa-
tion required to define the process. Process
cure cycle (temperature and pressure against
time), pre-cure instructions for vacuum bag,
bleeder plies, resin preheating for pultrusion,
tool preparation, removal of the part from the
tool, in-process inspection requirements, and
many other items.
Post-fabrication operations may include
drilling holes, sawing to length, removing
edges by grinding, secondary bonding of
items, painting, light sanding, and almost
 Detailed design 733

anything else. These operations are normally The advantage of documenting each NDE
specified on the drawing by means of notes. activity is traceability. If a problem arises in
Notes need to identify items such as the type development or production, NDE records can
of drill bit and cutting speed. usually identify potential sources and trends.
The disadvantage is cost. Each company per-
forms its own cost/payoff determination, and
31.4.4 DESIGN VERIFICATION PROCESS
develops its own verification processes from
A few words about design verification are that determination. One point for the designer
appropriate to a section dealing with compo- to keep in mind is the necessity and value of
nent design. Design verification encompasses this verification for composite parts. Variability
more than the nondestructive evaluation in raw materials, processes, and workmanship
(NDE) procedures specified on the compo- can and will affect the final part. The designer
nent drawing. Design verification is integral needs to be aware of all potential sources of
to the entire design and manufacturing variation, so that he knows where to look when
process. Figure 31.17 identifies verification final inspection reveals defects in his part.
activities in each phase of the component Part inspection methods are usually identi-
development process. Each of these activities fied on the drawing. These requirements
ranges from a formal, documented step in actually form the accept/reject basis for the
some industries, to undocumented, highly finished part, and can range from visual only
integrated steps in other industries. The key to extensive ultrasound methods. Table 31.11
point is that verification is the part of the presents a summary of which defects are
development process which ensures that the detectable with each of several established
developed component fulfills all design NDE techniques. The most commonly used
requirements. methods are X-ray and ultrasonic, particularly

Development Primary Verification

phase Activities actions

Development tests

Engineering Material
development Procurement Material acceptance tests

Tool tries

In-process inspection

Fabrication Processing records

Debulk
Bagging Tag end coupon test

F)
fabrication
Trim
Bonding
Drilling holes
Sawing
Witness panels
Dimensional verification

Non-destructive inspection

acceptance
Proof test / acoustic
emissions

Fig. 31.17 Component verification process.

734 Design of structure with composites

Table 31.11 Defects and nondestructive test methods

Defect or variable X-ray Gamma Ultrasonic Sonic Microwave Temperature Penetrant

“Y diferential
Unbond X X X
Delamination X X X X X
Undercure A
Fiber misalignment X X
Damaged fibers X X
Variation in resin
Variation in thickness X X X
Variation in density X X
Voids X X X X X
Porosity X X X X
Fracture X X X
Contamination X X
Moisture X

C-scan. These methods require proper equip- SOURCES OF MATERIALS DATA FOR
ment, cumbersome setup in some instances, PRELIMINARY DESIGN
and time. X-ray and ultrasonic methods can
detect a wide range of defects, and are sensi-
tive in ranges where other methods are not. Military Specifications
However, these methods have definite limits. Mil-R-9300B Resin, Epoxy, Low Pressure
In fact, no single method can detect all types Laminating
of defects or variations. Moreover, it is impor- Mil-C-47257C Compound, Epoxy, Filament
tant to understand, in advance, what a defect Winding
looks like. For this reason, it is common prac- Mil-R-24719 Resins, Vinyl Ester, Low
tice to perform calibration with intentional Pressure Laminating
defects built into test panels. Mil-Y-1140 Yam, Cord, Sleeving, Cloth
Table 31.11 is an oversimplification of an and Tape, Glass
extensive and complicated subject. It is Mil-R-60346 Roving Glass, Fibrous (for
included here as a handy reference for the Filament Winding
designer and a starting point for determining Applications)
which techniques are appropriate for a given Mil-Y-83371 Yarns, Graphite, High
part. Inspection requirements will, of course, Modulus, Continuous
be related to the function of the part, and will Filament
be focused on the critical aspects of the design. Mil-Y-87125A Yam, Graphite, 1000/3000
In some companies, it is common practice to
Filaments
limit part inspection to simple dimensional Mil-F-87121A Fabric, Graphite Fiber
and visual checks, and to rely on a ‘proof’ test
Mil-T-29586/ 1 Thermosetting Polymer
to verify the structural adequacy of the com- (Epoxy) Matrix, 350°F (177°C)
ponent. Since inspection requirements tend to
Cure, Intermediate Modulus
be unique to each component, it is usually nec- Carbon Fiber Reinforced
essary to make inspection requirements an Prepreg Tape
integral part of the design drawing.
 Sources of materials data for prelimina y design 735
Aerospace Material Specifications
AMS 3828 Glass Roving, Epoxy Resin
Preimpregnated, Type E
Glass
AMS 3892/8-84 Tow or Yarn, Carbon
(Graphite) Fibers - For
Structural Composites
AMS 3894/11-83 Carbon (Graphite) Fiber
Tape and Sheet, Epoxy
Resin Impregnated
AMS 3822 Cloth - Type 'E' Glass, 'B'
Stage Epoxy Resin
Impregnated, Style 181-75DE
Federal
Mil-Handbook 17C, Polymer Matrix Composites,
Volumes 1 and 3, Standardization Documents
Order Desk, Building 4D, 700 Robbins Avenue,
Philadelphia, PA 19111-5094
Professional Society Publications
Society for the Advancement of Material and
Process Engineering (SAMPE)- Conference
Proceedings
Society of Manufacturing Engineers (SME) -
Conference Proceedings
Handbooks
Handbook of Reinforced Plastics. (eds. S.S.
Oleesky, J.G. Mohr). Van Nostrand Reinhold,
New York.
Modern Plastics Encyclopedia, McGraw Hill,
New York, yearly edition.
Composite Design Encyclopedia, University of
Delaware, Newark, 1984.
Composite Materials Handbook, (ed. Me1 M.
Schwartz,) McGraw Hill, New York, 1984.
Periodicals
Modern Plastics Magazine, 1221 Sixth Avenue,
New York, monthly periodical
S A M P E Quarterly Journal
Journal of Advanced Composites
Material Suppliers
Plastic Design Guide Owens/Coming Fiberglas
Corporation, 1974
Reinforced Plastics By Design PPG Industries,
Fiberglass Reinforcements Market Series
Hexcel Design Guide
ICIFiberite Materials Handbook
Data Sheets from material suppliers:
ICI/Fiberite
Hexcel Aerospace Products
AMOCO Performance Products
Nippon Oil Company, Ltd.
ANALYSIS METHODS 32
V V Vasiliev

32.1 INTRODUCTION appropriate model for the structural element

A detailed analysis of composite structures can
provide information about the stress-strain
state, strength, stiffness, stability and vibra-
tional behaviour of structural elements. The
analytic methods are those used in solid
mechanics; the equations are modified to
reflect the structural behaviour of composite
structures. These equations are based on a sys-
tem of assumptions that take into account the
key features of a structure and establish the
under consideration.
To start the analysis (Fig. 32.1), one must
know the geometric configuration of the struc-
ture, material properties, environmental and
operational conditions along with the applied
loads. It must be noted that the available data
on material properties and loading conditions
affect accuracy, duration and cost of the analy-
sis. As an illustration, consider a cylindrical
shell loaded with a concentrated radial force.
The solution for this problem can be obtained

EQUl L I BRI UM STRAIN-DI SPLRCEMENT

EQUATIONS EOURTIONS
LOROS

I I
ENUIRONMENTRL RNO
--+-b
I

+ OUERRLL STRRINS
OPERRTI ONRL
CONDITIONS
RSSUMPTIONS
A N 0 MOOELS
GOUERNING
EQURTIONS
* RNO
OISPLRCEMENTS
A I
r I
CONSTlTUlTlUE
INLRMINRR
EQUATIONS

I EXPERIMENTAL
RNRLYSIS
I-- STRENGTH

EXPERIMENTAL
UERlFlCRTlON

Handbook of Composites.Edited by S.T. Peters. Published Fig. 32-1 Outline of analysis for composite StrUC-
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 tures.
 Introduction 737

in the form of a Fourier series that has a very the experimental method can not be used
poor convergence at the loaded point. for unique structural designs.
However, a closer inspection of the loading 0 To minimize the degree of uncertainty, a
conditions often shows that the concentrated second method is applied. According to this
force is the resultant of some distributed load method, the stiffness coefficients are calcu-
over an infinitesimal area; this distributed load lated from data that specify the composite
can then be expressed by the series with a material, ply co-ordinates, ply thickness,
finite number of terms to achieve convergence. ply orientation and mechanical properties
Operational requirements for the composite of individual plies. The latter, in principle,
structures are also of great importance. For can be predicted by analytical or numerical
example, a filament wound composite shell of methods of micro-mechanics of composite
revolution can be a model for either a gas pres- materials; these results, however, have
sure vessel or a solid propellant rocket motor more academic than practical value.
case for which, in contrast to the pressure ves- Idealized micro-mechanical models, that
sel, time dependent material properties need approximate the real structure of the mater-
not be considered. On the basis of this knowl- ial, do not account for material porosity,
edge, assumptions are formulated for the non-uniform fiber distribution, possible
model of the structural component under variation of physical properties in each
study. This model should consider only the batch of resin, variation in strength of the
key factors affecting the capability of the struc- resin/fiber interface and a number of other
ture and ignore the secondary effects that factors associated with the manufacturing
complicate the analysis without significant process; in many instances, the above varia-
improvement. tions can not be described in formal analytic
The next step implies analytical formula- terms.
tion of the problem, i.e. development of a
For important structures, usually, the mechan-
complete set of the governing equations with
ical ply-properties are experimentally
the pertinent boundary conditions. For struc-
determined by testing specifically fabricated
tural analysis, the governing set of equations
plates, rings, or tubular unidirectionally rein-
consists of equilibrium equations (or equa-
forced specimens produced by the same
tions of motion), strain-displacement and the
process as the structure under study'.
constitutive equations which are material
Once all of the pertinent data are together,
dependent. The constitutive equations include
the governing equations are solved by either
stiffness coefficients which are determined by
the analytic or the numerical methods applied
either of the following two methods:
in solid mechanics. The results by either
0 The first method is associated with direct method yield information on deformation,
experimental analysis of test specimens cut displacements, stiffness and strength. To eval-
out of the structure or its excess length. This uate stiffness, the calculated displacements
method is used mainly for structures in due to an applied loading can be used
mass production. For simple laminates (e.g. directly. Evaluation of strength requires trans-
for cross-ply laminates), this method gives formation of the calculated global strains to
rather accurate results while for the more ply strains in terms of principal material co-
complicated (e.g. including angle-ply lay- ordinates, determination of the ply stresses
ers) laminates, separation of a specimen can and application of some strength criterion.
cause a disruption in the material structure One must note that the numerous strength cri-
and induce specific edge-effects with ques- teria, that have been developed to date, are no
tionable mechanical properties. Obviously, more than analytical approximations of the
738 Analysis methods

experimental results with a significant scatter.

Also, the failure of a composite material is a
rather complicated process that defies accu-
rate theoretical description. Therefore, the
strength of important structures should be
't SI

always verified by testing either sub-scale or

full-scale models.
Finally, a thorough analysis of a composite
structure, based on macrostructural models,
effective stiffnesses and approximate displace-
ment fields, does not preclude the possibility
of a detailed analysis of inlaminar or interlam-
inar stresses. To accomplish this analysis, the
ply under study is separated out of the struc-
ture, loaded with unknown contact forces,
deformed in accordance with the known Fig. 32.2 Element of a composite structure.
global strains of the structure and described by
the proper microstructural model.
1. Equations of motion
32.2 GENERAL EQUATIONS FOR COMPOSITE
STRUCTURES
Composite structural elements consist of a large
number of plies with different angular orienta-
tion of fibers. The general equations, describing
the behaviour of the composite elements, are
based on the following assumptions:
0 the structural element consists of perfectly
bonded anisotropic layers made out of lin-
ear elastic materials;
= 0 (1, 2 )
0 the laminate thickness (h) is much smaller
than the other dimensions;
0 the radii of curvatures are assumed to be
the same for each lamina;
0 loading does not affect laminate thickness.
The differential composite element (Fig. 32.2)
is described in terms of curvilinear coordi-
nates a, p and y. The coordinate axes a and p
coincide with lines of principal curvatures of
the basic surface located at a distance e mea-
sured from an outer element surface. The
geometry of this basic surface is defined by the
coefficients of the first quadratic form A,, A ,
and the principal radii of curvature R, and R,.
Therefore, the governing equations of com-
posite structural analysis become as follows:
 General equations for composite structures 739

where
1 dA,
a1 = _ _ _ _ (L2)
A 1 4 aa
The symbol ( I I 2) indicates, hereafter, that an
equation written for the a variable yields one
and F = (N/
M). more analogous equation for the /3 variable by
commutating the indices a, /I, 1 and 2.
The foregoing set of equations (32.1, 32.2
2. Constitutive equations and 32.3) include 23 equations and the same
number of unknowns, namely:
0 the stress resultants N,Q and the couples M
acting on the basic surface shown in Fig.
32.3;
0 displacements ua, up/ w of the points on the
basic surface in the a,p and y directions;
0 rotations ea, 8, of the normal to the basic
surface;
0 rotations of the tangents ma and osto the
basic surface in the cry and ,by planes;
0 strains E and flexural deformations K of the
basic surface;
0 transverse shear deformations 3, and $in J,
the ay and ,by planes.

’t
3. Strain-displacement equations
1 au, w 1
& =---- + a u +-+-w; (1,2)
a A, aa P R, 2
1 auB 1 aua 1
Eap = -- +---ulu,-au +-w
2 wa
A , aa A, ap 2 8 P

+
1 ao, 1 ae, + u p a + u2ep
Kap = -~
A , aa
--
A, $3
”P
Fig. 32.3 External and internal forces and moments.

1 aw The equations of motion (32.1) contain inertia

0 = (1,2) (32.3) terms with time derivatives of displacements
a R, A, aa
and rotations; the equations reduce to static
740 Analysis methods

equilibrium without these derivatives. The

coefficients B and Dpcharacterize the inertia
properties of the element in Fig. 32.2 with
respect to displacements and rotations. C,, on
the other hand, is the coupling coefficient
describing the interaction between displace- where the Fs are the body forces and p , 9 are
ments and rotations. the simultaneously applied surface forces as
shown in Fig. 32.3. Functions 7 and 6 reflect
variation of the wall thickness, h (a,B) = e + s,
along the coordinate lines, i.e.

It is assumed that functions s (a,/I) and e (a,p)

vary rather slowly, therefore sin 7 = 7,cos 7 =
Fig. 32.4 Layer coordinates. 1, sin 6 = 5 and cos 6 = 1. It must be noted that,
for variable thickness, the layer coordinates ti
in Fig. 32.4 can also depend on a and p. For
For a thin walled laminate (Fig. 32.4) these structures with constant thickness, 7, = l;lp= 0
coefficients become and Ea = 6,= 0. The governing set of equations
B = I(0) (32.1, 32.2 and 32.3) accounts for geometric
P P nonlinearity and is applicable for small strains
C = I(1)- and moderate rotations o,(sin w = w ,cos w = 1)
P P P of the structural element in Fig. 32.2. For thin-
walled composite structures, the first-order
D P = I (P2 ) - 2eI P(1) + $1P(0) (32.4)
nonlinear effects, associated with variation of
where (r = 1,2) radii R, and R2 under loading, can play an
important role; in this case, the underlined
rotations w are omissible when compared with
their derivatives describing the changes in the
p is the material density, and ti- ti are coordi- curvature of the basic surface under loading.
nates of layers. The external loads in (32.1), The linearized buckling equations are formu-
reduced to the basic surface, are specified by lated by modifying eqns (32.1), (32.2) and
the following relations: (32.3) using the following assumptions:

fa = 1h

0
Fadt + Pa + 9, +ma + 0,) + 9(7, - u p )
0 equation (32.1) excludes the terms corre-
sponding to inertia, body and surface
forces;
(112) 0 in nonlinear terms of eqn (32.1), N, = N :,
N,= Np”, Nap= N u t where N,O, Np”, Nap”are
the stress resultants that correspond to
membrane prebuckling state of the struc-
ture;
0 constitutive equations (32.2) should exclude
terms W and Mr.
 General equationsfor composite structures 741

e Strain-displacement equations (32.3)

exclude non-linear terms.
The membrane (B,,), the bending (D,,), the
coupling (Cmn),and the shear (Kmn),stiffness
coefficients in the constitutive equations (32.2)
are determined with the following equations:
B mn = I mn
(0)
and (32.10) depend on the thermo-elastic con-
stants of the material. For a composite
layer-referred to principal material coordi-
nates 1, 2, 3 in Fig. 32.5, with axis 1 enclosing
an angle 'P, or -ql with the a axis as in Fig. 32.6.
These coefficients are
A,:) = E ([IC 4 + EC')s4 + 2E ( 1 ) ~2s 2
1 1 2 [ 12 1 I

A12(1)= A 0) = yl$)Ey)+ (Et) + EO - 2El$))c;s;

Cmn = 1:)- el::) 21

A$] = + E~]c:+ 2E 12( ' 1 ~ 2 ~ 2

1 1

f
K = K4Ks5-K4; (32.6)
where (mn = 11,12,13,23,22,33; r = 0, 1,2)

-
_
l
r +_l 1kAtA(t;+ )-
i=l
::;t (32.7)

and (rnn = 44,45,55)

k Fig. 32.5 Element of a unidirectional ply.
z h
h210 mn
1
Kmn= Knm = - a dt = -
h2 il a{Ahi

(32.8)
. ,
Constitutive equations, (32.2), include also
temperature terms
N,' = J:)

M,' = J:) - e]:) (32.9)

where (m = 1,2,3; r = 0 , l )

The stiffness and the temperature coefficients

of the ith layer, A,,, Am,in eqns (32.7), (32.8) Fig. 32.6 Angle-ply laminate.
 thermal strains and stresses are taken to be
zero. The constitutive equations (32.2) also
allow for hygrothermal effects if AT) = &'1A€li
and A$) = @)AHi where AHi is the change of
moisture concentration in the ith layer of the
material.
For an orthotropic layer! with the
orthotropy axes coinciding with the a and the
/3 axes, the nonzero stiffness and thermal coef-
ficients are as follows:

ci = cos pi var = fi)

pa
=
"'i

where Es (s = 1,2,3) is the modulus of elastic-

ity in the sth direction; G,, is the shear modulus
in the st-plane; v,, and v,,are Poisson's ratios
satisfying the following symmetry condition
Ey,, = E, vts;alTand aZTare thermal expansion
t
coefficients; ATi is the temperature change of
the ith layer measured from the value at which Fig. 32.7 A sandwich wall.
 General equationsfor composite structures 743

For a sandwich wall with a light core and thin

facings as in Fig. 32.7, the transverse shear
b
deformation of the facings can be negligible in
comparison with the corresponding deforma-
tion of the core (AZ’W = 03, = 03) . On the
other hand, the in-plane stiffness of the core
can be ignored in comparison with the corre-
sponding stiffnesses of the facings (A): = A 12
= A,?) =A (2) = 0).
33

Therefore, eqns (32.7) and (32.8) yield

k

h,
K mn = -a (2)
h2 mn Fig. 32.9 Rib parameters.
ii
As a first approximation a system of densely A, = cjEjsin4pj
arranged equivalent ribs can be also treated as j=1
a system of continuous layers as depicted in n
Fig. 32.8. For the layers, simulating the rib ele- A,, = A,, = cjEisin2pjcos2pj
ments in Fig. 32.9, the non-zero inplane 1=1
stiffness coefficients are

A:) = E-d
d
A, = Ill
j=1
c.G.cos’pj

n
rn
A,, = cjGjs’n2p,
A$) = E-C j=1
d
where cj = di/uj, Ej and G. are the elasticity and
the shear moduli for the jth system of ribs. The
A$) = E-b stiffness coefficients in the constitutive equa-
d
tions (32.2) are associated with the following
where it is assumed that the ribs are parallel to deformations of the composite structure:
the a axis, and E is the rib modulus. (a) Bll, B,,, B,, stretching and contraction of
For a lattice structure in Fig. 32.10: the basic surface due to corre-

A,, = Cn

j=1
cj~ps4pj
sponding loading or Poisson’s
effect;
shear of the basic surface;
@) 4 3

Fig. 32.8 A stiffened wall.

744 Analysis methods

JP
Fig. 32.10 Lattice composite structure.

(c) D,,, D,,, D,, bending of the basic surface These equations (note that mn - 11, 12, 22, 13,
due to corresponding loading 23,33) can be satisfied for the following struc-
or Poisson’s effect; tures:
(4 D33 twisting of the basic surface; homogenous or symmetric with respect to
(e) K1,, K2, transverse shear of the wall in the middle surface of thin laminates for
the a y and by planes;
which e = s = h / 2 (see Fig. 32.2);
(f) B13, B23 stretching-shearing coupling
laminates consisting of isotropic layers with
deformation (a) and (b);
different moduli of elasticity (E,) and thick-
(g) Cll/ C,,, C,, bending-stretching coupling ness (hi)but the same Poisson’s ratio, vI= Y,
deformation (a) and (c);
for which
(h) c3, shearing-twisting coupling k k
n
deformation (b) and (d);
(i> ‘23 stretching-twisting (a) and (d)
i=l i=l
and shearing-bending (b) and
sandwich structures with facings made
(c) coupling deformations;
from the same material but having different
(j) D13,D, bending-twisting coupling
thicknesses (see Fig. 32.7) for which
deformation (c) and (d);
(k) K,,, KZ1 interaction of transverse shear 1
e= [h,2+ h3(h3+ 2h, + 2h,)]
deformations in the a y and by 2(h, + h3)
planes.
In the general case, eqns (32.12) are incom-
The coordinates of the basic surface, e, in eqns patible, because it is impossible to find a basic
(32.4), (32.6) and (32.9) can be taken arbitrarily surface for an arbitrary stacking sequence
and as a rule, is used to eliminate coupling such that all the coupling stiffnesses simulta-
stiffnesses Cmnin the constitutive equations. neously become zero. However, one of the
Thus, in accordance with eqn (32.6): coupling stiffnesses can always be eliminated
with the aid of the corresponding equation in
Cmn = lmLl)- elmlo)= 0 (32.12)
eqns (32.12).
 Composite beams 745

There exists the so-called method of

reduced bending stiffnesses according to
which each of eqns (32.12)is used to obtain the
corresponding coordinates
- 1 (1)/I (0)
emn- mn mn

Then, eqns (32.6) yield

B mn = Imn(0) eap (a,PI Y)= Eap (a,P) + Fap(a'P)
Strains in the k p, plies, whose stiffnesses are
cmn
=0
specified by eqn (32.11),have the form
e?) = e$ cos2pf + ep(l) sin2p, rt e$) sin p, cos p,

The method of reduced bending stiffnesses is

not formally established and can give both sat-
isfactory results and large errors. Also, it can
be noted that eqns (32.12) can sometimes be
satisfied if there exists a possibility to change
the stacking sequence ot the layers, i.e. to use
coordinates ti as unknown factors.
The governing set of equations, (32.1),
(32.2), (32.3), is of the tenth order with respect
to variables a and P; five boundary conditions
need to be formulated at each point of the
boundary. If the edge of a composite structural
element is clamped, then
u = u =w=O
a P a P
=o
For a simply supported edge a = constant (1,2)
N, = up= w = M a = Op = 0 (1,2)
For a free edge a = constant (1,2)
elit)= f (e:) - e:')) sin 2pl + e,:) cos 2pf
where, e.g. ea(') = ea (a,P, y = yl). The stresses, in
terms of the principal material coordinates of a
ply (see Fig. 32.5), are as follows:
0:) = Ey)(el(l)+ y 12(')e2( 1 ) ) (1, 2)
= G (')e ( i )
r12(i)
12 12
To evaluate the strength of the ply, these
stresses should be substituted into any avail-
able strength criterion.
32.3 COMPOSITE BEAMS
32.3.1 LINEAR BENDING AND AXIAL
LOADING

N, = Nap= Sa = M a = M a , = 0 (1,2) Combined linear bending and tension (or

compression)of a composite beam in Fig. 32.11
where are described by the following equations:
Sa = Q, - Nama - Napup
(h2) N' = 0
For a linear problem, S, = Q,.
The solution of the governing set of equa- M' = Q
tions, satisfying the proper boundary
conditions, specifies generalized strains -E, K, 11) Q'+jT= 0
and displacements u,,up, w, 8 , 8, as functions
of a and P. Then, the displacements of any N = Bu'
point of the structure can be found in terms of
a, B and y by the following expression: M = DO'
746

Fig. 32.11 Composite beam. bk

Q = K(8 + V') (32.13)

where ( )' = d( )/dx, j7 = pb, - qb,. The axial and
the bending stiffnesses of the beams are
B = Io

D = I2 - el,
where e = Il/Iois the coordinate of the neutral
axis. For a laminated beam with a cross section Fig.32.12 Layer coordinates.
shown in Fig. 32.12
M = M, + Q,x -Mp -MR

M0x Qox'
8 = 8,+- D f-
2D - 0 -P 0 ,
( n = O , l , 2)
and the transverse shear stiffness is defined by 1
V = Vo + -(Q$
K - MP- MR)

Mox2 Q0x3
Successive integration of eqn (32.13) yields the -88- ~ - ~ + vp+ VR
20 60
following general solution:
where quantities with subscript '0'correspond
N = No to the initial cross section at x = 0.
NO The following integral terms:
u = uo + -x
B
QP = Iljidx
Q = Q O - Q, - QR
 Thin-walled beams 747

force, should be taken into account. The corre-

sponding equations describing such a type of
beam behavior have the following form:
M' = Q

Q' + NV" + jj = 0
Vp = I j p d x
N = B[u' + %(V')2]
account for the distributed loads (see Fig.
32.11) and these next terms M = DO'

(Qp MR,OR, VR> = PQ,",M,",e,", v,") Q = K(8 + V')

describe the action of the concentrated forces. where N is a constant axial force. If the beam
For x < xm, the forces should be Q," = M," = 8," has fixed ends, N is determined from the
= V," = 0 and for x 2 xm boundary conditions. For combined axial
Q," = E m loading and bending, N is a known applied
load.
M," = Ern(. - xm)
- 32.3.3 BUCKLING
Rm
0,m = - ( x - xm)2 The critical magnitude of an axial compressive
20
force, causing the column to buckle, can be
-
Rm determined as
VRm = - ( x - xm)3
6D NE
Nc =
1 + (N,/K)
Rm= xm- F~
where, NE= c7c2 D/L2 is the critical Euler force,
Displacements and stresses at any point of the L is the column length, and c is the coefficient
beam are defined by dependent on boundary conditions. For a col-
u r n with simply supported ends c = 1, for a
q x , y > = 4 x 1 + ijw
cantilever column c = 1/4, and for a column
[ M(x)
N +-
ax(x,y) = Ex 7 D
with clamped ends (c = 4).

32.4 THIN-WALLED BEAMS

qsy) =- ~ E: ) loy€xbijdy Composite thin-walled beams are used as

ij = y - e
32.3.2 NONLINEAR AND LONGITUDINAL
BENDING
For nonlinear transverse or longitudinal bend-
ing, the axial strain, due to the large lateral
deflection developed by the applied axial
members of trusses, aircraft propellers, heli-
copter rotor blades, drive shafts, etc. For an
orthotropic beam whose cross section with
two axes of symmetry (Fig. 32.13), the normal
stress resultant nZ (Fig. 32.12) due to combined
axial loading and bending has the following
form:
nz=B-+-y (2 X )
748 Analysis methods

Fig. 32.13 Thin-walled beam. X

f(
where Fig. 32.14 Normal and shear stress resultants acting
in a thin-walled beam.
S = $Bds

D = §By2ds uy(z,s)= v(z) - xOz(z)

and B is the axial stiffness of the beam wall. uZ(z,s)= w(z) + yex(z)+ f ( s ) (32.15)
For a beam with a non-deformable cross sec-
tion contour B = Bl1. For a beam whose where o, w are the displacements in the y and
cross-section contour can be treated as z directions and Ox, Oz are the angles of rotation
absolutely compliant in its plane B = B,, - about the x and z axes of the beam cross sec-
B1,2/B,,, where Bmn are determined with eqn tion. These displacements are defined as
(32.6). follows:
The shear stress resultant nzs (Fig. 32.14)
developed by a transverse force and a torque
is
'0 =
:I
v,, + (V,, - Bx)dz

where

D
] (32.14)
ez = e; + c z k z d z
SX(s) =
I
By ds

where A is the area bounded by the contour of

the cross section and Y is the length of the nor-
where o,, w,,Ox0,O: are the displacements and
the rotations of the initial cross section at z = 0,

cz = -9-1 ds
mal to the contour shown in Fig. 32.14. The 4A2 B33
displacements of an arbitrary point on the and V,, is the beam shear
beam cross-section contour (Fig. 32.14) along deformation having the following f01-m:
the x, y and z axes can be expressed as
u x W= Y q z )
 Rectangular plates 749

F (s) is specified by eqn (32.6) and B,, is the 32.5.1 LINEAR BENDING OF SYMMETRICALLY
d e a r stiffness of the beam wall given by the LAMINATED PLATES
corresponding equation in (32.6).
If the laminate has a symmetric lay-up, the
Function f(s), entering the last equation in
basic surface is at e = h / 2 and eqns (32.6) and
(32.15), determines the free warping of the
(32.7) yield
beam cross section under torsion and bending
and has the form
Bmn = 2 c
1=1
A m n Y z-

cmn= 0
z zZ-J

i=l
Note that the ),‘( and the transverse (Q,)
where z i are the layer coordinates shown in
as as the bending moment (Mx) -
Fig. 32.16. Then, the problem of bending of an
acting on the beam cross sections and entering
orthotropic plate under the combined action of
the foregoing equations - are governed by the
surface pressures p and q (see Fig. 32.3) is
equilibrium equations for a beam element sim-
reduced to the following equation in terms of
ilar to equation (32.13).
plate deflection w (note that the transverse
shear deformation is ignored):
32.5 RECTANGULAR PLATES
a4w
D1lF
+ 2 ( q 2+ 2 4 - a4w a4w =F)
Composite plates possess high specific axzayz
strength and stiffness. They are used as struc- where =
+ ’22-
af
- 4. The strains at an arbitrary
tural elements for aircraft, ships and other
point of the plate are defined
structures. The governing equations for a plate
(Fig. 32.15) can b e obtainedin Cartesian Soor-
dinates from eqns (32.1), (32.2), (32.3) if we
take A, = A, = l , l / R , = 1/R, = 0 and replace a,
PI Y,with x,y, z.

kl2
i

Y
Fig. 32.16 Layer coordinates for a symmetric lami-
Fig. 32.15 Rectangular plate. nate.
750 Analysis methods

where
k, = Wi (X = a/2)
they allow to find strains and stresses in terms
of principal material coordinates of the com- k, = W. (X = ~ /2)
posite plies.
The variational approach, based on the k, = W;’ (X = a/2)
approximate analytic expression for the i = 1, 2 and ()’= d ()/dx. Functions W,(x) and
deflection in the y-direction while satisfying W,(X) are particular solutions that are symmet-
the corresponding boundary conditions, ric with respect to coordinate x and satisfy the
yields the following approximate (but rather following ordinary differential equation:
accurate) solutions for a plate (Fig. 32.15)
w”” - 2s2w” + p w = 0
loaded with a uniform pressure jf = po = con-
stant. The approximate deflection equations where
for different boundary conditions are as fol-
lows: 52 =
c2(D,, + 2033)
C P l l
(a) Plate with simply supported longitudinal
and transverse edges
W(XIY> = wp [1 -&)lP,(y) (32.16)
(b) Plate whose longitudinal edges (y = 0 and c parameters in these equations have the form
y = b) are simply supported and transverse b

edges (x = * a/2) are clamped c1 = p d Y

W(X1Y) = wp 11-f,(X)lP,(y) (32.17) b

(c) Plate with clamped longitudinal and sim- c2 = l0(PWY

ply supported transverse edges
b
W(XlY> = wp [1 -f,(41P2(y) (32.18) c3 = l0(Pf7ZdY
(d) Plate with clamped longitudinal and trans-
verse edges b

w(x,y) = wp [1 -f2(X)IP2(y) (32.19)
The following are used:
c = ITdY
For solutions in eqns (32.16) and (32.17) it
should be taken c, = 0.04921 b9, c, = 0.48571 b7,
c3 = 4.8b5, c = 0.2 b5. For solution in eqns (32.18)
and (32.19) c, = 0.001587 b9, c2= 0.01905 b7, c3=
0.8 b5, c = 0.03333 b5.
32.5.2 BUCKLING AND POST-BUCKLING
BEHAVIOR OF SYMMETRICALLY LAMINATED
PLATES
In-plane compression or shear (Fig. 32.17)
(where the forces Tx, T,, Tx, are uniformly
 Rectangular plates 751

(b) if the edge y = 0 is simply supported and

the edge y = b is free, then

Under pure shear (Tx= Ty = 0), the critical load

for an orthotropic symmetrically laminated
plate is expressed as
7e
Tx; = k--.\j(D,,D,) (32.22)
ab
Fig. 32.17 In-plane loading of a rectangular plate. Coefficient k is given in Table 32.1 for typical
values of the following parameters:

distributed along the plate edges) can result in

plate buckling. For a simply supported rectan-
gular (a 2 b) plate under uniaxial compression
(T, = Txy= 0), the critical load is expressed as
T,' = k--./(D,,D,)
7c2 Since the value of the critical load for an
(32.20) orthotropic plate does not depend on the
b2
direction of shear forces, the parameter p in
where
)
k = 2 1 + D12 + 2033
TvJ
Table 32.1 can be replaced by 1/ p , so that Table
32.1 presents coefficients k as p varies from
(32.21) 0.02 to 50.
Critical combination of compressive and
Note that eqn (32.21) is valid if the longitudi- shear forces can be determined using the fol-
nal edges of the plate (y = 0 and y = b in Fig. lowing equation:
32.17) can experience displacement along the
y-axis. If these edges are fixed in this direction q+[+]
T X
2
=I
(which is often the case), then the compressive
forces Tx give rise to transverse compressive where T,' and Tx; are specified by eqns (32.20)
forces Ty = vq T, due to Poisson's effect. Then and (32.22).
Used as the skin elements of stringer panels
k = [DllA + 2(D1, + 2D,,) +-- or shear webs, composite plates (just as metal
1 + (vx,/4 A
ones) can sustain high compressive or shear-
should be substituted into eqn (32.20) and ing loads after buckling. However, in contrast
minimized with respect to 1 = (rnl/a)2 where rn to metal panels whose ultimate loads are usu-
is the number of half waves in the x-direction. ally determined by rib fracture, buckling
The following approximate expressions are failure of composite panels (particularly made
derived for the k coefficients with different from carbon-epoxy composites) is often
plate edge supports: caused by skin fracture due to bending.
(a) if the edges y = 0 and y = b are clamped, Therefore, traditional engineering methods of
then strength analysis, such as the method of
reduced width for compressed panels and the
Dl2 + 2033 concept of diagonal stress field for shear webs,
can hardly be used for composite panels; more
752 Analysis methods

Table 32.1 Buckling coefficient k for pure shear

P
q 0.02 0.04 0.06 0.08 0.10 0.14 0.18 0.24 0.32 0.40 0.50 0.60 0.80 1.00
0.2 25.5 18.4 15.3 13.5 12.4 10.9 10.4 9.61 8.40 7.50 6.77 6.32 5.87 5.76
0.4 28.9 20.8 17.3 15.2 13.9 12.2 11.5 10.4 9.27 8.36 7.66 7.20 6.73 6.66
0.6 32.2 23.1 19.2 16.9 15.4 13.4 12.4 11.5 10.2 9.24 8.52 8.08 7.68 7.56
0.8 35.3 25.4 21.0 18.8 16.8 14.6 13.6 12.4 11.0 10.1 9.39 9.05 8.55 8.47
1.0 38.4 27.5 22.8 20.0 18.1 15.8 14.7 13.3 11.9 11.0 10.4 9.93 9.45 9.34
1.2 41.3 29.6 24.4 21.4 19.4 16.9 15.7 14.2 12.8 11.8 11.2 10.8 10.3 10.1
1.4 44.1 31.5 26.0 22.8 20.7 18.0 16.7 15.2 13.6 12.7 12.1 11.6 11.1 11.0
1.6 46.8 33.4 27.6 24.1 21.8 19.0 17.7 16.0 14.5 13.7 12.9 12.4 12.0 11.9
1.8 49.4 35.2 29.0 25.4 23.0 20.1 18.6 16.8 15.4 14.4 13.7 13.3 12.9 12.8
2.0 51.8 36.9 30.3 26.6 24.0 21.1 19.5 17.8 16.4 15.2 14.6 14.1 13.8 13.7
2.2 54.2 38.5 31.6 27.7 25.0 22.0 20.4 18.4 17.1 16.1 15.4 14.9 14.6 14.5
2.4 56.4 40.1 32.8 28.8 26.0 23.0 23.1 19.3 17.9 16.7 16.2 15.8 15.4 15.3
2.6 59.3 42.1 34.4 30.8 27.1 24.1 22.3 20.3 18.8 17.9 17.1 16.7 16.3 16.2
2.8 62.1 44.0 36.7 31.4 28.3 25.3 23.3 21.0 19.5 18.7 17.9 17.4 17.1 17.0
3.2 67.8 48.0 39.3 34.2 30.8 27.4 25.1 22.8 21.3 20.4 19.7 19.1 18.7 18.7
3.4 70.6 50.0 40.9 35.6 32.1 28.5 26.0 23.7 22.1 21.2 20.4 19.9 19.6 19.5
3.6 73.4 52.0 42.5 37.1 33.4 29.5 26.8 24.5 22.9 22.0 21.2 20.7 20.3 20.2

rigorous solutions of the corresponding non-
linear problems are required.
32.5.3 NONSYMMETRICALLY LAMINATED
PLATES
p, z) is reduced to the following set of equa-
tions in terms of radial displacement of the
basic surface ut, deflection w,and rotation of
the normal to the basic surface 6 , i.e.
?ut’”’ + ~ Y ~ U +~ (7
“ ’ - np2 - n2)Yur” + (1 - np2

In contrast to symmetrically laminated plates,

bending of plates with an arbitrary stacking - n:)ur’ + (n?: - n 4)2
=-‘ [ -(C
‘ 1
C Y
sequence of the layers is accompanied by Bll Dll
stretching of the basic surface. Also, the plate
deflections depend on boundary conditions
imposed on the inplane displacements2.
For in-plane compression, nonsymmetri-
- I p’rdr) - Y ( Y F ~ )-” ( Y F ~ )+’ n;F,
1 (32.23)

cally laminated plates experience bending

which should, in general, be described by
nonlinear equations. This longitudinal bend-
ing can be unstable and can be usually 1
w = -(CllIn r -
accompanied by the so-called mode-jumping. Kll
Here, ()’ = d()/dr, j7 = p - q (see Fig. 32.3), Fr(r)
32.5.4 AXISYMMETRIC DEFORMATION OF is a radial body force (e.g. a centrifugal force
CIRCULAR PLATES AND DISKS for a spinning disk), C,, C, are constants of
integration, and
The problem of axisymmetric bending and in-
plane deformation of orthotropic composite
plates and disks (in cylindrical coordinates Y,
 Cylindrical shells 753

32.6 CYLINDRICAL SHELLS

D22
nb2 = ~

Dll Filament wound composite cylindrical shells

are used as pressure vessels, reservoirs, pipes,
n: = ___
c2; aircraft and ship elements. The governing
BllDIl equations for a cylindrical shell (Fig. 32.18) can
be obtained from eqns (32.1)-(32.3) if we take
Coordinates of the basic surface e = I $ ) / I z )
provide, in accordance with eqn (32.12), the
zero value of the radial coupling stiffness (Cll
=
with yTz.
’,
= l / R i = or ‘ 2 = and rep1ace 7
a j

= 0). -
h
Radial and circumferential strains at an
arbitrary point of the plate are expressed as
er = u,’ + zOrf
1
ep = -(ur
r
+ z0,)
The general solution for eqn (32.23) has the
form
Fig. 32.18 Cylindrical shell.
1c p +
6

ur = up
1=3
where up is a particular solution and si are the 32.6.1 AXISYMMETRIC DEFORMATION
roots of the equation One of the most important loading cases for
s4- (nP + n,’)s2 + np2n: - n: = 0 cylindrical shells is the axisymmetric loading
with pressures p , q and axial forces N (Fig.
Six constants of integration can be found from 32.18). In this case, the equations account for
the corresponding boundary conditions the first-order nonlinear effects of the axial
according to which ur = w = Or = 0 for a forces on the curvature of deformed shell
clamped edge, w = Nr= M , = 0 for a simply meridian. These equations have the following
supported edge, w = ur = Mr = 0 for a hinged form:
edge fixed in the radial direction, and Nr= Mr
= Q, = 0 for a free edge. To write the force M,’- Q, = 0
boundary conditions in terms of displace-
ments, the following expressions can be used: N
Q,‘+ Nw” - 2 + j7 = 0
Ur O R
Nr= Bllu,’ + B 1 2 T + C122
r N,= N
W
N, = B,,u‘ + B l2-
R
U 0
M, = C12& +DllBr’+ D 12 r _f_
W
N, = B,,u‘ + B 22 - + C,,Ox’
R

W
M, = C -
l2 R
+ D,,OX’
754 Andysis methods

Q, = K,,(ex + w') (32.24)

where ( )' = d( )/dx, j? = p - q. Stiffness coeffi-
cients B, C, D, K are specified by eqn (32.6) in Boundary conditions should be written in
which terms of w and force Sx = Nw'.
e = I (,)/I(0)
11 11
32.6.2 NONSYMMETRIC DEFORMATION
The foregoing set of equations, (32.24), can be
reduced to the ordinary differential equation
In the general case of loading, composite cylin-
w""- 2s2w"+ PW = kp (32.25) drical shells can be usually described rather
adequately by the so-called semimembrane
where theory that, in addition to membrane theory,
takes into account the circumferential bending
s2 = C,, (1 + C ) + RN + ___ moments. The model of a semimembraneshell
2RCD
~

can be represented by a system of rings with

inextensible axes that take only circumferen-
t4 = B tial bending moments and by a system of
R2B,,CD absolutely flexible beams that connect the
rings and sustain axial and shear forces only.
The semimembrane theory assumptions lead
to the following equations:
aNx
-+- a%, = o
ax ay
= '11[' +
C,, + RN
RCK,, 1 %+-
ay
a%,
ax
+ - Q,
R
+q
Y
=o

B = B,,B, - B,:
Constants of integration entering the solution
of eqn (32.25) can be found from the corre-
sponding boundary conditions according to
which w = Ox = 0 for a clamped edge, w = M x =
0 for a simply supported edge, and M x = S , = 0,
where Sx= Q, + Nw' for a free edge.
Thin-walled composite pressure vessels can
be described by nonlinear membrane equa-
tions using the assumption that D,, = C, = 0.
These equations can be reduced to
W" - k2W = kp

where Q, = K,VY

a u w
E =-+-=(I
' a Y R
 Cylindrical shells 755

= Nx; = 0 for a free edge. The following expres-

8 = q + - -v - aw
Y R ay (32.26) sions can be used for the boundary conditions
where j7 = p - 9, 9Y is the circumferential sur- BllR ‘11 ,,, Wnr
face traction, and stiffnesses B, D are specified Un = ~ wnr------w, -__
by eqn (32.6) in which e = I$)/I$).
A,2B3: m t F 3 3 mnz
Decomposition into Fourier series, i.e.
N,”= BllR wn - R4 E1 ,
~

Z~~
I,

m
B33

n=l 5 1 BllR
Nx; = wn’
m,3
~

- An’s3
...! Ny”(x),My”@),p,(x)lcos Any Wnlfr ~

m where

..., Qy”(x),qy”(x)lsinAny It must be noted that the semimembrane theory

is not valid for the case of axisymmetricloading
whereAn= n/R, allows reduction of eqn (32.26) (n = 0) and reduces to the membrane theory for
to the following governing equation: n = 1. Proper combination of solutions of eqn
(32.25) for n = 0 and of eqn (32.27) for n 2 1
+ t4wn= kp (32’27) allows
w ~ ” ”- 2s’~~’’
consideration a wide range of practical
where problems for composite cylindrical shells.
A;(n2 - l)D,
52 =
32.6.3 BUCKLING
2B33
Under axial compression by forces N (here, in
contrast to Fig. 32.18, N are compressive
forces), cylindrical shells can experience three
modes of buckling: column-type, axisymmet-
ric, and nonsymmetric buckling. The actual
critical load is the smallest of the three values.
For a column-type buckling

n2rn2R2B
Nc =
2L2B2,(1 +
n2rn2R2B
L2B22B33
)
where B = Bl1B2, - B1: and rn depends on the
9;
Fn = P, -n
character of end fixity. If the end cross sections
are fixed in such a way that they can freely
Four constants of integration entering the rotate (hinged column), then rn = 1.If the ends
solution of eqn (32.27) can be found from the are clamped, then rn = 2.
corresponding boundary conditions according Axisymmetric mode of buckling is typical
to which u, = vn= 0 for a fixed edge (it is essen- for thick and sandwich shells. The corre-
tial that inextensibility condition E = 0 yields sponding critical load is specified by the
w,, = -RAnvn,so wn = 0 for a fixed edge) and N,” following equation that allows for transverse
756 Analysis methods

shear and radius variation through the shell where

17 I=[."."
BllD,
+{(l +=)I BP22

where

1
; =(y) 2

For a homogenous shell

Stiffnesses B, C, D are specified by eqns (32.6)

and (32.7) in which e = I$)/Iio); Am,,should be
changed for Am,, where
- where Ex= Ex/(l - vX,,vy,).
(i) - A (1) A (11 = A (i), 421 = A ~ ( ~ ) / S ~
41 - i 11 12 12
The critical value of the lateral external pres-
and sure can be approximated by
1
si = 1+ - (ti + ti-,-2e)
2R
Transverse shear stiffness is Here, B,, and D, are specified by eqn (32.6) in
which e = I$)/I$) and parameter c depends on
the boundary conditions. For a simply sup-
ported shell c = 1,for a hinged shell whose end
Note that the shell is assumed to be simply
cross sections cannot move in the axial direc-
supported at x = 0 and x = L (see Fig. 32.18).
tion c = 1.5, and for a shell with one end
If transverse shear deformation is not taken
hinged and the other end free c = 0.6.
into account, then
Buckling pressure for an infinitely long
shell is
3D2,
The critical load, corresponding to the general 9, = x3
mode of buckling of a thin simply supported Finally, note that the derivation for equations
orthotropic shell, can be found as presented in this chapter can be found else-
N, = DllA:,, + D, 2
II", + where3.
R2Ai($+%]
 References 757

REFERENCES 2. Whitney, J.M. 1987. Structural Analysis of

Laminated Anisotropic Plates. Lancaster,
1. Tarnopolskii, Yu.M. and Kincis, T.Ya. 1985. Static Pensylvania: Techomic Publishing co,,Inc,
Test Methods for New Van 3. Vasiliev, V.V. 1993. Mechanics of Composite
Nostrand Reinhold. Structures. Washington: Taylor & Francis.
DESIGN ALLOWABLES SUBSTANTIATION
Christy Kirchner Lapp
33.1 INTRODUCTION
Designing with composite materials requires
knowledge of a significantly greater number
of properties than for conventional isotropic
metals. The selection of lamina and laminate
allowables can be critical in the analysis of a
composite structure. However, composite
design allowables may not always be obtained
from a single source of data. Several references
must often be consulted to determine all the
properties in the necessary directions, espe-
cially if several fibers or matrices are being
considered in the design. This can be a time-
consuming effort, especially during the initial
design phase. In addition, some organizations
may not have easy access to all the necessary
references required to collect the data. This
chapter assembles lamina data from numerous
sources so that the engineer may have a single
reference point for initial design and analysis
of composite structures. A broad range of
fibers has been included since composites are
increasingly being applied outside the aero-
space community.
Design allowables in this section are for
both elastic and strength properties. Elastic
properties are necessary for laminate design or
the analysis of composite structures. These
properties include elastic moduli and
Poisson’s ratios. Strength properties are
required to predict laminate strengths or per-
form a failure analysis of the structure.
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
33
Strength properties for compression, tension
and shear must be determined. Both elastic
and strength properties can be influenced by
numerous variables such as the fiber, matrix,
fiber volume and processing method. The test
method used to determine the allowable can
also affect the property. In addition, some
allowables cannot be readily tested, especially
properties through-the-thickness of the com-
posite. Often, complete characterization of a
fiber/matrix system may not be available and
the engineer must estimate or assume proper-
ties. It can be expensive and time-consuming
to completely characterize a fiber/matrix sys-
tem during the initial design phase, so it is
important for the engineer to have allowables
based on reliable data and to understand the
limitations.
This chapter concentrates on providing the
material database and techniques for assem-
bling the necessary composite allowables for
preliminary design. Final design allowables
may require additional testing. The allowables
provided in this chapter should be considered
preliminary design values. Allowables for
both two dimensional (2-D) and three dimen-
sional (3-D) properties are included. As a
starting point, lamina allowables for com-
monly used fiber/matrix systems are
described and listed. The references for these
allowables are included. Several references
may be listed for a single material. Methods
for estimating properties when data is not
available or testing cannot be readily per-
formed are also defined. The effects of
processing methods on allowables and methods
 Lamina allowables 759

for adjusting lamina properties for these vari- 33.3 LAMINA ALLOWABLES
ables is described. The intent is to provide a Lamina allowables may be used in a laminated
baseline for design allowables which can then plate code to predict laminate elastic and
be expanded with additional testing data as strength properties, or they may be used
required or modified for a specific application. directly in a finite element analysis code. Table
33.1 defines the lamina properties and the
33.2 NOMENCLATURE FOR DESIGN basis for each property. Most of the properties
ALLOWABLES are based on test data for the 2-D properties.
The 3-D properties typically represent calcu-
The nomenclature used to describe composite lated values based on the equations shown in
lamina and laminate properties is not consis- Table 33.1.
tent within the industry. For this chapter, the Properties for commonly used fiber and
lamina properties parallel to the fiber are spec- epoxy resin systems are included and the con-
ified with a 1 and the lamina properties struction is assumed to be continuous fiber
transverse to the fiber are designated with a 2. reinforcement. A wide variety of reinforcing
Figure 33.1 illustrates this nomenclature for fibers is included since composites may be
composite lamina and laminate properties. used in variety of applications, each with very
The properties in the 1-2 plane are often different design requirements. Glass, polyeth-
referred to as the in-plane lamina properties ylene, aramid and graphite fibers are covered.
whereas the properties through-the-thickness Graphite fibers include standard, intermediate
(out-of-plane)of the composite are designated and high modulus types. The fiber/resin sys-
with a 3. The 1, 2 and 3 directions can be tems have very different properties and the
referred to as the longitudinal, transverse, and actual composite application will dictate the
through-the-thickness properties respectively. selection. For example, glass fibers are less
expensive and more impact resistant than

Laminate property definition

amina property definition

Fig. 33.1 Nomenclature for lamina and laminate properties.

760 Design allowables substantiation

Table 33.1 Definition of lamina properties and equations used to calculate material properties

Lamina material Definition Equation used to calculate

properties material property
Elastic

El
Elastic modulus in the fiber direction Property based on test data
E2 Elastic modulus transverse to the fiber direction Property based on test data
E3
Elastic modulus through-the-thickness Transverse isotropy: E, = E,
GI2 Shear modulus in the 1-2 plane Property based on test data
E3
G23
Shear modulus in the 2-3 plane G23 = 2(1 + YB)
G13 Shear modulus in the 1-3 plane Transverse isotropy: G,, = G,,
v12
Poisson's ratio in 1-3 plane Property based on test data

'23

Poisson's ratio in 1-3 plane Transverse isotropy: v13= vI2

Tensile strength in the fiber direction Property based on test data

Compressive strength in the fiber direction
Tensile strength transverse to the fiber
Compressive strength transverse to the fiber
Tensile strength through-the-thickness
Compressive strength through-the-thickness
'12
Shear strength in 1-2 plane (in-plane)
t13
Shear strength in the 1-3 plane (interlaminar)
'23
Shear strength in the 2-3 plane (interlaminar)
Property based on test data
Property based on test data
Property based on test data
u3 = u2
a3= a,
Property based on test data
Property based on test data
'23 = '13

graphite fibers, but have a higher density and
lower modulus. Since the lamina properties
are assumed to be used as preliminary design
and analysis parameters, the effects of temper-
ature, environment and fatigue are not
considered. However these conditions must be
considered during the final design develop-
ment.
33.3.1 TWO-DIMENSIONAL (2-D) LAMINA
PROPERTIES
The elastic lamina properties required for a
composite 2-D analysis are typically E,, E,, G,,,
and vI2. The specific properties may depend
upon the type of analyses being performed or
the analysis code being used. If a strength or
failure analysis is performed, then the follow-
ing strength allowables may be required; q,
o,,-q,-0,and T,,. Tables 33.2 and 33.3 include
these elastic and strength properties, which
were compiled from various sources, such as
military standards, material supplier data and
published literature. References are included
for each property so that the engineer may
directly consult a particular reference if further
information is required. These references are
listed in Tables 33.4 and 33.5.
The lamina properties for glass, polyethyl-
ene and aramid fibers are listed in Table 33.2.

Polyethylene and aramid fibers are more com-
monly known by their trade names as Spectra
and Kevlar. Kevlar 29 and 49 are included for
aramid properties. The polyethylene fibers
include Spectra 900 and 1000. E-glass and S-
glass (trade names) are included for glass
fibers. Table 33.3 lists lamina properties for
standard, intermediate and high modulus
graphite fibers. Data for non-USA produced
fibers is not included.
The type of material system is also indi-
cated in Tables 33.2 and 33.3. Design
allowables for a prepreg material system ver-
sus a wet filament wound system may result
in different properties. It is important to con-
sider the processing method when selecting
the properties to be used in a design. One pro-
cessing method may result in a lower moduli
or strength than another. The effects of differ-
ent processing methods on design allowables
is discussed in further detail at the end of this
chapter.
The majority of the 2-D properties is based
on test data, not micromechanics equations.
The test data is typically based on 'thin speci-
mens' (typically less than 2.54 mm (0.10 in)
thick). Properties based on thin specimens
may not represent those for thick composites
(typically greater than 6.35 mm (0.25 in) thick).
The exact definition of a thick composite is not
consistent within the composites community.
Thick composite structures may have proper-
ties lower than those of thin composites, so the
engineer may need to perform additional test-
ing for certain applications.
33.3.2 THREE-DIMENSIONAL (3-D) LAMINA
PROPERTIES
Irutially the majority of analyses performed on
composite structures were two dimensional.
However with advancement of finite element
analysis programs and as new applications for
composites arise, more analyses are being per-
formed for the 3-D case. Thus through-the
-thickness lamina properties have become nec-
essary in performing certain analyses. Often
Lamina allowables 761
these properties are difficult to test and data is
not always readily available. The 3-D lamina
properties listed in Tables 33.2 and 33.3 are
estimated based on 2-D properties. The fol-
lowing section describes the methods for
calculating lamina properties in the 3-direc-
tion when data is not available.
33.3.3 ESTIMATING LAMINA PROPERTIES
WHEN DATA IS NOT AVAILABLE
Lamina properties through-the-thickness (3-
direction) are often not readily available,
although they may be required to perform an
analysis. When data is not available, these
properties can be determined by assuming
that the lamina is transversely isotropic. For a
transversely isotropic lamina, the properties in
the 2- and 3-directions are assumed to be the
same. Thus the following equations may be
used to determine elastic properties in the 3-
direction':
E, = E,
G*, = G12
r
L3
G23 = 2(1 + vz3)
'13 = '12
The transverse Poisson's ratio, v23, can be
determined from the following relationship2:
where vf is the fiber Poisson's ratio, V , is the
fiber volume fraction, vm is the matrix
Poisson's ratio, and Em is the matrix elastic
modulus. Therefore to calculate certain prop-
erties in the 3-direction, the engineer needs to
know certain fiber and matrix properties, and
these have also been listed in Tables 33.2 and
33.3. For initial design purposes, it is simplest
762 Design allowables substantiation
to assume that the fiber and matrix are
isotropic, although certain fibers are consid-
ered to be anisotropic. The fiber or resin shear
modulus can be calculated by:
E the limitations of the selected processing
G=----'--
2(1 + v)
The following equations may be used to esti-
mate strength properties in the 3-direction.
u3= u2
-a3= -u2
The equations listed above should be consid-
ered a starting point for estimating 3-D lamina
properties when actual test data is not avail-
able. The values may need to be verified by
testing as the design progresses.
33.4 LAMINATE ALLOWABLES
Laminate elastic properties and strengths can
be determined by testing or by using a lami-
nated plate code. During the initial design
phase, laminate allowables are typically deter-
mined by using a laminated plate code. This is
especially true if the composite lay-up devi-
ates from a 'standard' lay-up, such as a
quasi-isotropic laminate ([90, +45, 4 5 , OIJ.
There is typically more test data available for a
quasi-isotropic lay-up than any other lay-ups.
Laminate testing is often performed after com-
pletion of the initial design, material selection
and composite lay-up has been decided.
Laminate testing would be performed to con-
firm predictions and processing effects.
33.5 EFFECTS OF PROCESSING
VARIABILITIES ON DESIGN ALLOWABLES
The actual fabrication method used to build a
composite structure can have an impact on the
design allowables. Some processing methods
can result in a higher fiber volume fraction
and lower void content than others. For exam-
ple, an autoclave cured part using prepreg
tape will typically have a higher fiber volume
and lower void content than a wet filament
wound part. This can affect properties such as
the elastic modulus (E,) or tensile strength (uJ.
It is important that the engineer understand
method and adjust the design allowables
accordingly. Processing parameters which can
affect the lamina allowables are fiber volume
fraction and void content. Design allowables
should be modified if the process used to
determine the lamina properties deviates from
the intended process for the final composite
part; this ensures that unrealistic properties
are not being used to design the part.
There are numerous fabrication methods
applicable for composites. The methods which
will be discussed are those that apply to con-
tinuous fiber reinforcement. These include
filament winding, hand lay-up and resin
transfer molding (RTh4). The method of cure
can also affect the lamina properties. For
example, one part can be filament wound with
prepreg tow and another can be hand layed up
with prepreg tape. These parts have different
fabrication methods, but they may be cured in
the same manner; in an autoclave with vac-
uum and pressure. It is very likely that these
two parts would have similar properties and
require no adjustment of lamina properties.
However, if the filament wound part was wet
wound and cured in an oven without vacuum
or pressure, then the lamina properties would
need to be adjusted if they were based on
properties derived from testing using prepreg
tape. A wet filament wound part typically has
a lower fiber volume fraction and higher void
content. Thus in determining if lamina proper-
ties need to be modified, the engineer must
consider the complete method of processing,
including the raw material and cure method,
not just the automated or manual process
which is being used to fabricate the part.
In general, if a part is wet filament wound,
it will possess a lower fiber volume fraction
and a higher void content than a hand-layed
up part using prepreg tape and cured in an
autoclave. Wet filament wound parts cured in
 References 763

an oven without vacuum and pressure typi- E , (wet filament wound)

cally have a fiber volume fraction between
0.55 and 0.60 with a void content between 1 V,(wet filament wound)
and 5%. Parts fabricated from prepreg tow or
tape, which are cured in an autoclave with
Adjusting properties by the ratio of fiber vol-
vacuum and pressure will typically contain
ume fraction is applicable for modulus,
fiber volume fractions between 0.60 and 0.65.
tensile and compressive strength, but does not
Parts which are fabricated using the RTM
serve well for Poisson’s ratios which would
process will typically possess fiber volume
require micromechanics. The Poisson’s ratio
fractions of approximately 0.50. Determining
can be calculated based on the following
lamina properties for RTM parts is particularly
equation,:
difficult since the preform is usually woven
and properties are not readily available. Also Y1, = v,v,+ vm(l - V,)
weaving in some conditions may slightly
where vf is the fiber Poisson’s ratio, Vf is the
degrade the properties.
fiber volume fraction and vm is the matrix’s
The adjustment of lamina properties should
Poisson’s ratio.
focus on the 2-D elastic properties; E,, E,, G,,,
v,, and the 2-D strength properties; u,, -ol, u,,
-pz and rl,. The simplest method is to adjust REFERENCES
the desired property by multiplying the value Whitney, J., Daniel, I. and Pipes, B., 1984.
by the ratio of the fiber volume for the selected Experimental Mechanics of Fiber Reinforced
processing method to the fiber volume listed Composite Materials. Brookfield Center,
in Tables 33.2 and 33.3. For example, if one has Connecticut: The Society for Experimental
properties based on prepreg tape which has Mechanics.
been autoclaved cured and wants to adjust Vinson, J. and Sierakowski, R. 1987. The Behavior
these properties for a wet filament wound part of Structures Composed of Composite Materials.
Boston: Kluwer Academic Publishers.
the following calculation would be used to
adjust the longitudinal elastic modulus (El):
764 Design allowables substantiation

Table 33.2 Lamina properties for glass, aramid and polyethylene fibers in epoxy matrices

Properties E-glass/ S2-glass/ S2-glass/ Kevlar

DER 332 DER 332 xP251 s 29/934
Material system Wet wound Wet wound Prepreg Prepreg
Fiber type E-Glass S-Glass S2-Glass Aramid
Supplier Owens Owens Owens DuPont
Resin type Epoxy EPOXY EPOXY EPOXY
Supplier Dow Dow 3M Fiberite
Fiber volume 60% 60% 60% 58%
Composite density, g/cm3 2.05 1.98 1.98 1.38
(ib/in3) (0.074) (0.072) (0.072) (0.050)
Lamina elastic properties
E,, GPa 48 54 51 54
(psi x lo6) (7.0) (7.9) (7.5) (7.9)
E,, GPa 12 16 17 5
(psi x lo6) (1.8) (2.3) (2.5) (0.7)
E,, GPa 12 16 17 5
(psi x lo6) (1.8) (2.3) (2.5) (0.7)
G,,,GPa 6 7 7 2
(psi x lo6) (0.84) (0.98) (0.98) (0.24)
G,,,GPa 5 6 7 2
(psi x lo6) (0.70) (0.89) (0.95) (0.24)
G,,,GPa 6 7 7 2
(psi x IOh) (0.84) (0.98) (0.98) (0.24)
'12
0.19 0.25 0.25 0.40
'23
0.26 0.32 0.32 0.47
VI i 0.19 0.25 0.25 0.40
Lamina strength properties
01
Tension, MPa 1613 1779 1069
(psi x lo3) (234) (258) (155)
Compression, MPa 462 -641 -272
(psi x lo3) 467) 493) 439)
(72
Tension, MPa 39 58 9
(psi x lo3) (54 (8.4) (1.3)
Compression, MPa -103 -186 -130
(psi x lo3) -05) -(27) -09)
ff3
Tension, MPa 39 58 9
(psi x lo3) (5.6) (8.4) (1.3)
Compression, MPa -103 -186 -130
(psi x lo3) 415) 427) -09)
212
MPa 28 75 37
(psi x lo3) (3.3) (4.0) (10.9) (5.3)
 Tables 765

Kevlar Kevlar 49 Kevlar Spectra Spectra

49/934 /DER332 149/934 9OO/EPON 826 1000/EPON 826
Pprepreg Wet Wound Prepreg Wet Wound Wet Wound
Aramid Aramid Aramid Polyethylene Polyethylene
DuPont DuPont DuPont Allied Allied
EPOXY EPOXY EPOXY EPOXY EPOXY
Fiberite Texaco Fiberlite Shell Shell
58% 60% 58% 55% 55%
1.38 1.35 1.38 1.12 1.12
(0.050) (0.049) (0.050) (0.040) (0.040)

72 82 106 31 50
(10.5) (11.9) (15.4) (4.5) (7.3)
5 5 6 4 1
(0.7) (0.7) (0.9) (0.5) (0.1)
5 5 6 4 1
(0.7) (0.7) (0.9) (0.5) (0.1)
2 2 2 1 1
(0.24) (0.26) (0.24) (0.21) (0.10)
2 2 2 1 0
(0.24) (0.27) (0.32) (0.21) (0.05)
2 2 2 1 1
(0.24) (0.26) (0.24) (0.21) (0.10)
0.41 0.31 0.34 0.32 0.28
0.48 0.38 0.42 0.40 0.36
0.41 0.31 0.34 0.32 0.28

1151
(167)
-281
441)

12
(1.7)
-134
419)

43 24 49 24 17
(6.3) (3.5) (7.1) (3.5) (2.5)
Continued on next page
766 Design allowables substantiation

Table 33.2 continued Lamina properties for glass, aramid and polyethylene fibers in epoxy matrices

Properties E-glass/ S2-glassl S2-glass/ Kevlar

DER 332 DER 332 XP251S 29/934

213
MPa 66 66 77 34
(psi x lo3) (9.5) (9.5) (11.1) (5.0)
r23
MPa 66 66 77 34
(psi x lo3) (9.5) (9.5) (11.1) (5.0)
Constituent properties
Fiber
E,, GPa 72 87 87 83
(psi x lo6) (10.50) (12.60) (12.60) (12.00)
vf 0.09 0.18 0.18 0.44
G, GPa 33 37 37 29
(psi x IO6) (4.8) (5.3) (5.3) (4.2)
Tensile strength, MPa 3103 3792 3792 3620
(psi x lo3) (450) (550) (550) (525)
Density, g/cm3 2.60 2.49 2.49 1.44
(lb/in3) (0.094) (0.090) (0.090) (0.052)
Resin
E , GPa 3.4 3.4 3.4 4.1
(psi x lo6) (0.49) (0.49) (0.49) (0.60)
213
0.35 0.35 0.35 0.35
G , GPa 1.2 1.2 1.2 1.5
(psi x lo6) (0.18) (0.18) (0.18) (0.22)
Tensile strength, MPa 64 64 64 83
(psi x lo3) (9.3) (9.3) (9.3) (12)
Density, g/cm3 1.22 1.22 1.22 1.30
(ib/in31 (0.044) (0.044) (0.044) (0.047)
 Tables 767

Kevlar Kevlar 49 Kevlar Spectra Spectra

49/934 DER332 149/934 9OO/EPON 826 1OOO/EPON 826

50 50 38 23 23
(7.2) (7.2) (5.5) (3.4) (3.4)

50 50 38 23 23
(7.2) (7.2) (5.5) (3.4) (3.4)

124 124 172 117 172

(18.00) (18.00) (25.00) (17.00) (25.00)
0.45 0.28 0.33 0.30 0.22
43 48 65 45 70
(6.2) (7.0) (9.4) (6.6) (10.2)
3620 3620 3448 2586 2992
(525) (525) (500) (375) (434)
1.44 1.44 1.47 0.97 0.97
(0.052) (0.052) (0.053) (0.035) (0.035)

4.1 3.4 4.1 2.8 2.8

(0.60) (0.49) (0.60) (0.40) (0.40)
0.35 0.35 0.35 0.35 0.35
1.5 1.2 1.5 1.0 1.o
(0.22) (0.18) (0.22) (0.15) (0.15)
83 64 83 83 83
(12) (9.3) (12) (12) (12)
1.30 1.22 1.30 1.30 1.30
(0.047) (0.044) (0.047) (0.047) (0.047)
768 Design allowables substantiation

Table 33.3 Lamina properties for graphite fibers in epoxy matrices

Properties AS4/3501-6 lM6/3501-6 IM7/3501-6 lM8/3501-6

Material system Prepreg Prepreg Prepreg Prepreg
Fiber type Graphite Graphite Graphite Graphite
Supplier Hercules Hercules Hercules Hercules
Resin type EPOXY EPOXY EPOXY EPOXY
Supplier Hercules Hercules Hercules Hercules
Fiber volume 60% 60% 60% 60%
Composite density,
g/cm3 1.58 1.55 1.57 1.58
(ib/in3) (0.057) (0.056) (0.057) (0.057)
Lamina elastic properties
E,, GPa 143 159 159 186
(psi x IO6) (20.7) (23.0) (23.0) (27.0)
E,, GPa 10 10 10 10
(psi x lo6) (1.4) (1.4) (1.4) (1.4)
E,, GPa 10 10 10 10
(psi x lo6) (1.4) (1.4) (1.4) (1.4)
GI,, GPa 6 5 5 6
(psi x lo6) (0.85) (0.71) (0.72) (0.80)
G,,GPa 3 3 3 3
(psi x lo6) (0.41) (0.41) (0.41) (0.41)
G,,,GPa 5 5 5 5
(psi x lo6) (0.68) (0.68) (0.68) (0.68)

'12
0.30 0.30 0.30 0.30
'23
0.52 0.52 0.52 0.52
'13
0.30 0.30 0.30 0.30
Lamina strength properties
01
Tension, MPa 2172 2413 2620 2689
(psi x lo3) (315) (350) (380) (390)
Compression, MPa -1558 -1655 -1862 -1931
(psi x lo3) -(226) -(240) -(270) -(280)
0 2
Tension, MPa
(psi x lo3)
Compression, MPa
(psi x lo3)

03
Tension, MPa 59
(psi x lo3) (8.5)
Compression, MPa -186
(psi x lo3) 427)
 Tables 769

T300/5208 T40/1962 T50/1962 P55/1962 P75/1962

Prepreg Prepreg Prepreg Prepreg Prepreg
Graphite Graphite Graphite Graphite Graphite
Amoco Amoco Amoco Amoco Amoco
EPOXY EPOXY EPOXY EPOXY EPOXY
Fiberite Amoco Amoco Amoco Amoco
62% 62% 62% 62% 62%

1.60 1.60 1.72 1.72

(0.057) (0.058) (0.058) (0.062) (0.062)

141 172 241 241 338

(20.5) (25.0) (35.0) (35.0) (49.0)
9 10 7 8 7
(1.2) (1.5) (1.1) (1.1) (1.0)
9 10 7 8 7
(1.2) (1.5) (1.1) (1.1) (1.0)
6 7 6 5 6
(0.92) (1.00) (0.84) (0.79) (0.85)
3 4 3 3 3
(0.41) (0.54) (0.39) (0.39) (0.36)
5 7 6 5 6
(0.68) (1.00) (0.84) (0.79) (0.85)
0.30 0.33 0.28 0.34 0.30
0.52 0.40 0.35 0.41 0.37
0.30 0.33 0.28 0.34 0.30

1524 3241 1413 931 965

(221) (470) (205) (135) (140)
-1482 -1724 -965 -510 441
-(215) -( 250) -(140) 474) 464)

36 69 37 33 33
(5.2) (10.0) (5.3) (4.8) (4.8)
-159 -159 -159 -159 -159
-P3) 423) 423) 423) 423)

36 69 37 33 33
(5.2) (10.0) (5.3) (4.8) (4.8)
-159 -159 -159 -159 -159
423) 423) 423) 423) 423)

Continued on next page

770 Design allowables subsfantiation

Table 33.3 continued Lamina properties for graphite fibers in epoxy matrices

Properties AS4/3501-6 lM6/3501-6 IM7/3501-6 lM8/3501-6

212
MPa 87 85 96 80
(psi x lo3) (12.6) (12.3) (13.9) (11.6)

13
MPa 124 121 121 131
(psi x lo3) (18.0) (17.5) (17.5) (19.0)

‘23
MPa 94 94 94 94
(psi x IO3) (13.6) (13.6) (13.6) (13.6)
Constituent properties
Fiber
E , GPa 234 276 276 303
(psi x lo6) (34.0) (40.0) (40.0) (44.0)
Vf 0.26 0.26 0.26 0.26
G,, GPa 93 109 109 120
(psi x lo6) (13.5) (15.9) (15.9) (17.5)
Tensile strength, MPa 3930 5102 5309 5447
(psi x lo3) (570) (740) (770) (790)
Density, g/cm3 1.80 1.74 1.77 1.80
(ib/ i n 3 ) (0.065) (0.063) (0.064) (0.065)
Resin
Er, GPa 4.4 4.4 4.4 4.4
(psi x IO6) (0.64) (0.64) (0.64) (0.64)
vr
0.36 0.36 0.36 0.36
G , GPa 1.6 1.6 1.6 1.6
(psi x lo6) (0.24) (0.24) (0.24) (0.24)
Tensile strength, MPa
(psi x lo3)
Density, g/cm3 1.26 1.26 1.26 1.26
(lb/ in3) (0.046) (0.046) (0.046) (0.046)
 Tables 771

T300/5208 T40/1962 T50/1962 P55/1962 P75/1962

77 97 63
(11.2) (14.0) (9.2)

115 97 69
(16.7) (14.0) (10.0)

94 97 69
(13.6) (14.0) (10.0)

231 283 393 379 517

(33.5) (41.0) (57.0) (55.0) (75.0)
0.27 0.32 0.24 0.33 0.27
91 107 159 142 204
(13.2) (15.6) (23.0) (20.6) (29.5)
3241 5654 2413 1724 2069
(470) (820) (350) (250) (300)
1.77 1.80 1.80 1.99 1.99
(0.064) (0.065) (0.065) (0.072) (0.072)

3.9 3.7 3.7 3.7 3.7

(0.56) (0.54) (0.54) (0.54) (0.54)
0.35 0.35 0.35 0.35 0.35
1.4 1.4 1.4 1.4 1.4
(0.21) (0.20) (0.20) (0.20) (0.20)
50 66 66 66 66
(7.3) (79.6) (9.6) (9.6) (9.6)
1.27 1.27 1.27 1.27 1.27
(0.046) (0.046) (0.046) (0.046) (0.046)
772 Design allowables substantiation

LAMINA PROPERTY REFERENCES D Y~~was calculated based on the following equa-

A Weight density was calculated based on the fol- tion:
lowing relationship:

pf = fiber density
Vf = fiber volume fraction
p, = resin density
AAAS4 and IM6 fiber properties are based on DD Hercules data for IM7/3501-6 from the Graphite
Hexcel supplied data which was based on tow Fiber Products Handbook, based on mechanical
test data for the fiber modulus and strength. test data.
The fiber Poisson's ratio was 'back' calculated E Assumed:
based on the composite Poisson's ratio ( Y ~ , ) ,the o3= o2and *3 = +T~
matrix Poisson's ratio and the fiber volume
(see reference H). EE IM7 and IM8 fiber properties are based on
B L.L. Clements and R.L. Moore, Composite prop- Hercules supplied data (Graphite Fiber Products
erties for E-glass fibres in a room temperature Handbook) which was based on tow test data
curable epoxy matrix, Composites, 1978, 9(2), for the fiber modulus and strength. The fiber
93-99. Properties for tI3were set equal to val- Poisson's ratio was 'back' calculated based on
ues for S2-glass/DER 332 since no data was the composite Poisson's ratio (Y~,), the matrix
reported. Poisson's ratio and the fiber volume (see refer-
BB Hercules supplied data for IM6/3501-6 from the ence H).
Graphite Fiber Products Handbook based on F The following was assumed:
mechanical test data.
C Composite is assumed to be transversely '23 = 31'
isotropic. A transversely isotropic composite is FF Hercules data for IM8/3501-6 from the Graphite
a material which exhibits a special case of Fiber Products Handbook, based on mechanical
orthotropy, whereby the properties are identi- test data.,
cal in two orthotropic dimensions, but not the G Owens Corning fiber data and short beam
third. The properties are the same in both shear data.
transverse directions, but not in the longitudi- GG Properties based on test data listed in BASF
nal direction. The following equations apply Hexcel Technical Information handbook.
for transversely isotropic materials: H Equation for calculating the fiber Poisson's
E, = E, ratio (vf):
Y12- Y,(1 - VJ
Vf =
GI3 = GI2 Vf
HH Amoco data for T300 fibers. Actual test
'13 = '12 method for fiber modulus and strength was not
defined. The fiber Poisson's ratio was 'back
E3 calculated based on the composite Poisson's
G23 = 2(1 + Y2J ratio using the equation in reference H.
I Fiber and resin are assumed to be isotropic,
CC Properties were set equal to those for
therefore G, or GI is calculated as follows:
AS4 / 3501-6.
E*
Gf = 2(1+ VJ

I1 Properties based on test data supplied by
Amoco for the T40/1962 system. Amoco sup-
plied data for the 1962 resin system.
Resin properties from publication by Texaco,
J Swanson, G.R. Toombes, and S.W. Beckwith,
Huntsman Chemical Co. ’Jeffamine’, resin
properties are based on 100 parts of epoxy resin
and 45 parts of Jeffamine T-403. The DER 332
epoxy resin was cured with Jeffamine T-403.
JJ Properties were set equal to T300/5208 value.
KJK Amoco data for T40 and T50 from technical
information sheets. Test method for fiber mod-
ulus and strength was not specified. The fiber
Poisson’s ratio was ‘back‘ calculated based on
the composite Poisson’s ratio (vlJ , the resin
Poisson’s ratio and the fiber volume (see refer-
ence H).
L H. Hahn, D. Hwaug, H. Chang, S. Lo, Flywheel
Materials Technology: Design Data Manual for
Composite Materials, UCRL-15365 Volume 1,
P.O. 6641009, Lawrence Livermore Laboratory,
July, 1981.
LL Amoco test data for T50/1962
M Assumed
u3= u2and -u3 = +2
MMAmoco test data for P55/1962.
N Mil Handbook 17.
NN Amoco data for P55 from technical information
sheets. Test method for fiber modulus and
strength was not specified. The fiber Poisson’s
ratio was ‘back’ calculated based on the com-
posite Poisson’s ratio (vlJ , the resin Poisson’s
ratio and the fiber volume (see reference H).
0 Properties were set equal to S2-glass/DER332.
00 Amoco data for P75/1962.
P Properties for XP251S epoxy were set equal to
DER 332 since no data was available.
PP Amoco data for P75 which was based on tow
test data for fiber modulus and strength. The
fiber Poisson’s ratio was ’back’ calculated
based on the composite Poisson’s ratio (vI2),
the resin Poisson’s ratio and the fiber volume
(see equation D).
Q DuPont supplied data for Kevlar 29/934,
Kevlar 49/934, and Kevlar 149/934. Laminates
were fabricated and tested by Boeing
Lamina property references 773
Technology Services, Boeing Commercial
Airplane Co.
R No data was listed in DuPont literature for
G12, therefore values for Kevlar 29/934, Kevlar
49/934, and Kevlar 149/934 were set equal to
those for Kevlar 49. Hexcel rubber-toughened
epoxy system based on a paper by S.R.
In-Plane Shear Properties of Composites Using
Torsion Tests of Thin-Wall Tubes, 29th National
SAMPE Symposium, April 3-5,1984.
S DuPont supplied data for Kevlar 29, Kevlar 49,
and Kevlar 149 based on tow tests (ASTM
D2343).The fiber Poisson’s ratio was ’back‘ cal-
culated based on the composite Poisson‘s ratio
(vIz), the resin Poisson’s ratio and the fiber vol-
ume (see reference D).
T Fiberite data for 934 resin system from Fiberite
Material Handbook.
U Values for Kevlar 49/DER 332 set equal to
those for Kevlar 49/Epoxy XD7575.03-XD7114-
Tonox 60-40 from Reference 6 of this list.
V D.F. Adams, R.S. Zimmerman and H.W.
Chang, Properties of Polymer-Matrix
Composites Incorporating Allied A-900
Polyethylene Fiber, SAMPE J., September/
October, 1985, pp. 44-48. Note: The modulus of
Spectra composites is much lower than
expected from the rule-of-mixtures relation-
ship. A possible explanation is that the Spectra
fiber modulus is a function of strain rate. For
example a single fiber tested at 100%/min
strain rate exhibited a modulus of 17 msi ver-
sus 11msi for a 8’%/min strain rate.
W H.W. Chang, L.C. Lin, A. Bhatnagar, Properties
and applications of composites made of polyethylene
fibers, 31st Intern. SAMPE Symp., April 7-10,
1986.
X t I 3for Spectra 1000 set equal to the value for
Spectra 900.
Y Hercules supplied test data for AS4/3501-6
determined by independent firms; Delsen Labs
and McDonnell Aircraft Company. Hercules
supplied data for 3501-6 resin. All data is listed
in the Hercules Graphite Fiber Products
Handbook.
Z R.Y. Kim, E Abrams and M. Knight,
Mechanical characterization of a thick compos-
ite laminate, Proc. Amer. SOC.Composites, 3rd
Technical Conference, 1988, pp. 711-718.
774 Design allowables substantiation

Table 33.4 References for lamina properties of glass, aramid and polyethylene fibers in epoxy matrices

Properties E-glass S2-glass S2-glass Kevlar

DER 332 DER 332 XP251 S 29/934

Material system
Fiber type
Resin type
Fiber volume
Composite density A A A Q
Lamina elastic properties
L N
L N
C C
0
G23
C
G13 C
'12
0
'23
D
1' ? C
Lamina strength properties (psi)
ff1
Tension B L N Q
Compression B L N Q
0 2
Tension B L N Q
Compresson B L N Q
0 3
Tension E M M M
Compression E M M M
212 B L N Q
'13 B G N Q
'23 F F F F
Constituent properties
Fiber
E, G G G S
f' H H H H
Gf I I I I
Tensile strength G G G S
Density G G G S
Resin
Er J J P T
r' K K K K
GI I r I I
Tensile strength J J P T
Density K K K T
 Tables 775

Kevlar Kevlar Kevlar Spectra Spectra

49/934 DER332 149/934 900/€ PO N 82 6 1OOO/EPON
826

Q L Q A A

W
W
C
W
C
C
W
D
C

Q L Q V W
Q U Q V W

Q L Q V W
Q U Q K K

M M M M M
M M M M M
Q L Q V W
Q L Q V X
F F F F F

S S S V W
H H H H H
I I I I I
S S S V W
S S S V W

T J T K K
K K K K K
I I I I I
T J T K K
T K T K K
776 Design allowables substantiation

Table 33.5 References for lamina properties of graphite fibers in epoxy matrices

Properties ASA /3501- lM6/ lM7/3501- lM8/

6 3501-6 6 3501-6
Material system
Fiber type
Resin type
Fiber volume
Composite density A A A A
Lamina elastic properties

El BB DD FF
E2 BB cc cc
E3
C C C
G12 BB DD FF
G23 cc cc cc
G,, cc cc cc
v12 cc cc cc
v2.3 cc cc cc
31' C cc cc
Lamina strength properties (psi)

0,
Tension Y BB DD FF
Compression Y BB DD FF
02
Tension Y BB cc cc
Compression Z cc cc cc
03
Tension Z cc E E
Compression Z cc E E
21' Y BB DD FF
31' Y BB DD FF
32' Z cc cc cc
Constituent properties
Fiber
Ef AA AA EE EE
Yf H H H H
G* I I I I
Tensile strength AA AA EE EE
Density AA AA EE EE
Resin
Er Y Y Y Y
vr Y Y Y Y
Gr I I I I
Tensile strength Y Y Y Y
Density Y Y Y Y
 Tables 777

T300 T50/ P55/

5208 T40/ 1962 1962 P75/1962
1962

A A A A A

GG I1 LL MM 00
GG I1 LL MM 00
C C C C C
L I1 LL MM 00
cc C C C C
cc C C C C
L I1 LL h4M 00
cc D D D D
C C C C C

GG I1 LL Mh4 00
GG I1 LL MM 00

L I1 LL MM 00
L JJ JJ JJ JJ
E E E E
E E E E
GG LL MM 00
GG LL Mh4 00
cc F F F

HH KK KK NN PP
H H H H H
I I I I I
HH KK KK NN PP
HH KK KK NN PP

GG I1 11 I1 I1
K K K K K
I I I I I1
GG I1 I1 I1 I1
GG I1 I1 11 II
MECHANICAL TESTS
Yu.M. Tarnopol’skii and VI L. Kulakov
34.1 STRUCTURAL HIERARCHY OF FIBROUS
COMPOSITES
Fibrous composites are inhomogeneous mate-
rials with multiple levels of structural scale.
The three levels of structural scale can be
arranged in a hierarchy. The characteristic
dimensions for the three levels are: fiber diam-
eter, lamina thickness and plate thickness. The
most appropriate test methods and structural
analysis techniques are different for each level
in the hierarchy. Test objectives and associated
problems are also different for each level.
The smallest scale is the diameter of the
reinforcing fiber. The properties of the rein-
forcing fiber and polymer matrix and their
interaction are studied in the field of microme-
chanics.
The second level scale is the thickness of the
unidirectional lamina. Macromechanics
describes the properties of a monolayer under
loading at an angle to the fiber direction. A
monolayer is defined as a flat or curved ele-
ment of material composed of a polymeric
matrix and reinforcement of the same type and
orientation throughout the layer. It is the basic
structural element of laminated and fibrous
composites. The characterization of monolay-
ers by mechanical test methods is given
particular emphasis in this chapter since test-
ing of anisotropic materials is a relatively
novel and seldom studied field of mechanics.
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
34
The test results are used to calculate the
properties of materials with more complex
configurations of fiber arrangement and of
hybrids, i.e. materials with different reinforce-
ments in the same lay-up.
For multilayered composites, the largest
structural scale is the thickness of the lami-
nated plate that is equal to the sum of stacked
laminae and interleaves. The theory of lami-
nated plates allows one to determine the
properties of the plate using the properties of
the monolayers and their stacking sequence. If
the monolayers are part of a structural ele-
ment, then the highest level of scale is the
characteristic size of the object. The dimen-
sions of structural elements typically exceed
the thickness of the plate by several times. The
properties of components are measured by tra-
ditional mechanical and physical test
methods’.
The results of the analyses or tests at the
first level are used as input for the analyses at
the second level. The same relationship holds
for the second and third levels. Upon convert-
ing each scale to a continuum at the next
higher scale, it is important that for each level
under consideration the number of elements
be sufficient, e.g. through the width and thick-
ness of the lamina or through the thickness of
the plate, so the transition from a discrete
medium to a continuum is performed without
great error. This progression up the hierarchy
eventually leads to solutions of real life prob-
lems involving structural elements or
prototypes.
 Problems of composite testing 779

34.2 PROBLEMS OF COMPOSITE TESTING systems of coordinates are introduced: the

axes of elastic symmetry in the material (1, 2,
34.2.1 HISTORY 3) and axes of loading (x, y, z for flat speci-
The first reference to mechanical testing of a mens; 8, z and Y for ring and tubular
structural material for an engineering applica- specimens). It is preferable to use methods in
tion is dated July 4,1662. The objective of the which the x, y, z axes (or 8, z, Y ) coincide with
tests was to compare the tensile strengths of the 1 , 2 , 3 axes.
cords made of Riga and Dutch yarns. The The majority of laminated and fibrous com-
stronger in this contest was the thinner cord posites exhibit low interlaminar shear and
manufactured in Riga. In the years that fol- transverse tension strengths. Shear strength is
lowed, equipment and methods for testing characterized by the relations between E x / G x Z
engineering materials, particularly metals, (shear stiffness) and a;/zx; (shear strength).
have reached a high degree of perfection and Transverse tension and compression strengths
consistency. The appearance of composites perpendicular to the fibers are determined by
the relations E x / E Z , axt”/a;, where Ex
ax’u/az’u,
and their ever-expanding use has once again
made it necessary to improve mechanical test and EZ are the moduli of elasticity in the x and
methods. Although significant progress has z directions; GxZ is interlaminar shear modulus;
been made, there are vast differences in their a,“ and a; are strengths in the x and z direc-
maturity. The methods differ primarily in the tions; zxzuis shear strength in xz plane. The x
degree to which they minimize extraneous and y axes are located in the fiber lay-up (rein-
stresses and strains. Although test methods forcement) plane, the z-axis is perpendicular
tend to become more complex as their accu- to this plane; the (t) and (c) designate tension
racy increases, economics must be considered and compression, respectively.
in their selection. Factors such as complexity
of specimen preparation, amount of material 34.2.3 UNIQUE REQUIREMENTS OF
required, and the requirements for specially COMPOSITE TESTING
designed equipment must be considered.
The anisotropy and unique structural proper-
ties of composite materials cause serious
34.2.2 DETERMINABLE VALUES difficulties. For example, a large number of
strength and elastic properties must be deter-
The purpose of mechanical tests is to deter- mined for complete characterization of the
mine the strength and elastic properties of a material. Since the number of determinable
material. However, only loads, displacements characteristics depends on the state of stress
and strains can be measured in a mechanical and the degree of anisotropy23, one should
test. The theory of elasticity for an anisotropic select the loading methods for which the
body is used to determine the desired proper- experimentally determinable values are most
ties of composites from these measurable simply related to the material characteristics.
quantities. It should be remembered that The selection of techniques for analyzing the
advanced fibrous composites with unidirec- data is critical as well as the determination of
tional, laminated or spatial fiber lay-ups are their range of validity. Since the composite
inhomogeneous, essentially anisotropic mate- analysis techniques are based on the theory of
rials. The customary terms, i.e. tension, elasticity for an anisotropic body, it is neces-
compression, shear and bending, are meaning- sary to consider the error in treating an
less without specification of the direction of inhomogeneous anisotropic medium as a con-
the load and its relationship to the axes of elas- tinuous anisotropic medium. For example, the
tic symmetry of the material. Therefore, two number of structural elements (fibers, lamina,
780 Mechanical tests
etc.) must be sufficiently large to support this
approximation43r6.
Once the general test method has been
selected, the details of the loading and the
sample geometry must be selected. For fibrous
composites, the principal difficulties lie in the
generation of a uniform stress field in a repre-
sentative volume of material, i.e. the
elimination of end and edge effects. This is dif-
ficult even for the most simple types of tests.
The difficulties increase with increasing
degree of anisotropy, i.e. materials reinforced
by high-modulus or high-strength fibers
(boron, carbon and organic fibers).
End effects are primarily influenced by the
method of fastening and loading of the speci-
men, the length of the grip section, and the
fiber orientation. The region involved in end
effects extends in the direction of the greatest
stiffness of the material and increases with the
anisotropy of the material.
Edge effects are primarily influenced by the
size and shape of the specimen, the fiber ori-
entation and the angle of specimen cutting. If
strength anisotropy is present, improper load-
ing and fastening can lead to changes in the
failure mode and the resulting strength value.
A most important considerationis the selec-
tion of the specimen width. The width must be
large enough to avoid the effect of cut fibers at
free edges which is important for specimens of
off -angle, angle-ply and cross-ply materials.
Edge effects are manifested as interlaminar
stresses at the free edges of the specimen, the
direction and magnitudes of which depend on
the fiber lay-up.
Material quality also causes unique require-
ments for testing composites. Quality cannot
be ignored during testing because the material
and structure are formed simultaneously. In
addition, composites are extremely sensitive
to mechanical and thermal history. Structural
imperfections, in particular porosity, waviness
and misalignment of fibers, require special
attention. The presence of porosity affects the
measurement of polymer matrix dominated
properties, e.g. shear strength. Small amounts
of fiber waviness can cause the measured val-
ues of longitudinal modulus of elasticity and
strength to be considerably lower than those of
materials with ideally straight fibers. Fiber
waviness also influences on the coefficient of
thermal expansion in the fiber direction. The
modulus of elasticity perpendicular to the
fiber direction and the in-plane shear modulus
are not significantly affected by fiber wavi-
ness.
All of the aforementioned unique testing
requirements apply to composites of a fibrous
and laminated structure. Additional difficul-
ties arise when spatially reinforced composites
are tested because the transverse strength and
stiffness are derived from a rigid framework
rather than from a compliant matrix.
34.2.4 SUMMARY TABLES
The most common methods of testing com-
posites in tension, compression, torsion and
bending are described in Tables 34.1-34.5 . The
high performance test fixtures designed
specifically for composite testing, their
description and recommended applications
are given in Reference 7.
34.3 TEST SPECIMENS
The important relationships between fabrica-
tion methods, test methods and required
specimen shapes are shown in Fig. 34.1.
Specimens for mechanical testing are classified
as flat specimens (bars and plates), rings (com-
plete and segments) and tube@.
The specimens and test methods in Fig. 34.1
are used to characterize the monolayer. Flat
monolayers can be characterized with speci-
mens that have a different fiber lay-ups but the
same general, flat, long, narrow shape. To ade-
quately characterize wound monolayers, it is
necessary to use both rings and tubes. Ring
specimens of a unidirectional fiber lay-up are
used to assess characteristics in the fiber direc-
tion. Tubular specimens with a 90" wind angle
are used to measure properties perpendicular
 Test specimens 781
x
Ir
2h"
.. I1
782 Mechanical tests
h
w
W
h
9
t l
 Test specimens
..
%
J . 4
784 Mechanical tests
0
0
m
2
&
m
d'
0
4
r3
a-
d
2
v)
.r(
X
T
N
Y
3
0
%
v
.3
aJ
8
t
cn
m
U
Y3
.
m
h
.r(
aJ
Y
U
2
d
8
aJ
Y
6
 Test specimens 785
I m u
c\
II
%
bn
@
786 Mechanical tests

t
Fig. 34.1 Methods of material fabrication and respective specimens for testing.

to the fiber direction. Tubular specimens with methods, loading types, and failure modes are
different balanced fiber lay-ups (fiber angles all different for the two test methods (Table
are symmetric with respect to the longitudinal 34.1).
specimen axis) are employed to assess shear A uniaxial tension or compression test
characteristics and to study complex states of specimen has several functionally different
stress. parts: two loading sections, a gage section,
The specimen shape, to a great extent, and two transition sections. The loading sec-
tions provide a means of fastening the
depends on the objective of the test: verification
of scientific hypotheses, engineering specifica- specimen in the testing machine. They receive
tion of the material, or quality control of the and transmit the external loads to the gage
materials. The most rigorous requirements are section of the specimen. In the gage section,
imposed on specimens of the second group. deformations are measured and stresses are
calculated according to the geometrical
dimensions and external load. The transition
34.4 TENSION AND COMPRESSION
sections serve to attenuate stress-strain per-
turbations in the loading section to isolate
34.4.1 TENSION TESTING OF FLAT SPECIMENS
them from the gage section. The specimen
In spite of any analogy that may be drawn dimensions that are recommended in the
between loading of flat composite specimens existing standards meet these requirements.
in tension and compression, only the calcula- The specimen dimensions (length, width and
tion relationships (taking into account the sign thickness) specified in standards as a function
of the stresses and strains) are common to both of the type of fiber lay-up are shown in Table
cases. The specimen shape and size, gripping 34.1 (Methods (a) and (b)).

The greatest technical challenge in tension
testing of composites, especially unidirec-
tional composites, is the reliable transmission
of tensile forces from the grips to the speci-
men. This is generally performed through the
use of friction forces. Tabs bonded to the spec-
imen improve the efficiency of load
transmission considerably. The tabs should be
made of a material that has a much lower
modulus of elasticity and a higher total elon-
gation than the respective characteristics of the
specimen material. Tabs have been made of
fiberglass reinforced composites, aluminum
and wood veneers. The thickness of tabs
should be between 1.5t and 4t, where t is the
specimen thickness. The tabs must have a
large enough area that the ultimate shear load
capacity of the bond between the tabs and the
specimen is greater than the breaking load of
the specimen gage section.
The mode of failure in tension depends on
the relationship between the external load
and the reinforcing fibers and on the type of
reinforcement lay-up. When unidirectional
composites are loaded in the reinforcement
direction, they fail by breakage of the rein-
forcing fibers. This is accompanied by
transverse cracks, longitudinal shear cracks
and delamination of the polymer matrix.
Increasing the angle between the load and the
reinforcing fibers causes the mode of failure
to change gradually from shear and splitting
of the polymer matrix parallel to the fiber
direction to pure transverse tensile cracking
of the polymer matrix. The failure mode of
composites with a balanced angle-ply rein-
forcement depends on the angle of the fiber
lay-up.
34.4.2 COMPRESSION TESTING OF FLAT
SPECIMENS
The main problem in compression testing of
flat specimens is the selection of a loading
method that ensures compressive failure.
When the loading is achieved by normal
Tension and compression 787
forces acting on the specimen ends (Table 34.1,
Method (c)),it is impossible to achieve a suffi-
ciently uniform stress distribution over the
faces of the specimen. As a result, premature
local failure of the specimen occurs. When the
loading is achieved by shear forces acting on
the sides of the specimen as specified by
ASTM D3410 (Method (d)), the stress distrib-
ution in the specimen is also non-uniform,
especially when flat wedge grips are used.
The best method is a combination of the two
methods in which normal forces are applied
at the ends and shear forces are applied along
the faces of the specimen grip section
(Method (e)).
In compression testing of unidirectional
composites in the fiber direction, three basic
modes of failure are observed: buckling of the
reinforcing fibers, transverse cracking of the
matrix, and shearing of reinforcing fibers at a
45" angle without local buckling of the rein-
forcement. Transverse cracking is caused by
differences in the Poisson's ratios of the mate-
rial components and by a non-uniform
transverse strain distribution along the speci-
men length. Materials reinforced at an angle to
the specimen's longitudinal axis fail in shear
without crumpling at the end faces because all
of the shear load is taken up by the matrix. The
aforementioned basic modes of failure can be
accompanied by a series of other phenomena:
inelastic and non-linear deformation of the
reinforcing fibers and matrix, delamination,
surface peeling, overall buckling and crushing
of the end faces. Failures with different combi-
nations of these phenomena can make the
determination of the failure mode very diffi-
cult.
In compression testing, great care must be
taken to ensure stability of the specimen, espe-
cially in the gage section. Buckling of the
specimen side face is not always detectable
and will cause erroneous strain measure-
ments. Special test fixtures are used to prevent
overall buckling of the specimen.
788 Mechanical tests

34.4.3 TENSION TESTING OF RINGS The stress concentration problem is elimi-

The most popular means of tension testing nated in tests that use uniform internal
rings uses a half-disk loading device (Table pressure generated by the use of a compliant
34.2, Methods (a) and (b)). This is because the ring (Method (d)) or by a hydraulic system
test is easy to perform and the data is easy to (Method (e)). The disadvantages of the com-
analyze. However, it has several significant pliant ring test method are the need for
disadvantages: the strain distribution over the periodic calibration of the loading element
specimen circumference is non-uniform, fric- and the need for very careful preparation of
tion between the specimen and the half-disks the specimen surface. The disadvantage of the
has a strong effect on the results, and there is a hydraulic test technique is the need for expen-
stress concentration in the specimen at the gap sive hydraulic equipment.
between the two half-disks because of a varia-
tion in the radius of curvature of the specimen.
In thin-walled rings, the stress concentration 34.4.4 COMPRESSION TESTING OF RINGS
takes the form of a slight increase in radial ten- Radial compression of rings is accomplished by
sile stresses that causes a minor effect on the external pressure (Table 34.2).The analog of the
test results. However, in thicker specimens, half-disk tension test is the simplest compres-
the resultant interlaminar shear stresses can be sion test method (Method (c)). The primary
high enough to cause failure at lower loads difference is that in the compression test, it is
than failure due to the circumferential stresses possible to reduce the stress concentration in
alone. The error increases with increases in the the specimen at the split line. The best results
relative specimen thickness t / R , the degree of are obtained with a semi-circular housing that
anisotropy, and the ultimate strain of the mate- has a locking arrangement that prevents radial
rial. Since this test method yields erroneously growth at the split-line (Fig. 34.2). There are
low strength values, it can only be used for also compression analogs for the compliant
qualitative comparison of composites. ring (Method (f)) and the hydraulic system
Corrections have been suggested but have not (Method (g)).In the compliant ring method, the
been used in practice. compliant ring is the elastic foundation of the

Fig. 34.2 Typical interlocking features for ring compression fixture.


specimen and to a certain extent it prevents
buckling of the specimen. The external pressure
may also be applied by mechanical devices
such as multiple cam.
The primary difficulty in compression test-
ing of rings by external pressure is the
selection of a relative thickness, t / R , to reduce
secondary loading effects. Depending on the
relative thickness of specimen, t / R , and the
degree of anisotropy of the material E,/G,,
three different failure modes have been
observed. Thin-walled rings fail by buckling,
thick-walled rings fail by biaxial compression,
and optimum thickness rings fail by circum-
ferential compression. Analysis of the test data
must consider the radial as well as circumfer-
ential stresses.
Delamination of the inner layers of the ring
makes it difficult to correctly calculate the
compressive strength. This delamination is
often noisy. The occurrence of this failure
mechanism also depends on the relative thick-
ness of the ring. Delamination of helical
windings can lead to unwinding of the speci-
men. Hoop wound rings can fail by
layer-by-layer delamination.
34.5 SHEAR
34.5.1 IN-PLANE SHEAR
Shear properties, especially shear strengths,
are difficult to measure. The simple and eco-
nomical rail shear test is often used for this
purpose (Table 34.3, Methods (a) and (b)).The
extent of edge effects and the uniformity of the
shear stress distribution over the specimen
width depends on the length-to-width ratio of
the specimen gage section L/w and on the
relation of elastic constants G,/E of the mate-
rial. Edge effects are negligible tor L/w > 10.
Edge effects cannot be eliminated for materials
with v, = vyxG -1. Thus, this method cannot be
used for such materials. The elastic constants
obtained by the rail shear test are less sensitive
to the relative ratio, L/w, since the measure-
ments are taken in the center of the specimen
Shear 789
gage section where the state of stress is the
most uniform. However, edge effects have
considerable influence on the shear strength.
Therefore, it is better to bond the specimen to
the rail links than to use mechanical fasteners.
The stress distribution is not affected by the
loading direction, i.e. along the diagonal or
parallel to the sides of specimen gage section.
Measuring the shear properties by tensile
loading of an anisotropic strip is distinguished
by its apparent simplicity (Table 34.1, Method
(f)). The strip can have one of several different
fiber lay-ups. This method is not used to deter-
mine in-plane shear strength because it yields
low values. A state of pure shear is not assured
even with a +45" lay-up.
A similar test method involves tensile load-
ing of a strip of a unidirectional material cut at
an angle, 8, to the reinforcing fibers. The opti-
mum angle is the one for which the relative
shear strain y 1 2 / ~is
x maximized and the shear
stress rI2reaches its critical value. This angle
depends on the anisotropy of the elastic and
strength properties of the material tested. For
advanced composites, the optimum angle is 10
to 15". Because the stress ratios are very sensi-
tive to changes in the angle, rigid tolerances,
4 degree, are set on the specimen cut angle,
the strain gage angle, and the direction of
loading. In order to ensure that the stress state
is uniform, relatively narrow strips, L/w = 14
to 16, are used.
The in-plane shear modulus is often mea-
sured by twisting a square plate with four
point loading (Method (c)). The wide accep-
tance of this method may be attributed to the
simplicity of its calculations. However, the
experiments should be performed with utmost
care. This method is only applicable for small
deflections, wp < O.lt, on plates made of mate-
rials which are uniform in thickness and
orthotropic along the specimen axes. Test
results for several different materials have
shown that the P-wp relationship remains lin-
ear up to wp/t z 1. However, in practice, the
deflection, w should be limited to 0.5t to pre-
P'
vent instability. Only the initial linear section
790 Mechanical tests
of the P-wp curve should be used to determine
the shear modulus. The optimum range of rel-
ative plate thickness, L / t , is determined by
two conditions: the contribution of transverse
shear to the deflection at small values of L / t
and the possible loss of stability at large values
of L / t . The limits of L / t are given for BFRP in
Table 34.3. However, tests run on GFRP (glass
fiber reinforced plastic), CFRP (carbon fiber
reinforced plastic) and BFRP (boron fiber rein-
forced plastic) with different fiber lay-ups have
shown that reliable data can be obtained at L / t
> 15. The specimen must be flat and of constant
thickness because the calculated shear modu-
lus is related to t3. The distance from the point
of support or load application to the corners of
the plate should not exceed 2t. Experimental
evaluation of these three shear test methods
has shown that they all yield comparable val-
ues of in-plane shear modulus9.
The successful application of the double V-
notch or Iosipescu shear test (Method (d)) to
all types of fiber lay-ups is well known'O. It is
invaluable for testing spatially reinforced com-
posites since these materials do not possess
planes of low shear strength. All other shear
strength test methods use this characteristic of
laminated composites to induce shear failure
first and therefore are useless for spatially
reinforced materials. In-depth investigations
have shown that the Iosipescu method and its
modifications yield good results in shear tests
of carbon-carbon composites reinforced along
three mutually perpendicular directions (3-D)
and four principal diagonals of cube of 4-D".
Spatially reinforced composites are less sensi-
tive to the dimensions of the notches and gage
length than laminated composites. The distrib-
ution of shear stresses is essentially uniform
throughout the gage section of 3-D and 4-D
materials cut at a 90" angle with a total notch
depth equal to a half of the specimen thick-
ness. Moreover, it is possible to prevent stress
concentrations at the notch tips. Specimens
with extra side notches yield the best shear
strength data.
34.6 TORSION
Torsional loading of thin-walled tubes is a
standard test for measuring in-plane shear
modulus and strength (Table 34.4, Method (c)).
In this test, the stresses are distributed uni-
formly around the circumference and along
the length of the specimen. The shear strains
are practically constant through the thickness
of the specimen wall. In torsion, the definition
of 'a thin-walled tube' is a function of the
degree of material anisotropy EJE,, which can
vary over a wide range. The disadvantages of
this method are that it requires relatively large
specimens, special test fixtures, inserts to pre-
vent buckling of some specimens and wound
specimens or specimens of special configura-
tions, e.g. materials in which the fiber lay-up is
parallel to the specimen axis.
The results obtained by torsional shear tests
compare favorably with results obtained by
test methods using flat specimens.
Torsional loading of split rings is also used
to measure shear moduli (Method (b)). If the
sample size limitations indicated in Table 34.4
are followed, bending effects are negligible.
34.6.1 INTERLAMINAR SHEAR
Good estimates of interlaminar shear proper-
ties, especially for spatially reinforced
materials, have been obtained by torsion test-
ing of rods with a circumferential notch
(Method (a)).The specimens can be tested with
or without a central bore. The important geo-
metric parameters of the notch are the relative
width, Lp/d, diameter, d, and wall thickness, t.
It has been shown that within a range of L / d
= 0.2-1.0, the length of the notch does not afPect
the measured shear strength, tnu.The gage sec-
tion diameter can be increased from 5 mm to 15
mm (0.6 in) without affecting rnu. However,
increasing the diameter beyond 15 mm (0.6 in)
causes a sharp drop in the measured strength.
 Bending 791

34.7 BENDING for measuring interlaminar shear strength.

However, refined analysis has shown that the
34.7.1 THREE-POINT BENDING state of stress in a short bar of anisotropic
The most popular type of bend test is the material is significantly different from the
three-point bend test (Table 34.5, Methods (a) state of stress predicted by isotropic theory2J2.
and (b)).The four-point and five-point bend The shear stresses through the thickness of a
tests are less popular in spite of their consider- relatively short anisotropic bar have a para-
able technical advantages over the three-point bolic distribution only in the middle of the
bend test. span. At the loading points, the distribution of
Theoretically, the moduli of elasticity of shear stresses through the thickness of the
homogeneous materials in tension, compres- specimen has peaks near the surface directly
sion, and bending are the same, i.e. Exf = E; = beneath the loading points. In relatively short
E:. However, due to imperfections, the state of anisotropic bars, there are no planar regions of
stress in bending and differences in the fiber constant maximum shear stress. Moreover, on
lay-up through the thickness of the material, relatively short bars (L/w 4 5), the compres-
the bending modulus of elasticity E: can differ sive transverse stresses from the load
somewhat from Exf or E;. This difference is application points can extend over the entire
emphasized by the superscript ’b’. length of the specimen and can exceed mean
The formulae used to determine the elastic shear stress by up to a factor of 15. These com-
bending constants, E: and GxZb, from the deflec- pressive stresses constrain crack opening at
tion of a bar at its midspan must take into sample delamination and result in an apparent
consideration the effect of interlaminar shear. increase of interlaminar shear strength. As a
The effect of interlaminar shear can be result of these deviations from the ideal para-
neglected for large values of relative span bolic stress distribution, the experimentally
length L / t . For highly anisotropic materials, the determined interlaminar strength appears to
relative span length must be greater than 40. decrease with increasing relative span width.
When determining bending strengths, fail- Therefore, shear testing of relatively short bars
ures limited by the normal strength, ., ””,
and can provide only a qualitative comparison of
failures limited by the shear strength, zxF, different composites.
Interlaminar shear strength can also be
must be separated. Unlike those of isotropic
materials, the two strengths for composite measured by three-point bending of curved
segments. The shear strength is calculated
materials can differ by an order of magnitude.
The shear stresses can have a considerable with the same equations used for bending of
effect on the failure. prismatic bars. However, the additional inter-
laminar normal stresses unique to curved
Failure due to normal stresses occurs by
beams must be taken into consideration. The
fracture of the extreme outer layers in com-
normal stresses act over the entire length of
pression or tension. Failure due to shear
stresses occurs by delamination approximately the specimen. The sign of the stress depends
on the orientation of the specimen. In the case
at the midplane of the specimen. Laminated
materials can fail by a violent debonding of the of segments loaded with their convexity
compressed outer layer. Very short bars experi- upwards (center load applied to the outer
ence a third failure mode. They fail by diameter of the specimen) the stresses are ten-
crumpling and shearing which is accompanied sile, 0. When the convexity is downwards, the
:

by an apparent increase in shear strength. radial stresses are compressive, a;. In the for-
Three-point bend testing of short bars or mer case, shear and tensile radial stresses
ring segments is the most widely used method combine to decrease the apparent shear
strength. In the latter case, the compressive
792 Mechanical tests

radial stresses impede the growth of the shear and 11),and the Arcan Test (mixed Modes I and
delamination crack and raise the apparent 11). The geometry of the specimens, prepara-
interlaminar shear strength. For accurate tion methods, and analysis procedures have
determination of the interlaminar shear been described in detai113J4.
strength, r&bu,segment dimensions must be Advanced composites, especially those
selected so that the normal circumferential reinforced with carbon and aramid fibers,
stresses, as, and normal radial stresses, or,are have highly anisotropic thermophysical prop-
negligible compared to the shear stresses. erties. This is reflected in the thermomechanical
behavior of the structures fabricated with these
materials. The combination of a polymer
34.7.2 BENDING OF RINGS
matrix having a high coefficient of thermal
Bending of complete rings by diametrically expansion and fibers having a negative coeffi-
opposed loads (Method (c)) is used to deter- cient of thermal expansion allows the
mine elastic and strength properties of fabrication of composites with extremely low
composites. Reliable results are obtained if the thermal expansion. This property of compos-
relative specimen thickness, t l r , is properly ites is used in the fabrication of structures
selected. The acceptable range of relative which are stable over wide temperature
thickness for determining the shear modulus, ranges. Low thermal expansion is commonly
Go,: is based on the material anisotropy, achieved in two directions and the process can
E,b/G,b. The shear modulus is calculated from be extended to materials which are spatially
the load-diametral deflection data using the reinforced in three directions (3-D) or along
same equations for three point bending of four diagonals of a cube (4-D)15.These com-
prismatic bars with a correction factor for the posites possess a thermal expansion coefficient
fraction of deflection induced by shear which is both isotropic and very low.
stresses. When the test is used to determine Measurement of the thermal expansion
the interlaminar shear strength, rOpU,the rela- coefficients of carbon and aramid composites,
tive specimen thickness must be chosen to especially in the reinforcement direction, is not
ensure failure by shear delamination at the a trivial experiment. It must employ modem
specimen mid-radius rather than failure by dilatometer and interferometer methodsI4.
normal circumferential stresses, a?.
34.9 STRUCTURAL TESTING
34.8 SPECIAL TESTS
The unique challenges of designing and test-
Laminates can fail by interlaminar delamina- ing composite parts are due to the fact that the
tion along specific planes. Toughness data is as material and its micro- and macro-structures
important for characterization and failure pre- are created at the same time as the part. The
diction of composites as strength and stiffness design of critical structures must include the
data. Cracks in composites can propagate by design of the material and must consider the
Mode I, (crack faces opening normal to the unique behavior of composite materials which
crack plane), by Mode I1 (crack faces sliding in is influenced by processing techniques, actual
their planes), or by Mixed-Mode (combination service loading, and environmental condi-
of Mode I and Mode 11).The interlaminar frac- tions. Structural testing should start with tests
ture tests include the Double Cantilever Beam of small-scale models fabricated by the same
Test (Mode I), the Edge Delamination Test manufacturing process as the full-scale struc-
(Mode I), the End Notched Flexure (Mode 11), ture, followed by tests of prototype parts,
the Notched Three-Rail Shear Test (Mode 11), specimens cut from structural elements, and
the Cracked Lap Shear Test (mixed Modes I finally, full-scale tests9J9.
 References 793

REFERENCES 11. Greszczuk L.B., Shear Modulus Determination

of Isotropic and Composite Materials. ASTM
1. Lubin, G. (ed.). Handbook of Composites, New Special Technical Publication, 1969,460: 140-9.
York: Van Nostrand Reinhold, 1982. 12. Uemura M., Problems in Mechanical Testing
2. Tamopol‘skii, Yu.M. and Kincis, T.Ya, Static Test Methods of Advanced Composite Materials. In
Methods for Composites. New York: Van Proc. 10th Tsukuba General Symp., 1990, pp.
Nostrand Reinhold, 1985. 43-54.
3. Witney, J.M., Daniel, I.M. and Pipes, R.B., 13. Pagano, N.J. (ed.), Interlaminar Response of
Experimental Mechanics of Fiber Reinforced Composite Materials, (Composites Materials
Composite Materials, Rev. Ed., Society for Series; 5) Amsterdam: Elsevier, 1989.
Experimental Mechanics. Englewood Cliffs, NJ: 14. Carlsson, L.A. and Pipes, R.B., Experimental
Prentice-Hall, 1984. Characterization of Advanced Composite Materials.
4. Kelly. A. (ed.). Concise Encyclopedia of Composite Englewood Cliffs, NJ: Prentice-Hall, 1987.
Materials, Oxford: Pergamon Press, 1989. 15. Tarnopol’skii, Yu.M., Zhigun, I.G., and
5. Tarnopol’skii, Yu.M. and Vasiliev. V.V. (eds.). Polyakov, V.A., Spatially Reinforced Composites.
Structural Composites. A Handbook, Moscow: Lancaster: Technomic, 1992.
Mashinostroyenie, 1990. 16. Mechanical Testing of Advanced Fibre Composites,
6. Tsai, S.W., Theory of Composites Design, Dayton, Imperial College of Science and Technology,
Paris and Tokyo: Think Composites, 1992. London: University of London, 1992.
7. W y o m i n g Test Fixtures. High Performance Test 17. Sims G.D., Nimmo, W., Johnson, A.F. and
Fixtures. Product Catalog, Laramie: Wyoming Ferriss, D.H., Analysis of Plate-Twist Test for In-
Test Fixtures Inc, 1993. Plane Shear Modulus of Composite Materials.
8. Peters, S.T., Humphrey, W.D. and Foral, R.F., Teddington: National Physical Laboratory, 1992.
Filament Winding Composite Structure Fabrication. 18. Lee, S. and Munro, M., Evaluation of in-plane
Covina: SAMPE, 1991. shear test methods for advanced composite
9. Nikolaev, V.P., Panfilov, N.A., Popov, V.D., and materials by the decision analysis technique.
Sinitsyn, E.N., Analysis of the Failure Composites, 1986,17(1), 13-22.
Mechanism of Large-Scale Structures. Mech. 19. Nikolayev, V.P., Popov, V.D. and Sborovskii,
Composite Mater., 1993,29(2):203-11. A.K., Strength and Reliability of Wound
10. Pinderra, M.J., Gurdal, Z.C., Hidde, J.S. and Fiberglass Reinforced Plastics. Leningrad:
Herakovich, C.T., Mechanical and Thermal Mashinostroyeni ye, 1983.
Characterization of Unidirectional Aramid/
Epoxy. Report CCMS-86-08, VPI-E-86-29,
Virginia Polytechnic Institute and State
University, Blacksburg, VA, 1987.
DURABILITY AND DAMAGE TOLERANCE 35
OF FIBROUS COMPOSITE SYSTEMS
Ken Reifsnider

35.1 DEFINITIONS AND ISSUES simple, and are illustrated in Fig. 35.1.
Damage tolerance is the remaining strength
Durability and damage tolerance are critical
after some period of service, and durability, in
to the design of composite structures.
general, has to do with how long the compo-
Damage tolerance is the approach often
nent will last, i.e. with the life of the structure.
required for the certification of safety-rated
In this context, durability is often discussed in
structures such as aircraft components; dura-
terms of the resistance or susceptibility to
bility has been identified as one of the most
damage initiation. Both concepts imply that
important technical drivers for the design of
the subject component is being exposed to
major composite structures such as the High
applied conditions such as mechanical loading
Speed Civil Transport. Recent reports from
and environments such as temperature and
the National Materials Advisory Board and a
chemical agents over long periods of time that
great volume of other literature focus on
are typical of the projected service life of the
these
component.
Of course, there are many nuances in the
There are several technical concepts that
definitions of durability and damage toler-
form a foundation for our discussion of these
ance. However, the basic concepts are quite
closely related topics. The first of these is the

Damage Tolerance (Remaining strength)

1

Normalized
stress level

Life Locus
Durability (Life) 4

Time / Cycles

Handbook of Composites. Edited by S.T.Peters. Published Fig. 35.1 Basic definitions of ’durability’ and ‘dam-
in 1998 by Chapman & Hall,London. ISBN 0 412 54.020 7 age tolerance’.

question of the relationship of material
strength to structural strength. In general, the
strength of (fiber reinforced) composite mate-
rials is represented by an array of values that
reflect the anisotropic nature of the materials
(Fig. 35.2). For planar materials, at least the
tensile strength and compressive strength in
the fiber direction and transverse to the fibers
and the in-plane shear strength are required
for a complete answer to the question of ’how
strong is this material’. However, as an array,
those values do not directly show ’how strong
is a composite structure’. Several possible
answers to that question are typically given.
One may use a ’failure criterion’ that compares
all of the point stress components with all of
the material strength components (such as the
Tsai-Hill or Tsai-Wu riter ria)^ in some collec-
tive form based on concepts such as critical
energy, critical shear resistance, etc. The salient
point to be made is that the complexity of
(inhomogeneous) composite materials and
their array of anisotropic material strengths
give rise to the development of a correspond-
ing array of damage and failure modes in
these materials that must be understood and
correctly modeled to answer the question of
Five in-plane strength values for fiberous composites:
Tension and compression
strength in the fiber
direction
Xt or X,
-S
f 1
Composite *
IL-kr
Fig. 35.2 Schematic illustration of ’principal strength’ directions in a unidirectional continuous fiber com-
posite laminate.
Definitions and issues 795
’how strong is this composite structure’, even
if the array of material strengths are known
(shown in Fig. 35.2). Hence, there is a need to
develop understandings and representations
of the critical damage and failure modes that
control the performance of engineering com-
ponents. This technology is currently
incomplete, but discussions of those topics
will follow.
A second fundamental concept is
microstructural architecture. As shown in Fig.
35.3(a), many fibrous composite components
are made in layered or laminated form, with the
fibers in different layers having different direc-
tions; in some cases the plies are made from
different materials to form a ’hybrid’ compos-
ite. In addition, the fibers may not be straight,
but may be woven, braided, or arranged in
mats of various types (Fig. 35.3(b),(c)). These
details have a major influence on the durability
and damage tolerance of the materials. In fact,
most composite material systems are ‘designed’
to be ’fiber dominated’, to take advantage of
light, strong and stiff (but brittle) fiber materials
that are available. Typically, the fibers, their
geometry and their arrangement are important
parts of the question.
Tension and compression
strength in the direction
transverse to the fibers
Yt orY,
in-plane shear strength
Strength tensor:
796 Durability and damage tolerance offibrous composite systems
Fig. 35.3 Typical engineering composite reinforcement types: (a) fibrous, unidirectional pile; (b) fibrous
woven; (c) fibrous, braided.
A third technical issue has to do with the
degradation of intrinsic strength and stiffness.
For metals, the material stiffness and strength
are generally constant during the life of the
engineering component. This may not be true
for composites. Stiffness changes of the order
of 10-20% may be caused by micro-cracking,
for example. Since many structures are stiff-
ness designs, this mode of degradation must
be considered. In addition, the intrinsic mate-
rial strengths (indicated in Fig. 35.2) may also
be degraded, especially by such things as
physical or chemical aging. This behavior
must also be part of the supporting predictive
technology developed for these materials.
Nondestructive methods of tracking such
degradation are under development, but this
remains as a challenge currently.
Methodologies for the assessment and pre-
diction of durability and damage tolerance of
composite materials typically involve the fol-
lowing features:
0 Remaining strength and life models are
developed and predictions are made for
each independent failure mode (such as
fiber failure in tension or micro-buckling in
compression, etc.).
0 Mechanics representations of the state of
stress and state of material are constructed
on the basis of a 'representative volume' of
the material that is typical of the distributed
damage state that controls the remaining
stiffness and strength of the composite. A
typical representative volume of material is
a controlling ply in a laminate, but may be a
micro-buckling ligament, a small group of
fibers, etc.
0 Various methods are used to characterize
and monitor the rate of strength degrada-
tion in composites. A typical parameter
which is useful for that purpose is stiffness
change; however, that parameter is not
appropriate in some cases.
0 Micromechanics (mechanics analysis at the

fiber/matrix level of representation) is
increasingly used for remaining-strength
modeling, for the calculation of stiffness
change (which leads to internal stress redis-
tribution), and for the estimation of
remaining strength for a given failure
mode.
Statistical considerations are essential for
the correct representation of the long-term
behavior of composites. Composites typi-
cally fail because of the statistical
accumulation of defects, which eventually
interact to create a critical condition. This is
in contrast to self-similar single crack prop-
agation that is the typical mechanism of
failure for common metals.
Time-dependent behavior such as vis-
coelastic creep, creep rupture (driven by
such things as internal stress redistribution
or oxidation), and aging are typically
important in the consideration of the long-
term durability and damage tolerance of
polymer composites, particularly for com-
ponents that serve at elevated temperatures.
This chapter will discuss the range of physical
and engineering details that define and control
this subject. Of course, a complete discussion
would fill several volumes, so the reader
should regard this discussion as only a start-
ing point for further study.
35.2 DAMAGE MODES AND FAILURE
MODES
The failure of 'typical' (homogeneous
isotropic) engineering materials is a familiar
topic. The subjects of ductile rupture and brit-
tle fracture are widely discussed and taught in
undergraduate and graduate courses.
However, composite materials generally do
not behave in a manner easily described by
either plasticity (or yield) theory or by self-
similar crack growth concepts.
The reason for this different behavior is the
fundamental difference in the micro-structure
of composite materials, i.e. in the way they are
Damage modes and failure modes 797
made. Composites consist of mechanical 'mix-
tures' of distinct phases (such as fibers or
particles) in a matrix material. The geometry
and arrangement of the reinforcement phase
is carefully chosen to achieve the desired com-
posite properties. As a result, such material
systems are always inhomogeneous, often
anisotropic, and often brittle. These three
basic characteristics control the nature of
damage development and failure in compos-
ite materials.
The most salient single feature of damage in
composites is the process of damage accumula-
tion. Damage development usually involves
many damage modes which create a widely
distributed damage state, and failure is usually
the result of a statistical accumulation of dam-
age (rather than the statistical occurrence of
damage). As discussed below, these multiple
damage accumulations on failure modes are
often closely related to the manner in which
the composite is made, especially to the basic
nature of the inhomogeneity and anisotropy of
the material. This damage development
process ultimately controls durability and
damage tolerance, so we will discuss some typ-
ical major features of that phenomenon.
The most pervasive damage mode in com-
posite materials is microcracking, most often
in the matrix material. Figure 35.4 shows two
embodiments of this mode. Figure 35.4(a)
shows an X-ray radiograph of a cross-ply lam-
inate with cracks in both ply types, and Fig.
35.4(b) shows matrix cracking parallel to the
fibers in the off-axis plies of a laminate, as seen
from a tracing of those cracks as they appear
on the edge of this [0,45,45,90Is laminate. A
typical scenario for the development of such
cracks is the formation of matrix cracks as a
function of increasing applied load or increas-
ing cycles of loading. These cracks typically
extend through the thickness of a ply and gen-
erally extend quickly in the fiber direction if
the local stress is uniform.
Several other important features of matrix
cracking are suggested by Fig. 35.4. As shown
by Fig. 35.5, matrix crack formation releases
798 Durability and damage tolerance offibrous composite systems

"'r! 'r!-.e-

I
rt
.1!

.I: I

Strain

Fig. 35.5 Change in slope of the elastic stress-strain

curve induced by microcracking.

APPLIED STRESS (MPo)

100
I
200
I
300 400 500 600
I
m
b I

Fig. 35.4 Microcracking in the matrix, parallel to

the fibers; a radiograph of a cross-ply laminate with
(a) inter-ply delamination at crack intersections
(arrow) and (b) a tracing of matrix cracks on the
edge of a [0,+45,-45,90] laminate.

stored energy in the cracked ply or material,

and changes the stiffness of material propor-
tionately, a matter of concern to engineering
applications, as noted earlier. However, the
density of cracks in the ply of a laminate
reaches a stable saturation value, as first
observed by Reifsnider et a1.5,8,called the char-
acteristic damage state (or CDS) of the ply.
That CDS is a function only of the properties
of the plies, their thickness, and their stacking
sequence. Figure 35.6 shows that the same
CDS is formed by static or cyclic loading. This
CDS can be readily predicted since the crack
spacing is determined by the rate at which the
surrounding material can transfer stress back
into the broken ply. Moreover, the stiffness
change caused by this cracking can also be
predicted as well7r9-*l.
A second important damage mode is delam-
ination, as shown in Fig. 35.7. Delamination is
driven by the fact that local regions of the com-
posite would deform differently in response to
01 I I I I
0 0.2 0.4 0.6 0.8 I .o
NO. OF CYCLES (MILLIONS)
Fig. 35.6 Data showing identity of the equilibrium
crack spacing ('characteristic damage state' or CDS)
for quasi-static and cyclic loading of a laminate.
the local loads if they were not bonded together
in the composite. Hence, stored energy is
released if they separate, and that energy drives
the separation process. The most common
example of this damage mode is the separation
of the plies of a laminate near a free edge, as
shown in Fig. 35.7. This process has been
widely studied and is well described. More will
be said of this driving mechanism below.
It should be noted that delamination is usu-
ally nucleated by other damage modes (such
as matrix and although it is a
common damage mode, it is not usually a fail-
ure mode, per se. Delamination usually begins
 Damage modes and failure modes 799

fW"82tr'tiKT W 7 K " V q T 4 ~ K ~ W m ~ Tcracks in one ply may cause fiber frac-

matrix
ture in an adjacent ply due to the local stress
concentrations21,2z.
Figure 35.8@) shows a second feature of
importance. When the matrix and fibers have
comparable stiffness and strength, the fibers
may break many times along their length
before the composite fractures. In this situa-
tion, fiber fracture can cause a significant
stiffness loss as well as a strength reductionu.
I
-7 Another generic damage mode is micro-
'
1
buckling, induced by local or global
compressive loads, as shown in Fig. 35.9.
Fig. 35.7 Edge micrograph of delamination (arrow)
showing (a) relationship to matrix cracking; (b) plan
view radiograph of edge delamination in a cross-
ply laminate (shaded regions).

at an edge, such as a cutout, bolt hole, rivet

hole, etc. If it is in a region of nonuniform
stress, it may stop growing when it reaches the
boundary of that region. Even if it grows to
large dimensions, it usually does not cause
significant loss of strength in engineering
sized structures. Still, the loss of integrity can
lead to other damage and failure modes, so it
should be avoided.
A third generic damage mode is fiber frac-
ture. Many composites are 'fiber dominated',
i.e. they depend on the fibers for their stiffness
and strength. Hence, fracture of the fibers is
both an important damage mode and failure
mode. However, fiber fracture is difficult to
detect and has been studied less completely
than many other damage modes. However,
considerable data have been ~ollected'~'~.
Figure 35.8 shows two examples of such data,
driven by two important mechanisms. Figure
35.8(a) shows fibers broken beside one
another, a typical situation. In many compos-
ites, the fibers are coated with a material that
decreases the tendency for the fracture of one
fiber to cause the fracture of neighboring fibers
by forming an 'interphase region' around the
fibers that tends to 'isolate' the fracture
effectslS2O.It is also important to note that the
800 Durability and damage tolerance offibrous composite systems
There are several aspects of this phenomenon
that are of importance to durability and dam-
age tolerance. For example, the compression
strength (or remaining strength) of the com-
posite may be controlled by the local stress
required to initiate the local instability, in
which case one wants a large diameter, stiff
fibers in a stiff matrix. Or, the strength may be
controlled by local resistance to shear defor-
mation after buckling begins, in which case
one would choose a tough matrix or inter-
phase region between the fibers and the
matrix. This is another case in which a damage
mode may or may not be a failure mode, an
important distinction.
Fig. 35.9 Localized microbuckling in a polymer
matrix composite. Printed with permission, I.M.
Daniel and 0. Ishai, Engineering Mechanics of
Composite Materials, Oxford University Press,
Oxford, 1994.
Another 'damage mode' of considerable impor-
tance to polymer composites and all composites
used at high temperatures is the phenomenon
of creep, i.e. time-dependent deformation at
constant applied stress. Figure 35.10 shows a
typical form of that behavior, with an initial
transient region, a steady state region (in which
most engineeringdesign is done), and a tertiary
(usually unstable) region. This phenomenon is
usually represented by introducing viscoelastic
Time
Fig. 35.10 Schematic of typical creep deformation
at constant load and temperature.
or rheological models that represent the behav-
ior in terms of a change in the stiffness of the
material with time, as a function of tempera-
ture. Quite often, the reinforcing fibers do not
show creep behavior at low temperatures, but
at high temperatures, essentially all con-
stituents may creep. The changes of stiffness
with time can be characterized in the labora-
tory, and must be modeled carefully, based on
those data. In fact, this part of the behavior is
critically important to the correct calculation of
internal stress states, since the creep of the con-
stituents changes the internal stress distribution
greatly in some cases. For example, if the matrix
creeps more than the reinforcing fibers (a typi-
cal situation), that creep 'relaxes' the stress in
the matrix, and increases the load carried by the
fibers. If we wish to calculate a fiber-controlled
strength, for example, a correct representation
of this behavior must be included in our model.
Finally, another failure mode is creep-rup-
ture. This is a fairly general terminology used
to refer to a variety of physical phenomena
that produce time-dependent failure. This can
be due to, say, oxidation of the fibers, or to
other physical degradation processes which
eventually cause rupture. It is clear that these
phenomena must also be modeled correctly if
we are to discuss durability and damage toler-
ance of material systems.

35.3 DAMAGE DRIVERS AND DAMAGE
'RESISTANCE'
In the previous section, a number of damage
and failure modes that occur in composite
materials, and ultimately control durability
and damage tolerance, were identified. Many
of these modes are related to the manner in
which the composites were put together. This
raises the basic question of 'can one design
composite materials to be durable and damage
tolerant?' Most of the rest of this discussion
will address this question.
Some general concepts will be followed by
some micro-mechanics methods of quantifymg
answers. Microcracking is likely to be the most
pervasive damage mode in typical composites,
especially under long-term loading, and most
especially under cyclic loading. Even though
most matrix materials are chosen because they
offer some level of ductility, in most composite
systems the matrix is highly constrained so
that cracks develop due to local constraint,
local stress concentrations, and local defects
that grow rapidly under what is generally a
'plane strain' condition. Hence, matrix tough-
ness, in the general sense, is the key to the
reduction of matrix cracking. Increasing the
strain to failure of the matrix material is a pri-
mary objective, and increasing the plane-strain
fracture toughness of the matrix is a compan-
ion objective. There is a richly developed
science and technology associated with matrix
toughening; some starting points are listed in
Wilkinson et al.24and Hedrick et al?5.
A second damage mode identified earlier is
delamination. This problem is a strong combi-
nation of structural and material concerns. The
material concerns are essentially the same as
those discussed for matrix cracking, with one
important exception. Matrix toughness does
not translate directly into interlaminar tough-
ness. Hence, resistance to delamination cannot
be controlled entirely with material property
increases. The structural part of the problem
does, however, present opportunities. It was
mentioned before that delamination is driven
Damage drivers and damage 'resistance' 801
by local discontinuitiesin stress state, typically
caused by neighboring plies or ply groups
(bonded together) that would have very dif-
ferent strain states if they were not bonded.
Hence, the orientation of the plies in a lami-
nate and the stacking sequence of those plies
are controlling players in the development of
the interlaminar stresses that drive delamina-
tion. This problem has been exhaustively
studied, and methods of reducing interlami-
nar stresses have been widely d i s c ~ s s e d ' ~ - ~ ~ ,
but because of the inhomogeneous and often
anisotropic nature of composites, interlaminar
stresses generally cannot be eliminated in lam-
inated systems, so mechkical methods are
widely used to control that tendency. The most
successful of these is weaving, i.e. to use
woven fiber architectures to reduce the
anisotropy of a given ply, and therefore, to
reduce the 'disagreement' between the
response of any two or more plies. Woven
materials are now widely used, especially for
this reason. A second approach is to 'stitch' the
composite in the region of non-uniform stress,
typically near an edge of the laminate.
Stitching simply 'clamps' the edge of the mate-
rial to prevent it from separating; the internal
stresses are still present. Stitching has a some-
what smaller number of proponents, but is a
successful method as well. Finally, three-
dimensional reinforcement, such as mats or
braids, also serve the purpose of providing
constraint to the delamination drivers. These
methods are not as widely used at this time,
largely because of the difficulty associated
with manufacturing.
A less obvious influence on durability and
damage tolerance is the bonding between the
fiber and matrix. The nature of this influence
has only come to light in recent years. Some of
the mechanics models needed for this discus-
sion will be developed in the next section; only
a few general points will be made here. First,
the properties of composite materials are
determined not only by the properties of the
constituents, but they are also greatly influ-
enced by the manner in which the constituents
802 Durability and damage tolerance of fibrous composite systems
interact. This critical interaction is, of course,
controlled by the bonding between the con-
stituents, between the fibers and matrix in our
case. Typically, this bonding is ‘controlled’ by
a fiber coating or ’sizing’. However, it is now
known that such things as notched fatigue
behavior can be improved by as much as two
orders of magnitude by carefully ’designed’
’interphase’ regions between the fibers and the
matrixz6.There are at least two basic concepts
operating in these effects. First, if one can
toughen the composite by toughening the
interphase between the fibers and matrix, the
composite is likely to be more durable, as dis-
cussed above. Second, the interphase region
can greatly influence the local stress state, and
reduce the driving force for fiber-matrix
debonding. An illustration of that is shown in
Fig. 35.11. If one considers the strength of a
composite under loads applied perpendicular
to the fiber direction, then it is clear that the
fiber causes a local stress concentration,in pro-
portion to the difference between its
properties and those of the matrix. However, if
a coating around the fiber is introduced, this
local concentration can be greatly reduced. In
fact, for a ’rigid’ fiber, compared to the matrix,
it is not surprising that a compliant coating on
the fiber will increase the transverse composite
strength by as much as a factor of two, and the
Interphase region
Composite
Fig. 35.11 Schematic diagram of the geometry of
the interphase region in a fibrous composite, sub-
iected to loading.
” transverse to the fibers.
strain to failure by as much as a factor of
In general, although design rules are
not yet fixed, design of the interphase region is
a new and important opportunity for the
enhancement of the durability and damage
tolerance of composite system^^^^*.
The final subject in this section is ’failure
criteria’; which are used to describe remaining
strength. In general, failure criteria are chosen
on the basis of the known failure mode. If fiber
fracture controls strength, then a suitable crite-
rion may be just the stress in the fiber direction
divided by the strength in that direction. If
matrix behavior is controlling, a shear stress or
combined stress criterion may be appropriate.
Figure 35.12 shows a comparison between
strength ‘envelopes’predicted by two popular
criteria. It is important to note that the inputs
to the failure function will, in general, change
as a function of time and loading history. The
general form of any failure criterion will usu-
ally be some function of the ratios of stress in
principal material directions to strength in
those directions, as mentioned earlier. Under
long-term conditions which induce damage,
the local stress changes as damage causes
redistribution, and the principal values of
material strength change, due to such things
as constituent degradation or micro-damage.
Hence, to calculate damage tolerance by using
Criterion:
I -
Maximum stress -
Applied
Stress (ksi)
0 90
Angle of Loading (deg)
Fig. 35.12 Allowable uniaxial loading as a function
of angle of loading relative to the fiber direction in
a unidirectional lamina, estimated from a maxi-
mum stress and a popular effective stress criterion.
 Composite micro-strengthand remaining strength models 803

failure functions (or criteria) to calculate utility of such models. The example is a recent
remaining strength, one must be careful to use model of tensile strength. (Figure 35.13). The
the correct local stress state and material state
stress in the broken fibers builds back up to the
in those expressions, especially when degra- undisturbed level by shear transfer from the
dation has changed those states from their surrounding matrix, composite, and inter-
initial values. phase region. That rate of buildup is directly
proportional to the stress concentration in the
next nearest fibers; if the buildup occurs over a
35.4 COMPOSITE MICRO-STRENGTH AND
short distance (a short 'ineffective length), the
REMAINING STRENGTH MODELS
stress concentration in the neighboring fibers
The importance of material principal strengths is great, and they tend to break causing very
was noted, and the importance of composite brittle composite behavior. However, if the
microstructure in the determination of those buildup occurs over a large distance (i.e. if the
strengths has been emphasized. The proper- material around the fiber is very compliant or
ties, geometry, arrangement, and bonding of breaks easily ), the strength of each fiber is lost
the constituents determine the resulting val- completely when the first local fiber break
ues of composite principal strengths. So, if occurs. A model has been developed that
those factors are understood, strong, durable, describes the physics and mechanics of this
damage tolerant composites can be designed. behavior, which estimates the fiber strength as:
That understanding is currently incomplete, 2z0L l / m + l 2 l / m + l m + 1
but some models are available. Such models
are very valuable since they can tell us the
4= ...'-+1(7r) ( K T ) m +2
preferable way to make composite materials, (1 + m)l/"
in contrast to how they can be made (the job of (C," + q m - 1 + ... + ly" (35.1)
the materials science community).
In this limited space, one example will suf- where a, is the Weibull characteristic strength
fice to demonstrate the general nature and of the fibers, z, is the shear stress between the

Composite
4 zt: Normal stress In:
broken fiber

EE
: P nelghboring
FlbersC

Fiber
breaks

t . I
Average global values
away from fiber fracture

Fig. 35.13 Schematic diagram of the local stress distribution around broken fibers in a unidirectional
composite.
804 Durability and damage tolerance offibrous composite systems

fibers and the matrix (usually taken as the continuous fiber reinforced composites is
interphase strength), m is the Weibull shape outlined. A great many details will have to be
parameter for the fiber strength distribution, omitted due to space limitations; the inter-
and Cnis the local stress concentration when n ested reader can find them in other
fibers are broken together in a local region. publication^"^^.
Hence, the tensile strength in the fiber direc- A start is to identdy a well-defined failure
tion can be estimated on the basis of the mode, as defined earlier. Since damage is dis-
properties of the constituents and the inter- tributed, this damage mode will be 'typical' of
phase region between the fibers and the any 'representative volume' of material; a
matrix. If any of those constituent characteris- mechanics boundary value problem on such a
tics change, the model can show how the representative volume (RV), as suggested in
strength of the composite changes, i.e. the Fig. 35.14 can be 'set'. This RV may be discon-
model can be used to calculate the damage tol- tinuous; i.e. it may have cracks, delamination,
erance of the composite if the failure mode is debonds, etc. But some part of it will remain
controlled by fiber strength in tension. intact until fracture of the composite, and this
Comparable models can be constructed for part of the RV that defines the fracture event is
compression failure, and for other failure a 'critical element'. Therefore the objective is
mode^^*^^. the calculation of the state of stress and state of
material in the 'critical element.' One can write
all failure functions, Fa, in that critical element,
35.5 ESTIMATION OF REMAINING
and claim that when these failure functions
STRENGTH AND LIFE
(for each distinct failure mode) predict failure,
As indicated earlier, damage tolerance is the composite will fail.
defined by remaining strength, and durabil- Invoking kinetic theory we can derive an
ity is usually discussed in terms of life. In this equation that relates changes in stress state and
final section, one approach to the estimation material state with time and loading history to
of the durability and damage tolerance of remaining strength, i.e. allow the incorporation

failure modes

Fig. 35.14 Diagram illustrating how experimental observation of failure modes define the representative
volume (used to set the boundary value problem) and the critical elements in which all continuum states
are defined.

of the explicit time, cycles, and environmental
dependence that leads to phenomenological
behavior such as creep, creep rupture, fatigue,
and aging into the calculation of remaining
strength. From thermodynamic principles, the
F, = 1 - lyl(l
following expression can be derived:
- Fa),( n d( $)
N)1-1 (35.2)
where
in the critical element, F, is the normalized
remaining strength, n is cycles, and N is the
life of the critical element under the current
state of stress and state of material. The
methodology of this calculation is shown in
Fig. 35.15. Remaining composite strength, F ,
is calculated directly; life is calculated by the
coincidence of Fa and Fr. Numerous compar-
isons of such calculations with experimental
data have been made over the last 10 years or
so, and there are a few examples at the end of
this chapter. The immediate purposes are
served by using eqn(35.2) to examine the
effects of some hypothetical change in mater-
ial state and stress state on remaining strength
(damage tolerance). If the failure mode is ten-
State of State of
Subcritical Critical
Fig. 35.15 Schematic flow diagram of the manner in which the MRLife simulation scheme calculates
remaining strength and life.
Estimation of remaining strength and life 805
sile fiber failure, and it is assumed that some
fatigue behavior of unidirectional material
under uniaxial stress in the fiber direction has
been measured, a 1-D SN relationship can be
derived, of the form:
s,
S"
= A + B (log N)p (35.3)
where, for our example, A = 1, B = -0.1, Su =
100 ksi (the initial ultimate strength), p = 1,and
Sa is the applied stress amplitude. Equation
(35.3) provides an input, N, into (35.2) since
where u,, is now the current local ply stress in
the fiber direction, and X , is the current local
principal material strength in tension, given
by eqn (35.1). Substituting eqn (35.4) in
eqn (35.2) and assuming that no other
phenomena are present (and using j = 1.2, a
known typical value), the curve (a) in Fig.
35.16 results. Now, suppose the ply is the
critical element in a multiaxial laminate
having off-axis plies that crack and 'dump'
stress into the critical element as a function of
I I
life N, N2
reipresentative volume
806 Durability and damage tolerance offibrous composite systems
Remaining
Strength
Cycles
Fig. 35.16 Calculated remaining strength predic-
tions for (a) 0" lamina degradation alone; (b) added
effect of matrix cracking; (c) added effect of fiber
degradation (e.g.by oxidation).
cycles, according to the rate shown in Fig.
35.17 (from cracking rates that must be
measured or estimated). With this internal
stress redistribution, only, added to eqn (35.2),
the damage tolerance changes to curve (b) in
Fig. 35.16. Of course, if creep occurs in the
matrix (perhaps because of increased
temperature), in which case the local fiber
stress will increase again as a function of
cycles to change the form shown in Fig. 35.17.
Finally, suppose creep rupture is occurring,
driven, for example, by oxidation of the fibers
that is reducing the diameter of the fibers, D,
in eqn (35.1), in the manner shown in
Fiber- Stress increase due
Direction
Stress
40 ' 1
I
Cycles
4
5x10 9.999~10
4
I
Fig. 35.17 Assumed increase in stress in the 0" ply
due to matrix cracking.
I
-
Cycles
Fig. 35.18 Assumed degradation of fiber strength
for the sample laminate.
Fig. 35.18. Then the strength model, eqn (35.1),
correctly integrates that micro-change into the
global calculation, and eqn (35.2) shows the
damage tolerance to be curve (c) in Fig. 35.16
for that situation. Hence this 'micro-kinetic'
approach has the capability to estimate
durability and damage tolerance for very
complex situations involving combinations of
many time and cycle dependent phenomena
in composite systems, using a mechanistic
approach.
An example follows. Using the methods
described above, the rate of matrix cracking
and the unidirectional SN curve of a carbon
fiber reinforced PEEK matrix composite were
determined, and used to estimate the remain-
ing strength and life of several different
laminates made from that material. Figure
35.19 shows an example of the predicted and
observed life for several load levels of a quasi-
isotropic laminate made from such material
and Fig. 35.20 shows comparisons of the pre-
dicted and observed remaining strength of
such laminates for two load levels and cycles
of load application. It can be seen that this
approach can produce quite useable results.
Many such predictions have been compared
using the MRLife performance simulation
code based on this
 Estimation of remaining strength and life 807

AS-4lPEE K (APC-2)
Quasi-Isotropic Notched Fatigue (R=-1)
0.75

I 1 I
0.45
3 4 5 6 7
Log N (Cycles)
Simonds B Stinchcomb MRLife
(1 989) Prediction
0

Fig. 35.19 Predicted (line) and observed life for a quasi-isotropicAS-4/PEEK notched coupon under fully
reversed loading.

Residual Strength at 0.70 Suit Residual Strength at 0.90 SI,,

11.05 1.05

1.00 1.w
r r
F
E!
P
E!
5 5
3 0.95 3 0.05

P P
;
2
.-
0
0.w ......................................................
d
x1
N

€0
0.w

z z
0.85 ..................................................... 0.85 ......................................................

0.80 0.80
2 5 1 0 2 0 5 0 1 0 0 2 0 0
Cycles Cycles
M E h Expepnt Mfih Expepml

Fig. 35.20 Predicted (lines) and observed residual strength of AS-4/PEEK specimens subjected to under
fully reversed cyclic loading.
808 Durability and damage tolerance offibrous composite systems
35.6 SUMMARY
This has been a short outline of the physical
behavior associated with the durability and
damage tolerance of composite material sys-
tems, and a few modeling approaches to the
estimation and prediction of that behavior have
been indicated. It should be noted that there is
every evidence that composite materials are
remarkably durable and damage tolerant.
Fatigue allowables for carbon fiber reinforced
polymer composites, for example, exceed those
of structural steels, and the durability and dam-
age tolerance of ceramic composites make them
the only choice for ultra-high temperature
applications in turbines, etc. Understanding of
this subject, which is admittedly incomplete,
has reached a level that is sufficient to support
engineering applications of composites to even
the most demanding situations in the most
severe environments. In fact, that is exactly the
situation in which the application of compos-
ites is most beneficial and cost effective.
Composite material systems can provide many
new opportunities to design for damage toler-
ance and durability.
REFERENCES
1. Life Prediction Methodologies for Composite
Materials, NMAB-460. Washington, D.C.:
National Academy Press, 1990.
2. High-Temperature Materials for Advanced
Technological Applications, NMAB-450.
Washington, D.C.: National Academy Press,
1988.
3. Horton, P.E. and Whitehead, R., Damage
Tolerance of Composites, Vol. I and 11, Air Force
Wright Aeronautical Laboratories, AFWAL TR-
87-3030, 1988.
4. Daniel, I.M. and Ishai, O., Engineering Mechanics
of Composite Materials. New York: Oxford Univ.
Press, 1994.
5. Reifsnider, K.L. and Highsmith, A.L.,
Characteristic damage states: A new approach
to representing fatigue damage in composite
laminates. In Materials: Experimentation and
Design in Fatigue, Guildford, U.K.:
Butterworth/IPC, 1981, pp. 246-260.
6. Damage in Composite Materials: Basic Mechanisms,
Accumulation, Tolerance, and Characterization,
STP 775, American Society for Testing and
Materials, (ed. K.L. Reifsnider), 1982.
7. Highsmith, A.L., Stijfrzess Reduction Resulting
from Transverse Cracking in Fiber-Reinforced
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Blacksburg, Virginia: Virginia Polytechnic
Institute and State University, 1981.
8. Reifsnider, K.L., Some fundamental aspects of
the fatigue and fracture of composite materials.
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Bethlehem, PA: Lehigh University, 1977.
9. Highsmith, A.L., Damage Induced Stress
Redistribution in Composite Laminates. PhD
Dissertation. Blacksburg, Virginia: Virginia
Polytechnic Institute and State University, 1984.
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ment of damage in multi-axial fibre-reinforced
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Mechanical Behavior of Materials. Cambridge,
U.K., 1979.
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Reifsnider), Amsterdam: Elsevier Science
Publishers, 1990.
12. OBrien, T.K., Characterization of delamination
onset and growth in a composite laminate. In
Damage in Composite Materials, ASTM STP 775,
1982, p. 140.
13. OBrien, T.K., Analysis of local delaminations
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behavior. In Delamination and Debonding of
Materials, ASTM STP 876, 1985, pp. 282-297.
14. OBrien, T.K. and Hooper, S.J., Local delamina-
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Part I, Tension tests and stress analysis. In
N A S A TM 104055,1991.
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18. Ishida, H. (ed.), Controlled Interphases in
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20. Reifsnider, K.L. (ed.), Fatigue of Composite
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21. Jamison, R.D., Fiber fracture in composite lami-
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23. Tiwari, A., The Development of an Interpretive
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Monitoring Damage in Ceramic Composites Under
Dynamic Loads. PhD Dissertation. Blacksburg,
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24. Wilkinson, S.P., Liptak, S.C., Lesko, J.J., Dillard,
D.A., Morton, J., McGrath, J.E. and Ward, T.C.,
Toughened bismaleimides and their carbon
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Studies. In Proc. 6th Japan-U.S. Conf Composite
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25. Hedrick, J., Patel, N.M. and McGrath, J.E.,
Toughening of epoxy resin networks with func-
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C.K. Riew and A.J. Kinloch), 1993, pp. 293-304.
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El-Zein, M., Interface/interphase concepts in
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Comp. Mater., 1990, 3, 13-23.
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Phenomena in Composite Materials. MS Thesis.
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Institute and State University, 1993.
28. Carman, G.P., Eskandari, S. and Case, S.W.,
Analytical investigation of fiber coating effects
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phase in unidirectional fiber-reinforcedepoxies:
effect of residual thermal stresses. Comp. Sci.
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31. Jayaraman, K., Reifsnider, K.L. and Swain, R.E.,
Elastic and thermal effects in the interphase:
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Tech. Res., 1993,15(1):14-22.
32. Jayaraman, K., Reifsnider, K.L. and Swain, R.E.,
Elastic and thermal effects in the interphase:
Part I. comments on characterization methods.
J. Comp. Tech. Res., 1993,15(1):3-13.
33. Gao, Z . and Reifsnider, K.L., Micromechanics of
Tensile Strength in Composite Systems. Fourth
Volume, ASTM STP 2256, (eds W. W. Stinchcomb
and N. E. Ashbaugh), Philadelphia, PA:
American Society for Testing and Materials,
1993, pp. 453-470.
34. Xu, Y. and Reifsnider, K.L., Micromechanical
modeling of composite compressive strength. J.
Comp. Mater., 1993, 27(6):572-587.
35. Reifsnider, K. L. and Gao, Z., Micromechanical
concepts for the estimation of property evolu-
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Spacecraft Structures and Mechanical Testing,
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ENVIRONMENTAL EFFECTS ON COMPOSITES 36
Ann F. Whitaker, Miria M . Finckenor, H a r y W. Dursch,
R.C. Tennyson and Philip R. Young

36.1 INTRODUCTION stabilizers, vertical fins and fairings were

flight-tested with annual inspections.
Composite usage has increased dramatically
Satisfactory performance of the composite
over the last three decades due to the advan-
materials was noted over fourteen years, with
tages of light weight, specific strength and
some parts experiencing more than 39 000
stiffness, dimensional stability, tailorability of
hours of flight loads. Also evaluated were
properties such as coefficient of thermal
composite parts from military aircraft such as
expansion and high thermal conductivity.
the C-130 center wing box, S-76 tail rotors and
Environmental effects on these properties may
horizontal stabilizer, 206L fairing, doors, and
compromise a structure and must be consid-
vertical fin and the CH-53 cargo ramp skin.
ered during the design process.
Because of the variety of uses, the compos- Boron/epoxy, graphite/epoxy, Kevlar/epoxy
ite environment cannot be exactly defined. and Nomex honeycomb were used in these
aircraft and helicopter components.
This chapter details the major environmental
concerns for the composite designer, problems
encountered with these environments in the 36.3 ENVIRONMENTS AND EFFECTS
past, and some materials or protective systems
effectively used. The use of trade names, how- 36.3.1 BIOLOGICAL ATTACK
ever, does not constitute endorsement, either
Biological attack on composites may consist of
expressed or implied, by the authors.
fungal growth or marine fouling. As reported
in the literature, fungal growth does not
36.2 HISTORICAL PERSPECTIVES appear to be as damaging as the wet condi-
tions that promote growth. Fungicide has been
Use of composites in commercial aircraft
increased under two NASA programs, the mixed in with resins to retard this growth.
Flight Service Evaluation Program and the Marine boring organisms do not appear to
Aircraft Energy Efficiency Program, begun in attack glass-reinforced composites. Even
the 1970s. These programs included evalua- though marine organisms will grow on com-
tion of environmental effects on the composite posite surfaces, mechanical properties do not
parts of the Boeing 727, McDonnell Douglas appear to be affected, and the fouling can be
DC-10 and Lockheed L-1011 commercial air- removed by scraping (Fried, 1969).
craft. Elevators, rudders, ailerons, horizontal Composites with graphite fibers have been
used in medical applications for both internal
and external purposes. Internal composite
Handbook of Composites. Edited by S.T. Peters. Published structures, such as artificial joints or plates for
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 bone fracture support, must be biocompatible
 Environments and effects 811

or the material may degrade over time. further if heat is present or if the composite is
External composite designs, such as artificial undercured or has a large amount of voids.
limbs or orthotic braces, may experience Moisture is absorbed into the composite
impact damage, flexural and torsional loading until a saturation point is reached. This has
during use. been described as a non-Fickian process,
meaning the rate of relaxation in the material
due to water absorption is comparable to the
36.3.2 FATIGUE diffusion rate of water. As the material proper-
Fatigue, either through mechanical loads or ties change, such as a decrease in glass
acoustic vibrations, can cause crack growth or transition temperature, the diffusion process
local defect formation. Fatigue design depends changes. Swelling stresses due to non-uniform
not only on the load, but also on the use tem- water absorption have been investigated
perature range and amount of moisture (Ashbee, 1989). Volume expansion due to
present. Very cold temperatures (below -50°C water absorption can be a few percent at satu-
(-58°F)) may increase the stiffness of some ration. Moisture absorption is usually
composite materials, thereby increasing the dependent on the matrix, but aramid fibers
susceptibility to fatigue damage (Staunton, will also absorb water. The mechanical proper-
1982). ties degrade in relation to the amount of
Destructive effects of fatigue vary with the moisture absorbed, with no further deteriora-
composite system tested. One example of tion after saturation is reached. Strength
fatigue resistance is the B-1 horizontal stabi- reductions in polyester laminates have been
lizer torque box, an all-mechanically fastened found to be 10-1570, while epoxy resins are
hybrid composite structure (Staunton, 1982). less vulnerable.
Acoustic fatigue testing produced no degrada- In a few cases, drying of the composite
tion, nor did the service environment of restored the original mechanical properties.
moisture, mechanical fatigue, and tempera- Testing of a glass/polyester laminate allowed
ture cycling from -12 to +167"C (10 to 260°F). to dry after ocean exposure at 1700 m (5700 ft)
below sea level for three years showed little
change in compressive strength and modulus,
36.3.3 FLUIDS flexural strength and modulus, or interlaminar
shear strength (Fried, 1969).
Moisture
Fiberglass composites with either polyester
Moisture effects on composites have been stud- or epoxy resins have been used extensively in
ied for decades. Water acts as a plasticizer marine structural applications because of their
when absorbed by the matrix, softening the strength-to-weight characteristics and resis-
material and reducing some properties of the tance to the marine environment. Glass
laminate. Moisture may also migrate along the reinforcement is preferred over carbon fibers
fiber-matrix interface, affecting the adhesion. due to carbon's electrical conductivity, which
Moisture in composites reduces matrix-domi- may result in severe dissimilar metals galvanic
nated properties, such as transverse strength, corrosion with sea water acting as an elec-
fracture toughness and impact resistance. trolyte.
Lowering of the glass transition temperature MIL-HDBK-l7B, besides providing guide-
may also occur in epoxy and polyimide resins lines for characterizing materials and
with an increase in absorbed moisture. designing a composite system, contains a
Debonding can occur due to formation of dis- wealth of mechanical property and environ-
continuous bubbles and cracking in the matrix. mental effects data. The effect of moisture
Mechanical properties can be reduced even absorption or water immersion on weight,
812 Environmental eflects on composites

operational temperatures, and mechanical (150°C (302°F)) environment, microcracking

properties such as stress rupture characteris- occurred. The amount of moisture absorbed, as
tics is discussed. measured by weight gain, is directly related to
the change in mechanical properties. Salt water,
antifreeze and gasoline had the most pro-
Aircraft fluids
nounced effect. Dqmg did restore some, but
The aircraft fluid environment consists of fuel, not all, of the strength and modulus.
hydraulic fluid, lubricants, deicing com- Volkswagen of Germany tested composite
pounds, and water. Polysulfone has been systems for compatibility with gasoline, oil
found to be sensitive to phosphate ester based and coolant for engine use (Beckmann and
hydraulic fluids. Some polymer resins, such Oetting, 1985). These materials were tested
as PEEK, may have lower glass transition both as pure resin and in fiber reinforced lam-
temperatures after exposure to fluids with a inate form. Among the materials tested were
high aromatic content. A study of stressed and glass, carbon and aramid fibers, high-temper-
unstressed composite materials (Dexter, 1987) ature epoxy, polyimide and polyester resin
evaluated short-beam shear strength and ten- systems. Mechanical properties of the samples
sile strength after immersion in JP-4 fuel, were measured after each 100 h of immersion
hydraulic fluid, a fuel-water mixture and up to 1000 h total. Adverse reactions of the car-
fuel/air cycling for 5 years. The composites bon reinforced materials with metal parts, oil
tested were T300/5208 graphite/epoxy, and combustion residues were noted.
T300/5209 graphite/epoxy and Kevlar
49/5209 in (k45)s configuration. The
Other fluids
fuel-water immersion appeared to be the
most damaging, reducing the tensile strength Liquids accidentally spilled on composite sur-
of the T300/5209 and the Kevlar/5209 by 11% faces may also affect the mechanical
and 25%, respectively. Fuel-water exposure properties. Methylene chloride, found in paint
also degraded short-beam shear strength by strippers, may cause severe damage to epoxy
as much as 40%. resins and a number of other polymers.
Graphite/polyimide composites samples were
immersed in various fluids for 10 min then
Automotive fluids
tested for flexure strength and modulus
The automotive fluid environment consists of (Lisagor, 1979).Slight increases in these prop-
gasoline, oil, battery acid, brake fluid, transmis- erties were noted for samples immersed in
sion fluid and coolant. A study by University of hydraulic fluid, nitrogen tetroxide liquid,
Michigan and General Motors (Springer, monomethyl hydrazine liquid and unsymmet-
Sanders and Tung, 1981) details the effects of rical dimethyl hydrazine. Samples exposed to
prolonged exposure of E-glass/polyester and hot hydrazine vapors were degraded beyond
E-glass/vinylester to automotive fluids. the ability for mechanical testing. Solvents,
Composite samples were immersed in water, bases and weak acids at room temperature do
salt water, No. 2 diesel fuel, lubricating oil, not appear to affect graphite/epoxies and
antifreeze or gasoline. Property changes mea- Kevlar/epoxies. Molten metal, such as alu-
sured were weight, ultimate tensile strength, minum or titanium, may react with carbon
tensile modulus, short-beam shear strength and fibers.
shear (flexural) modulus. Specific materials
exposed were OCF-E-920-1 polyester/E-glass,
OCF-E-980 polyester/E-glass, and vinyl
ester/E-glass. In a moist high-temperature
 Environments and efects 813

36.3.4 WEATHERING effects on composite materials. Over 35 differ-

Warm, moist climates may affect the perfor- ent types of organic matrix composites were
mance of composites. Decreases of 10-20% in flown on LDEF during its 69-month mission in
tensile strength have been noted for fiber- LEO. The post-flight testing and analysis of
glass/polyester and fiberglass/epoxy (Graner, composites flown on LDEF has become the
1982)where the surface resin has been eroded basis of understanding the long-term effects of
away due to extended weathering. Resins the LEO environment on composites. Data
which are more weather-resistant have been from the Solar Array Materials Passive LDEF
developed since this study. In a 10-year study Experiment (SAMPLE), the Space
of real-time weathering of graphite/epoxy, Environment Effects on Spacecraft Materials
graphite/polysulfone, and Kevlar/epoxy Experiment, the University of Toronto
(Dexter, 1987), the materials that absorbed the Institute for Aerospace Studies (UTIAS)
most moisture were most affected by UV radi- Experiment, and the Space Exposure of
ation. Composite Materials for Large Space
Erosion due to rain, snow or ice impact Structures Experiment are presented here and
may be a problem for some aircraft parts, in the section on design considerations.
such as radomes or leading edge parts. Further information may be found in the
Coatings, such as polyurethane, may be used LDEF Post-Retrieval Symposium Proceedings
to make composite parts more resistant to (Levine 1991,1992).
this erosion. A real-time weathering study
was performed by Grumman on fiberglass Atomic oxygen
parts from E-2A and A-6A aircraft (Staunton,
1982). Length of service varied from 12 to 19 Atomic oxygen is formed through the dissoci-
years. Effects of weathering were dependent ation of 0, by UV radiation. It is the
on the material used and whether a protec- predominant molecular species at 100-1000
tive coating was intact. When a hygroscopic km orbital altitudes. Its destructiveness is
BF3400 curing agent was used, the fiber- caused by its strong chemical reactivity com-
glass/Epon 828 epoxy lost nearly half of its bined with its translational energy of 5 eV
flexural strength. Fiberglass/Epon 828 epoxy (8 x J) from the high velocity of the space-
with methylene dianiline/benzyl dimethyl craft. Studies on the effects of atomic oxygen
amine (MNA/BDMA) curing agent per- have been performed both on samples
formed well, retaining tensile and flexural exposed to the low earth orbit environment
strength. Tensile and flexural test samples and in ground-based simulators.
taken from a fiberglass rotodome demon- The Mass Spectrometer Incoherent Scatter
strated the value of good coatings. Where the (MSIS) neutral atmosphere model is generally
used for predicting the atomic oxygen fluence
paint was intact, the material retained more
during a mission. Orbital altitude, inclination,
than 90% of its original strength and 82-94%
of modulus. Where the paint had been eroded other orbit parameters and solar activity are
used as inputs. The amount of atomic oxygen
away, the composite retained only 68% of its
original strength. received by a surface also depends on its ori-
entation to the RAM or velocity vector.
RAM facing composites (facing into the
velocity vector) flown on LDEF were sub-
36.3.5 SPACE
jected to an atomic oxygen fluence of
The Long Duration Exposure Facility (LDEF) approximately 9 x IOz1 atoms/cm2 which
has provided a wealth of information on the resulted in a thickness loss up to 0.013cm
low-earth-orbit (LEO) space environment (0.005 in) of material, the equivalent of
814 Environmental effects on composites
I 3 Meteoroiddebris impacts
A spacecraft in any orbit is susceptible to
micrometeoroid impact. These small particles,
fragments of asteroids or comets, may impact
at velocities up to 60 km/s (37 mi/s) but aver-
age 17km/s (10.5mi/s). Those spacecraft in
near-earth orbit are also susceptible to impact
from pieces of space junk or debris, also trav-
elling at high speeds. Damage from impact
may reduce the strength of composite struc-
tures or cause rupture in filament-wound
tanks. Damage may consist of cratering, pene-
tration, including penetration of thermal or
protective coatings, and spallation Fig. 36.2 is
Fig. 36.1 Cross-sectional photomicrograph of of a classic Whipple-type meteoroid/debris
atomic oxygen exposed LDEF graphite-reinforced shield before and after particle impact.
OMC showing approx. one ply (0.013 cm/O.OOS in)
of erosion.

approximately one ply of laminate (Fig. 36.1).

For unidirectional reinforced specimens, the
reduction in mechanical properties was pro-
portional to the reduction in cross-sectional
e- Impact particle

area. The SAMPLE experiment flown on the /

LDEF contained tensile specimens of One or more protectivetpmpers
graphite/epoxy systems and S-glass/epoxy.
The composite systems flown were HMF Pressure wall
322/P1700 polysulfone in a ( d 5 ) s weave,
HMS/934 in both 0" and 90" unidirectional
configurations, and P75S/934, also in both Before imDact
0"and 90" unidirectional lay-ups. The S-
glass/epoxy was flown with and without Debris cloud
aluminized thermal control tape as a protec-
tive coating. These samples received direct
atomic oxygen, as well as UV radiation, ther-
/
mal cycling and micrometeoroid/debris
impacts. Atomic oxygen reaction efficiency
was calculated to be approximately 1 x
cm3/ atom.

-
I
The thickness loss due to atomic oxygen Penetration or
erosion of the S-glass/epoxy samples in this 0 0 spallation of
experiment is estimated to be 9.14 pm (0.36 f pressure wall may
Spallation or may not occur
mil). The glass fibers are not susceptible to ero-
sion, and thus protect the underlying matrix. After imDact
The atomic oxygen reaction efficiency for
these samples was calculated to be 0.13 x lowz4 Fig. 36.2 Hypervelocity impact of Whipple bumper
cm3/atom. design.

The potential hazard of a meteoroid or
debris particle is dependent on its size, veloc-
ity, density and angle of impact. NASA
SP-8042 may be used to predict the meteoroid
environment encountered by a spacecraft in
near-earth orbit, earth-to-moon space and
near-lunar orbit. The space debris environ-
ment in earth orbit is continually changing as
more debris is being added with every launch.
At the time of publication, NASA TM-100471
is being used as the definition of the space
debris environment.
Prediction of damage caused by mete-
oroid/space debris impact can be made either
by using a variety of models, study of impact
sites in flight hardware, or simulation in the
laboratory. Hydrocodes such as CTH and
HULL use finite elements or finite differences
to predict penetration or spallation of a com-
posite laminate. Inspection of composite
samples from LDEF (Fig. 36.3) revealed 2-5
impacts of <0.1 cm diameter. (<40 mil) per
sample. These impacts did not affect tensile
strength as much as the atomic oxygen erosion
(see previous discussion), but the potential
effect of many impacts on a composite struc-
ture is obvious.
Ground simulationsin the NASA/Marshall
Space Flight Center Space Debris Impact
Fig. 36.3 Cross-sectional photomicrograph of
coated graphite-reinforced OMC showing impact
damage and post-impact atomic oxygen erosion.
Environments and efecfs 815
Facility have been performed on a number of
composite materials. These materials were
Kevlar 49/epoxy, non-impregnated Kevlar 49,
Spectra 900/epoxy and IM6/3501-6
graphite/epoxy. The test configuration con-
sisted of a classic Whipple design with the
composite material used as a bumper protect-
ing a 2219-T87 aluminum pressure wall
sample.
The results of these tests (Schonberg, 1990)
indicated that some composite systems, such
as the Kevlar 49 cloth and Spectra 900/epoxy,
performed better than equivalent weight alu-
minum systems as measured by damage to the
pressure wall. However, the Kevlar 49/epoxy
and IM6/3501-6 graphite/epoxy panels did
not perform as well as an equivalent weight
aluminum system at protecting the pressure
wall plate from damage, but damage by spal-
lation was far less for composite than metal
bumper plates. The composite bumpers did
experience large areas of delamination,
though this was restricted to the outer layers
with peeling in the direction of the surface
laminate fibers. Some charring and melting
did occur with the Kevlar 49 cloth (Fig. 36.4)
and Spectra/epoxy test articles.
I; ‘I
..-
c
-.
Fig. 36.4 Simulated meteoroid/debris impact in
Kevlar 49 cloth panel.
816 Environmental efects on Composites
Particulate radiation
Particulate or ionizing radiation in the space
environment consists of trapped radiation in
the Van Allen radiation belts, solar and galac-
tic cosmic radiation and bremsstrahlung
radiation. Protons, electrons, neutrons, alpha
particles, X-rays, gamma rays and other
charged particles bombard spacecraft in orbit.
Bremsstrahlung radiation is ionizing radiation
resulting from the deceleration of electrons.
Various computer models exist for predicting
the radiation dose during a mission at a par-
ticular orbit, but the high variability of solar
activity and the resulting magnetic storms
may give radiation calculations an uncertainty
of an order of magnitude or more.
Protons, electrons and cosmic rays may
affect composite materials by surface chemical
changes. The radiation threshold for observing
effects is between 108 and 109 rads for
graphite/epoxy and graphite/polysulfone. In
a cooperative effort between Boeing and
Langley Research Center (Fogdall, Russell and
Cannaday 1980), these materials were irradi-
ated with high-energy protons and electrons
(approximately 1MeV) then tested for flexural
durability. The composite systems tested were
T300/934, T300/5208, and C6000/P1700.
Radiation doses of 5 x lo9 rads or more
resulted in surface blistering of the T300/934,
although this had a limited effect on mechani-
cal properties. Flexural testing of irradiated
samples showed no significant changes for
low radiation doses.
A follow-on study performed at Boeing
(Fogdall et al., 1983) involved high radiation
doses to T300/934, C3000/934, C3000/PMR-
15 and C3000/P1700 composites. In this test,
compressive breaking strength at a 45" fiber
orientation and dynamic mechanical analysis
(DMA)were used to measure the effect of 1O1O
rads of electron radiation. As much as 15%
degradation in breaking strength was noted.
The DMA tests also showed a decrease in
glass-transition temperature for irradiated
samples.
Thermal extremes
As a spacecraft orbits, it moves from sunlight
to shadow. Solar radiation, both direct and
reflected from the earth (albedo), and thermal
radiation from the earth cause temperature
extremes of -185 to +150"C (-300 to +300"F).
Spacecraft heat sources, such as engines, elec-
tronic equipment and batteries, also contribute
to the thermal environment. Active thermal
control systems or protective coatings with
optimized solar absorptance and infrared
emittance can minimize thermal extremes.
Solar absorptance is defined as the ratio of
absorbed light to incident light, and infrared
emittance is defined as the ratio of emitted
heat to input heat. Low absorptance values
reduce the maximum temperatures when
exposed to direct or albedo radiation and low
values of emittance reduce minimum temper-
atures when exposed to deep space. Stability
of these properties is important for long-term
exposures. Thermal cycling effects on compos-
ites will be discussed later in this chapter.
Spacecraft leaving and returning to earth
must endure heating during ascent and re-
entry through the atmosphere. Re-entry
temperatures can reach 1482°C (2700°F).
Reinforced carbon-carbon composites are cur-
rently utilized in the Space Shuttle nose-cap
cover and wing leading edges. Another appli-
cation under investigation is a composite nose
cone for the Space Shuttle External Tank (Sigur
and Gray, 1990). This design not only weighs
less than an equivalent metallic design but
also can maintain the internal environment
within desired temperature limits without
thermal insulation. Temperatures on the Space
Shuttle External Tank nose cap may range
from -150°C (-297°F) around the liquid oxy-
gen vent louvers to 500°C (930°F) during
ascent. Mechanical property tests, including
tensile, compression, in-plane shear and inter-
laminar shear tests, have been performed on
laminates, moisture saturated per ASTM-D618
to reproduce the high humidity at the launch
site. These composite materials were also
 Environments and efects 817

tested for 'ply lift' or moisture-induced delam- Because moisture is removed from the com-
ination at high temperatures. Several posite in a vacuum, mechanical properties,
composite systems were studied, including such as compressive and interlaminar shear
graphite/bismaleimide and graphite/PMR- strengths, may be improved through expo-
15, but Celion G-30/500-3K graphite/BASF sure. However, the designer must consider
506 phenolic was chosen because of its dura- possible dimensional changes due to moisture
bility during the ply lift testing. desorption. Dimensional stability is critical for
space hardware such as optical benches and
Ultraviolet radiation truss structures. Another design concern is the
effect of outgassed moisture on sensitive
Ultraviolet radiation is that band of light from optics or electronic equipment present on a
300 to about 4000 A. Ultraviolet radiation may spacecraft. Vapor barriers of metallic foils have
cause degradation through molecular weight been used to prevent line-of-sight deposition
change and cross-linking in the resin system. of moisture and other outgassing products.
However, this damage is generally limited to The UTIAS experiment flown on LDEF
darkening of the resin in the surface layer. (Tennyson, 1991) contained a variety of flat
Figure 36.5 is a photomicrograph of a LDEF and tubular composite samples consisting of
composite laminate exposed only to UV. T300/5208, T300/SP-288 and T300/934
Coatings, such as thermal control tape, have graphite/epoxy samples, boron/SP-290 epoxy
been used to protect composite materials from and Kevlar/SP-328 epoxy. A data acquisition
degradation. system recorded outputs from 16 strain ther-
mal gages attached to the composite samples
for 371 days. Outgassing was measured, rang-
ing from 40 days for the T300/934 to 120 days
for the Kevlar/SP-328. Coefficient of thermal
expansion increased slightly for the 0" config-
uration (Table 36.1). This change should be
considered when designing zero CTE lami-
nates for space applications.

36.3.6 TEMPERATURE
Temperature effects on composite materials
discussed in this section include cryogenic
temperatures, elevated temperatures and ther-
mal cycling between these extremes.
Cryogenic temperatures do not appear to
Fig. 36.5 Cross-sectional photomicrograph of UV- affect the mechanical properties of
exposed LDEF graphite-reinforced OMC showing
minimal degradation. graphite/epoxies or graphite/polyimides sig-
nificantly.
Elevated temperatures for a prolonged
Vacuum and outgassing period of time can seriously affect the proper-
Orbital atmospheric pressure varies according ties of a composite, with even greater effect if
to altitude and solar activity. Average pressure moisture is present. Susceptibility to matrix
is generally 133 x N/m2 (1 x torr) in softening is not only dependent on the resin
low earth orbit, decreasing to 133x N/m2 but also the lay-up. A study of graphite/poly-
(1 x lO-I4torr) at geosynchronous orbit. imide properties used two different lay-ups, a
818 Environmental effects on composites

Table 36.1 Summary of LDEF/UTIAS composite material thermal data (Tennyson, 1991)

Material type Configuration Strain Thermal Ambient" Space Thermal

gage &?age CTE CTE vacuum
number number (1PPF) (1P P F ) facility'
CTE (lOd/W
Stainless Steel
(calibration) 1 1 9.84 10.0 10.0
Graphite/Epoxy 2 (0") 2 1.32 3.33 2.50
T300/934 3 (90") 14.7 13.9-15 16.1
Kevlar/Epoxy 4 (90") 3 33.9 30-35 35.3
93-328 5 (0°) 0.10 0.71 0.63
Graphite/Epoxy 6 (90") 4 14.6 13.6-14.3 15.4
T300/SP388 7 (0°) 0.97-1.57 -1.14-3.33 3.75
Graphite/Epoxy 8 (90") 5 15.6 12.5-15.3 16.1
T300/5208
Boron / Epoxy 9 (GO") 6 1.57 1.67-2.22 0.44-2.0
SP-290 10 ( 6 0 ) 11.7 7.5-11.1 12.7
aAt atmospheric pressure prior to launch.
Measured in space environment on LDEF during first 371 days in orbit.
Measured in laboratory thermal vacuum test facility (22 h at 133 x l t 5N/mZ (1 x l t 5torr), -40°F to 150°F) after 2114
days in orbit and 184 days at ambient conditions.

0" unidirectional lay-up and a (0, +45,90), lay- composites, and advanced carbodcarbon
up, tested at temperatures ranging from -157 composites.
to +315"C (-250 to +600"F) (Lisagor, 1979).Test Temperature effects are not limited to the
results showed little change in interlaminar matrix material. Extended operation at 350°C
shear strength for the quasi-isotropic lay-up (660°F) and 450°C (840°F) can cause oxidation
while the 0" unidirectional samples dropped of low-modulus PAN-based fibers and high
to approximately 40% of original strength at modulus PAN- or pitch-based fibers, respec-
elevated temperatures. Reduction of normal tively. Oxidation resistance can be improved
moisture content by vacuum drying reduced with higher purity fibers.
the loss to only 70% of room temperature Thermal cycling conditions are common for
strength. a number of applications, including aircraft
High-temperature resins under develop- and spacecraft. Thermal cycling may induce
ment, such as AFR700B developed by the Air microcracking in some composites. A study of
Force (Brown, 1991),have reached glass transi- this microcracking behavior in graphite/PMR-
tion temperatures of 416°C (780°F). AFR700B 15 composite materials was performed at Rohr
retains 50% of its mechanical properties up to Industries (Sullivan and Ghaffarian, 1988).
370°C (700°F). PMR-15 is another high-tem- Woven laminates of C3000/PMR-15 and unidi-
perature resin with excellent properties, but rectional tape lay-up of C6OOO/PMR-15 were
large or thick structures require debulking a thermally cycled between -18 and +232"C (0
few layers at a time due to the high volatile and 450'F) up to 2000 cycles. The C3000/PMR-
content. Other materials being developed for 15 developed microcracks, with the number of
high-temperature applications include tita- microcracks dependent on the number of ther-
nium matrix composites, ceramic matrix mal cycles. Decreases in compressive and shear

strengths were noted, although tensile
strength, a fiber-dominated property, was not
significantly affected. The unidirectional tape
lay-up, C6OOO/PMR-15 did not crack during
testing.
36.4 PROTECTIVE COATINGS
When an environmentally resistant composite
material cannot be utilized, protection of the
material through the use of coatings is neces-
sary. A variety of coatings have been developed
for protecting composites from various envi-
ronments. Standard marine paint, pigmented
gel coatings and polyurethanes have been used
to prevent ultraviolet damage and weathering
erosion of marine composites. The following
coating examples have been used in space but
Fig. 36.6 Micrometeoroid/debris impact in thermal control tape. Substrate is S-glass/epoxy.
Protective coatings 819
may be applicable to other environments.
On the LDEF, S-901 glass/epoxy compos-
ites were exposed to the space environment.
Three of these samples were flown with ther-
mal control tape, consisting of 50.8 pm (2 mil)
aluminum with 50.8 pm (2 mil) pressure-sensi-
tive SR574 silicone adhesive. The glass/epoxy
samples without tape suffered more mass loss
than the protected samples, and solar absorp-
tance of the unprotected samples increased
5.4%, probably due to ultraviolet radiation.
Post-flight peel tests of the thermal control
tape showed an increase in strength with some
embrittlement of the adhesive. Figure 36.6, a
SEM photograph, also shows the degree of
micrometeoroid/debris protection provided
by the tape.
.
.- -
b
820 Environmental effects on composites
A 60nm (600A) Si0,/100nm ( 1 O O O A )
nickel vapor-deposited coating appears to
have prevented resin loss in graphite/epoxy
samples flown on LDEF (Young et al., 1991).
Inspection of selected composites
(C6000/P1700, C3000/P1700, T300/934 (with
two different fiber areal weights) and
T300 /5208) revealed dramatic visual effects,
material loss and a deterioration in mechanical
performance for unprotected composites.
Chemical characterization suggests that there
is no significant change in molecular structure
of the surviving polymeric matrix resin in
these composites. No change in glass transi-
tion temperature was apparent. The majority
of the unprotected flight samples showed a
decrease in tensile strength and modulus.
Coating/composite systems for large space
truss structure applications have been tested
in ground simulations of atomic oxygen, ultra-
violet radiation, and thermal cycling (Dursch
and Hendricks, 1987; Dursch and George,
1993). Coatings studied were chromic and
phosphoric acid anodized aluminum foil,
sputtered SiO,/sputtered Al/Al foil, bare A1
foil, electroplated nickel with and without
SiOxcoatings and inorganic sol gel solutions.
P75S/934 composite was used to form the
truss tubes.
The aluminum foil used was 1145-H19 alu-
minum alloy with a thickness of 50.8 pn (2
mil). Thicker foils can be used, depending on
weight constraints and flexibility of any coat-
ings applied to the foil. The foil was bonded to
the graphite/epoxy truss tube with an epoxy
film adhesive and was co-cured. The chromic
acid anodized foil provided good protection as
well as optical properties. The phosphoric acid
anodized foil also provided good protection
while maintaining adhesion. Desired optical
properties were obtained by varying thickness
of silicon dioxide and sputtered aluminum on
top of the aluminum foil. The optimized thick-
nesses were 1pn (0.04 mil) SiO, and 300 nm
(3000 A) Al.
The electroplating process was chosen for
study because of its low application costs,
good corrosion resistance and good unifor-
mity. Irregular shapes, such as end fittings,
may also be coated with this process. The com-
posite surfaces were sanded prior to plating to
improve adhesion. However, atomic oxygen
attack resulted in loss of adhesion in the nickel
coating without SiOxovercoat.
Numerous other coatings have been stud-
ied for space environment resistance. Braided
and double-braided aluminum coverings,
indium-tin eutectic coatings, various silicone-
based paints and zinc oxide pigment in a
potassium silicate and silicone elastomer
binder have been tested (Piellisch, 1991). A
proposed design for solar array backing on the
NASA space station employs woven E-glass
sandwiched between two layers of silicon
dioxide-coated Kapton.
REFERENCES
Anon. 1970.Meteoroid Damage Assessment. NASA
SP-8042
Ashbee, Ken. 1989. Fundamental Principles of Fiber
Reinforced Composites. Lancaster, PA: Technomic
Publishing.
Beckmann, Hans-Dieter and Oetting, Hermann.
1985. Fiber reinforced plastics move inside
engine. Automotive Engineeying 93(5):34-41.
Brown, Alan S. 1991. The Air Force finds an ultra-
high temperature resin. Aerospace America 29
(10):56-57.
Dexter, H. Benson. 1987. Long Term Environmental
Effects and Flight Service Evaluation of
Composite Materials. NASA TM-89067.
Dobyns, Alan. 1991. Structures. Aerospace America
29(12):38-39.
Dursch, Harry W. and Hendricks, Carl L. 1987.
Protective coatings for composite tubes in space
applications. S A M P E Quarterly 19(1):14-18.
Dursch, Harry W. and George, P. 1993. Composite
Protective Coatings for Space Applications.
Paper read at Third LDEF Post-Retrieval
Symposium, November 8-12, 1993, at
Williamsburg,VA.
Fogdall, L.B., Russell, D.A. and Cannaday, S.S. 1980.
Radiation Exposure of Composite and Polymer
Materials. Report for Contract NAS1-15606.
Fogdall, L.B., Lindenmeyer, P.H., Sheppard, C.H.,
Russell, D.A. and Cannaday, S.S.. 1983.

Development of Facilities, Quality Control
Procedures, and Testing Techniques for
Irradiation of Spacecraft Composite Materials.
Report for Contract NAS1-16854.
Fried, N. 1969. Marine Applications. In Handbook of
Fiberglass and Advanced Plastics Composites, (ed.
George Lubin) pp. 747-783. New York: Van
Nostrand Reinhold.
Graner, William R. 1982. Marine Applications. In
Handbook of Composites, (ed. George Lubin) pp.
514-529. New York: Van Nostrand Reinhold.
Kamenetzky, R.R. and Whitaker, A.F. 1992.
Performance of Thermal Control Tape in the
Protection of Composite Materials to Space
Environmental Exposure. NASA TM-103582.
Kessler, D.J., Reynolds, R.C. and Anz-Meador, P.D.
1989. Orbital Debris Environment for Spacecraft
Designed to Operate in Low Earth Orbit. NASA
TM-100471.
Levine, Arlene, (ed.). 1991. LDEF-69 Months in
Space: First Post-Retrieval Symposium. NASA
CP-3134.
Levine, Arlene, (ed.). 1992. LDEF-69 Months in
Space: Second Post-Retrieval Symposium.
NASA CP-3194.
Lisagor, W. Barry. 1979. Mechanical Property
Degradation of Graphite/Polyimide Composites
After Exposure to Moisture or Shuttle Orbiter
Fluids. In Graphite/Polyimide Composites, (ed. H.
Benson Dexter and John G. Davis, Jr.)
pp.273-287. NASA CP-2079.
Piellisch, Richard. 1991. New solar arrays mean
new materials. Aerospace America 29(5):20-23.
Pilpel, Edward D. 1982. Expanded Design Analysis
of the Use of Composites in Determining Snow
Ski Characteristics. In Materials Overview for
2982, SOC.Advanc. Mater. Proc. Engng, pp.
616-627.
Schonberg, W. 1990. Hypervelocity Impact Testing
of Non-metallic Materials. 17th Cong. Intern.
Council of the Aeronaut. Sci., Sept. 9-14, 1990,
at Stockholm, Sweden, paper ICAS-90-1.7.3.
Sigur, W.A. and Gray, C.R. 1990. Composite
Applications on the External Tank. Final Report
from Martin Marietta Manned Space Systems,
NASA Contract NAS8-33708.
References 821
Springer, George S., Sanders, Barbara A. and Tung,
Randy W. 1981. Environmental Effects on Glass
Fiber Reinforced Polyester and Vinylester
Composites. In Environmental Effects on
Composites Materials, pp. 126-144. Westport, CT
Technomic Publishing.
Spry, William J. 1987. Sports and Recreational
Equipment. In Engineered Materials Handbook,
Vol. 1, (ed. Theodore J. Reinhart et al.) pp.
845-847. Metals Park, Ohio: ASM International.
Staunton, R. 1982. Environmental Effects on
Composites. In Handbook of Composites, (ed.
George Lubin) pp. 514-529. New York: Van
Nostrand Reinhold.
Sullivan, Lawrence J. and Ghaffarian, Reza. 1988.
Microcracking Behavior of Thermally Cycled
High Temperature Laminates. Paper read at
33th Intern. SAMPE Symp. Exhib., March 7-10,
1988, Anaheim, CA.
Tennyson, R.C. 1991. Composite materials in space
- results from the LDEF satellite. Canadian
Aeronautics and Space J. 37(3):120-1 33.
Vette, J.I., Lucero, A.B., Wright, J.A., King, J.H. and
Lavine, J.P. 1967. Models of the Trapped
Radiation Environment. NASA SP-3024.
Whitaker, A.F. 1991. Coatings Could Protect
Composites from Hostile Space Environment.
Advanced Materials and Processes 139(4).
Whitaker, A.F. and Young, L.E. 1991. An Overview
of the First Results on the Solar Array Materials
Passive LDEF Experiment (SAMPLE), A0171.
Paper read at First LDEF Post-Retrieval
Symposium, June 2-8,1991, Orlando, FL.
Whitaker, A.F. 1991. Preliminary Assessment of
LEO Effects on LDEF Experiment A0171
Composite Material Surfaces. Paper read at
LDEF Materials Workshop, Nov. 19-22,1991, at
Langley VA.
Young, Philip R., Slemp, Wayne S., Witte, Jr.,
William G. and Shen, James Y. 1991.
Characterization of Selected LDEF Polymer
Matrix Resin Composite Materials. Paper read
at 36th International SAMPE Symposium and
Exhibition, April 15-18,1991, at San Diego, CA.
SAFETY AND HEALTH ISSUES
Jennifer A. Heth
37.1 INTRODUCTION
On a weekly basis, there are conflicting media
reports indicating that something is good or
bad for us, depending on the study done, the
topic and the amount of press given to it.
However, by reviewing the information and
adding common sense and moderation to our
lifestyles, we are able to discern good from bad,
thus allowing us to lead healthy and safe lives.
Working with composite materials, or any
chemicals for that matter, should be viewed in
the same manner. Know what material is used,
how it is handled, what is known about it and
how to reduce the risk of injury from any haz-
ard associated with it.
From a safety perspective, proven engineer-
ing and administrative techniques and
controls exist that can make the workplace
safe if implemented correctly. There are fairly
universal industrial hygiene protocols that
merely need to be implemented to effectively
minimize potential exposure to any hazard,
whether it be chemical or physical.
On health issues, there are numerous toxi-
cological papers published on chemicals used
in the composites industry. However, without
a toxicological background or proper analysis
and interpretation of the data, it is difficult to
know what the studies’ conclusions are and,
more importantly, if they are valid.
To assist users in understanding safety and
health issues for composite materials, the
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
37
Safety and Health Subcommittee of the
Suppliers of Advanced Composite Materials
Association (SACMA) researched and pub-
lished Safe Handling of Composite Materials (3rd
Edn, April 1996). This chapter is an edited ver-
sion of the booklet, with new information
added as appropriate. The information is not
meant to be inclusive. Rather, the reader
should be aware of the issues addressed and
make further investigation as needed. Note
that data cited was current in 1997.
37.2 HEALTH INFORMATION
TERMINOLOGY
It is important to understand the terminology
in order to read and assess toxicological data.
This section will concentrate on some of the
basic terms and definitions that are applicable
to the composite user, especially in reading
Material Safety Data Sheets, the most common
source of information on materials.
37.2.1 TOXIC, HAZARD AND RISK
These three words are used frequently and
sometimes interchangeably. To avoid confu-
sion, they are defined as follows.
Toxic refers to a poison or poisonous sub-
stance that may cause a harmful effect in the
body. A substance’s toxicity characteristic is a
property of the chemical, similar to its color or
odor. This is as true for chemicals like water,
salt or sugar as it is for cyanide, snake venom
or botulism toxin (Fig. 37.1).
 Health information terminology 823

Risk describes the probability or likellhood

‘All chemicals are toxic, there
are none which is not ...
\ /
The right dose differentiatesa
poison from a remedy.’
/ Paracelsus
,6th Century
that a hazard will result in a harmful effect.
Regardless of the toxicity, hazard or risk
associated with a substance, care should
always be taken to minimize exposure. This is
because what is known today may be inade-
quate compared to what tomorrow’s science
may discover (e.g. asbestos usage and asbesto-
sis or tobacco and lung cancer).

37.2.2 ACUTE TOXICITY VERSUS CHRONIC

Fig. 37.1 Toxicology principle.
Hazard takes into account the toxicity of a sub-
stance along with exposure to it. Something
can be extremely toxic, but if there is no expo-
sure, there is no hazard (Fig. 37.2). Conversely,
it is important not to be negligent in handling
low toxicity substances, as extreme exposure
(high concentration or long exposure time)
could result in high hazard.
TOXICITY
When discussing toxicity, reference will typi-
cally be made to two types: acute or chronic.
One can be instantaneous and the other mani-
fests itself over a long period of time.
Acute toxicity occurs when a harmful effect is
experienced after a single or short-term expo-
sure to a substance. It usually occurs instantly
or within a short time period. Typically, expo-
sure will be by skin or eye contact or
inhalation. In industrial settings, it would be
unlikely for exposure to be by ingestion,
though this is another route.

K = Minimal hazard
Low exposure

High toxicity

0 9- AM 6

nw
Extreme exposure
X = Elevated hazard

Low toxicity

Fig. 37.2 Risk assessment equations.

824 Safety and health issues

The most common measure of acute toxicity (possibly years or decades). Because chronic
through the oral or dermal routes is called the effects develop slowly and are measured later,
median lethal dose or LD,,. The LD,, (mg of and it is not possible to keep the workplace
chemical per kg of body weight) is the amount toxic-free, it is important to eliminate or mini-
of material that kills 50% of a group of experi- mize exposure.
mental animals, usually mice or rats (Fig.
37.3). The measure by inhalation is LC,,, or 37.2.3 SENSITIZATION
median lethal concentration. It is expressed as
an airborne concentration in milligrams of In some cases, an allergic reaction to a sub-
chemical per cubic meter (mg/m3) of air, or stance will develop with one exposure, or over
parts per million (ppm) in the air (Fig. 37.3). time with repeated exposures. This is called
sensitization. Once a person is sensitized to a
0 Oral and dermal routes:
substance, the extent of the reaction does not
necessarily relate to the degree of exposure.
Median lethal dose - LD, (mg/kg) Also, people who are sensitized to one chemi-
A large LD, (e.g., 5000 mglkg) equals a low degree cal may react to other similar materials. This is
of acute toxicity, typically relating to a low health known as cross sensitization (Fig. 37.4).
hazard. Certain individuals may be sensitized to some
chemicals used in the composites industry. For
0 Inhalation route: example, there have been reported cases of
Median lethal concentration - LC,, (rng/rn3)
epoxy sensitization. In these instances, it is
For rats, a four hour exposure period is commonly
important that an employee not be exposed
used. Because other time durations are used, data further, or allowed the opportunity to be
will usually be reported with time specified. exposed. To do this, engineering or adminis-
trative controls should be implemented. If
these are not possible or practical, then the
Fig. 37.3 Acute toxicity measures. employee should be removed from chemicals
causing reaction.
The acute inhalation hazard is dependent on
the material's toxicity, together with its physi-
cal properties, such as vapor pressure for gases 37.2.4 EXPOSURE LIMITS
or particle size for aerosols, particulates and
There are limits or values (Fig. 37.5) estab-
dusts. Knowledge of the physical properties
lished by health groups to assist the user in
will assist in determining whether a material is
controlling exposure to certain chemicals;
likely to become airborne, thus inhalable.
some are regulated (OSHA's Permissible
Chronic toxicity occurs when adverse health Exposure Limit, PEL), others are recom-
effects are manifested after exposure to a sub- mended (ACGIH's Threshold Limit Value,
stance over a long period of time (e.g. TLV). These limits are based on actual indus-
throughout a working lifetime) or by long-term trial experience, experimental animal and
effects resulting from one or a few doses. These human studies and, when possible, a combi-
effects can occur following repeated exposures nation of all three.
to chemical substances through dermal or ocu- Exposure limits are developed for protec-
lar contact, halation or ingestion routes. tion against serious health effects or irritation,
Chronic toxicity testing includes systemic narcosis, or nuisance. They are intended for
toxicity, mutagenicity carcinogenicity, repro- the control of potential health hazards in the
ductive toxicity and sometimes epidemiological workplace. Because each individual is differ-
studies, all of which are very time consuming ent, there will be incidents of people affected
 Industrial hygiene 825

Once sensitized (have an allergic reaction), the following may occur:

fl
0

0 .
9.

X
Low exposure
Low toxicity

fl0 9.

nw
X Extreme exposure = Allergic reaction
0 .

Low toxicity

Chemicals similar to
X = Allergic reaction
substance causing Low exposure
sensitization
Fig. 37.4 Sensitization equations.

by some substances at concentrations below 37.3 INDUSTRIAL HYGIENE

the PELs or TLVs (Fig. 37.5). This is because the Potential hazards can be controlled through the
limits/values are based on the exposed popu- implementation of sound industrial hygiene
lation being 'normal', and does not address practices. Whether employees are working in a
aggravation from pre-existing conditions, ill- high or low hazard area, the recognition, evalu-
nesses or lifestyle choices. It is best to maintain ation and control of conditions are necessary to
concentrations of atmospheric contaminants at avoid occupational illness or discomfort. This is
the lowest level reasonably possible through industrial hygiene.
process or engineering controls. It is important to apply good engineering,
When referencing PELs and TLVs, a 'skin' process and administrative controls in the work-
notation may be assigned. This indicates that place along with effective industrial hygiene
dermal exposure should also be considered practices (e.g. monitoring, surveys, proper per-
when evaluating exposure to that substance. sonal protective equipment usage). Without
Always check the current OSHA standards for addressing the fundamentals, it is difficult to
PELs and the latest edition of the ACGIHs maintain employee comfort and, hence, protec-
TLVs: Threshold Limit Values and Biological tion against exposures that may be present.
Exposure Indices, along with the supplier's Industrial hygiene practices for composites
Material Safety Data Sheet, for information on are common to those for other industries.
limits and protection against exposure.
826 Safety and health issues

Exposure limits
PEL (Permissible Exposure Limits) Airborne exposure limits issued by the OccupationalSafety and Health
Administration (OSHA), 29 CFR 1910.1000, which are legally binding.
TLV (Threshold Limit Values) Recommended exposure limits for airborne concentrations of substances.
They are issued by the American Conference of Governmental Industrial Hygienists (ACGIH) and pub-
lished annually.

Exposure limit descriptions

Both PEL and TLV are expressed in similar terms describing exposures:
TWA (Time Weighted Average) This represents a normal 8 h day and a 40 h work week, to which nearly all
workers may be exposed without adverse health effects. In literature, data will appear as PEL-TWA or
TLV-TWA.
STEL (Short-Term Exposure Limit) Concentrations to which people can be exposed for a short period of
time without suffering from
irritation;
0 chronic or irreversibletissue damage; or
0 narcosis of sufficient degree to increase likelihood of accidental injury, impairment of self-rescue or
reduction of work efficiency
provided the daily PEL or TLV-TWA is not exceeded.
Data will appear as PEL-STEL or TLV-STEL in written works.
C (Ceiling) The concentration not to be exceeded during any part of the working exposure. This will
appear as PEL-C or TLV-C in documentation.

Fig. 37.5 Exposure limit terminology.

Periodic exposure assessments should be con-
ducted taking into consideration routes of
exposure associated with composite use (Table
37.1). Monitoring should be routine, and on
demand whenever unusual odors are noticed,
visible contamination is heavier than normal,
or a new process is to be used. After any new
process or modification of an old one, good
work practice is to ensure that existing con-
trols to prevent exposure are implemented
and effective.
Two potential exposures posed by composite

Table 37.1 Routes of exposure for composite users

Skin and eyes Typically hands, lower arms and face are exposed. However, if personal hygiene is not
good, other areas of the body may be susceptible to exposure. Avoid exposure,
especially in cases where dermatitis or sensitization has been confirmed. Avoid contact
with chemicals that can be absorbed through the skin, as systemic and/or local
effects may occur.
Inhalation Good ventilation will minimize possible exposure from the release of solvents or dusts
generated.
Ingestion Thorough washing of the hands prior to eating or smoking provides sigmficant
protection from the effects of accidental ingestion.
Injection Needles and sharps are not normally a concern. However, shards from cured
composites or brittle fibers, or needles from weaving or sewing processes can
puncture the skin and chemicals could enter the body.
 Industrial hygiene 827

usage are skin contact with materials that
could result in irritation leading to dermatitis
or sensitization, and inhalation of particulates
from operations such as cutting, grinding and
finishing. Both concerns can be eliminated or
minimized with implementation of proper
gloves/clothing, good ventilation and process
conditions, and effective training.
37.3.1 ADMINISTRATIVE CONTROLS
In the National Safety Council’s Fundamentals
of Industrial Hygiene (3rd Edn), administrative
Table 37.2 Workplace tools to prevent exposures
controls are defined as ’methods of controlling
employee exposures by job rotation, work
assignment, or time periods away from the haz-
ard’. These controls may be implemented when
e n p e e r i n g controls cannot reduce the exposure
to permissible levels (Fig. 37.6). Administrative
controls also encompass ’other work rules’, such
as company policies (Table 37.2).
One example of a process hazard in the
composites industry, controllable through
engineering and administrative rules, is an
out-of-control exothermic reaction. This is an
unintentional runaway chemical reaction of a

1. Safety controls Confined space entry; hot work permits; lockout/tagout procedures; pipeline
breaking permits; safe work permits.
2. Personal controls Knowledge and use of Material Safety Data Sheets (MSDS);company policies
and procedures; regulation of employee’s exposure time in a work area.
3. Education and Training in the use and handling of materials and any associated hazards;
training understanding of the training.
4. Materials handling Information from MSDS on proper handling of materials
5. Process controls Isolation of process controlled work areas; eating, drinking, smoking should be
separate from any work area as should food storage; control of process-related
hazards, such as an out-of-control exothermic reaction potential. There should
be procedures, equipment, ventilation systems and process hazard analysis
and training in place; wet processes to reduce dust generation.
6. Personal hygiene Thorough washing of hands before each job break and eating/drinking/smoking
and toilet use along with use of good hand creams after each wash.
7. Warnings Proper labels on chemicals; follow OSHA’s Hazard Communication
and labels Standard.
8. Housekeeping Keep work areas clean and free of clutter; remove dust by vacuuming instead of
blowing it off work areas into the air.
9. Emergency plans Plans and procedures for dealing with any chemical emergency; personnel
should have the knowledge, skills and equipment to respond appropriately.
10. Ventilation General, diluted (supplied air) and local exhaust ventilation.
11. Medical controls Good occupational medical program and protocol.
12. Engineering Design, maintenance and hazard studies; shielding, monitoring devices, and
practices alarm systems.
13. Personal protective Respirators, gloves, body suits, boots, jackets, goggles, eyewear, face shields,
equipment safety shoes/boots, headgear.
14. Administrative Job rotation, scheduling machine times to reduce number of workers exposed,
controls scheduling work times to avoid exposures (eg. cooler times of day to avoid heat
stress), reduction of work periods.
828 Safety and health issues

I Engineering controls
I Exothermic reactions can be avoided and min-
imized by clearly defining and following the
J. proper procedures, thoroughly training
I-Administrativecontrols 1 employees who work with resins and prepreg
materials, making certain that equipment is in
1 good working order, and that safety devices or

Personal protective equipment (PPE) benzyl phthalate, ABP) are in place and func-

Fig. 37.6 Industrial hygiene order of priorities.

resin system, alone or in prepreg form, typi-
cally called an exotherm. It may occur under
any of these conditions:
0 heating or mixing a resin too long;
0 heating a resin too fast;
0 allowing a resin to get too hot;
0 contamination or mislabeled chemicals.
These factors have been known to start or
extend an exotherm:
0 resin mass scale up and equipment cannot
dissipate heat;
0 deviating from procedures;
0 disabling safety equipment;
0 casting hot melt resins too deep;
0 process equipment malfunction;
0 variability in raw materials;
0 mixing incompatible chemicals and curing
agents;
0 contaminating chemicals, e.g. poor house-
keeping;
0 uneven dispersing or mixing of chemicals;
0 trying to mass cure resin oE prepreg in an
oven or autoclave.
37.3.2 PERSONAL PROTECTIVE EQUIPMENT
(PPE)
Personal protective equipment is used to con-
trol exposures when they cannot be reduced to
an acceptable or practical level using engineer-
ing and administrative controls. In the
composite industry, there are three main expo-
sure areas that may require PPE to protect the
skin, eyes and lungs.
37.3.3 SKIN PROTECTION
Hand contact exposure is most common when
using composites. The use of proper protective
gloves is important to control exposure. Along
with gloves, other equipment such as jackets,
arm protectors, or body suits may be neces-
sary depending on the process or potential for
exposure.
Gloves
Glove selection should take into account the
parameters in Table 37.3 to ensure the correct

Table 37.3 Proper glove selection criteria

Chemical resistance Glove must be impermeable to the chemical being used. An incorrect glove
choice may allow the material to come in contact with the skin.
Dexterity and If the user cannot work comfortably with the glove, it will not be used.
comfort
Glove lining Lining material may cause irritation or excess sweating. Consider liners or other
alternatives.
Glove surface The outer surface may contain residual coatings that may contaminate and
possibly delaminate a composite part.
 lndustrial hygiene 829

glove choice and use by the employee. aramid protect well against heat, cuts or
Additionally, Table 37.4 gives a brief listing of scrapes. Glove choice must depend on the
glove types used in the composite industry job and its duration.
and what they protect against. SACMA's com-
panion video to the Save Your Skin! booklet
demonstrates correct glove selection and Skin creams
usage for composite users.
There are creams that are applied directly to
It is important to know that there is not an
the hands and forearms for protection. Two
'all purpose' glove for protection from all
types of cream discussed in Table 37.5 indicate
exposure. Proper protection may require
the difference between moisturizers (no pro-
wearing one type of glove over another.
tection against chemicals) and barrier creams
Basically, there are two glove types:
(limited protection). Barrier creams may be
1. Chemically resistant: used alone or in combination with gloves.
A selection of gloves used for protection When using barrier creams, there is a possi-
against exposure to chemicals. Depending bility of contamination to the composite
on the permeability of the glove material to material. If there is a heavy reliance on the use
the chemical used, the glove chosen will of barrier creams, process engineers need to
protect the wearer for only a limited time. investigate alternatives in engineering, process
Even the proper glove does not last forever. changes or alternate PPE. Since barrier creams
2. Mechanically or thermally resistant: are not moisturizing creams, a good moisturiz-
These gloves, such as leather, cotton or ing cream should also be applied after work to

Table 37.4 Examples of glove types

Glove type Hazard ...

Aramid Cutting, intense heat
Cotton Abrasions
Disposable plastic (Latex) Microorganisms, mild irritants, fibers
Natural rubber (Latex) Acetone (< 1 h), epoxies, methyl ethyl ketone (MEK), light work
Leather Abrasions, punctures, fibers
Metal mesh Cuts, scrapes
Neoprene Acetone (< 1 h), solid epoxies, DMSO, isopropyl alcohol
Nitrile Solid epoxies, TDI, isopropyl alcohol
Polyvinyl alcohol Methylene chloride, bisphenol A epoxies, toluene, MIBK, TDI,
styrene, THF (< 4 h), l,l,l-trichloroethane
Polyvinyl chloride TDI, isopropyl alcohol, (< 4 h)
Rubber, butyl Isopropyl alcohol, Dimethylformamide (DMF), DMSO. MEK, MIBK,
acetone, N-methyl-2-pyrrolidone (NMP)
Rubber, insulated Electrical shocks and burns
VITON@ Toluene, xylene, styrene, isopropyl alcohol, l,l,l-trichloroethane
Sources: Save Your Skin!, SACMA 1990; Safe Handling of Advanced Composite Materials, SACMA 1996.
830 Safety and health issues

Table 37.5 Skin creams

Moisturizingcreams Replenish moisture in the skin which is lost after washing up. Use regularly to
avoid dry skin conditions which could lead to dermatitis. Gloves must always be
worn when moisturizing creams are used.
Barrier creams 1. Water repellent creams: Leave a thin film of lanolin, beeswax, petroleum or
silicone on skin. Used mainly in machine shop operations.
2. Solvent repellent creams: Leave a thin film on the skin, visible or not, which
will repel oils, paints, and solvents. Barrier creams do wear off and must be
reapplied for constant protection.

keep skin healthy. Additionally, barrier creams 37.4 POTENTIAL HEALTH AND SAFETY
may actually increase abrasion from fiber dust, HAZARDS IN COMPOSITE PROCESSES
so their effectiveness needs to be monitored. When designing equipment, processes and
modifications, complete containment of
37.3.4 EYE PROTECTION vapors and dusts should be a goal. General
ventilation should be provided to all work
Eye protection should be selected based on areas, with local exhaust equipment designed
impact (flying particles) and/or chemical to pull contaminants away from the
splash possibilities. Selections should include employee's breathing zone. In almost every
appropriate safety glasses, goggles, face composite process, the engineering emphasis
shields or a combination of these. is on good ventilation to control solvent and
dust exposures, along with other contami-
37.3.5 RESPIRATORY PROTECTION nants.
Figure 37.7 gives a summary of potential
During operations such as resin mixing, health and safety exposures that could occur
prepreg lay-up, machining or clean-up, respi- in composite processes. However, with good
ratory protection may be necessary to reduce engineering, administrative and industrial
exposures to vapors or dusts. hygiene practices, personal exposure can be
There are two main types of respirators: air minimized.
purifying and air supplying. Before using any Process improvements are driven by tech-
respirator, familiarity with OSHA's Respiratory nology and regulation (e.g. CA's South Coast
Protection Standard (29CFR 1910.134) is essen- Air Quality Management District Rules 1171
tial. Not everyone can or should use a and 1128 are for emission reduction of volatile
respirator. An employee must be medically organic compounds in coating and cleaning
approved, fit tested, and trained to assure that operations). In the composites industry, some
the respirator used is both appropriate and examples of minimized solvent vapors and
protective.
exposures include closed loop systems, cabin
If using a cartridge (filter) respirator, the surroundings for processes, improved ventila-
cartridges are specific to hazards and must be
tion designs and capture efficiencies, and
maintained and changed periodically to pre- elimination of solvents or substitution of low
vent exposure. If they are the wrong type, are vapor pressure solvents for high vapor pres-
used too long, or become dirty, respirators are
sure solvents.
ineffective.
 Toxicological properties of composite components 831

COMPOSITE PROCESSES

Fig. 37.7 Potential health and safety exposures in composite processes.

37.5 TOXICOLOGICALPROPERTIES OF effects, the resin system is of primary concern.

COMPOSITE COMPONENTS The reinforcement is secondary due to its lower
hazard potential compared to resin systems.
The supplier’s Material Safety Data Sheet
Solvents are addressed as a separate category as
(MSDS) and other sources of toxicological
they are major sources for potential skin and
information should be used for practical haz-
inhalation exposures. Some are part of the resin
ard assessment on any material. Rarely will
systems, while others are only used for clean-
data be available on the composite system
up purposes.
itself because the methodology has not been
fully developed to adequately test these kinds
of materials. Therefore, the hazards of com-
37.5.1 RESINS
posites are generally expressed in terms of the
components’ hazards. This is a conservative Composites are by definition based on a resin
approach that provides the user with the most system matrix applied to some reinforcing
protective information because it is based on material. The resin system is often quite com-
the most hazardous component which may plex, consisting of a basic resin (e.g. epoxy),
only be a percent or less of the entire mixture. which is formulated with other materials,
Typically, when discussing toxicological such as curing agents, diluents, accelerators,
832 Safety and health issues

pigments or solvents. Components of the
resin system may be supplied individually
and formulated by the user, supplied as ‘Part
A and Part B’ and blended before use, or sup-
plied mixed as a ’one-pack’ system.
any product containing additives with known
or potential health effects. Reference to the
MSDS will advise you of hazardous materials.
Some commonly used additives are listed in
Table 37.7.

Epoxy resins Other resin types

Epoxy resins, also known as glycidyl com- Over the years, epoxies have been the back-
pounds, are commonly used in composite bone of the composite industry. However,
matrix resin systems. In addition to the stan- other resin systems play an important role and
dard bisphenol A based epoxies, other are used for particular applications and perfor-
glycidyl ethers, glycidyl esters, glycidyl mance properties. Table 37.8 discusses health
amines, and epoxy novolacs are used in com- effects of some of these other resins. The asso-
posite matrices. ciated health hazards may appear severe, but
The greatest concern with epoxies is their exposures are avoidable through engineering
potential to cause skin irritation, dermatitis or and industrial hygiene practices, especially
skin sensitization, depending on the base good ventilation for control of vapors.
epoxy used and the sensitivity of the individ-
ual exposed. Table 37.6 discusses epoxy based 37.5.2 REINFORCING MATERIALS
resins and associated hazards.
Most reinforcement materials (Table 37.9) are
fibers, such as graphite or carbon, glass,
Hardenerskuring agentskatalysts
aramid or ceramic. Others may be used, but
One or more of these additives are used to the application is typically specialized, result-
enhance properties of composite materials. ing in small specialty runs. Overall, data
Their percentage of the resin system may be indicates that most fibers have a low hazard
small, but precautions ought to be taken for potential in initial form. However, they may

Table 37.6 Health effects of various epoxies

EPOXY type CAS nurnber(s) Known health efects Key notes

Bisphenol A based 1675-54-3, Possible skin sensitizer; Insufficient evidence to classify as
25036-25-3, low order of acute a carcinogen according to IARC.
25068-38-6, toxicity; slightly to Considering the many studies as
25098-99-8 moderately irritating. a whole, the evidence does not
show the resins to be carcinogenic.
Glycidyl amines 28768-32-3 Possible skin sensitizer; Mutagenicity tests gave both
low order of acute negative and positive results.
toxicity.
Cycloaliphatics 2336-87-0, Irritant to skin and mucous Not considered mutagenic or
30583-72-3 membranes. carcinogenic.
Glycidyl ethers 2210-79-9, Possible skin sensitizer. Neopentylglycol diglycidyl ether
2426-08-6, Moderate to severe skin has caused skin tumors when
3101-60-8, and mucous membrane applied repeatedly to skin of
17557-23-2, irritant. shaved mice.
26447-14-3
Toxicological properties of composite components 833
834 Safety and health issues
(.j
 Toxicological properties of composite components 835

Table 37.9 Health effects of fibers

Reinforcement type Known health effects Key notes

Carbon or graphite Mechanical abrasion and irritation
fibers of the skin; possible dermatitis;
physico-mechanical properties
of the fibers rather than a
toxico-chemical reaction. Possible
reaction from the fibersizing.
See resin health hazards.
Glass fibers Mechanical irritation
of eyes, nose, throat;
possible skin sensitization,
either from sizing or fiber.
Para-aramid fibers Minimal evidence for skin
irritation, none for skin
sensitization.Prolonged
overexposure to respirable
fibrous particles (RFP)
has potential for lasting
lung damage.
Ceramic fibers Skin, eye, or upper respiratory
irritation is possible.
PEL-TWA is 15 mg/m3 total dust, and PEL-
TWA of 5 mg/m3 for synthetic graphite
respirable dust. ACGIH has a TLV-TWA of
2 mg/m3 respirable dust for all forms of
graphite except fibers. There are no limits for
carbon fiber, though the US. Navy has set 3
carbon fibers/cc. EPA did not classify the
potential carcinogenic properties of
carbon fibers due to insufficient data.
Continuous fiber (used in composites, >6 km
in diameter) is probably not carcinogenic
(IARC, 1988).Wool fiber is classified as a
possible human carcinogen (IARCGroup 2B).
Commercial fibers are too large to inhale, but
RFP can be created when the fiber is abraded
or cut. Airborne RFP concentrations from
composite machining have been acceptably
low. Inhalation studies in rats demonstrated
fibrous particle breakdown in the lungs and
no carcinogenicity. IARC classifies para-
aramid RFP in Group I11 (not classified as a
carcinogen).
EPA proposed ceramic fibers, such as refrac-
tory aluminum oxide and zirconium oxide, as
not classifiable to human carcinogenicity.
Also, EPA proposed that aluminum silicate
fiber be classified as a human carcinogen.
Refractory ceramic fibers are classified
as 2B by IARC.

be chemically coated or stiff enough to cause
irritation by penetrating the skin or tissues of
the nose, throat or bronchi. Little has been
studied and is known about cured materials
being ground, drilled, milled, cut or sanded.
Should fragments of fibers be small enough to
be respirable, there is concern that a general or
fibrous dust hazard to the lungs can occur.
Therefore, precautions should be used to min-
imize exposure.
Knowledge of the fiber used should include:
length, diameter, aspect ratio and fragmenta-
tion propensity. Knowledge of fiber
parameters, along with how the composite will
be handled, is critical to protect from exposure.
Fiber diameter size for respirability is
believed to be 3.5 pm or less. Anything larger
than that will be removed from the body via
nose and throat functions. If the fibers are res-
pirable, the toxic effects may vary
significantly. There are low risk fibers (irritants
such as fiberglass) and there are significant
risk fibers that can result in asbestosis or can-
cer (such as asbestos fibers). Therefore, each
fiber should be assessed on its own toxicolog-
ical properties.
37.5.3 SOLVENTS
Solvents are used in many aspects of compos-
ites manufacturing, from resin formulation to
clean-up activities. There are several groups of
836 Safety and health issues

Table 37.10 Health effects of solvents

Solvents CAS Known health effects Key notes

nurnber(s)
Ketones Mild to moderate skin irritant; moderate to
severe eye irritant; if overexposure by
inhalation, possible central nervous system
(CNS) depression.
1. Acetone 67-64-1 Irritation of mucous membranes; headache,
2-propanone, DMK nausea. Skin contact can cause defatting,
dermatitis. Systemic effects only d e r repeated
overexposure. If ingested, vomiting may cause
acute chemical pneumonitis (lung damage).
2. Methyl ethyl 78-93-3 Few ill effects have been reported.
ketone, MEK Objectionable odor is reported. MEK has an
2-butanone odor threshold of 0.25-25 ppm. Eye, nose
and throat irritation at greater than 200 ppm.
3. Methyl isobutyl 108-10-1 Moderate to severe eye irritation; slight to PEL-TWA of 100 pprn and
ketone, MIBK moderate skin irritation; toxic by ingestion and TLV-TWA of 50 pprn and TLV.
dermal exposure; may cause CNS depression. STEL of 75 ppm.
Overexposure may cause kidney and liver effects.
Chlorinated solvents Exposure to high concentrations can cause cardi-
ovascular effects (sensitizationof the cardiac
muscle); CNS depression; chronic animal
exposures have caused liver and kidney changes.
1. Methylene chloride 75-09-2 Vapors below TLV levels; no adverse health
Dichloromethane responses expected; overexposures may cause
possible respiratory irritation due to vapors
which could lead to delayed pulmonary edema
and CNS depression. Liquid may cause skin
and eye irritation.
2. l,l,l-trichloroethane 71-55-6 Drowsiness; overexposures can cause CNS
Methyl chloroform depression which could lead to respiratory
arrest; animal studies indicate possible liver
and kidney damage.
Other solvents
1. Dimethylformamide, 68-12-2 Irritating to the skin, eyes and mucous
DMF membranes; stomach pain and cramps; nausea
and vomiting; DMF is readily absorbed through
the skin and may aid in absorption of other
materials; possible link to testicular cancer.
2.- N-Methylpymoli- 872-50-4 Severe dermatitis possible; irritating to skin,
done, NMP severe eye irritant; inhalation of high concen-
trations can cause headaches, giddiness, mental
confusion, nausea, gastric upset, and vomiting;
eye irritation.
PEL-TWA of 1000 pprn and TLV-
TWA of 500 ppm. ACGIH
indicates a TLV-STEL of 750 ppm.
PEL and TLV-TWA of 200 pprn
and TLV-STEL of 300 ppm. At the
TLV, workers complain of odor,
but few ill effects have been
reported.
TLV-TWA of 50 ppm, A2.PEL-
TWA at 25 ppm, PEL-STEL of
125 ppm. Possible human
carcinogen. IARC Group 28, NTP
Group 2.
PEL and TLV-TWA of 350 pprn
and TLV-STEL of 450 ppm.
MOSH has a recommended
exposure limit of 350 pprn as a
15 minute ceiling.
Possible human carcinogen (IARC,
Group 2B) PEL and TLV-TWA of
10 pprn (skin).A lethal single oral
dose of DMF for humans is
estimated to be 10 g.
Maximum airborne levels not
established. Manufacturers
suggest a TWA limit of
10-100 ppm (vapor), TWA of
5 mg/m3 (mist).

solvents, ketones and chlorinated, which have
dominated the industry. Known health effects
of major solvents are outlined in Table 37.10.
With increased concern for safety, health
and environmental impacts of solvents in the
workplace, the use of solvents is decreasing
and exposures are being minimized. When
choosing a solvent, make certain that regula-
tory investigation is done to avoid
unnecessary rework. It is possible that a sol-
vent of choice may become obsolete due to
emission regulations or toxicity concerns.
37.6 CONCLUSION
Every industry or business has hazards. The
maturity of the industry, its products, and his-
tory are all factors in what the hazards or risks
are and how they are controlled.
There are known potential health and safety
hazards in the composites industry, even
though it is a young technology compared to
mature ones such as steel. As the composites
industry develops, processes may change and
more specific health and safety issues may be
identified. Until then, each composite user has
the opportunity to implement the National
Safety Council’s ’engineering, education and
Although safe and healthful working conditions can be
justified on a cold dollars-and-cents basis, I prefer to
justify them on the basic principle that it is the right
thing to do. In discussing safety in industrial
operations, I have often heard it stated that the cost of
adequate health and safety measures would be
prohibitive and that ‘we can’t afford it.’
My answer to that is quite simple and quite direct. It is
this: ‘If we can’t afford safety, we can‘t afford to be in
business.’
Admiral Ben Moreell
President
Jones and Laughlin Steel Corp., 1948
Fig. 37.8 Safety philosophy (Laing and Schmidt,
1992). Used by permission of the National Safety
Council, Itasca, Illinois.
References 837
enforcement’ safety philosophy to control haz-
ards. This encompasses all the workplace tools
and techniques discussed.
Safety, encompassing health, should be
treated as a value. It is not a priority to be
raised or lowered with business cycles or man-
agement changes. It should be a constant
philosophy exhibited each day (Fig. 37.8). If it
is a value in the composites industry, then the
technology of composite materials can
develop naturally, without unnecessary hin-
drances impeding growth.
REFERENCES
American Conference of Governmental Industrial
Hygienists. 1997. 1997 TLVs@ and BEIS@,
Threshold Limit Valuesfor Chemical Substances and
Physical Agents, Biological Exposure Indices.
ACGIH.
International Agency for Research on Cancer, World
Health Organization. 1997. IARC Monographs on
the Evaluation of Carcinogenic Risks to Humans.
Vol. 68. IARC.
Laing, Schmidt. 1992.Accident Prevention Manual for
Business G. Industry, Administration G. Programs,
10th Edition. National Safety Council.
Laing, Schmidt. 1992.Accident Prevention Manual for
Business t3 Indust y, Engineering G. Technology,
10th Edition. National Safety Council.
OSHA Instruction CPL 2-2.20B CH-2. 1993. Polymer
Matrix Materials: Advanced Composites, Chapter
16. OSHA.
Plog, Benjamin, Kerwin, Schonfeld. 1988.
Fundamentals of Industrial Hygiene, Third
Edition. National Safety Council.
Suppliers of Advanced Composite Materials
Association. 1996. Safe Handling of Advanced
Composite Materials, Third Edition. SACMA.
Suppliers of Advanced Composite Materials
Association. 1990. Save Your Skin! A Guide to the
Prevention of Dermatitis. SACMA.
ACKNOWLEDGEMENT
Thanks and appreciation to the chemists,
industrial hygienists, toxicologists, and safety
professionals in the composite industry, par-
ticularly those in SACMA’s Environmental,
Safety, and Health Committee.
NONDESTRUCTIVE EVALUATION METHODS 38
FOR COMPOSITES
Thomas S. Jones
38.1 INTRODUCTION
The development and selection of nondestruc-
tive evaluation (NDE) techniques for
application to composite materials and struc-
tures presents several challenges and
considerations that are quite distinct from the
considerations given to the similar processes
for metallic materials and structures. A princi-
pal consideration is the nature of advanced
composites as typically layered, anisotropic
materials. The materials of interest include
fiber-reinforced plastics such as 'fiberglass' and
carbon epoxy, as well as some of the more
exotic materials such as metal-matrix or
ceramic matrix composites. In some cases, nat-
urally occurring composites, such as wood,
with its mix of differing density summer and
winter growth rings and fibrous structure, may
be treated with approaches similar to those
used for the man-made composites.The advan-
tages offered by composites are focused on the
high strength, low weight properties of typical
constituent materials. Yet, if the materials are to
exhibit high strength, they must be manufac-
tured as the designer envisioned and they must
maintain their integrity in service. N D E pre-
sents a technology to help assure the reliability
of the materials.
Inhomogeneities that may affect the perfor-
mance of a composite include the concentration
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
of constituents (fiber-resin ratio, resin-starva-
tion, etc.), orientation and distribution of
reinforcement, voids, matrix-reinforcement
bonding and similar characteristics. The pur-
pose of the NDE is to detect these
inhomogeneities and others, including foreign
material, fiber breakage, degradation due to
moisture, ultraviolet (W)or other reasons,
cracks, abrasion, impact damage, fire or exces-
sive heat, etc. This chapter describes many
N D E methods that can be used to detect anom-
alies in composite materials during
manufacture and in-service.
Although composite materials have been in
use on military aircraft for many years, the last
few years have seen a rapid escalation in both
the number and structural criticality of com-
posite applications entering service. The
falling price of composite raw materials has
vastly increased the number of applications in
non-aerospace industries, including automo-
tive, sports, boating and construction. While
the service record for composites has been
excellent, they are subject to damage from
sources such as overload, hail, lightning, low
velocity impact, ballistic rounds and moisture
intrusion. Low strain designs, coupled with
less critical applications, have made for rela-
tively large acceptable flaw sizes and lax
inspection criteria. As composite structures
representing a more aggressive design criteria
and less tolerant materials (such as some of the
ceramic matrix materials) begin to accumulate
service hours, we will see a new level of

demands placed on nondestructive inspection
techniques to support the in-service mainte-
nance and repair requirements for composites.
Several a ~ t h o r s l -have
~ reviewed a variety
of nondestructive methods applicable to the
evaluation of composites. Several of these
methods have, so far, been suitable only for
laboratory applications. Some of these inspec-
tion methods are adaptations of inspection
techniques that have been used for the evalua-
tion of metallic components for years'O. New
methods are being developed to address the
special needs of composite materials. Many
inspection approaches have been automated
for production applications; but in-service
inspection of composites is frequently per-
formed using conventional manual inspection
equipment. Inspection times with manual
approaches can be long, but more significantly,
interpretation of the inspection results may
require special training or familiarization for
the inspectors. The long inspection times may
restrict inspections to local areas based on crit-
icality, loading, or suspicious areas detected by
visual inspections.
In recent years, there have been quite a few
government sponsored research programs
directed at the development of new nonde-
structive inspection systems providing high
throughput for the increasing volume of com-
posite structures in service and/or providing
some level of advanced signal analysis which
will aid in the recognition and mapping of
flaws. As an example, a recent research pro-
gram resulted in the development of a
computer-controlled ultrasonic scanning sys-
tem for field applicationsll. In this article the
capabilities and limitations of some of these
typical inspection approaches are considered.
38.2 VISUAL INSPECTION
Some translucent composites can be
inspected by transmitted light.
Inhomogeneities such as voids, delamina-
tions or inclusions can be detected by this
straightforward approach in materials such
Visual inspection 839
as nonpigmented glass reinforced plastic
(GIG'). Stress whitening in GRP, which results
in a loss in optical transparency, may result
from fiber-resin debonding or resin cracking.
Another visual inspection approach, which
has been considered for the detection of impact
damage, is to paint the composite surfaces with
a paint containing micro-encapsulated dye.
When crushed by the impact, the dye is
released and reveals the location of the impact.
Dyes can be formulated either for visual obser-
vation of a color change or using UV excited
fluorescence in the dye. This method provides
good indications to locate suspicious areas for
further inspection so that the extent of the
impact damage can be determined.
Visual aids, such as magnifiers, borescopes,
television cameras, etc., can be used to
enhance the detectability of surface-related
damage. Small diameter, flexible borescopes
permit the inspection of inaccessible areas
without teardown of components.
The most common visual inspection is
exemplified by the typical walk-around visual
inspection of aircraft. These inspections cer-
tainly apply to much of the composite
structures currently in use. Many of the more
severe conditions associated with composites
are visually detectable. Punctures, surface ply
delaminations, scratches, gouges and heat
damage can frequently be detected by visual
inspection. Disbonds between a composite
skin and some substructure may also be
detectable in some cases as a blister in the skin,
an edge separation, or a distortion in the
geometry of the component. This inspection is
clearly valuable, but one cannot expect to
detect all of the forms of damage which may
be present in a composite structure. Further, if
damage is detected, it is important that other
tools are used to assess the extent of the dam-
age, since the subsurface damage may
drastically exceed the surface detectable dam-
age. One common example is low velocity
impact damage. S t u d i e ~ l ~on
, ' ~this form of
damage, which may result from hail, runway
debris, or ground handling abuse, have shown
840 Nondestructive evaluation methods for composites
that substantial subsurface damage can result
with little or no surface detectable condition.
38.3 TAPTEST
The tap test method, using either a coin or a
special tap hammer continues to be a common
in-service inspection tool despite the avail-
ability of less subjective inspection tools. The
use of this method has persisted for several
reasons. The most obvious is that it does not
require sophisticated or expensive equipment.
Another is that many of the composites in use
consist of thin laminates in low strain designs.
This combination yields critical flaw geome-
tries which are fairly large and close to the
surface, two conditions necessary to the suc-
cessful use of the tap method. Under these
conditions, the tap method can be a useful
tool for the detection of problems in relatively
large areas of laminate, particularly where the
substructure of the tested skin is relatively
consistent. The tap test method is sensitive
only to laminar type flaws, such as delamina-
tions or unbonds, and relies on the different
acoustic resonance of the loose upper layer
compared to the surrounding material. The
tap method suffers from subjective interpreta-
tion (particularly with complex geometries),
variable application, declining sensitivity
with flaw depth and an inability to calibrate
effectively for either flaw size or depth. The
more recent applications of composites in
thicker laminates and more highly loaded
designs make this approach inadequate in
many cases.
Several attempts have been made to instru-
ment the tap test by providing a machine-type
tapper and instrumentation to interpret the
signals. The mechanical tappers offer the
advantage of improved repeatability in terms
of tap impact and location. The instrumenta-
tion developed centered on spectral analysis
of the detected audio signals. These instru-
mented tappers have not made a significant
impact on the composite NDE instrument
market. They suffer from many of the same
disadvantages as manual tapping with the
additional disadvantage of increased cost.
38.4 ULTRASONIC METHODS
38.4.1 ULTRASONIC THROUGH-
TRANSMISSION TESTING
Ultrasonic inspection makes use of €ugh fre-
quency (above 20 kHz) mechanical vibrations.
Typical ultrasonic frequencies for inspection of
composite materials are in the megahertz
range. Ultrasonic signal strength in a material
is reduced both by attenuation and by reflec-
tions from interfaces. Large reflection signals
are obtained when ultrasound is directed from
one medium to another with the two media
having very different acoustic impedances.
For example, more that 99.9% of an ultrasonic
wave is reflected from a metal-air interface as
might be encountered with a crack in a metal.
The ultrasonic signal is typically introduced in
a pulsed mode. The inspection geometry can
be through-transmission, with the receiver ’lis-
tening’ for the ultrasonic pulse on the opposite
side of the component from the transmitter, or
a one-sided pulse-echo test, in which a single
transducer first transmits a pulse and then ‘lis-
tens’ for the reflections of that pulse from the
interfaces of the inspection object.
Ultrasonic through-transmission test sys-
tems measure the signal strength of a pulse of
ultrasonic energy transmitted through the
structure or material under test. Locations
where there may be a delamination or a for-
eign material, for example, will show a
reduced exit ultrasonic intensity. This test
approach is probably the most commonly
used production inspection method for com-
posite structures. It is relatively easily
automated, provides approximately constant
sensitivity to flaws, regardless of their depth
within the structure and is fairly easy to inter-
pret. Sophisticated computer controlled
inspection systems, such as the McDonnell
Douglas Automated Ultrasonic Scanning
System (AUSS)14, shown in Fig. 38.1, are
 Ultrasonic methods 841

Fig. 38.1 McDonnell Douglas AUSS ultrasonic system.

common in aircraft production facilities. These mated systems is usually not available for field
systems scan the composite component while inspection. This is, however, changing. Many
collecting and recording the ultrasonic pulse
transmission amplitude. The method is sensi-
tive to most flaws which are planar in nature
and lie roughly parallel to the surface. Since
I

.
,
+
, ,
1
.. , , .- -, .
.
,
of the military depot inspection facilities now

.
I

I
8 4 -
, -,
I

this describes most of the common flaw types

for layered composite structures, the method
is very appropriate. Where automated testing
systems are used, the test can be performed
very efficiently and can yield a recording, or
map of the inspection results, called a C-scan.
An example of a through-transmission C-scan
showing a delamination caused by a foreign
material inclusion is shown in Fig. 38.2.
Generally, the method requires access to
both sides of the part and alignment of ultra-
sonic search units on opposite sides of the
part. These factors drastically restrict the use-
fulness of this approach for in-service
inspection, since in many cases, access to both
sides is not available or not practical. Further, Fig. 38.2 Computerized through-transmission
the speed and recording advantages of auto- C-scan showing foreign material.
842 Nondestructive evaluation methodsfor composites

have automated ultrasonic inspection systems

for composite inspections. Further, inspection
systems such as the Automated Real-time
Inspection System (ARIS)15provide a semiau-
tomated through-transmission inspection and
data recording capability for some on-aircraft
inspections. A 9 kg (20 lb) yoke provides the
mechanism to place an ultrasonic transducer
on either side of the field inspection object.
One-sided pulse-echo testing can also be
accomplished.

38.4.2 ULTRASONIC PULSE-ECHO TESTING

The ultrasonic pulseecho inspection approach Fig. 38.3 McDonnell Douglas LACIS portable ultra-
sonic scanner.
typically uses a single search unit as both the
transmitter and receiver. The approach
C-scan shown in Fig. 38.4 shows the multiple
requires access to only one side of a material or
delaminations associated with impact dam-
structure to be tested. Flaws are detected by
age. In this scan, the delaminations show as
monitoring the time of arrival and/or the sig-
gray to black areas in which the darkness of
nal strength of returning echoes.
the indication reveals its depth. The darker
Delaminations cause the returning echo to
indications are closer to the surface. The foot-
arrive prior to its expected travel time from the
ball shaped delamination of the far surface ply
round trip from the front surface to far surface
is seen as a gray shape only slightly darker
and back to front surface. This method is com-
than the normal background thickness.
monly used for in-situ inspection since the
The pulse-echo method is also advanta-
single transducer approach usually makes it
geous in that it offers increased sensitivity to
simpler to apply in a manual test. On the other
foreign material inclusions associated with the
hand, the more complex signal patterns and
manufacturing process for laminated compos-
more critical sound entry angle, make this test
ites. Many expendable paper and plastic
more difficult to automate than the through-
materials are used in handling and transporting
transmission test. Even so, computer
automated pulse-echo inspection systems
have gained popularity in recent years.
An example is the Large Area Composite
Inspection System (LACIS). This semiauto-
mated pulse-echo inspection system is useful
for in-service inspection of composites. The
LACISll (Fig. 38.3) uses a reciprocating arm
holding two to four transducers to perform
pulse-echo inspection of large composite com-
ponents quickly. Inspection speeds in excess of
9.3 m2/h (100 fP/h) have been reported with
this hand-held scanning device.
An advantage to the pulse-echo systems is
that flaws at multiple depths can be distin- Fig. 38.4 pulse-echo time-of-flight C-scan showing
guished from one another. The pulse-echo impact damage.

uncured composite materials. These materials
have at times found their way into a compos-
ite laminate and are cured in place. Some of
the plastic materials are particularly problem-
atic in that they may bond into the laminate
and go undetected by the through-transmis-
sion inspection. Fortunately, however, most of
these materials offer a reflected signal strength
sufficient to be detected by pulse-echo ultra-
sonics.
38.4.3 ULTRASONIC POLAR BACKSCATTER
This inspection approach makes use of slightly
angled ultrasonic beams to detect flaws in
composite materials. The angle orientation fre-
quently allows one to associate flaws with a
particular ply orientation. The method is par-
ticularly useful for characterizing matrix
cracking within the composite plies. It is also
sensitive to linear voids or porosity. It has been
successfully used"j to characterize the various
levels of damage in impacted laminates. The
approach has also been used to measure direc-
tional velocity variations and elastic properties
in composite^'^. From these measurements, the
anisotropic elastic properties can be calcu-
lated. At the current time, this inspection
method remains primarily a laboratory tool.
The angulating mechanism would be some-
what difficult to manipulate and control in the
field and the inspection times can get long,
since multiple scans at a variety of orientations
are required. Further, the composite designs
currently in use have not required the detailed
level of inspection provided by this method.
38.4.4 ULTRASONIC RESONANCE
This one-sided ultrasonic inspection method
detects laminar discontinuities within com-
posites or bonded structures by setting up a
continuous ultrasonic wave within the mater-
ial and sensing the mechanical stiffness, or
impedance of the material. A delamination or
disbond reduces the surface normal stiffness
of the material and this, in turn, reduces the
Ultrasonic methods 843
surface loading on the ultrasonic probeI8.This
can be seen as a phase, amplitude, or resonant
frequency shift in the ultrasonic element. This
method is particularly useful in complex
bonded structures where access limitations
restrict the use of ultrasonic through-transmis-
sion testing and the complex internal
reflections make pulse-echo signals difficult
or impossible to interpret.
38.4.5 ULTRASONIC CORRELATION
Ultrasonic correlation offers a novel approach
to the ultrasonic inspection of highly attenua-
tive materials19. It has proven effective in the
evaluation of some of these materials where
conventional pulsed ultrasonic systems have
experienced difficulties in penetrating the
material. The correlation approach achieves
this increased sensitivity using a continuous
wave, cross-correlation technique which
enhances the sensitivity of the test but sacrifices
inspection speed. A block diagram of a continu-
ous wave correlator is shown in Fig. 38.5.
The principal advantage of the correlator is
that it provides substantial enhancements in
the signal-to-noise (S/N) ratio of the ultra-
sonic signals. This S/N enhancement is
achieved through a modification of the time
scale required to produce an A-scan trace.
Since the correlator uses continuous genera-
tion and accumulation of the ultrasonic
signals, the maximum possible efficiency of
data accumulation can occur. The S / N
enhancement allows the correlator to produce
usable A-scan traces where conventional
pulsed ultrasonic systems are unable to pro-
duce a recognizable pattern.
For example, the correlator has been used to
characterize polytetrafluoroethylene (PTFE,
Teflon@),a material very difficult to penetrate
with conventional ultrasonic techniques. The
results have been obtained by measuring
ultrasonic velocity as the temperature of the
PTFE sample changed. Figure 38.6 shows a
velocity versus. temperature profile with an
excellent indication of a change in the slope of
844 Nondestructive evaluation methods for composites
7

Transmit
Test
Noise Specimen

I I

Fig. 38.5 Block diagram of ultrasonic correlator.

the curve at the phase transition temperature 38.5 X-RADIOLOGY

of 30°C. The correlator has been shown effec-
tive for the inspection of thick and highly
attenuative composites. Effective signals have
also been obtained through over 30 cm
(11.8in) of cured wood and through
wood/plastic laminates, such as countertops.
1340
X-ray imaging relies on the differential absorp-
tion or scattering of the X-ray photons as they
pass through a material. Flaws which either
allow more X-ray photons to pass or which
absorb or scatter the photons can be imaged if
the effect is significant. X-ray inspection sys-
tems are usually sensitive to changes which
result in an apparent change of at least 1-2% of
the material thickness or density. Composite

i
1
flaws tend to lie between plies and present a
1320
1300 very small apparent thickness change, particu-
Velocity larly for thick laminates. However, the low
(dS) i280 density of most composite materials permits
1260 the use of low energy X-rays which help to
1240 enhance the sensitivity*O.X-rays can be used to
detect porosity and matrix cracks as well as
1220 I
20 25 30 35 40
some foreign materials. More highly loaded
Temperature ('C)
applications and/or the use of more brittle
matrix materials, both of which seem to be on
Fig. 38.6 Ultrasonic velocity transition in PTFE the horizon, will make the detection of some of
measured with correlator. these conditions much more critical than they

are today. While carbon fibers are not gener-
ally imaged by X-rays, boron and silicon
carbide fibers are typically deposited on a
tungsten filament and this filament can be
imaged in X-radiographs. This allows one to
detect fiber fractures and determine fiber ori-
entations and placements, so long as the
number of plies does not get too large.
X-radiography is particularly useful for the
detection of honeycomb core defects in
bonded sandwich assemblies. The low density
and thin composite skins usually provide min-
imal interference for the X-rays to image the
honeycomb core materials. Core defects such
as blown core, crushed core, condensed core,
fatigued, corroded or cut core and foaming
adhesive voids can be detected by radi-
ographic methods. It is also frequently
possible to detect water intrusion into the hon-
eycomb core using X-ray methods.
Significant progress has been made in
recent years in the use of non-film electronic
imaging systems for X-rays. These systems
allow the real time viewing of X-ray images
and can drastically reduce the demand for X-
ray film. While video imaging systems do not
Fig. 38.7 Microfocus X-radiograph of honeycomb cell showing onset of damage.
X-radiology 845
typically possess the resolution of X-ray films,
the use of very small X-ray sources and geo-
metric magnification techniques have
permitted the recovery of much of this sensi-
tivity. Figure 38.7 shows a magnified image of
a honeycomb core area. This 'bee's eye view'
of the honeycomb core reveals the onset of
damage in the cell wall. In practice, one must
find a suitable compromise between spatial
resolution and area of coverage. The cost
advantages of this approach have made it very
attractive. Many military aircraft maintenance
facilities either have or are acquiring real-time
X-ray inspection equipment.
38.5.1 X-RAY BACKSCATTER IMAGING
Conventional radiographic inspection tech-
niques rely on the attenuation of a beam of
penetrating radiation to form an image of a
part. At low X-ray photon energies typically
used with composites, a large portion of that
attenuation is due to Compton scattering. This
suggests the use of scattered radiation to ana-
lyze the inspection object. One approach
utilizing a novel, X-ray backscatter camera
846 Nondestructive evaluation methods for composites

Lamina insulator and a rubber liner, as shown in Fig.

38.9(a).Figure 38.9(b) is the X-ray backscatter
inspection result for a single location. The
illustration shows the relative X-ray backscat-
ter intensity versus thickness of the inspection
sample; depth through the sample can be cor-
related with detector number. Region A
represents the near-surface graphite-epoxy
region. The sharp dip in response at B repre-
sents the decreased X-ray backscatter intensity
typical of an air gap or delamination. The insu-
lator response is given in region C; note the
differing response slope for this lower density
material, as compared to the response for the
second graphite-epoxy layer shown in region
D. The response from the rubber deeper in the
Fig. 38.8 X-ray backscatter system geometry.
assembly is shown in region E.
The X-ray backscatter signal contains quan-
employing a slot instead of the more common titative information about variations in
pin-hole approach has been developedz1.This density as caused by changes in material or
technique is illustrated in Fig. 38.8. The delaminations and the location of such varia-
backscattered X-rays are detected by an array tions within the depth of the material. These
of scintillation detectors. The backscatter characteristics, coupled with the one-sided
intensity information is obtained as a function inspection feature, represent advantages for
the inspection of composite assemblies.
of detector position; this in turn, relates to dif-
ferent depths in the inspection object. One
interrogates the entire object thickness at one
38.5.2 COMPUTED TOMOGRAPHY
time (composite structures as thick as 7cm
(2.7 in) have been inspected). The inspection Tomographic inspection systems, developed
results provide indications of material density originally for medical diagnostics, have been
changes by a change in the slope of the inten- further developed for applications in the
sity/position graph and of voids or foreign industrial inspection A tomographic
material by an abrupt change in backscatter image looks like a slice taken across the
intensity. The inspection method is particu- inspection object. A collimated single pencil
larly useful for the inspection of laminated beam or a flat fan beam of X-rays is directed at
structures such as pressure vessels and rocket the sample. The sample is shifted and rotated
motor cases. In some of these designs, ultra- relative to the X-ray beam while the X-ray
sonic inspection approaches are ineffective or beam intensity is measured by individual
impractical and the backscatter X-ray imaging detectors (typically arrays of detectors) at each
approach offers a potential solution. Tight position and rotation. The measurements per-
delaminations, with gaps less than 50 p m in mit a computer reconstruction of a density
width, can be detected. map of the inspection object. One advantage of
An example of an X-ray backscatter inspec- tomographic inspection is the extremely good
tion is shown in Fig. 38.9. The sample was a contrast sensitivity; variations of less than
graphite-epoxy composite structure as used in 0.1% are detectable. The major advantage of
a rocket motor case. The assembly included computed tomography is that the resultant
several layers of graphite epoxy composite, an image shows all the variations across the
 X-radiology 847

BACKSCATTER
INCIDENT X-RAYS
X-RAYS

GRAPHITE
EPOXY

r
(4

98.

54.

43.

32.

21.

IO. 1111
1 2 3 4 5 8 7 8 9 10 11 12 13 14 15 18 17 18 I9 20
(b)
D€ECTORNWBW

Fig. 38.9 X-ray backscatter examination results (a) composite sample configuration and (b) system
response.

image slice in the true three-dimensional per-
spective. A typical radiograph is a
two-dimensional projection of a three-dimen-
sional object. The tomographic result retains
the three-dimensional nature of the image. A
computed tomography image of a tree, for
example, would appear similar to the visual
image if one sawed through the tree at one
location. The tomographic image would show
the differing density of summer and winter
growth and the presence of knots, voids, etc.
For composites, tomography offers similar
advantages. The tomographic image shown in
Fig. 38.10 shows variations in density across
the width of the composite material.
38.5.3 NEUTRON RADIOGRAPHY
X-rays are attenuated as a function of the den-
sity of the material through which they pass. If
X-ray attenuation is plotted as a function of
increasing atomic weight of the attenuating
848 Nondestructive evaluation methods for composites

radiography. Recent advances in moderating

and collimating accelerator fast neutron beams
. .'
,
1
,
have led to significant improvements in
I portable system thermal neutron beamsz6.A
typical thermal neutron image of a composite
structure, as obtained with the transportable
inspection system shown earlier, is shown in

I
ap
Fig. 38.10 Computed tomogram of graphite silica
composite tube.

material, one finds a monotonically increasing

function. The attenuation of thermal neu-
trons", plotted similarly, shows a generally
random pattern in which there is high attenu-
ation for several light materials, hydrogen,
boron and lithium in particular and relatively
low attenuation for most For bonded Fig. 38.11 Photograph of transportable thermal
structures, the high sensitivity of neutrons to neutron radiographic system.
hydrogen means that thermal neutron radiog-
raphy can display images of adhesives, water,
or corrosion in a metal bonded assembly more
readily than X-ray techniques. For composites,
neutron techniques offer promise for the
detection of variations in the organic matrix
materials and moisture take-up.
Advances in transportable neutron sources
have been made including source systems for
depot and field inspections. A photograph of
one system= is shown in Fig. 38.11. The neu- '
tron source is a Cockroft-Walton accelerator
that produces neutrons by accelerating
deuterons on a tritium target, a D-T reaction
that produces neutrons of about 14Mev in
energy. These neutrons are slowed, or moder-
I
ated, in a low atomic number assembly and Fig. 38.12 Thermal neutron radiograph of a bonded
collimated into a beam for thermal neutron fiberglass-epoxy structure.
 Eddy current testing 849

A major neutron radiographic facility for One area where acoustic emission testing has
the inspection of military aircraft has been found acceptance is in the detection of mois-
installed at McClellan Air Force Base. A ture and corrosion in honeycomb assemblies.
maneuverable, crane-based system permits If an aluminum honeycomb assembly contain-
near real-time neutron inspection of wing and ing water is locally heated in the vicinity of the
empennage assemblies on the aircraft. Film water, the increased vapor pressure will force
techniques are used to inspect lower doors. the water to move through the leakage path
These on-aircraft inspection systems employ along which it entered the honeycomb cell.
the radioisotope 252Cfas the neutron source. The motion of the water through the leakage
The system has emphasized the inspection of path can be detected using acoustic emission
metal bonded assemblies to detect water intru- equipment.
sion and corrosion damage. A nuclear reactor
facility is available at this facility to inspect
38.7 ACOUSTO-ULTRASONICS
components removed from the aircraft.
Consideration is being given to replacement of The acousto-ultrasonic, or stress wave factor,
the californium source with an accelerator test method uses an ultrasonic transducer to
source of neutrons. inject a simulated acoustic emission pulse into
the material under test. The wave form of the
pulse is then monitored a fixed distance away
38.6 ACOUSTIC EMISSION
with an acoustic emission transducer. Damage
Acoustic emission testing involves the detec- to the material will affect the manner in which
tion of elastic energy that is spontaneously the wave is transmitted through the materialz8.
released by materials when they undergo The stress wave factor will be affected most by
deformationz7.For example, when a piece of discontinuities which impede the motion of
wood is stressed, audible cracking noises can the stress wave through the material. The
be detected just before the wood breaks. The method can be applied in a through transmis-
same phenomena occurs in other materials, sion mode, but is generally used with both
including composites. The detected signals are transducers on the same side of the part; one
frequently in the ultrasonic rather than audi- monitors the transmission of signals parallel to
ble region. the surface. In this mode the method is most
Acoustic emission testing monitors the sensitive to matrix cracking and laminate
material under test for spontaneous noise gen- porosity. It is also sensitive to fiber breakage
erated under load. It has been used extensively and, particularly in the through transmission
in the proof testing of fiberglass pressure ves- mode, delaminations. The method has suf-
sels and beams. It has also been used to fered from problems in obtaining consistent
monitor and characterize damage growth results. Some of these problems have been
mechanisms in composites under cyclic load- solved or reduced and the method shows
ing. Acoustic emission testing is capable of potential for evaluating the severity of matrix
detecting and characterizing matrix cracking, degradation in composites. One approach has
delamination and fiber breakagez7.It is used been to use completely non-contact generation
extensively in the testing of composite pressure and detection of the signalsz9.
vessels and in the evaluation of some struc-
tures, such as 'cherry picker' booms; however,
38.8 EDDY CURRENT TESTING
the method has not found particular applica-
tion in the aircraft inspection arena for these Eddy current methods rely on the principles of
flaws. This may be partly due to the need to magnetic induction to interrogate a material
have the component under load during testing. under test?. Current loops, or eddy currents,
850 Nondestructive evaluation methods for composites

are induced in a conducting material by a vary- (T = Stefan-Boltzmann constant = 5.7 x lo4

ing magnetic field. While most resin matrix (W/m2K4)
materials are very poor electrical conductors, T = absolute temperature, degrees Kelvin
some of the carbon fibers are relatively good
conductors. In order to form current loops, The emittance in a particular differential
multiple fibers must make electrical contact wavelength band is governed by the Planck
with one another at various places along the distribution criterion. Important criteria for
practical infrared imaging are the spectrum of
length. Fortunately, the use of carbon fiber tows
of 3000 to 10000 fibers or more clearly pro- the emitted energy and the wavelength of
motes this. Eddy currents can then be used to maximum emittance. These are given by the
monitor fiber orientation since the current single temperature evaluation of Planck's Law
loops are not circular, but greatly elongated and Wien's Displacement Law, respectively.
Figure 38.13 shows a family of such energy
along the fiber direction. Eddy currents can also
be used to detect fiber breakage. Eddy current distribution curves. For the practical case of a
techniques have been demonstrated to provide body at a temperature of 25°C (77"F, approxi-
effective results for many of the damage mech- mately room temperature), the wavelength
anisms, including impact damage and fatigue range of peak emission is in the range
damage, in carbon fiber composite^^^. Even so, 9 - l o p . This turns out to be a very useful
eddy current techniques have not received a wavelength range. Various components of our
great deal of acceptance to date for productionatmosphere, notably water, absorb a great deal
or in service inspection of composites. of the emitted infrared energy. However, there
are two fairly transparent windows through
the atmosphere: one between 3-5 p and the
38.9 INFRARED THERMAL TESTING other at about 8-14 p.Specific infrared
Infrared thermography has been gaining detector elements have been developed which
rapidly increasing acceptance as a nondestruc- respond well to each of these wavelength
tive evaluation tool for composite (as well as bands. As seen in Fig. 38.13, the intensity of
many other) structures. All bodies above the infrared emittance within such a band can be
temperature of absolute zero emit electromag- used to indicate the temperature of the object
netic radiation by virtue of the motion of the surf ace.
constituent atoms. The spectrum and intensity
of the radiation depend on the temperature 0.0005 -

and nature of the surface. When a surface is -T=50 'C

heated, there is an increase in energy of the 0 . m.
atomic particles leading to a corresponding
increase in temperature and emitted f 0.0003-
en erg^^^,^^. The wavelength-independent rate -e
of emission of radiant energy per unit area is m
-
governed by the Stefan-Boltzmann law: I o.ooo2
w = &UT4 o.ooo1-

where: 07
0 2 4 0 8 10 12 14 I0 18
W = rate of emission, radiant energy per unit Wavelength (pm)
area
E = emissivity (ratio of emittance of the sur- Fig. 38.13 Spectral radiant emittance distribution at
face relative to a black body) three surface temperatures.

Typical thermographic applications involve
the introduction of a controlled thermal load
on the object of interest. Variations in the ther-
modynamic properties of the object then
produce surface temperature patterns which
can be detected with an infrared imaging sys-
tem. Composite materials typically offer an
excellent combination of thermal properties
for the useful application of infrared thermog-
raphy.
Thermographic methods have been used to
display object temperature differences for a
variety of inspection applications. Many of the
inspection systems provide a television-type
image display. Typical sensitivityof the instru-
ments under ideal conditions is 0.1"C (0.2"F).
Thermal patterns can be produced by heating
the inspection surface and monitoring the sur-
face of the part for relatively hot spots caused
by the blockage of the thermal flow away from
the surface by a laminar flaw. This method is
particularly sensitive to flaws near the inspec-
tion surface; the sensitivity reduces rapidly
with flaw depth3. The thermal images can also
be produced by heating the far side of the
object and monitoring the surface for cold
spots where the heat flow toward the inspec-
tion surface in impeded by the flaw. This
'through-transmission' approach somewhat
improves the depth sensitivity, but the method
is still more sensitive to near side flaws.
Impact damage often results in matrix dam-
age near the surface of a composite material.
Figure 38.14 shows an infrared image of an
impact damaged graphite epoxy composite
sample. The object was heated and imaged on
the same side. The diamond shaped indication
is typical of the delamination pattern pro-
duced in a cross-plied laminate. Infrared
thermography has been demonstrated to be an
effective tool for evaluating many glass fiber
composite structures used in marine applica-
ti0ns353.
Infrared thermography has been gaining
increased acceptance in recent years as a viable
nondestructive testing tool. A significant num-
ber of effective applications has been
Laser shearography/holography 851
Fig. 38.14 Thermogram of impact damage in
graphite epoxy composite.
developed for composite materials and struc-
tures. This increased acceptance has been
assisted by improvements in the infrared
imaging technology, development of
improved heat applications techniques and
significant efforts to model and understand
the heat flow characteristics in anisotropic
media. Effective applications have been identi-
fied for a wide range of materials and
applications. Thermography has been used for
aerospace laminates of graphite epoxy as well
as for marine applications of fiberglass up to
around 8 cm (3 in) thick. In many instances for
materials which are most difficult for more tra-
ditional nondestructive tests, such as
ultrasonics, infrared thermography has pro-
duced rapid, effective results. An example is
foam core fiberglass boat hull structures.
While this structure poses substantial difficul-
ties for ultrasonic techniques, infrared
thermography has produced rapid, effective
results5.
38.10 LASER SHEAROGRAPHY/
HOLOGRAPHY
A hologram is an interference pattern that can
be used to reconstruct the optical wavefront
that originally emanated (due to reflection or
transmission) from an object. The hologram is
852 Nondestructive evaluation methodsfor composites
formed by the superposition of two wave-
fronts, an object beam and a reference beam,
on a suitable recording material, such as pho-
tographic film.When properly illuminated by
the reference beam, an observer looking
through the developed hologram sees a virtual
image of the original object. When the real
object undergoes a small displacement over
part of the surface, due to stressing by thermal
or mechanical means, a variation in the rela-
tive phase of the wavefronts will be produced
and a fringe pattern can be observed. Laser
illuminationprovides the spatial and temporal
coherence in the light beam to permit the
observation of the fringe pattern, a technique
called holographic interferomeW7.An exam-
ple of a holographic interferometry inspection
of a composite tube to reveal impact damage is
shown in Fig. 38.15.
Laser interferometric holography tech-
niques were evaluated for composites testing
in the 1960s. In fact, several composites and
bonded assembly testing systems were con-
structed. In spite of the use of massive optical
Fig. 38.15 Holographic interferogram of impact damage in a composite tube.
benches and elaborate vibration isolation sys-
tems, however, the vibration problems of
working in a production environment (much
less an in-service environment) were not satis-
factorily solved. The holographic inspection
approach is sensitive to very small amounts of
relative motion in the part surface. Typically a
part is tested by taking an image of the part at
rest, then stressing the part surface, either with
a small amount of heat or a mild vacuum. This
light stressing causes the area of the surface
over the flaw to deform slightly more than the
surrounding material. Displacements as small
as one-quarter wavelength of the laser light
being used cause a fringe to appear in the
interference pattern. Unfortunately, unwanted
test object motion of an equally small ampli-
tude will also cause fringes. The development
of phase locked loop holographic systems has
gone a long way to eliminate the problems
associated with low frequency vibration.
Holographic inspection systems which use
video imaging systems and 'develop-in-place'
reference holograms are currently being used.
 Conclusions 853

Another development in the area of video

holographic systems, electronic shearography,
has recently provided even greater immunity
to test object vibration and motion problems,
making possible the rapid scanning of large
areas of composites on aircraft. Electronic
shearography uses no film and compares a
live video image with a stored video image to
produce interference fringes.
Conventional interferometric holography
interferes two holograms of a component to
produce the interference pattern. Each holo-
gram is produced by recording the speckle
interference between a coherent reference
beam and the coherent object beam which illu-
minates the surface of the test part. Fig. 38.16 Electronic shearography image of
Deformations between the two exposures pro- graphite*poxy/foam core panel with edge delam-
ination.
duce the interference fringes. Phase-locked
holography uses the same basic technique, but
38.11 MICROWAVE TESTING
uses the diffuse reflection of an unexpanded
coherent beam shone on a small portion of the The use of microwave energy to interrogate
test object as the reference beam. This and characterize composite materials has been
approach minimizes the influence of full sur- investigated for some years. Microwaves are
face motions, typical of environmental very sensitive to small changes in the dielectric
vibration and is sensitive to differential sur- properties of low conductivity composites,
face displacements typical of defect such as glass and aramid fiber composites.
indications. Microwave techniques have also been investi-
Shearographf8, on the other hand, uses no gated for applications to composites with
separate reference beam. Rather, the returning higher conductivity fibers such as graphite
object beam is doubly imaged, with one of the fibers. Successful results have been reported
images slightly shifted or 'sheared' relative to for the measurement of fiber content and ori-
the unshifted image. Thus, the interference entationgo, material thickness41and porosity
pattern does not reveal bulk surface motion, content42. To date microwave techniques
but only the degree of differential motion of remain largely laboratory tools and have not
the surface along the direction of the shearing. gained great acceptance as production evalua-
This makes shearography particularly well tion techniques. However, these techniques
suited to many production and depot environ- offer excellent sensitivity to conditions, such
ments because of its relative immunity to as matrix porosity and cure state of the matrix,
vibration problems39.An example of a shearo- that are difficult to establish by more conven-
graphic inspection is shown in Fig. 38.16. In tional nondestructive testing techniques.
this case the inspection object is a sandwich Increased applications for these techniques
panel consisting of graphite-epoxy laminate can be anticipated in the future.
skins and a foam core. The indication arises
from a delamination created by a pull-out in
38.12 CONCLUSIONS
the skin-to-core bondline. The side-by-side
pattern of concentric rings is characteristic of A wide variety of nondestructive testing tech-
the shearography technique. niques are applicable to the evaluation of
854 Nondestructive evaluation methodsfor composites

various composite structures. The selection of too cumbersome to apply. Delaminations in

the most appropriate test technique for a par-
ticular application can be a formidable task.
The nondestructive inspection methods most
widely used in industry for composite inspec-
tion, ultrasonics and radiography, have much
to recommend them in that many different
types of discontinuities can be detected and
characterized. Shearographic and infrared
inspection methods present the attractions of
noncontact, large area coverage and good sen-
sitivity to discontinuities close to the inspected
surface. These techniques are finding a rapidly
growing list of applications where the more
traditional tools encounter difficulties or are
the order of 1 cm (0.4 in) in size can usually be
detected by shearography and even smaller,
near-surface discontinuities can be detected by
infrared imaging. Both methods offer a televi-
sion image display which offers straight
forward interpretation. Both methods also
offer good sensitivity in low density material
systems which are frequently difficult to evalu-
ate using the more traditional techniques.
The overall summary of inspection methods
as related to composite inhomogeneities
includes many inspection methods. Table 38.1
provides a sorting approach that can be used
for the selection of inspection methods for par-

Table 38.1 Summary of applicability of NDE methods

Flaw Type
Porosity 1 1 2 2 1 1 1 2 2
Foreign material 3 2 1 2 2 2 2 2 2 2 2 3
Shallow delamination 2 1 1 2 1 1 1 1 3 2 1 1
Deep delamination 1 1 3 3 1 1 1 3 2 2
Matrix cracks 3 1 1 2 2 1 3 2
Fiber breaks 2 2 2 2 1 1
Impact damage 3 2 1 1 2 2 1 2 2 1 3 2 1 1 1 1
Skin/skin disbond 3 2 1 2 1 1 2 1 2 2 2 3 1 1
Skin/core disbond 3 1 2 2 1 3 3 2 2 1 1
Crushed core 1 3 1 1 2 2 2
Condensed core 1 1
Blown core 1 1 1 1
Core node disbonds 1 1
Water intrusion 3 2 3 2 2 1 2 2
Corroded core 2 2 2 3 1 3
Fatigued core 2 2 1 2
Foam adhesive voids 3 2 1 2
Bondline adhesive voids 1 2 1 1 2 2 2 1 2 1
Key:
1. Good sensitivity and reliability. Good candidate for primary method.
2. Less reliability or limited applicability.May be good supplementarymethod.
3. Limited applicability. May provide some useful information.

ticular comDosite discontinuities. While this
table cannot be considered definitive, it does
give general guidance to the applicability of
the various technologies to various material
conditions. In any specific application, a large
number of considerations will influence the
selection of nondestructive testing technolo-
gies. It is hoped that the discussions provided
in this chapter will offer some assistance in the
selection and application of nondestructive
testing methods. However, final selection
should be based on the evaluation of a greater
number of parameters than can be considered
here. Experience, training, experiment and
clear understanding of the inspection objec-
tives are required to develop effective
nondestructive testing applications.
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REPAIR ASPECTS OF COMPOSITE AND 39
ADHESIVELY BONDED AIRCRAFT STRUCTURES
Anton L. Seidl

39.1 INTRODUCTION the composites industry, is an unfamiliar lan-

guage to the uninitiated. Inspectors are often
39.1.1 MANUFACTURABILITY AND at a loss when attempting to describe a condi-
MAINTAINABILITY OF COMPOSITE AIRCRAFT tion they perceive as a defect; the words
STRUCTURE simply do not exist in their standard lexicon. It
To the manufacturer, weight reductions, struc- is intuitively clear to even the casual observer
tural requirements, manufacturability and that repairs using mechanically fastened con-
production costs have long been obvious pri- ventional materials can be effected quickly,
orities. Only recently, however, and only as a under almost any atmospheric conditions, and
consequence of persistent user demands, have with minimal investments in tooling, raw
maintainability and repairability been added materials, and training. In contrast, repairing
to this list. From the operator’s perspective, even relatively minor damage on composite
nevertheless, composite structures continue to structure requires an array of non-conven-
be a mixed blessing. Clearly, and despite state- tional materials, highly skilled and
ments being heard to the contrary, the experienced technicians, special tooling and
industry would be loath to give up the many equipment, access to production drawings (to
obvious advantages gained through the use of locate and interpret the many hidden features
composites and revert to all-metal airplanes. characteristic of composite structures), a con-
However, the maintenance problems associ- trolled environment in terms of temperature
and humidity, time-consuming preparatory
ated with composites cannot be
work, cold storage of shelf-life limited and
underestimated and may well be regarded as
occasionally hazardous materials, lengthy
the weak link in the new technology chain.
resin cure cycles, post-repair NDT, and legally
mandated record-keeping and follow-up
39.1.2 METAL REPAIRS COMPARED WITH activities.
COMPOSITE REPAIRS
Compared to the relative simplicity of conven- 39.1.3 COMPOSITE REPAIRS: AN AIRLINE
tional metallic structures, composites are PERSPECTIVE
replete with complexities that continue to baf-
The aim and purpose of this presentation is to
fle and confuse maintenance workers trained
highlight the principal aspects of composite
only in the traditional, i.e. metalworking,
structure repairs from an airline perspective.
skills. The glossary of terms alone, as used by
An attempt will be made to:
1. describe some of the more common defects
Handbook of Composites. Edited by S.T. Peters. Published and conditions encountered in service;
in 1998by Chapman & Hall, London. ISBN 0 412 54020 7
858 Repair aspects of composite and adhesively bonded aircraff structures

2. give a brief summary of common mainte- subsequent repairs more difficult to perform.
nance practices; When surface defects are detected, it is imper-
3. describe a limited number of typical repairs. ative to determine the extent of the damage
that may already have occurred and if possi-
ble, evacuate and decontaminate the panel. As
39.2 DAMAGE ASSESSMENT
a first line of defense against any further struc-
tural deterioration, foil tape should be applied
39.2.1 IMPACT DAMAGE - NON-METALLIC
at the earliest opportunity2.
STRUCTURE Severe degradation is generally quite obvi-
ous, having resulted in visible disbonds and
Foreign object impact without skin delaminations. If the damage is due to a recent
penetration event, and the process of deterioration has
Prior to any repair action, it is important to only begun, the amount of ingested fluid may
determine the extent of the damage sustained still be relatively small and if the precise loca-
by the structure. One must always assume that tion of the contaminant can be determined,
the actual damage is more extensive than the complete evacuation and purging may be suc-
visible damage'. This is especially true for car- cessfully accomplished.
bon fiber-reinforced composites with
non-toughened 177°C (350°F) cured matrix Limitations of moisture detectors3
resins. After a foreign object impact, there is
generally, but not invariably, some visual indi- Commercial moisture detectors are extremely
cation in the form of damaged paint. However, useful devices requiring no special training.
because of the elasticity of high modulus Where appropriate, they may be used to deter-
fibers, the laminate often 'springs back', leav- mine how far any ingested water has spread
ing residual subsurface damage in the form of into the core cells adjacent to the point of
broken fibers, ply separations and in the case impact. Moisture detectors, however, are effec-
of sandwich panels, crushed core and dis- tive only on non-metallic (typically glass or
bonded face sheets. Tap testing is generally aramid-reinforced structures); they cannot be
sufficient to delineate the extent of the damage used on panels containing carbon fibers, or in
and should be conducted before removing any zones reinforced with metals. Nor are mois-
damaged materials. Defects may also propa- ture detectors effective through surfaces
gate during the removal process, often as the coated with carbon-filled conductive paints,
result of stress relief. on panels having metallic coatings, metal-
coated fibers, or similar lightning protective
and EM1 shielding features.
Skin penetrations: holes, cracks, tears,
gouges, cuts and abrasions
E@cacy of radiography
On the 'wetted' outer surface of the aircraft,
even minor penetrations of the face sheet must Radiography (X-ray) is presently the only
be regarded as serious because once an open- available practical technique for determining
ing exists, the part has been rendered moisture contamination in panels containing
permeable to atmospheric moisture and air- electrically conductive elements. Given the
craft system fluids. Ingested water can and limitations of moisture detectors and the lim-
will degrade the affected part, leading to pre- ited availability of X-ray equipment in the
mature failure. Fluids such as hydraulic oil, field, water detection by X-ray and subsequent
when allowed to enter, contaminate both lam- evacuation are generally carried out only dur-
inates and honeycomb core materials, making ing depot level maintenance opportunities.
 Damage assessment 859

Interim repair actions - ‘speed tape’ repairs Effects of skin penetration: corrosion, resin
plasticization and core dissolution
When a composite panel is found to have been
penetrated, it is important to prevent further
Any impact damage resulting in skin penetra-
deterioration of the panel. When fluid detri-
tion must be regarded as serious damage.
mental to adhesion (hydraulic oils, deicing However, unlike non-metallic core materials,
fluid, engine oils, etc.) is present, the affected
which absorb and diffuse water, non-perfo-
area must be thoroughly decontaminated rated aluminum honeycomb cores tend to keep
before attempting a repair, or the contami- any ingested water concentrated about the area
nated material removed entirely. of the penetration. Left unattended, prolonged
When a permanent repair is to be deferred,
exposure will cause the ingested water to
fractured material should be trimmed away migrate to other areas of the panel by gradual,
and the opening covered with foil tape before
progressive diffusion through the adhesive
the aircraft is dispatched to a location where
bondlines and, preferentially, through the core
the appropriate repair facilities exist. Foil tapes
splice adhesives. As the bonding adhesives
must be applied with care to prevent their absorb moisture they become plasticized and
coming loose in flight. Loose foils have been
their bond strength weakens.
known to create static noises that can interfere
At the same time, unprotected areas of the
with radio communications. face sheet, doublers, substructural compo-
nents, cut edges and fastener holes, i.e. where
39.2.2 IMPACT DAMAGE ON METAL-SKINNED the anodic and primer protections have been
SANDWICH PANELS removed during the manufacturing process,
and machined edges of the honeycomb core,
Unlike laminated face sheets, which may are rendered vulnerable to corrosion attack.
show little evidence of an impact having Ingested water, if left unevacuated for long
taken place, thin metal face sheets (common periods, has been known to initiate chemical
on many honeycomb sandwich panels) reactions that lead to complete dissolution of
invariably become dented or gouged by for- the aluminum honeycomb core.
eign object impact. The resulting surface
irregularities are readily seen.
39.2.3 DAMAGED PROTECTIVE COATINGS
Minor damage - no skin penetration AND SEALANTS: LEAK PATHS
Shallow dents may be present that do not nec- Water ingestion and fluid contamination must
essarily result in disbonding of the skin, but be presumed to exist whenever the protective
there will always occur some crushing of the coatings or sealants of a panel have been dis-
core cells. A tap test will usually, but not turbed. The cause may be erosion of the
always, determine whether the skin is dis- protective finish, substrate corrosion, hail
bonded. Dents that have not resulted in skin damage, minor collisions, or similar foreign
disbonds are generally considered negligible object damage episodes. Leak paths, no matter
damage and may be filled with an appropriate how small, are detrimental to the long-term
compound to restore aerodynamic cleanness, structural integrity of the panel because they
provided the added weight does not affect the allow atmospheric moisture, aircraft system
balance of a critical control surface. Flight con- fluids, or a combination of contaminants, to
trol surfaces damaged by hailstones frequently enter the structure.
exhibit multiple dents that cannot be repaired Subsequent ’ground-air-ground’ and
by dent fillers without creating an out-of-bal- ‘freeze-thaw’ cycling are capable of introduc-
ance condition. ing considerable quantities of water and other
860 Repair aspects of composite and adhesively bonded aircraft structures
fluids into the core of a panel. Sandwich pan-
els with thin face sheets of aramid/epoxy are
especially vulnerable to moisture contamina-
tion via small cracks in the resin gelcoat and at
the resin-fiber interface. This phenomenon
has been explained as the result of the thermal
expansion behavior of the aramid fiber, which
is slightly negative in the longitudinal direc-
tion and strongly positive in the transverse
direction, leading to excessive strain build-up
within the weave itself.
39.3 ENVIRONMENTAL DAMAGE AND
DEGRADATION
39.3.1 GENERAL EFFECTS OF AGINGz4
All polymeric materials are subject to degra-
dation over time. For this reason, the
importance of maintaining protective coat-
ings and sealants cannot be emphasized too
strongly. The 'normal' operating environment
of an aircraft exposes composite structures
not only to considerable static and dynamic
loads, but also to significant temperature gra-
dients, extreme variations in humidity
conditions, and to a number of chemical
agents necessary in aircraft systems, the most
detrimental being hydraulic fluid, a powerful
solvent.
39.3.2 EXPOSURE OF COMPOSITES TO THE
'NORMAL' FLIGHT ENVIRONMENT
There is abundant evidence that the combined
effects of stress, temperature, water and other
fluids expose bonded and especially fiber-
reinforced composite structures to a far wider
range of hazards than their baseline metal
analogs. Following is a brief description of the
most common environmental hazards com-
posite materials are exposed to.
Moisture
While demonstrably corrosive to metals,
moisture is far more pernicious in its effect on
composites because it plasticizes resins,
degrades their mechanical properties and
lowers their glass transition temperature4.
The latter effect becomes extremely critical
when carrying out hot bonded and/or
prepreg repairs that require the heating of the
structure.
Atmospheric electricity 22-z
Atmospheric electricity, of negligible con-
squence to metal structures having inherent
conductivities, can have a crippling effect on
non-metallics, which compels the operator to
place a high priority on periodic testing and
proper maintenance of anti-static and light-
ning protection schemes, i.e. ground paths,
bonding fasteners, bus strips, jumper cables,
conductive enamel and/or flame-spray coat-
ings, as well as discharge ports.
Chemical contamination
Aircraft fluids and chemicals that are harmless
on metals can effectively destroy a composite,
if allowed to penetrate its outer protective lay-
ers. Chemical paint strippers routinely used
on metal aircraft are occasionally - albeit inad-
vertently - applied to composite surfaces with
destructive consequences, even if the exposure
is but of short duration. Presently, composites
can only be stripped by abrasive, non-chemi-
cal methods5.
Overheat conditions
Heat, except for annealing temperatures, is of
minor concern with metals; by contrast, the
heat resistance of compositesis effectively lim-
ited by the maximum use temperature of the
polymeric matrix. Heat generated by lightning
strikes has been known to vaporize matrix
resins and create large areas of delamination
and fiber fracturing on composite rudders,

ailerons, wing and stabilizer tips, nose domes,
and nacelle cowling. When exposed to hot
gases over long periods, polymeric resin
binders, irrespective of chemistry, can become
completely destroyed through a process some-
times described as thermo-oxidation. This
condition may be found on all types of com-
posites, including those with inorganic
matrices, such as metal matrix composites.
Preventive maintenance may consist of the
application of heat-resistant, ablative or intu-
mescent coatings. Extensive redesign of the
detail may be necessary, using metals or, if a
fiber composite is to be used, choosing a poly-
imide or similar high temperature resistant
resin system.
39.4 DAMAGE REMOVAL TECHNIQUES
39.4.1 PLANNING THE REPAIR 'THINK
BEFORE CUTTING'
After determining the full extent of the damage,
the repair technician must consider a range of
possible approaches, based on such considera-
tions as damage location, access to the damage,
required disassembly to create better access,
available tooling and repair materials, as well
as the allotted out-of-service time. Because
most repairs are 'on-condition', i.e. the result of
damage events affecting the structure at unpre-
dictable locations in a multiplicity of manners,
allowing only limited pre-planning, the techni-
cian's experience and intuitive problem-solving
abilities are of paramount importance.
39.4.2 AERODYNAMIC SKIN DAMAGE
REMOVAL
If the damage affects the outer, aerodynamic
or 'tool' side of a panel and the backside (the
%ag side') is accessible, it is best to remove
material from the backside, and as much of the
core material as necessary, to gain access to the
damage. Using this method preserves as much
of the aerodynamically 'clean' surface as pos-
sible. Repair work is more easily accomplished
Damage removal techniques 861
from the backside, with the additional benefit
of causing only minimal disruption to the
aerodynamic surface. Figure 39.1 illustrates
this principle.
If the backside is inaccessible, the damage
must be repaired from the aerodynamic skin
side, inevitably enlarging the repair surface
and making the repair more difficult to per-
form. With only one side accessible, the
question of how best to apply vacuum pressure
is always problematic and requires consider-
able operator skills. (Applying vacuum
pressure for a bonded repair is an art form that
must be learned as any other.) As an alternative
to field repairs, panels are often removed from
the affected structure and routed to a repair
facility specially equipped to effect the appro-
priate restorations. It should be noted that the
damages affecting the aerodynamic skin sur-
face normally require 'flush' repairs to
preserve the original contour, particularly in
zones of the aircraft defined as aerodynami-
cally critical. Except for small damages, the
tooling and skill levels required to effect proper
repairs do not exist at field stations.
REPAIR PLIES-/ -FILLER
REPAIR PLIES- \
CORE PLUG
-iti--FLUSH SIDE
~NON-FLUSH
SIDE
Fig. 39.1 Aerodynamic skin side repair.
862 Repair aspects of composite and adhesively bonded aircraft structures
39.4.3 REMOVAL OF METAL FACE SHEETS
AND DOUBLERS
Metal-faced sandwich panels are used on
wing spoilers, wing and stabilizer panels,
flaps, slats, engine cowling, landing gear strut
doors, as well as in a multitude of other appli-
cations, including aircraft interiors. Damaged,
corroded, or disbonded face sheets are gener-
ally peeled away after the application of
carbon dioxide pellets ('dry ice'). The dry ice is
allowed to dwell on the surface until the ther-
mal shock has weakened the bond strength of
the adhesive sufficiently to allow the skin to be
removed. If done properly, the face sheets sep-
arate, leaving the core cells relatively
undamaged.
39.4.4 REMOVAL OF COMPOSITE FACE SHEETS
AND DOUBLERS
The outer surface of most non-metallic sand-
wich panels consists of only a small number
of prepreg fabric and/or tape plies co-cured
onto non-metallic honeycomb core, although
precured laminates, secondarily bonded to
the core, are also found. Removing damaged
or disbonded face sheet materials requires
either a rotary sander (physical abrasion) or
the use of a hot air gun combined with peel-
ing action. Heating the skin laminate has the
effect of weakening the resin fillets suffi-
ciently to allow the technician to peel the face
sheet materials with only minimal damage to
the core.
39.4.5 REMOVAL OF HONEYCOMB CORE
MATERIALS
After the face sheet material has been
removed, the condition of the honeycomb core
must be determined. Because of the high cost
and limited availability of some core materials,
repair shops attempt to salvage the original
material if at all possible.
Aluminum core removal
Severely damaged aluminum core (crushed,
corroded, failed node bonds, etc.) should
always be replaced. Removal is generally
accomplished by using non-metallic scrapers
or chisels mounted in a pneumatic rivet gun.
Care must be taken to avoid damaging the
intact face sheet on the far side. The remaining
adhesive fillets on the far side should be
abraded with a rotary sander, provided the
adhesive is still firmly attached, thils provid-
ing a good base for bonding in the
replacement core plug. If the far side adhesive
is plasticized or unbonded, or corrosion is
found between the adhesive layer and the
metal skin, the adhesive must be removed for
closer inspection and possible reconditioning
of the bonding surface. Corroded skins and
doublers are routinely replaced.
Non-metallic core removal
Non-metallic core materials are generally
replaced if crushed or split at the nodes, or if
irreversibly contaminated by oil, hydraulic
fluids, or other contaminants that would
inhibit subsequent repair resin adhesion and
cure. Repair shops often attempt to deconta-
minate core by flushing out the cells with
solvent, a method not always successful and
a potential environmental hazard. If the cont-
aminant is water, dehydration of the core by
evaporation, placing the part in an oven at a
low temperature, is often possible, allowing
the material to be salvaged (see Section 39.5).
When core replacement becomes necessary,
the affected sections are generally cut out
with knives or rotary cutters; the resin fillets
remaining on the far side are then removed
with rotary sanders, to create a proper sur-
face for bonding in the replacement core
Plug.
 Decontamination 863

39.5 DECONTAMINATION Effects of contaminants on structural

integrity
39.5.1 EVACUATION AND
DECONTAMINATIONOF POLYMER MATRIX
Dimensional swelling and plasticization of the
COMPOSITE STRUCTURES
resin matrix generally result from exposure to
high humidity at high temperatures, exposure
Vulnerability of polymers to fluids to many aircraft fluids, to chemical paint strip-
pers, and to a variety of common solvents.
Organic matrix composites typically absorb Absorbed moisture lowers the glass transition
between one and two percent of their dry temperature of the laminate*and may be con-
weight in moisture under normal service con- ducive to additional microcracking within the
ditions. There exists a certain risk when such matrix which, in turn, increases the potential
assemblies are subjected to the elevated tem- for additional moisture absorption. Micro-
peratures routinely applied during bonding cracks are considered irreversible, since they
and laminating repairs. During hot bond remain after the laminate has been completely
repairs, the absorbed moisture volatilizes. The dehydrated. Absorbed chemicals may or may
effect on the repaired structure may manifest not affect the structural or mechanical proper-
itself in the form of porosities in the bondline or ties of the composite, but generally render the
in the laminate. In severe cases, such as when affected part unrepairable because they inhibit
water is present in the core cells, the pressure repair resin adhesion and cure.
resulting from the entrapped steam often
results in uncontrollable skin-to-core disbond-
ing. For these reasons, it is always advisable to 39.5.2 GENERAL PRECAUTIONS
pre-dry composite panels when moisture cont-
amination exists in detectable quantities, or Water evacuation under vacuum pressure at
may be presumed to exist, given the general elevated temperatures
condition of the part. One should keep in mind Removing water is mandatory in all cases, but
that fibers, with the exception of aramid, do not the process becomes especially critical if the
absorb moisture. Moisture absorption is a phe- repair requires the application of elevated cure
nomenon that affects primarily the resin matrix temperatures under vacuum pressure, which
and, secondarily, non-metallic core made from is typical or many in situ heating blanket type
aramid fibers. As a general rule, resin systems repairs. The operator must be aware that,
cured at 170°C (350°F) or above are more resis- under a vacuum bag, lowering the vapor pres-
tant to moisture pick-up than resin systems sure also lowers the boiling point of the water;
cured at lower temperatures, which includes all at the same time, increasing the temperature
room temperature-curedrepair resins and cold- increases the steam pressure inside the sand-
bond adhesives-. wich (Fig. 39.2). The result is often a failed
repair: blown core and disbonded face sheets.
Effect of contaminants on weight and
balance Removing moisture barriers (coatings and
films)
Fluids absorbed by, or otherwise introduced
into a structure, induce weight gains and may Evacuation of composite laminates is best
cause out-of-balance conditions in flight con- accomplished by first removing any protec-
trol surfaces. Contamination detected should tive coatings and moisture barrier films that
always be evacuated, the leakage paths identi- may still be present and intact. Barrier mate-
fied, repaired and the structure resealed. rials may be various enamel finishes, sealer
864 Repair aspects of composifeand adhesively bonded aircraft structures

459.02 4

333.89 - e ,. 145

29.90
20.70
13.98

5.88

1.25
OThrough face
0.70 sheet evacuation
0.36
@zoneof ,

oc
OF
-
-
0.18
0
32
20
68
40 60
104 140
; 80
176
100
212
120 140
248 284
160 180
320 356
200
392
" risk
increasina

I
160

Fig. 39.2 Pressure and evacuation guidelines for honeycomb core repair.

coats, or bondable plastic films. Their solvents. Often, considerable quantities may
removal is essential to create a path for be necessary to purge the contaminated core,
volatiles to escape rapidly. creating potential environmental hazards. In
many cases, complete core replacement may
be the only appropriate action.
Removing face sheet materials
Evacuation of honeycomb sandwich panels is
39.5.3 SPECIFIC EVACUATION TECHNIQUES
most effectively done by removing one of the
face sheets. This method exposes the core and
Evacuation of fluids from core with face
allows the thorough flushing of any contami-
sheet removed ('open core' evacuation)
nants with an appropriate solvent. Complete
drying should be performed under vacuum Visible liquids should be evacuated by blow-
pressure at moderate heat. ing filtered, compressed air across the surface.
This should be followed up by flushing the
core with an oil-free solvent and then allowing
Flushing contaminants with solvents
the solvent to evaporate completely. Next, sev-
Evacuation of chemical contaminants may be eral layers of breather fabric are stacked over
accomplished by flushing the core cells with the panel, the assembly is envelope-bagged

and a vacuum of approximately 67 kPa (20
inHg) is applied. The panel is then heated
slowly to approximately 74°C (165°F) and
allowed to remain at temperature for a mini-
mum of one hour.
Evacuation of fluids from core with face
sheets intact (‘through-the-facesheet’)
evacuation
First, all protective coatings and moisture bar-
rier plies must be removed from the areas to be
evacuated. Then the gelcoat of the outermost
ply should be abraded to expose the fibers.
(Fibers inadvertently damaged during this
process require subsequent repair.) Next, sev-
eral layers of breather fabric are applied and
the assembly envelope-bagged. Then a vac-
uum of 34-40 kPa (10-12 in Hg) is applied and
the panel heated very slowly (5°C per minute
maximum heating rate) to approximately 75°C
(165°F) and maintained at that temperature
and vacuum pressure for a minimum of 24 h.
After this initial drying cycle, the temperature
should be increased to 107°C (225°F) and
maintained for an additional four hours.
Handling of dried details - inspection and
storage
After drying, details should be re-examined
and, if satisfactory, stored in a clean, dry envi-
ronment until the appropriate repair actions
can be taken.
39.6 TYPICAL REPAIRS
39.6.1 WET LAY-UP REPAIRS AT AMBIENT OR
ELEVATED TEMPERATURES
So-called ’wet lay-up’ repairs are the most fre-
quently recommended because they require
only the most basic in terms of equipment,
tooling, and repair materials. On the other
hand, they are also the most limited in terms
of size and applicability because such repairs
do not restore the full, pre-damage strength of
Typical repairs 865
the structure. Wet lay-ups normally involve
the use of the same type of fabric used in the
original construction, in conjunction with a
laminating resin capable of room temperature
cure under vacuum pressure. The quality of
the repair is generally enhanced by applying
moderate heat (100°C max) by means of heat-
ing blankets, heat lamps or hot air.
Heating blankets
Heating blankets used in conjunction with
vacuum pressure repairs should have an out-
put (watt density) of no less than 7750 W/m2
(5 W/in’). To facilitate draping over curved
surfaces, heating blankets with silicone rub-
ber-embedded elements are preferred over
mineral fiber-insulated pads, because of their
inherent flexibility. Stiffer pads should only be
used on flat surfaces.
Heat lamps
Heat lamps that are used either as the primary
heat source, or as a means of augmenting other
heat sources, should be 250-300 W tungsten or
quartz tube, explosion-proof types. When
using heat lamps as the primary source, the
effective heat input is controlled by the stand-
off distance, as shown in Fig. 39.3. To avoid
overheating any portion of the assembly being
repaired, thermocouples should be placed at
several locations to monitor the temperature
throughout the cure cycle. The stand-off dis-
tance or the positioning of the lamp should be
adjusted as necessary to maintain the cure tem-
perature within specified limits.
Hot air blowers
Hot air blowers similar to hair dryers are often
used to accelerate resin cure; they may also be
used for reticulation of unsupported film
adhesives. Such devices are typically designed
with 1000-2000 W heater elements and fan
drive motors.
866 Repair aspects of composife and adhesively bonded aircraft structures

3. Sand off any protective or decorative fin-

ishes and coatings; scrape off sealants,
especially silicone sealants.
4 Inspect detail for presence of water or other
fluid contamination.
5. Evacuate panel using one of the methods
14
I 5 l \ described in Section 39.5.
n
6. Remove damaged materials - face sheets,
v) doublers, and core, using the appropriate
f0 13 __ techniques described in Section 39.4.
.-
E
v Note: Steps (5) and (6) may be inverted,
$ 12 -- depending on the condition of the part.
is
11 --
Core plug repair
I O -_ 1. Obtain and prefit replacement core plug,
using same as original material, cell size,
and density (or an approved substitute).
I I
I 2. Apply resin compound to edges of core
plug to provide a shear tie and insert the
plug into the cavity.
3. Apply release film, breather fabric, thermo-
couples, and vacuum bagging materials.
Apply vacuum and check bag for leaks.
4. Cure core splice (shear tie) resin, observing
the appropriate time/ temperature relation-
39.6.2 USE OF ADDITIONAL PLIES OVER WET
ship specified for the core splicing resin.
LAY-UPS
Maintain vacuum pressure throughout the
Recognizing that wet lay-ups are inherently cure cycle.
inferior to autoclave-cured laminates, many 5. Remove bagging materials and thermocou-
repair specifications9 call for the addition of ples.
two or more plies of the type of material used
in the original construction, as a means of
Face sheet repair
compensating for the loss of stiffness implicit
in wet lay-ups. The added plies do, however, 1. Taper and splice joint area.
result in weight gain and some loss in aerody- 2. Sand core plug flush with innermost ply.
namic cleanness. 3. Vacuum up sanding dust, solvent clean
repair surfaces and allow solvent to dry
completely.
39.6.3 TYPICAL WET LAY-UP REPAIR
4. Using same as original fiber type and
PROCEDURES
weave style, and observing proper yarn ori-
entation, prepare and impregnate each
Damage assessment and removal
repair ply of fabric with an appropriate
1. Determine perimeter of damaged area by laminating resin mixture.
NDTlO. 5. Apply repair plies, observing ply stacking
2. Clean area with solvent. sequence and fiber orientation.

6. Apply perforated release film, breather/
bleeder fabric, thermocouples, and vacuum
bag. Apply vacuum and check bag for
leaks.
7. Cure laminate under 67-81 kPa
(20-24 in Hg) vacuum pressure, while
observing the appropriate time/ tempera-
ture relationship specified for the repair
resin. Maintain vacuum pressure through-
out the cure cycle.
8. Remove bagging materials.
Restoration of coatings, finishes and
sealants
1. Ensure resin is fully cured (must be hard
when tapped and resistant to solvents when
wiped with solvent-soaked cheesecloth).
2. Reactivate surface by mild abrasion.
3. Clean surface and allow to dry.
4. Reapply finishes, including any anti-static
and lightning-protective coatings that may
be required.
5 . Reapply any sealants or other coatings
removed for repair.
Materials, tooling, equipment and repair
environment 25
1.A two-part epoxy laminating resin of the
required chemistry.
2. A compatible core splice resin or com-
pound.
3. Same as original type and style of fabric
(unidirectional tape may be replaced with
two plies of fabric of equivalent thickness,
if allowed by the local structural repair
manual).
4. Same as original type, cell size, and density
core material, or an approved substitute.
5 . Release film materials, both solid and per-
forated.
6. Breather and bleeder fabrics.
7. Vacuum bagging film, vacuum gage, and
vacuum sealer tape.
8. Abrasive discs, hand-held pneumatic
motor.
Typical repairs 867
9.Oil-free solvents and clean cheesecloth
wipers.
10. Heat lamps and/or blankets, hot air gun.
11. Thermocouples and temperature monitor-
ing equipment.
12. Compressed air and vacuum source capa-
ble of being regulated.
13. Environmental conditions: Work should be
done indoors, under conditions of moder-
ate temperatures (ambient) and low
relative humidity (40-65%).
39.6.4 WET LAY-UPS USING PRECURED
PATCHES
Instead of repairing damaged face sheets 'ply-
for-ply', using dry fabrics and laminating
resins, prepreg materials may be precured,
between layers of peel ply fabric, under auto-
clave conditions, and stored for later use as
patching materials. Precured patches should
be perforated to facilitate resin flow and to
provide vacuum contact. (Perforations should
be of sufficient diameter and spacing to pro-
vide a vacuum path and resin bleed, without
causing resin starvation at the bondline.)
Perforated precured materials may be used
with laminating resins, film adhesives, or
adhesive paste. When using laminating resins,
3-5 wt% fumed silica ('CAB-O-SIL'TM,made
by Cabot Corporation, is generally specified)
or an equivalent thickener should be used to
improve resin filleting on the honeycomb core.
Limitations of precured materials
Precured carbon/epoxy patches are normally
applied only over flat surfaces. Precured
glass/epoxy patches (or similar low modulus
fiber) may be applied over mild curves. Since
precured patches are basically 'scab' patches,
they should not be used if the surface requires
a high degree of aerodynamic cleanness. If
precured patches are needed for repairing sur-
faces having compound shapes, special
contour molds must be fabricated and used as
a strongback to precure the material, so as to
868 Repair aspects of composite and adhesively bonded aircraft structures

produce a precise contour match. The pre- 39.6.5 PREPREG REPAIRS

cured patch may be regarded as the composite
equivalent of a metal stamping. Autoclave repairs
Restoring damaged laminates by utilizing the
Necessity of reducing vacuum pressure for same as original preimpregnated fabric or
bonding precured details and for co-curing tape, at the same as original cure temperature
prepregs and film adhesives and pressure, is normally recommended when
full restoration of the original design proper-
Available test data indicate that precured ties is a requirement. In practical terms,
patches, as well as prepregs and film adhe- however, full restoration should only be
sives being co-cured (unless cured in an attempted by depot level facilities, since any
autoclave under positive pressure conditions) such action necessitates:
should be processed under 3340 kPa (10-12
in Hg) vacuum pressure only. Significant 1. removal of the affected part from its parent
reductions in bond strength have been assembly;
observed when such repairs are cured under 2. availability of strongback tooling to main-
heating blankets and at full vacuum pressure. tain contours;
Many combination repair techniques, utilizing 3. an autoclave capable of meeting the origi-
both precured and resin-impregnated dry fab- nal cure parameters;
rics, prepregs and film adhesives have been 4. availability of same as original materials of
developed for specific damage conditions and construction and requisite facilities, equip-
damage locations. All such repairs should be ment and NDT capabilities.
cured under reduced vacuum pressure. Clearly, only major operators have the neces-
sary capabilities to conduct what can only be
Wet lay-ups cured at elevated temperatures described as a remanufacturing operation. At
the present time, only a limited number of the
Unlike low temperature (65°C maximum) cur- major airlines have the requisite equipment to
ing resins, laminating resins capable of being perform rebuilds to OEM specifications. To
cured under vacuum pressure and up to 150°C satisfy market demands, a number of repair
(300"F), so-called 'room temperature set/ele- facilities have been granted remanufacturing
vated temperature post-cure' resins, produce authority under Part 145 of the Federal
high quality repairs and are therefore consid- Aviation Regulations.
ered desirable alternatives to prepreg repairs.
Because of the hazards inherent in all elevated
temperature repairs, especially non-autoclave Non-autoclave repair methods
repairs performed under vacuum pressure For limited damage requiring only partial
only, a cautious approach is necessary. It is restoration, there are approved alternative
almost universally recommended to cure the repair methods. Nearly all these utilize
repair under the lowest possible cure temper- prepregs and film adhesives that are normally
ature at the expense of elapsed time. A given cured by means of heating blankets under
resin may be curable in two hours at 150°C 'vacuum pressure only' conditions. Such
(302°F) and may require six hours at 85°C repairs can be carried out with minimal capital
(185°F). To reduce the risk of part failure dur- investments. Because such repairs yield lower
ing the cure, it is generally advisable to opt for than original design strengths, size limitations
the longer cure cycle at the lower temperature. usually apply. These limitations are contingent
upon the specific location of the damage as
 Typical repairs 869

defined in the Structural Repair Manual for part.) It is generally accepted that, before con-
the aircraft in question. As a rule, repairs in the templating a prepreg repair, the following
vicinity of a load path, as defined by finite ele- factors be given
- serious consideration.
ment analysis, are severely restricted. The
1. The part must be completely dry (see
allowable repairs in so-called 'field areas', i.e.
Section 39.5).
at some predetermined distance away from
2. If at all possible, the part should be enve-
spars, ribs, hinge and latch points, etc., are
lope-bagged to prevent backskin disbonding
more generous in terms of size as well as
during the cure.
repair method.
3. The cure should always be effected at the
lowest permissible temperature specified
Vacuum pressureheating blanket repairs (using for the product.
prepregs and film adhesives) 4. If at all possible, a repair prepreg and/or
film adhesive should be selected that is cur-
In situ prepreg repairs are often preferred over
able at a temperature 40-60"C (104156°F)
wet lay-up/elevated temperature repairs
lower than the original cure temperature.
because the resin content of the repair is more
This is of particular importance when
easily controlled by using a prepreg. One of
repairing structures originally cured in the
the risks associated with the use of production
170-180°C (338-356°F) temperature range.
prepregs and adhesive films is that these prod-
(Several such products are becoming avail-
ucts were formulated for production and
able as a result of persistent industry
normally require high cure temperatures
demands. Representative products are
which, when applied to damaged parts likely
listed in Table 39.1. This listing is given for
to contain residual moisture, may cause severe
reference only and does not imply endorse-
disbonding of the remaining, thus far undam-
ment of any given product.)
aged, structure. (The repair action thus
severely damages or effectively destroys the

Table 39.1 Repair adhesives and resins curable at reduced temperatures

Product Class Manufacturer Min. cure temperature Max. use temperature

"C "F "C OF
FM300-2 Film Am Cy 120 250 150 300
FM250 Film Am Cy 112 230 80 180
FM73 Film Am Cy 105 225 120 250
FM123-5 Film Am Cy 95 200 120 250
EA9680 Film Hysol 120 250 150 300
EA9394 Paste Hysol 95 200 150 300
PL795 Film BFG 120 250 177 350
CYCOM 919 Resin Am Cy 112 235 70 160
SP377 Resin 3M 95 200 105 220
Epon9410 Resin Shell 80 175 See Note
DER 329 Resin Dow Room temperature See Note
Epocast35A/927 Resin Furane R.T. + postcure See Note
Note: Postcure raises upper use temperature.
870 Repair aspects of composite and adhesively bonded aircraft structures
Voids and porosities in vacuum-pressure cured
laminates and bondlines
Major disadvantages of ’vacuum-pressure-
only’ cures are a reduction in the compaction
of the laminate and the inevitable formation of
porosities in the laminate and/or adhesive
bondline. The finished repair yields, as a rule
of thumb, approximately only 80% of the
strength of an autoclave-cured part in terms of
shear and flexural properties. The problem of
compacting thick laminates may be overcome
to some extent by hot debulking each ply, or a
stack of several plies of a laminate, under vac-
uum pressure before the final cure. This
method is labor-intensive but useful; it draws
off entrapped gasses, improves resin flow,
fiber wet-out and therefore overall laminate
quality.
Prepregs co-cured with film adhesives
Repair technicians often use a compatible film
adhesive together with a prepreg when mak-
ing a repair. A layer of film adhesive is
especially desirable as a bond ply over honey-
comb core because it enhances the honeycomb
peel strength by providing a deeper glue fillet
than would be achieved with prepreg alone.
There is, however, beside the added cost, a
slight weight gain that must be considered
when repairing a weight and/or balance criti-
cal part.
Prepregs applied over metal substrates
Prepregs applied over metallic substrates
always require the use of a layer of film adhe-
sive between the metal and the non-metal. The
metallic substrate also requires the normal
surface preparations applicable for metal
bonding, by one of the methods described in
Section 39.6.8. Prepregs are often used to pro-
vide debris protection in damage-prone areas
of thin-skinned sandwich panels, notably
wing flaps and other panelling in line with the
landing gear. Occasionally, prepregs are used
as panel edge close-out in preference over
metal stampings.
39.6.6 SURFACE PREPARATION FOR NON-
METALLIC SUBSTRATES
Abrasion and cutting of plies
Taper-sanding is the preferred method of creat-
ing a scarf joint at the substrate/repair
interface, especially if the substrate material is
made from a woven fabric. Repairs in unidi-
rectional tape laminates often use step joints,
with each repair ply butted against the original
ply. Instead of sanding, the splice joint is then
prepared by cutting each ply carefully with a
sharp instrument such as an ’Exacto’ knife. It is
common to use a lap of 13-19 mm (0.5-0.75in)
per ply, although there is lack of agreement
with respect to the optimum lap distance or the
stacking sequence of fabric plies, i.e. whether
the smallest or the largest ply should be placed
first. Some authorities calculate the overlap as
a function of materials thickness (e.g. L = 187‘)
whereas others recommend a straightforward
13 mm (0.5 in) overlap per fabric ply and a
25 mm (1in) overlap per tape ply in the zero
degree orientation3,11-13.
Use of peel plies
Multi-stage processes using precured lami-
nates often use peel ply fabrics which, upon
removal, yield a surface that requires no fur-
ther cleaning or abrading. Chapter 29
contains some important observations about
peel piles.
Grit blasting
Grit blasting followed by solvent wiping is
sometimes used to prepare non-metallic sub-
strates for subsequent bonding and
laminating operations. Plastic media with a
Mohs hardness of 3.0-3.5 (US Plastic and
Chemical Corporation’s Polyextra and
Polyplus granulated plastics, sieve size 30/40,

propelled at a low incident angle (15-30") and
at moderate nozzle pressure (25-30 psig) have
been demonstrated to remove coatings effec-
tively without damage to fibers, and to leave
surface conditions of high quality5.
39.6.7 BASIC REPAIR JOINT PREPARATION
Whatever the specific surface preparation
method, the focus must be on producing a
smooth, contamination-free, activated bond
surface capable of promoting adhesion and,
after the cure, capable of transferring the struc-
tural loads across the joint with minimal
disruption of the load path and minimal stress
build-up. Stress risers of any kind, abrupt
changes in thickness, brittle adhesives, the
wrong scarf angle, poor detail fit-up, preloads,
etc. should be avoided.
39.6.8 REPAIR OF METAL BONDMENTS
Honeycomb panels with metal face sheets
Because thin-skinned honeycomb sandwich
panels are the most easily damaged, structures
of this type are most often in need of repair.
Several kinds of repair activity are considered
typical by the industry:
1. minor repairs consisting of the application
of cold or hot bonded metal patches;
2. partial skin and/or core replacement with
or without the benefit of autoclave pres-
sure;
3. rebuild or remanufacture (considered depot
level repair).
Aluminum surface preparations
The quality of the repair is directly related to
the quality of the surface to which the adhe-
sive is applied. Poorly or inadequately
prepared bonding surfaces are the primary
reason why bonded repairs fail.
Typical repairs 871
Cleaning, deoxidizing, anodizing, bonding primer
application /cure
For optimum joint strength and bond durabil-
ity, all metal surfaces that are to be adhesively
joined require the following essential steps: (1)
degreasing; (2) alkaline cleaning; (3) deoxidiz-
ing; (4) low voltage anodizing in chromic or
phosphoric acid; (5) application, and (6) pre-
baking of a bonding primer. For other than
complete rebuilds, which imply complete tear-
down of the bonded elements, stripping of all
adhesive residues, and full reprocessing of
details through solution tanks, tank etch-
ing/anodizing and primer prebaking are often
omitted at the expense of repair quality and
longevity. Comparable values of various pre-
bond surface treatments are shown in Fig.
39.4.
Non-tank anodizing
A process known as PANTA (Phosphoric Acid
Non-Tank Anodizing) exists but requires
extensive preparatory work, equipment and
special skills, and has therefore not been fully
accepted by the industry at the present time.
Parts processed in this manner have been
demonstrated to be almost equivalent to tank-
processed parts in terms of bond strength and
d~rability'~.
Surface preparation for in situ non-autoclave
repairs
Typically, the repair patches or partial
replacement skins are cleaned, acid etched,
anodized, primed and prebaked. Structure
not amenable to tank solution processing, i.e.
the lap joint areas of the structure being
repaired, is typically prepared with an acid
paste, followed by a deionized water rinse,
air drying, and spray application of a bond-
ing primer without, however, the benefit of
prebaking. Elevated temperature prebaking
is generally impossible without exposing the
structure to heat damage and is therefore
872 Repair aspects of composite and adhesively bonded aircraft structures

LOSS IN SHEAR STRENGTH OF 2024 -T3 SAMPLES

-
BONDED WITH FM 123 5 ADHESIVE, AFTER 30 DAYS
AT 120OF AND CONDENSING HUMIDITY

UNEXPOSED I
EXPOSED 1 TANK ETCH
+ PHOS. ANODRE + CIP
UNEXPOSED I
, EXPOSED I TANK ETCH + CIP
OSFD I
EXPOSED I TANKETCH

UNEXPOSED
EXPOSED ISCOTCHBRITE. MEK + PASA - JEL
I

I I I I I I I
0 1000 2000 3000 4000 5000 8ooo

SHEAR STRENGTH, (PSb

Fig. 39.4 Effect of various aluminium surface treatments on repair bond strength and durability.

omitted, at some sacrifice in terms of bond
strength and durabilityI5.
Abrasive cleaning of lap joints
For reasons of expediency, many repairs are
effected under conditions considered marginal.
One common practice is to abrade the joint
area with aluminum oxide paper, followed by
solvent wiping and the application of the adhe-
sive. Repairs of t h s type, whether the adhesive
selected be a paste or a film, are rarely of long
duration and should be considered ’interim’
repairs only. On the other hand surface prepa-
rations using three-dimensional abrasives such
as Scotchbrite@,a product of the 3M Company,
in conjunction with high quality bonding
primers, have been demonstrated to produce
joints of considerable durability and should be
encouraged in preference over abrasion with
aluminum oxide paper only.
Application of bonding pressure
Vacuum bagging and bondline thickness control
For non-autoclave repairs, the most common
method of applying bonding pressure is by
means of a vacuum bag. Film adhesives used
for repair are normally scrim-supported and
thus provide bondline thickness control. (A
listing of representative film adhesives avail-
able with supporting scrims is provided in
Table 39.2. This listing is for reference only and
 Typical repairs 873

Table 39.2 Scrim-supportedfilm adhesives

Manufacturer Product designation Cure temperature range Max. use temperature

-
"C O F "C O F
-
Curing at 120°C (250°F)
Am Cy FM73 107-150 225-300 120 250
FM123-2 107-120 225-250 120 250
FM123-5, FM137 95-120 200-250 120 250
Hysol EA9628 113-120 235-250 95 200
3M AF126-2, AF163-3 113-120 235-250 120 250
AF3109-2 107-177 225-350 See Note
Narmco a Metlbond 1113 95-143 200-290 See Note
Metlbond 1133 95-135 200-275 See Note
B.F. Goodrich Plastilock 7178 107-120 225-250 82 180
Curing at 177°C (350°F)
Am Cy FM61, FM150-2 163-177 325-350 150 300
FM96 160-177 320-350 177 350
FM300 163-177 325-350 177 350
FM400 163-1 77 325-350 204 400
FM300-1 150-177 300-350 150 300
FM350 171-182 340-360 177 350
Hysol EA9689 177-182 350-360 177 350
EA9649R 175-180 345-355 177 350
3M AF191 175-1 80 345-355 177 350
AF131-2 175-180 345-355 204 400
AF143-2 175-180 345-355 177 350
AF147 175-180 345-355 150 300
Narmco a Metlbond 328 163-19 1 325-375 150 300
Metlbond 329 135-185 350-365 204 400
Metlbond 1515 163-177 325-350 150 300
B.F. Goodrich Plastilock 729-3 171-182 340-360 177 350
Note: Use temperature increases as a function of cure temperature.
a Now marketed by American Cynamid

not an endorsement for any given product.)
When using paste adhesives, scrim cloth is
normally inserted between the adherends to
prevent adhesive squeeze-out and resin star-
vation in the bondline.
Bondline porosities resultingfiom vacuum
pressure
The repair technician must be aware that not
all film adhesives are equally suitable for bond-
ing under vacuum pressure; indeed, most
products are formulated for positive (i.e. auto-
clave) pressure applications. After curing
under vacuum, some adhesives exhibit bond-
line porosities that inevitably result in lowered
bond strength, which must be taken into
account during the repair design. In an effort to
overcome these negative effects, a unique bag-
ging method called 'double-bagging' was
developed a number of years ago. This method
provides for an inner, 'low vacuum' bag 34 kPa
(under 10 in Hg) for expelling volatiles, and an
outer, 'high vacuum' bag 81-98 kPa (24-29
in Hg) to provide the equivalent of 4147KPa
(12-14 psig) bonding pressure on the assembly.
The intent of this method is to minimize the
effect of full vacuum pressure on the resin dur-
ing cure by isolating the laminate within a
separate diaphragm.
874 Repair aspects of composite and adhesively bonded aircraft structures

Application of mechanical pressure Pressure damage affects primarily details made

Mechanical pressure applications are some-
times used when both sides of the part are
accessible for clamping. Anacoustical (sound
suppression) panels having perforated or oth-
erwise permeable skins make the application
of vacuum impossible unless the panel is
envelope-bagged. To do so generally requires
extensive tear-down of the assembly and
removal of the affected panel. Permeable face
sheet materials (perforated metal, feltmetal,
permeable glass fiber /polyimide laminates, or
various fine mesh wire cloth acoustic sheet
materials) may be successfully bonded under
mechanical pressure, using liquid adhesives,
pastes, or unsupported reticulating film adhe-
sives.
Sand bags
Pressure application methods employing sand
bags, shot bags, etc., exist but are cumbersome
and yield repairs of marginal quality and
questionable durability. Such repairs should
always be rendered 'fail-safe' by the addition
of mechanical fasteners to provide a secondary
load path should an adhesive failure occur
during subsequent flight service.
from light-weight honeycomb core, which is
easily crushed if not adequately protected by
well-anchored support blocks. Bondments are
especially vulnerable to damage when the
integrity of the vacuum bag is breached and
compressed gasses enter the assembly. Well-
designed fixtures, proper padding of potential
puncture sites, bagging films of high quality,
pressure levels appropriate for the materials
and part configuration, as well as constant
monitoring of the pressure cycle are imperative
to prevent damaging parts during the cure.
Table 39.3 shows the bonding pressures consid-
ered typical. It should be noted that for
assemblies incorporating honeycomb (sand-
wich structures) the recommended pressures
are predicated on the compressive strength of a
core being simultaneously subjected to both
autoclave pressure and elevated temperatures.
Panel edges are occasionally collapsed during
cure, if not properly supported against side
loads. Bevelled edges should have angles
between 15 and 20°, as shown in Fig. 39.5.
Steeper angles require that the core be stabi-
lized with additional resins or core fillers to
prevent collapse under pressure.
Application of heat

lnj7atable bladders How to introduce the proper amount of heat

for curing the repair adhesive or resin has long
A novel pressure application method using an been considered problematic. Unlike manufac-
inflatable rubber bladder system has report- turing processes, which can be optimized
edly been successful16.The loads generated by through cure cycle verification by destructive
the inflating bladder must be reacted out testing, most repairs are rather unique and
against one or several hard points on the air- influenced by a multitude of factors not easily
craft structure, which requires equipment of controlled. Heating blankets of a constant watt
model-specific design geometry. density tend to overheat thin sections, e.g. the
trailing edges of a bondment, while undercur-
ing the bondlines located over a heat sink, e.g.
Specific risks associated with pressure
a heavy metal fitting or a spar. It has often
Parts may be damaged during repair through been found necessary to protect thin sections
improper pressure application. Most damages against overheating by inserting silicone rub-
occur in the autoclave and are the result of poor ber pads between the heating blanket and the
fixturing and of insufficient attention being part, thus reducing the effective cure tempera-
paid to proper vacuum bagging techniques. ture in selected areas, while allowing the
 Typical repairs 875

Table 39.3 Recommended bonding pressures

Core material Thickness/cell size Density Max pressure

cm in kg/m3 p.c& kPa Psig
Honeycomb Sandwich and MetaYMetal Panels (AluminumBondments)
Aluminum over 12.7 over 0.5 48 or higher 3 or higher 118 35
less than 3 84 25
Aluminum under 12.7 under 0.5 48 or higher 3 or higher 35 40
less than 3 101 30
No core n/a n/a 169-338 50-100
Laminates and Panels Containing Non-metallic Honeycomb Cores
Aramid* 3.1 1/8 48-64 3.04.0 118 35
4.7 3/16 48 or lower 3.0 or lower 84 25
56-88 3.5-5.5 101 30
635 1/4 all 84 25
9.5 3/8 all 84 25
No core n/a n/a 152 or 45 or
higher higher
* Nomex HRH, HRP, Hh4X or similar core materials.

colder portions to reach the appropriate cure
temperature. Occasionally, heat lamps or other
auxiliary means must be employed in conjunc- 3.
tion with heating blankets to provide
additional heat inputs at critical locations to
make sure the resins are fully cured. It is
imperative that thermocouples be used at as
many locations as necessary to monitor the
cure cycle and to ensure the repair meets spec-
ification requirements when completed. 4.
Specific risks associated with heat
The principal risks associated with repair
activities on structures that require the use of
thermosetting resins and adhesives are:
1. Water or residual moisture in any portion of
the assembly may vaporize and cause addi-
tional damage such as ply separation, core
node bond separation, or skin-to-core bond
failure (see Section 39.5).
2. Overheat conditions may develop under a
heating blanket, causing irreversible dam-
age, occasionally a fire. Constant
monitoring or the incorporation of overheat
alarms may prevent part damage during
the cure cycle.
Heat sinks may drain away heat energy
required for resin cure, leaving residual
uncured materials of unacceptable struc-
tural value. Hot bonding should not be
carried out during adverse atmospheric
conditions or while the aircraft is cold-
soaked.
Improper heat-up rate control may cause
resin flow and gel anomalies resulting in a
product of marginal quality. Heat-up rates
must be monitored or appropriate control
devices used.
5. Foaming adhesives may generate exother-
mic reactions resulting in irreversible
damage. This hazard can be avoided by
minimizing the width of splice gaps to be
filled through careful sizing and fit-up of
details prior to and during lay-up. Non-
metallic core details should be joined by
crush splicing rather than by adhesive
foams to reduce the amount of reactive
polymers present in the panel during the
cure cycle.
876 Repair aspects of composite and adhesively bonded aircraff structures

'
0 15' 30' 45 goo
5052 100% 80% 76% 19% 2%

HRH 100% 86% 70% 15% 2%

*O fI I I
\
0
8'.
1
-- - - _
O0 15O 30° 450 900

OFF-AXIS BARE COMPRESSIVE STRENGTH

OFHONEYCOMB CORE
b

Effect of core edge bevel

on core stability under
bonding pressure
e
C

Fig. 39.5 (a) Bare compressive strength of honeycomb at various angles of loading; (b) Off-axis bare com-
pressive strength of honeycomb core; (c) Effect of core edge bevel on core stability under bonding pressure.
 Typical repairs 877

Lower cure temperatures enhance repair safety

~"
be the choice for repairs on aluminum, because
of its galvanic compatibility and its favorable
Problems associated with hot bonding
CTE with respect to aluminum. Graphite is
increase exponentially as a function of cure
inherently incompatible for the same reasons
temperature. Cure temperatures in excess of
and may be suitable only for repairing titanium
180°C (360°F) are several times more likely to
substrates. Composite repairs can be made by
result in a failed part than repairs performed
applying multiple layers of prepregged fabrics
at lower temperatures. Given the option,
or unidirectional tapes, which may be cured by
repairs should always be conducted at the
means of heating blankets under vacuum or
lowest practical cure temperature, using a
mechanical pressure. Overlays of this type have
suitable adhesive or resin system. See Table
been reported to enhance the fatigue life of con-
39.1 for typical products.
ventional metal structures by several orders of
magnitudez1.One major disadvantage is the
39.6.9 COMPOSITE REPAIRS APPLIED TO need for a chemically prepared surface involv-
METAL STRUCTURES ing the use of acids which, if entrapped under
the repair, could cause corrosion and premature
Resin-impregnated fiberglass cloth repairs structural failure, making periodic NDT of the
on aluminum repair mandatory for the remainder of the air-
frame life. For maximum effectiveness,
Wet lay-up, epoxy-impregnated fiberglass
phosphoric acid non-tank anodizing (PANTA)
cloth repair patches have been approved repair
and the use of bonding primers are essential.
methods via OEM Structural Repair Manuals
When using graphite as the backbone fiber, a
and Military T.0.s for many years1. Utilizing
barrier ply of fiberglass is necessary to prevent
room temperature curing resins in conjunction
galvanic coupling between the repair material
with fabrics, wet lay-up repairs can be applied
and the substrate. The risks involved have thus
over flat as well as curved surfaces with a min-
far inhibited the use of graphite on aluminum.
imum in equipment and under almost any
conditions. Experience has shown, however,
that in terms of overall quality and durability,
39.6.10 MECHANICALLY FASTENED REPAIRS
these repairs are the least desirable and should
be applied only when more advanced methods With increased use of composite materials in
are unavailable. All resin-impregnated cloth primary and principal structure not readily
repairs over metal require the use of primers removable from the aircraft after a damage
(typically nitrile rubber based liquids) to pro- incident, bolted repair concepts are being vali-
mote resin-to-metal adhesion. dated for major skin/stringer and skin/chord
damage repairs. Utilizing mainly precured
composite elements together with metal dou-
Repairs utilizing advanced fibers
blers and splice angles, such repairs can be
Repairs utilizing boron/epoxy and graphite/ effected where access is limited to one side of
epoxy prepregs over aluminum substrates have the structure only. Essentially, such repairs are
been under active consideration for use on mil- a logical extension of, and quite similar to,
Only recently, a conventional mechanically joined metal
itary aircraft for some time17-21.
large freight carrier made the decision to apply repairs, except that both metallic and precured
boron/epoxy patches on some of its large trans- composite elements are utilized. The Boeing
port category aircraft, malung this the first time B-777 is the first major program to approve
that boron is being used for this purpose on a this type of repair on its primary structures,
commercial fleet in the USA. Boron appears to chiefly its all-graphite composite empennage.
878 Repair aspects of composite and adhesively bonded aircraft structures

39.7 TECHNICIAN TRAINING AND SKILL 39.8.2 INSUFFICIENCYOF TECHNICAL

REQUIREMENTS TRAINING
Personnel engaged in designing and carrying Technical school curricula as well as regula-
out repairs to bonded and composite aircraft tory guidance materials dealing with
structure should be familiar with the funda- composite aircraft repairs are suffering from a
mental concepts listed in Table 39.4. technology lag that can, ultimately, only be
bridged by greater emphasis on education and
39.8 CONCLUSION AND SUMMARY training at all levels. Community colleges and
vocational schools should encourage the
39.8.1 TECHNOLOGICALEVOLUTION active participation of people experienced in
OUTPACING TRADITIONAL AIRCRAFT the field (even though they may not possess
MAINTENANCE SKILLS AT ALL LEVELS the requisite academic credentials) and seek to
enlist the help of subject matter experts.
It has been observed that with every new gen-
eration of commercial aircraft, there is an
increase in the utilization of composite materi- 39.8.3 DESIGN AIRCRAFT FOR
als and a corresponding increase in the MAINTAINABILITY
complexity of its design. The transition from
simple hand layed-up bonded aluminum hon- Design criteria focused on manufacturability
eycomb sandwich and fiberglass-skinned without regard to maintainability may ulti-
Nomex panels to monolithic carbon fiber mately result in compromising flight safety,
structures produced largely by means of auto- especially now that composites are finding
mated equipment has been a long, inexorable, increasing use in primary and principal air-
and not altogether painless process from the craft structure. New regulations mandating
operators’ point of view. ’damage-tolerant’ designs should be of great
The end users, principally the world’s value in the determining the design criteria of
commercial airlines, are finding it increas- future aircraft. Airline customer involvement
ingly difficult to keep up with the rapid in the design of new aircraft must go beyond
technological changes thrust upon them by payload, range, and other marketing concerns;
the manufacturers. Despite the large volume the time has come for the designer to solicit the
of technical literature available on the subject comments and suggestions of the maintenance
of composites, there is a dearth of practical engineer, the inspector and the mechanic.
information. One is tempted to say that the
industry is encumbered by a surfeit of highly
39.8.4 NEED FOR STANDARDIZATION
specialized data that is impenetrable to all
but the experts. There is no denying that this Standardization of repair methods, practices
research is both necessary and beneficial; and especially, repair materials is long over-
there is, however, a dire need to make this due. The emphasis must be placed on the
data amenable to all through thoughtful dis- typical and generic, rather than the peculiar
tillation. The worker in the field must know and proprietary. Cooperative efforts involving
the practical effects of this research on the manufacturers, materials suppliers, airlines,
daily exercise of his craft. He must be kept repair facilities, regulatory agencies, profes-
abreast of technological advances and given a sional societies as well as academia will be
chance to upgrade his skills in order to meet needed to ensure the long-term viability of
ever-changing demands. composites in aircraft structures.
 Conclusion and summary 879

Table 39.4 Composite repair training topics

Components of Composite Materials

Fibers and filaments Glass and quartz; carbon and aramid; boron
Product definitions Fiber; roving; strand; yam; woven fabrics, unidirectional tape; milled fibers
Fiber mechanical Density; strength; modulus; coefficient of thermal expansion
properties
Finishes and sizings Chrome; silanes; plasma treatments; resin solutions
Specialty fabrics Scrims; peel plies; bleeders and breathers; ceramics
Bonding adhesives, Epoxies; polyesters; phenolics; polyimides; bismaleimides; catalysts and
resins, prepregs hardeners; cyanate esters; acrylics; anaerobics; liquid adhesives; primers;
coupling agents; film adhesives; prepreg fabrics and tape
Procedures of Fabrication and Processing
Laminating The 'Laminate Code'; isotropic, anisotropic, quasi-isotropic laminates; cross-plied
laminates; hybrid laminates; anacoustic laminates
Other structures Filament/tape winding; RTM; braiding; pultrusions
Curing methods Autoclave; non-autoclave; single and multi-stage cures; postcuring; cure
monitoring - flow/gel/set
Vacuum bagging Bagging films; sealant tapes; breathers and bleeders; bagging techniques
Adhesive bonding Pastes; liquids; films; cements; pressure application
Sandwich panel Face sheets, doublers and close-outs/pans; core; properties of sandwich
construction construction:static strength and rigidity; adhesive filleting; shear ties
Core materials Metal/non-metal honeycomb; cell sizes and shapes: hexagonal, overexpanded,
flexcore; core density/weight; directional properties; compressive and shear
strengths
Surface preparation Cleaning, etching, anodizing, primer application; aluminum, steel, titanium,
for metals other metallic adherends
Surface preparation Abrasion; grit blast; taper sanding lap joints; step joints; use of peel plies
for non-steps
Joining and fastening Bonded joints; mechanical joints; fastener types and alloys; hole spacing; edge
distances; hole sizes for composite joints
Machining of Sawing; routing; drilling; sanding and grinding; water jet cutting; laser cutting
composites
Protective Coatings and Sealants
Organic polymers Pinhole fillers; sanding sealers; primers; surfacers; enamels: epoxy, polyurethane;
polysulfide coatings and sealants
Anti-static and Carbon-filled enamels; flame spray coatings; EM1 shielding materials
lightning protection
Heat and fire Silicone coatings; ablative and intumescent coatings; heat-resistant enamels
protection
Environmental Effects
Moisture Effect of moisture on uncured resins
Effect of moisture on cured systems
Temperature Effect of temperature on uncured resins
Effect of temperature on cured systems; glass transition
temperature; heat deflection temperature
Corrosion Galvanic corrosion: carbon/metal couples
Corrosion prevention
Erosion Effect of rain and particulates
Radiation Ultraviolet; thermal; nuclear Continued on next page
880 Repair aspects of composite and adhesively bonded aircraft structures

Table 39.4 (Continued)

Atmospheric Static charges; lightning strikes

electricity
Chemicals Aircraft system fluids: oils, hydraulic, deicing
Accidental exposures: paint stripper, solvent spills
Aging Fatigue and embrittlement effects on composites
Standard Tests for Adhesives and Prepregs
Metal adhesion Tensile shear; T-peel; honeycomb peel; crack extension (wedge) test
Prepregs Volatile and resin content; resin flow; gel time; tack
Cured laminates Interlaminar shear; short beam shear; flexure; 45" in-plane shear; tensile and
compressive strength and modulus; sandwich beam; hot/wet strength
Inspection and Quality Controls
Non-instrumented Visual inspection; tap test; penetrants
Instrumented X-ray; moisture detector; pulse-echo ultrasonic; through-transmissionultrasonic;
resonance ultrasonic; eddy current
Process quality Raw materials handling and storage; environmental controls; processing
controls materials controls; facilities and equipment controls; tool design and alteration;
detail preparation; in-process sampling inspections and witness coupons
Post-repair NDI Verification of compliance with specifications:cure cycle chart review; physical
tests and checks
Damage Assessment, Failure Analysis, Preventive Maintenance
In-service damage Foreign object impact; environmental degradation
Failed repairs 'Lesson learned'
Periodic inspections Coatings and sealants
Electrical continuity check
Specific Repair Methods
Repair categories Construction type; original materials; original cure temperature
Repair preparation Stripping; damage assessment and removal; decontamination
Repair materials Adherends and adhesives; auxiliary/ processing materials
selection
Surface preparations Metals; non-metals
Adhesive/resin cure Applying heat and pressure; cure and postcure; cure monitoring
Assembly completion Reassembly; finishes; weight and balance; final inspection
Health and Safety Aspects of Composites
Chemical exposure Dermal; ocular; inhalation; ingestion
routes
Hazard levels Acute vs. chronic toxicity
Material safety data The MSDS and how to interpret
Basic industrial Engineered control systems; personnel protection
hygiene
Toxicology of Resins and catalysts; solvent and diluents; fibers and fiber dust; sealants and
composite materials coatings

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Laboratories, Wright-Patterson AFB, OH 45433,
1982.
REUSE AND DISPOSAL
Harry E. PebZy
40.1 INTRODUCTION
As the United States and the world become
more conscious of the shortage of landfill
space and the need for conservation, they will
be driven to find ways to solve or alleviate the
problem by developing methods for reuse or
other disposal of materials. Composite materi-
als offer a particular challenge because of the
nature of the reinforcements and fillers. In the
case of thermoset composites, the matrix or
resin cannot be remelted or reprocessed as can
be done with thermoplastic matrices. Many of
the non-composite thermoplastics are rou-
tinely collected and recycled in towns and
cities throughout the world. This chapter will
primarily deal with thermoset composites
because of the challenge of finding methods to
put these materials back into use, and in a
viable economic scenario. Most of the recy-
cling effort involves reuse of sheet molding
compound (SMC) because of its considerable
potential in the automotive market and its
emerging economic viability. Technology
involving SMC is usually applicable to bulk
molding compound (BMC)also. Thermoplastic
composites will also be discussed. Hybrid
composites, presumably because of their rela-
tively small usage and more complex makeup,
have had no reported recycling attention, but
some of the reuse technologies described
herein should be useful. Several practical tech-
nologies for recycling and reuse have been
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
40
developed but the problem of markets for the
reprocessed composites remains largely
unsolved.
Plastics recycling is generally classified into
four categories by final product or by-product,
as follows:
1. Primary: Recycling a plastic product into an
identical or similar new product;
2. Secondary: Recycling a plastic product into
a new product that has less demanding
physical or chemical properties;
3. Tertiary: Converting plastic wastes into
basic chemicals or fuels through a process
such as pyrolysis;
4. Quaternary: Burning the plastics and recov-
ering their heat energy.
Composites are recycled in all of these cate-
gories, with the fourth, burning for energy
recovery, of the least value.
40.2 HISTORICAL PERSPECTIVE
Recycling of certain commodity thermoplas-
tics, particularly polyethylene (PE) and
polyethylene terephthalate (PET), has
become a routine matter in thousands of
cities and towns in the past few years. There
have been upturns and downturns in recent
years in balancing availability of PE and PET
with demand for products and markets. One
example is the demand for plastic soda bot-
tles for conversion to polyester for garments
(Disenhouse, 1994). The situation illustrates
an important point, common to all industries:
it is not only a question of developing tech-
884 Reuse and disposal
nologies for reuse but making it economically
viable to do so.
Activity in recycling thermoset composites
in Europe, particularly Germany, precedes
that in the USA. The action is driven by legis-
lation and public opinion, as is the case in
Japan also.
40.3 RAW MATERIAL FORMS
40.3.1 REINFORCEMENTS
Glass fiber
Glass fiber is the most widely used reinforce-
ment in the world, with nearly 1.2 million
metric tons used in 1992 to reinforce 50 or more
different engineering thermoplastic and ther-
moset resins. Various processes used to recycle
or separate the glass from the resin affect the
nature and quality of the recovered glass. First
quality glass can be reused directly, without
further processing, in a new composite mater-
ial. Other processes yield a glass that will
require chemical resizing to renew its interfacial
bonding to the resin. When the glass suffers
deterioration in strength or contamination in
recycling, the glass fiber must be refibered or
remelted before it can be used again.
Commercially viable technology that will
allow widespread use of recycled and contam-
inated glass in reinforcement manufacturing
processes is now being developed.
Implementation of this technology will open
up glass remelting and fiberization as a viable
recycling approach, making it possible to con-
template truly closing the loop for glass
reinforcement (Graham,Jutte and Shipp, 1993).
In thermoplastic recycling, a mixed stream
of resin often occurs. Addition of virgin glass
fibers has been shown to provide improved
properties in mixed thermoplastics. Use of
recycled glass fibers would therefore benefit
both thermoplastic recycling as well as glass.
The glass could be obtained from recycled
thermoplastics or thermosets, either as a
regrind or from one of the other approaches.
Carbon fiber
Carbon fibers can be recovered from uncured
epoxy prepreg scrap by two methods. One is
by use of an organic solvent agitated bath
which washes out the resin. The second
employs thermal degradation, below 400°C
(750"F), to eliminate the epoxy. The resulting
fibers are cut to length 23 mm (0.10 in) for use
with aligned discontinuous fibers and provide
improved drapability for complex shapes
(Norris, 1990). Because fiber and fiber scraps
are randomly oriented, the cutting operation
should be carried out in two directions, neces-
sitating a special cutting device (Richter and
Brandt, 1987). Aligning short fibers results in
composites with mechanical properties that
are below those of long fiber reinforced mate-
rials, but considerably above those of short
fiber reinforced injection and compression
molded composites.
40.3.2 RESINS
Work has been done to develop epoxies, poly-
imides and unsaturated polyesters for
recovery (Section 40.4.2). The reversal of
chemical reactions utilized to produce ther-
moset and thermoplastic polymers to
regenerate monomers or beginning chemicals
is covered below (Section 40.4.4). It is possible
to extract polyester resin from uncured SMC
and reuse the glass fiber in both SMC and
BMC. The extraction is done by solvent
extraction with mechanical agitation.
40.3.3 PREIMPREGNATED MATERIALS
(PREPREGS)
A multi-year program, beginning in 1991, is
underway on carbon/epoxy prepreg scrap
recycling at the Center of Excellence for
Composites Manufacturing Technology
(CECMT), operated for the US Navy by the
Great Lakes COmposites Consortium (GLCC).
The priority of the scrap program at CECMT is
illustrated by the fact that for every

0.45 kg (1lb) of composite materials used in
aircraft, ship or missile manufacture,
0.90 kg (2 lb) of material ends up in landfills.
The average ratio is 1.3 to 1. This waste
includes both material generated by the mate-
rial supplier and material generated by the
end item manufacturer. In time, composite
scrap produced at repair facilities will add to
this total. Approximately $1billion of all types
of raw prepreg is wasted annually and $25
million is spent on its disposal, according to
information prepared for the Naval Industrial
Resources Support Activity (Broudy, 1993).
Another concern is with the legal status of
prepreg waste: is it considered hazardous?
Both state and federal regulations must be
considered. California, for one, has require-
ments for cured and uncured waste and its
disposal. Other state requirements may vary
for both material forms.
The objective of the CECMT program is to
develop a plan for reclamation of
carbon/epoxy prepreg scrap and demonstrate
the recyclability of the material, based on a
survey of users which revealed that carbon/
epoxy is the major prepreg contributing to the
waste stream. This scrap or waste material is
sometimes referred to as 'offal'. The aerospace
industry generates 60-80% of the prepreg
offal, with 50% of the total in broad goods
form. The most widely used epoxide is
tetraglycidylmethylenedianaline (TGMDA)
cured with diaminodiphenylsulfone (DDS).
Other accomplishments of the program, as
reported by Lause (1993) of GLCC, are as fol-
lows. A low speed, high torque shredder was
found to be best for cutting high tensile and
high shear strength carbon fibers. Other cut-
ting blades evaluated were guillotine, carbide,
slitter and shear types. A low torque machine
did not give a clean cut. The shredder employs
two cutting blades, rotating inwards or
counter to one another, powered by a 30 hp
motor. Shredder input was the scrap prepreg
collected from Gerber cutters, i.e. random size
and shape. The offal was cut into 50 mm (2 in)
Reuse technologies 885
flakes and molded into test panels. Mechanical
and physical properties were found to be 80%
of that obtained with virgin prepreg. Work
was then begun to use material directly from
the shredder, to avoid cutting the high tensile
strength material into 50 mm (2 in) flakes.
Early indications are that approximately the
same strengths can be obtained with the ran-
domly oriented material. Preliminary analysis
indicates that most epoxies can be comingled
and coprocessed.
Niche markets are being sought for uses of
the reclaimed prepreg, based on the 80%
strength obtained and the comparatively lim-
ited amount of carbon/epoxy produced in the
US, estimated to be 5.5 x lo6kg (2.5 million lb)
annually. Markets are sought which would
provide highest profitability for the manufac-
turer; sporting goods and medical prosthesis
devices are possibilities.
40.4 REUSE TECHNOLOGIES
Cured thermoset composites undergo the fol-
lowing steps in preparation for reuse. Cutting
complete items ( e g boats) into small pieces
suitable for handling for shredding is the first
step in the process. Items 1.35-1.80 m2
(15-20 ft2).in size or scrap (cured or uncured)
may go directly to shredding. Shredding
reduces the material to sizes suitable for the
next step, whether it be particle preparation
(grinding, milling, granulating) or pyrolysis.
Shredding will not be necessary for pyrolysis
if the item can be accommodated in the pyrol-
ysis furnace. Classification of the shredded
material or of the resulting particles will be
required if more than one product is desired
(eg. glass fiber and powder). Shredding for
most experimental work provides chips (or
piecesj50 mm x 400 mm ( 2 in x 8 in) to 50 mm
x 50 mm ( 2 in x 2 in); granulation gives 9 mm
(3/8 in) and smaller particles; and grinding or
milling a powder, suitable for filler, of 50 pm
or less. Size of particles and powder is deter-
mined by screen size.
886 Reuse and disposal
40.4.1 MECHANICAL GRANULATION OR
MILLING
Mechanical granulation is probably receiving
the most attention as a method for reuse of the
final composite, whether it be waste from the
molding process or the cured product.
Polyester (unsaturated) SMC, because of its
predominant place in the total spectrum of
thermoset composites, is the material form of
most interest. For example, the total automo-
tive usage for SMC in 1993 is estimated to be
342 x lo6 kg (155.6 x lo6 lb) and the SMC
Automotive Alliance projected a 55%jump to
more than 594 x lo6 kg (270 x lo6 lb) by 1995
(Wigotsky, 1993).Phenolic and urethane-based
thermoset composites have also been demon-
strated to be recyclable by mechanical milling
to a reinforcing filler. Further, it appears that
fully milled thermoset can be reused as filler in
an indefinite number of cycles without loss of
performance.
Mechanical recycling methods are based on
using SMC scrap directly without alteration of
its chemical nature. The SMC scrap is shred-
ded and/or ground into a form which can be
used as a filler. Ball or hammer milling, cryo-
genic grinding and knife granulating are used
for mechanical granulation. A typical granula-
tor uses double cross-angled blades rotating
against an opposing angled blade, while a
hammer mill reduces material size by the
hammer revolving at high speeds and cutting
by impact in mid air. The entire SMC article
may be ground to a fine powder (including all
the glass fiber). The other approach is to shred
and mill the SMC article in a manner which
will recover some glass fibers which are sepa-
rated from the particulate material (powder).
Recovery of some glass fiber is important
from a cost-effectiveness basis because fibers
have more commercial value as a reinforce-
ment filler (versus particulate filler). Also, it
requires more energy to grind all of the fiber
into a powder, then to recover a portion of the
glass fibers. Premix found the most economi-
cal process to regrind scrap consisted of a
granulator, a hammer mill pulverizer and a
classifier. Each piece of machinery is commer-
cially available,: custom design is-not required
(Butler, 1991).
In the USA, the SMC Automotive Alliance,
Owens-Corning and Premix are among the
leaders in fiberglass composite recycling, but
other proprietary recycling activity is also
being carried on (Section 40.10).
Canadian work is being done by Phoenix
Fiberglass Inc. and Plastiglas Industries
(Darrah, 1993). Phoenix Fiberglass, through a
mechanical process, is able to separate the two
components of a laminate that include the
glass reinforcement in the form of fibers and
the thermoset resin in the form of a powder. In
the pilot plant, the waste laminate was
inspected for contaminants before it was intro-
duced into the recycling process, with the
result that long and short fibers as well as two
types of fillers or resin extenders were recov-
ered.
Plastiglas Industries Ltd recycles its own
waste composites, but has developed the
methodology to combine waste composites
with other materials from other sources, as
well as with other virgin materials. These
other materials may come from the blue box
program (a curbside collection effort), from
sandblasting operations that want to dispose
of their waste from sanding operations, and
even crushed concrete.
Materials that have been identified for use
according to a certain recipe will be sorted by
size. Depending on the end-use, pieces that
range in size from 6-200 mm (0.254 in) can be
used. When the material that is to be used in a
recipe is larger than 200 mm (8 in), it is
reduced to the required size. This part of the
operation may use a specially built water-
cooled diamond wire saw, which can handle
pieces up to and including 3 m (10 f t ) in diam-
eter and/or 3 m (10 ft) square. If further size
reduction is required, shredders and grinders
are used to achieve the proper particle size
A significant German program was
sparked by public and political pressure upon
 Reuse technologies 887

the plastics industry to become responsible Milled SMC is being used in several automo-
for the reuse and cost of their products at their tive parts. Up to now there has been no
end-of-life (Schaefer and Plowgian, 1993).The technical development reported of a fiber
major companies from the SMC/BMC market recovery method. Pyrolysis is another impor-
founded ERCOM Composites Recycling tant reuse technology.
GmbH. The proposed German Refuse Act for The Swedish Institute of Composites con-
car recycling, with its priority for material centrated on evaluating several proprietary
recycling, also provided impetus for action. formulations of SMC using two reground frac-
ERCOM offers a complete system to close the tions: one powdered fraction with sizes in the
loop between used parts from automotive ser- range of 200 pm - 1mm and one fibrous frac-
vice and disassembly plants and the reuse of tion with sizes of up to 500 pm (Pettersson and
fibrous reinforcing material in new SMC com- Nilsson, 1993).The reground SMC came from
pounds: automotive bumpers supplied by ERCOM.
Existing grinding and fractioning techniques
0 a mobile shredding truck that crushes used
were used.
parts at disassembly and production sites;
0 transport the compacted material to a cen-
tralized fractionizing plant; 40.4.2 REVERSIBLE CROSSLINKING
0 produce a range of fiber rich recyclate mate-
The Department of Energy has sponsored
rial to sell back to SMC producers and other
work at Polytechnic University, Brooklyn,
end users.
New York, to develop experimental thermoset
The mobile shredder and fractionizing plant polymers designed for recovery (Tesoro et al.,
have been in operation since the beginning of 1992). Tesoro has shown that it is feasible to
1992. The mobile shredder reduces the size of recover chemical compounds and polymers
large parts to a chip size of about from epoxies, polyimides and unsaturated
50 mm x 50 mm (2 in x 2 in). This is a volume polyesters. Designing the polymers for recy-
reduction of a factor of five. The commonly cling by introducing labile bonds is utilized for
used metallic inserts in automotive parts do epoxy resins crosslinked with disulfide-con-
not have to be removed beforehand. In fact, taining curing agents and for disulfide-
preshredding to this predetermined chip size containing polyimide copolymers. Stress-
is an essential requirement to assure removal strain curves for epoxy resins cured with a
of metallic parts in the next processing step. disulfide-curing agent, dithiodianiline
The preshredded material is then processed (DTDA) and a commercial aromatic diamine
automatically through a series of pneumatic curing agent (MDA) show the equivalence of
and mechanical fractionizing steps. It is essen- the DTDA to MDA. Solubilizationof the cured
tial to remove metallic parts in this sequence to thermosets by reduction of disulfide bonds
assure a metal free product. A hammer mill is provides sites for re-curing. Epoxies may also
used for the grinding step. The resulting fiber- be crosslinked with a polyfunctional reagent
rich recyclate can be produced in a series of which reacts with thiol groups formed in
fractions containing a mixture of glass fibers, reduction. Tesoro has also worked on obtain-
fillers and resin. ing chemical products from cured unsaturated
The emphasis in Japanese composite recy- polyesters (UP) (Tesoro and Wu, 1993). The
cling has been in dismantling or cutting up focus of the investigation was on chemical
large fabricated parts, particuarly fishing ves- reactions of well established UP structures to
sels and boats, bathtubs, and tanks (Kitamura, yield soluble, well-characterized chemical
1993).Shredding is best done by a non-gearing products that would be suitable as raw mate-
type or a rotary shock shearing type shredder. rials for synthesis. Neutral hydrolysis was
888 Reuse and disposal
found to be a viable approach through cleav-
age of ester bonds, giving phthalic acid in
good yield and soluble carboxyl-containing
oligomers of potential utility were isolated.
Recovered oligomers for acid curing of
epoxy resin systems have been explored with
encouraging results. Smooth transparent films
perhaps suitable for coatings have been
obtained. The use of recovered oligomer as
saturated acid in the ex novo synthesis of UP
resins has also shown promise.
40.4.3 PYROLYSIS
Pyrolysis is the controlled thermal degrada-
tion of an organic material into one or more
recoverable substances through the applica-
tion of heat in an oxygen-free environment.
Pyrolysis should not be confused with inciner-
ation, which is the total oxidation of all the
organic materials. Pyrolysis has been used for
years to reduce plastic and rubber wastes, par-
ticularly the stockpiles of used tires.
Pyrolyzing SMC in the USA, however, is rela-
tively new.
Primary emphasis to date has been applied
to scrap materials in the manufacturing
process. Ultimately, recycling of parts at the
end of their application life cycle must be
addressed if elimination of all SMC from land-
fill is to be achieved.
Pyrolysis has a major advantage in that it is
well suited to handling contaminated scrap,
i.e. SMC which contains paint, adhesives, fas-
teners or is mixed with other materials.
The SMC Automotive Alliance of the SPI
Composites Institute (1991), a group of mater-
ial suppliers and molders, has worked on
pyrolysis of SMC auto scrap. In its early
stages, the main problem was shredding and
feeding materials into the pyrolysis equip-
ment. A discrete chip with minimum polyester
breakup is needed to make the process cost
effective. By-product utilization is the other
factor which will influence the feasibility of
the process for SMC waste disposal.
In Japan, The Ship Research Institute (SRI)
carried out experiments in cooperation with
Michimae using a batch type external heating
pyrolysis furnace (Kitamura, 1993). The sys-
tem was conducted for scrapped reinforced
plastic (RP) ship material. When material is
heated for about 10 min, gas is produced and
more gas can be collected as the temperature
rises. The amount of gas which can be col-
lected reaches a peak at 275°C (527°F).The gas
produced is either water cooled or run
through a heat exchanger to yield some pyro-
oil and the rest, gas. The RP used in the
experiment had a 40 wt YOof glass content as is
common for RP used in ships. The residue is
fiberglass and carbon, i.e. 40 wt YO and 12
wt YO, respectively.
The Japan Marine Recreation Association
under the Ministry of Transport and Sasakawa
Foundation has been developing a mobile
pyrolysis/incineration system for RP ships
since 1990. It is economically advantageous for
large structures like RP ships to be treated as
they are without pre-processing. The mobile
pyrolysis/incineration system comprises two
trailers, each of which has a body 7 m (23 ft)
long, and 2.6 m (8.6 ft) wide, holding a
destructive distillation furnace and a rotary
kiln, respectively. The system first pyrolyzes
an RP ship into pieces less than 6 m (20 ft) in
length under a temperature condition of about
400°C (750°F). After shredding into small
pieces, removing metals and moving to the
second trailer on which a kiln is loaded, the
residue is then incinerated in the rotary kiln. A
pilot plant on land has been constructed and
tested and mobile pyrolysis/incineration sys-
tem trailers will be completed in 1993.
40.4.4 CHEMICAL DEGRADATION
Under the proper conditions, the chemical
reactions that are utilized to produce ther-
moset and thermoplastic polymers can be
reversed to regenerate the various monomers
involved. Among these are the 'chem-olysis'
processes: hydrolysis, glycolysis, methanoly-
sis, aminolysis, as well as polyurethane (PUR)

foam and reaction injection molding (RIM)
depolymerization, saponification, refinery
cracking, and thermal 'unzipping' of poly-
olefins.
Since these approaches take the organic
polymers back to more basic chemical build-
ing blocks, they have the potential advantage
of yielding known chemical streams that can
be converted, using existing purification and
polymerization technology, to new polymer
with properties equivalent to the virgin poly-
mer. The depolymerization processes will also
free up the glass reinforcement used in the
composite. In the polyester field, chemical
degradation is being utilized primarily for
polyethylene terephthalate (PET).Inasmuch as
this thermoplastic is primarily used without
reinforcement, e.g. bottles and film packaging,
no detailed attention will be given here.
Typical products obtained in chemical degra-
dation or depolymerization are dimethyl
terephthalate (DMT) and ethylene glycol (EG).
Pyrolysis, another form of chemical degrada-
tion, has been discussed previously; it is a
practical recycling process for unsaturated
polyester (SMC).
40.4.5 HEAT CLEANING
Heat cleaning has been utilized in recovering
useful products from scrap circuit board lami-
nates (Hanson, 1991). Pennisula Copper
Industries, after removing the copper from the
board, has found it can heat finished or inter-
mediate thermoset composite products,
completely volatilize the epoxy resin, and
recover the glass fibers with much of the
strength of new fibers. The key is a carefully
controlled temperature profile as the scrap
moves through the furnace (called a calciner),
and control of the process gases. The solidified
gases are also potentially useful by-products.
40.4.6 FUEL
Liquid waste from producing SMC and BMC
has found use as fuel. By introducing a chem-
Properties and products of recycled materials 889
ical solvent which is blended both in the waste
paste and waste resin, to keep them in a
pumpable state, Premix has used the waste to
fuel cement kilns (Butler, 1991). This waste
will be used to fire the kiln and then the ash
from the firing is put into the cement. This
process also eliminates the need to landfill the
ash. Some bathtub manufacturers in Japan use
special incinerators to recover the steam for
boilers from the waste. However, in this case,
secondary treatment equipment is necessary
to prevent air pollution.
40.4.7 DISPOSAL/RECYCLING MODELS FOR
REUSE TECHNOLOGIES
A disposal/recycling model for composite
waste material has been developed by Vital
Visions Corp. to help evaluate practical and
cost effective disposal or recovery methods
(Wood, 1991). The State of Minnesota has
funded a study for development of an eco-
nomic model to determine if collection of fiber
reinforced plastic scrap from processors can
produce profitable products, either materials
or end-use goods (McDermott, 1992).
40.5 PROPERTIES AND PRODUCTS OF
RECYCLED MATERIALS
Because of the big supply and the big market
(automotive), the most effort in thermoset
recycling has been in particle recycling of glass
fiber reinforced polyester, predominantly
SMC. It appears that fully milled thermoset
can be reused as a filler in an indefinite num-
ber of cycles without loss of performance.
Pyrolysis degrades the mechanical properties
of the glass fiber but fiber is still useful as a
particulate filler.
The approaches for the recycling of glass
reinforced thermoplastic composites utilize
the technology already developed for the
non-reinforced polymers used in packaging.
However, the thermally induced chemical
degradation of thermoplastics and the physi-
cal attrition of glass fibers that occurs during
890 Reuse and disposal

repeated extrusion and injection molding erties with the regrind. The density
require attention. decreases, as found by other researchers, in
this case about 10% at the highest loading.
LORIA@(a registered trademark of Ashland
40.5.1 SHEET AND BULK MOLDING
Oil Inc.) and Diffract0 analyses were also
COMPOUNDS
conducted. The outcome of both tests show
Owens-Coming reports in Table 40.1 some that 30 phr material gave the best surface.
properties of SMC containing filler made from Beyond the 30 phr loading, the surface deteri-
recycled SMC (Graham, Jutte and Shipp, 1993). orated.
Replacing the calcium carbonate filler with In the BMC evaluation, Premix found very
ground SMC actually improves most mechani- little effect on the mechanical properties, with
cal properties. Fibers that have been recovered slight decreases in tensile strength, flexural
from SMC by mechanical separation show modulus and notched Izod as the regrind
even greater potential reinforcement value. loading increased. Owens-Corning has shown
Premix Inc. evaluated several formulation that unfractionated, granulated SMC, still con-
of SMC and BMC, using scrap materials in taining fiber with considerable length and
varying ratios (30%, 58% and 8S0/0) (Butler, aspect ratio, provides some reinforcement
1991). Beyond 88%, the material viscosity was value in BMC (Table 40.3).
unmanageable. The SMC formula used for Work by ERCOM in Germany evaluated
the regrind studies was a typical automotive properties at three recyclate contents obtained
formulation (Table 40.2). Their data show that in SMC compounds using SMC recyclate
only slight changes occur in mechanical prop- obtained from scrap and used parts (Schaefer

Table 40.1 Propertics of SMC containing composite filler made from recycled SMC (20% carbon carbonate
replaced with composite filler)

Standard formulation Low Density formulation

Control Recycled Control Recycled
Tensile strength, MPa 77.6 97.9 105.6 95.5
(psi) (11250) (14 195) (15 310) (13 850)
Tensile modulus, MPa 11 590 12 970 8 927 10 670
(psi x lo6) (1.68) (1.88) (1.29) (1.53)
Flexural strength, MPa 186.0 210.0 163.2 195.1
(psi) (26 970) (30 450) (23 665) (28 290)
Flexural modulus, MPa 8 970 9 867 8 683 9 325
(psi x lo6) (1.30) (1.43) (1.26) (1.35)
Notched izod, J/m 953 1018 824 888
(ft lb/in.) (17.8) (19) (15.4) (16.6)
Unnotched izod, J/m 1164 1388 981 958
(ft lb/in.) (21.8) (26) (18.4) (17.9)
Water absorption (YO) 0.31 0.28 0.20 0.19
Specific gravity, g/cm3 1.76 1.81 1.32 1.33
(lb/fP) (110) (113) (82.4) (83)
 Properties and products of recycled materials 891

Table 40.2 Typical automotive formulation control

PHR Basted on paste % BOT %

Polyester resin 55 1.3 14.13
Polyvinyl acetate LPA 40 13.69 10.27
Styrene 5 1.71 1.28
Tertiary butyl perbenzoate 1.5 0.52 0.38
Zinc stearate 4 1.37 1.03
Wetting agent 8 2.60 1.95
Calcium carbonate 175 59.91 44.93
Magnesium hydroxide 4 1.37 1.03
Glass 25% 25.00

30 pkr regrind PHR Basted on paste % BOT %

Polyester resin 55 18.83 14.13
Polyvinyl acetate LPA 40 13.69 10.27
Styrene 5 1.71 1.28
Tertiary butyl perbenzoate 1.5 0.51 0.38
Zinc stearate 4 1.37 1.03
Wetting agent 8 2.60 1.95
Calcium carbonate 145 49.91 37.43
Regrind 30 10.00 7.50
Magnesium hydroxide 4 1.37 1.03
Glass 25% 25.00

Table 40.3 Properties of BMC reinforced with recycled glass reinforced SMC

Tensile Elongat ion Flexural ~-

Izod impact
sMc
Added
Stress,
Mpa
Modulus, (%) Stress, Modulus, Notched, Unnotcked,
(%) MPa MPa MPa J h J h
Sample (psi) (psi x IO6) (psi) (psi x IO6) cfl lb/in) (ftlb/in)
BMC 0 27.9 13 099 0.44 96.7 10 548 270
control (4 045) (1 9) (14 020) (1.51) (5.1)
Stnd. BMC 6 16.1 9 858 0.68 68.6 9 789 270
+ SMC (2 334) (1.43) (9 947) (1.40) (5.1)
Stnd. BMC 12 17.3 12 685 0.22 71.4 10 203 209
+ SMC (2 508) (1.W (10 350) (1.46) (3.9)
BMC Resin 70 25.8 7 859 0.36 55.4 6 411 89
+- SMC (3 740) (1.14) (8 033) (0.98) (1.6)

and Plowgian, 1993). Table 40.4 shows that
strength can be maintained and there is a
reduction in density. The latter implies a lower
weight for a given car part, an added benefit
for the auto recycling evaluation underway.
In Japan, the RTC (RP Recycling and
Treatment Council) of the Japan Reinforced
Plastics Society, as the final step in a complete
recycling evaluation beginning with cutting
up and shredding large RP parts, obtained
physical and mechanical property data for
SMC where CaCO, was replaced with varying
892 Reuse and disposal

Table 40.4 Comparison of properties of SMC com- (SICOMP) performed mechanical testing on a
pounds using recyclate low-shrink SMC with 20% 25 mm (1in) glass
reinforcement and a 50% reduction of the cal-
Base 5% 10% 15% cium carbonate filler, down to 80 phr
Flex-strength, 194 222 185 208 (Pettersson and Nilsson, 1993).Improved flex-
MPa (psi) (28 130) (32 190) (26 825) (30 160) ural strength together with slightly reduced
Impact,kJ/m2 102 107 126 145 flexural modulus was obtained for the SMC
(ft lb/in) (19.4) (20.4) (24.0) (27.6) containing 10% reground material.
Density, g/cm3 1.90 1.85 1.80 1.72
(lb/ ft") (118.6) (115.5) (112.4) (107.4) Evaluation of a virgin PET polyester and
one prepared from reclaimed PET has been car-
Note. Recyclate content calculated as a percent of total ried out by DeMaio (1991).Although the resins
weight of compound.
did not contain reinforcements and therefore
amounts of regrind (Kitamura, 1993). Tables may not truly belong in a book on composites,
40.5 and 40.6 present these data and confirm the test data are of interest while considering
results by other investigators that mechanical SMC and BMC above. Tables 40.7 and 40.8
properties are not harmed (in fact, in some show that no significant differences of liquid or
cases improved) and the density is lowered. physical properties exist between the two
The Swedish Institute of Composites materials once processed into a polyester resin.

Table 40.5 Physical/mechanical properties of recycled SMC - standard type

Formulation
Materials 1 2 3
Resin 100 100 100
CaCO, 125 78 36
Reground 0 32 60
GF (1in) (Yo) 30 30 30

Properties
Shrinkage (YO) 0.06 0.07 0.08
Specific gravity, g/cm3 1.73 1.64 1.59
(Ib/fP) (108.0) (102.4) (99.3)
Flexural strength, MPa 200 213 186
(psi) (29 000) (30 885) (26 970)
Flexural modulus, GPa 12.3 11.8 11.4
(psi x lo6) (1.78) (1.71) (1.65)
Tensile strength, MPa 78 77 79
(psi) (11310) (11 165) (11455)
Tensile modulus, GPa 11.8 11.5 11.2
(psi x lo6) (1.71) (1.67) (1.62)
Izod impact, mJ/mm2' 82.0 87.4 86.0
(ft lb/in) (15.6) (16.6) (16.4)

*edgewise, unnotched
 Properties and products of recycled materials 893

Table 40.6 Physical/mechanical properties of recycled SMC - class A SMC

Formulation
Materials 2 2 3
Resin 100 100 100
CaCO, 180 123 76
Reground 0 38 70
GF (1in), Yo 28 28 28
Properties
Shrinkage, Yo 0.00 0.00 0.00
Specific gravity, g/cm3 1.85 1.77 1.68
(lb/ft? (115.4) (110.5) (104.9)
Water absorption, % 0.44 0.39 0.30
Surface quality 3.6 3.8 5.6
average deviation (p)"
Flexural strength, MPa 190 178 167
(psi) (27 550) (25 810) (24 215)
Flexural modulus, GPa 11.5 10.9 10.4
(psi x IO6) (1.66) (1.58) (1.51)
Tensile strength, MPa 85 82 68
(psi) (12 325) (11890) (9 860)
Tensile modulus, GPa 11.0 10.7 10.2
(psi x lo6) (1.60) (1.55) (1.48)
Izod impact, mJ/mm2' 76.5 81.5 78.5
(ft lb/in) (14.6) (15.5) (14.9)
*edgewise, unnotched;
"Takeda method.

40.5.2 PHENOLIC (PF) AND POLYURETHANE
(PUR) COMPOSITES
While the major activity in thermosets has been
with unsaturated polyesters (SMC and BMC),
property data have also been reported on recy-
cled glass reinforced PF, Table 40.9 (Olson,
1992)and PUR, Table 40.10 (Graham, Jutte and
Shipp, 1993). Work to recycle reinforced PUR
will increase as structural reaction injection
molding (SRIM) finds more use in structural
applications and PUR presumably continues to
be the resin most used. Krauss-Maffei
(Germany)has a new RIM system that can pro-
duce exterior auto body panels with a Class-A
surface from reinforced PUR that includes up
to 30% recycled content. The recycled PUR
must be ground into a fine powder before
reprocessing to obtain the Class-A surface.
40.5.3 RECYCLED THERMOPLASTIC
COMPOSITES
Glass-filled polypropylene (PP) has received
the most attention, perhaps because of its
potential for automotive use. Owens-Corning
studied the effects of repeated recycling by
granulation of the PP and injection molding
(Graham, Jutte and Shipp, 1993). Table 40.11
shows a loss in properties caused by polymer
degradation and a decreasing fiber length.
894 Reuse and disposal

Table 40.7 Mechanical property comparison data; Table 40.8 Liquid property comparison data
recycled PET
Recycled Virgin
Measured property
Recycled Virgin PET PET
Measured property PET
PET 470 420
Viscosity, cps
Flexural strength, MPa 117.9 121.4
(17 400) (17 600) YO Solids 60.1 60.8
(psi)
Specific gravity 1.098 1.102
Flexural modulus, MPa 3586 3586
(lo6psi) (0.52) (0.52) Acid number, solids basis 17 20
Tensile strength, MPa 65.5 67.6 180°FSPI gel test
(psi) (9 500) (9 800) (catalyzed with 1% BPO)
Tensile elongation, YO 2.5 2.8 Gel time, min 6.5 6.0
Barcol hardness 49 47 Cure time, min 1.7 1.5
HDT, "C 419 414 Peak 225 229
(OF) (215) (212) temperature "C (OF) (438) (444)
Izod impact, kJ/m 0.16 0.18
(ft lb/in) (3.1) (3.4)
Water absorption, OO/ 2.0 1.8
glass fiber. The results of additional glass in
injection molded recycled PP are contained in
Two viable approaches to overcome the prop- Table 40.13.
erty loss are the introduction of polymer Jutte and Graham (1991) considered the
additives and the use of additional glass. Table effect on properties of PP containing granu-
40.12 presents data to show the improvement lated SMC. Both coarse and fine recycled SMC
in recycled PP with the addition of Polybond were evaluated at three filler levels. Modulus
3001 (BP Chemicals), an acid functionalized was improved and unnotched Izod impact
PP. The recycled PP was Himont Pro-Fax 6523 properties decreased; the data are tabulated in
with 6 mm (0.25 in) Owens-Corning R-34B Table 40.14.

Table 40.9 Mechanical properties of recycled glass reinforced phenolic

Regrind fypical
40% resin -+ 50% resin + 60% resin +
properties of
60% regrind 50% regrind 40% regrind
virgin material
Density, g/cm3 1.45 1.43 1.40 1.61
(lb/fP) (90.5) (89.3) (87.4) (100.5)
Compressive strength, MPa 252 263 273 230
(ksi) (36.5) (38.1) (39.6) (33.4)
Flexural strength, MPa 100.0 102.0 83 110
(ksi) (14.5) (14.8) (12) (16)
Notched Izod, kJ/m2 2.05 1.98 2.03 3.6
(ft lb/in) (0.39) (0.38) (0.39) (0.69)
Unnotched Izod, kJ/m2 7.8 8.6 6.4 8.0
(ft lb/in) (1.49) (1.63) (1.22) (1.52)
 Properties and products of recycled materials 895

Table 40.10 Properties of 10% regrind RIM in glass dation. NBC SRIM systems can be ground,
filled polyurethane dried and injection molded either neat or
blended with nylon-6. Recycling evaluations
Standard + utilized materials flaked to a granular size of
Standard 10% regrind
system < 200pm approximately 2 mm (0.08 in). Comparison of
NBC SRIM properties to recycled (via injection
Flexural modulus, N/mm2 900 836 molding) part properties masks the possible
(psi x lo6) (0.13) (0.12) effects of the injection molding process due to
Tensile strength, N/mm2 28.0 24.6 the inherent differences in reinforcement
(psi) (4 060) (3 570) length. For this purpose, comparison of unre-
Tensile modulus, N/mm2 750 569 inforced NBC RIM and injection molded,
(psi x lo6) (0.11) (0.08) recycled NBC provides a better understanding
of the effect of the recycling process on the
Elongation, YO 160 133
resin matrix (Table 40.15). As the test data indi-
Hardness, Shore D 59 63 cates, the initial injection molding cycle does
Density g/cm3 1.18 1.20 not adversely affect the properties of the NBC
(lb/fP) (73.6) (74.9) system. When an SRIM composite 3545%
fiber reinforcement package was recycled, the
recycled SRIM composite yielded properties
In the course of developing a thermoplastic comparable to virgin injection molded impact-
matrix for SRIM, DSM RIM Nylon Inc. devel- modified nylon, indicated in Table 40.16.
oped a family of nylon block copolymers
(NBC) named Nyrim (Reitz, 1992). Nyrim
40.5.4 YIELDS FROM PYROLYSIS
chemistry combines AP-caprolactam with an
activated ’rubbery’ prepolymer. NBC compos- Because pyrolysis occurs in an oxygen-free
ites can be readily recycled by conventional environment, SMC decomposes into three
injection molding techniques without degra- recoverable substances: pyro-gas, pyro-oil and

Table 40.11 Mechanical properties of recycled 30% glass reinforced polypropylene

~~~ ~

Sample Tensile Elongation Flexural lzod Impact

Stress, Modulus, (”) Stress, Modulus, Notched, Unnotched, Glass
MPa MPa MPa MPa J h I/m length,
(psi) (psi x IO6) (psi) (psi x IO6) (ftlb/in) (ft W i n ) (mm)
Control 80.0 6 688 2.19 126.6 7 562 103 421 361
(11600) (0.97) (18 355) (1.10) (1.93) (7.90)
Recycled 69.6 6 329 2.28 106.4 6 749 80 321 329
IX (10 090) (0.92) (15 430) (0.98) (1.49) (6.01)
Recycled 63.5 6 026 2.29 100.0 6 306 74 292 305
2x (9210) (0.87) (14 500) (0.91) (1.38) (5.47)
Recycled 55.9 5 461 2.47 89.8 5 557 64 253 280
3x (8 105) (0.79) (13 020) (0.81) (1.20) (4.73)
Recycled 52.0 5 261 2.50 86.1 5 288 60 241 271
4x (7 540) (0.76) (12 485) (0.77) (1.12) (4.51)
896 Reuse and disposal

Table 40.12 Propertics of polybond modified 30% recyclcd glass reinforced polypropylene

Sample Tensile Elongation Flexural lzod impact

Stress, Modulus, '%) Stress, Modulus, Notched, Unnotched,
MPa MPa MPa MPa J h J h
(psi) (psi x IO6) (psi) (psi x 109 (ftIb/in) cft lb/in)
Control 76.5 6 405 2.31 121.7 7 239 101 400
(11090) (0.93) (17 650) (1.06) (1.89) (7.49)
Recycled l x 62.5 5 798 2.45 97.6 4 888 73 314
(9 062) (0.84) (14 150) (0.71) (1.36) (5.88)
+ 5% Polybond 73.1 6 143 3.64 116.1 5 681 112 595
(10 660) (0.89) (16 830) (0.82) (2.10) (11.14)
+ 10% Polybond 75.8 6 260 3.69 120.9 5 632 121 638
(11000) (0.91) (17 530) (0.81) (2.26) (11.94)
+ 15% Polybond 77.2 6 316 3.45 124.2 5 729 126 679
(11200) (0.92) (18 000) (0.83) (2.36) (12.72)

Table 40.13 Properties of increased glass content recycled reinforced polypropylene

Sample Tensile Elongation Flexural lzod impact

(%)
Stress, Modulus, Stress, Modulus, Notched, Unnotched,
MPa MPa MPa MPa I/m I h
(psi) (psi x 104, (psi) (psi x IO6) cft lb/in) cft lb/in)
Control 76.5 6 405 2.31 121.7 7239 101 400
(30% glass) (11090) (0.93) (17 645) (1.05) (1.89) (7.49)
Recycled l x 62.5 5 798 2.45 97.6 4 888 73 314
(30% glass) (9 062) (0.84) (14 150) (0.71) (1.36) (5.88)
+ 2.5% glass 67.2 6 260 2.36 101.5 5460 81 317
(9 744) (0.91) (14 715) (0.79) (1.52) (5.94)
+ 5.0% glass 70.3 6 964 2.13 108.8 6101 82 302
(10 200) (1.01) (15 775) (0.88) (1.52) (5.66)
+ 7.5% glass 73.8 7377 2.08 112.2 6722 85 305
(10 701) (1.07) (16 270) (0.97) (1.59) (5.71)
+ 100% glass 75.8 8 067 1.87 117.4 8 169 83 281
(11000) (1.17) (17 020) (1.18) (1.55) (5.26)

solid by-product (essentially glass fiber and
filler). In one test by the SMC Automotive
Alliance, the resulting composition was gas
14%, oil, 14% and inert solid 72%. The gas gen-
erated was sufficientto fuel the pyrolysis unit,
making it self-sustaining. The energy content
was close to natural gas. The solid by-products
can be processed into fillers for SMC, BMC or
thermoplastics. When milled into a filler, the
pyrolyzed SMC can be recycled successfully
into general purpose and Class A automotive
SMC, at up to 30% of the calcium carbonate
filler loading with no adverse effects on pro-
cessing or physical properties (Rusch, 1993).
The pyrolysis experiments performed by
Michimae in Japan on scrapped RP ship mate-
rial gave the yields in Table 40.17. The pyro-oil
which was recovered had a strong acid content
 Properties and products of recycled materials 897

Table 40.14 Propertics of polypropylene containing granulated SMC

Sample Tensile Elongation Flexural Izod impacf

SMC Stress, Modulus, (") Stress, Modulus, Notched, Unnofched, HD-
(%) MPa MPa MPa MPa TUL
(psi) (psi x IO6) (psi) l/m 'Im
(psi x IO6) Cft lb/in) cft lb/in) "CPF)
Polypro- 0 22.13 1035 29.17 965 77.9 968.5 63.3
pylene (3210) (0.15) 9.72 (4230) (0.14) (0.14) (18.14) (146)
Polypro 15 21.56 1724 33.51 1310 84.4 236.5 67.2
pylene + (3 120) (0.25) 3.50 (4 860) (0.19) (1.58) (4.43) (153)
coarse
recycled 30 21.03 2 207 34.83 1655 89.2 155.4 78.3
SMC (3050) (0.32) 2.34 (5 050) (0.24) (1.67) (2.91) (173)
50 22.43 3 034 36.21 2276 101.4 148.4 94.4
(3250) (0.44) 1.61 (5250) (0.33) (1.90) (2.78) (202)
Polypro- 15 20.55 1448 32.41 1310 74.2 205.0 51.9
pylene + (2980) (0.21) 4.78 (4 700) 0.19 1.39 (3.84) (151)
fine recycled
SMC 30 20.96 2 069 33.93 1.655 82.2 163.9 84.4
(3 040) (0.30) 2.47 (4 920) (0.24) (1.54) (3 07) (184)
50 17.17 2 828 3.076 2483 73.14 104.1 82.7
(2 490) (0.41) 1.25 (4460) (0.36) (1.37) (1.95) (181)
Polypro- 0 37.93 2 000 50.69 1448 150.6 361.4 114.9
pylene + (5500) (0.29) 3.45 (7350) (0.21) (2.82) (6.77) (239)
9% chopped glass

Table 40.15 Properties of recycled neat NBC RIM Table 40.16 Properties of recycled NBC SRIM part

Property Virgin Recycled Tensile modulus, MPa 10 400

(psi x lo6) (1.51)
Tensile modulus, MPa 2 445 2 480
(psi x lo6) (0.35) (0.36) Tensile strength, MPa 120
(psi) (17 400)
Tensile stress, MPa 58 60
(psi) (8 410) (8 700) Elongation, YO 3
Elongation, YO 40 125 Flexural modulus, MPa 8 000
(psi x lo6) (1.24)
Flexural modulus, MPa 2 485 2 450
(psi x lo6) (0.36) (0.35) Notched Izod, kJ/m2 10
(ft lb/in) (1.9)
Izod, kJ/mZ 10 10
(ft lb/in) (1.9) (1.9) Values are dry, as molded

Mold shrinkage, YO 2 1.2 with a viscosity which resembled heavy

Melting point, "C 214 220 naptha, a flash point close to that of gasoline
("F) (417) (428) and was highly flammable.
The Government Industrial Research
Density, g/m3 1.10 1.14
(lb/fP) (68.7) (71.2) Institute and Shikoku/MITI conducted a pyrol-
ysis experiment using steam in a gas-heated
Water absorption, YO 3.1 3.1 continuous-batch method, with temperatures
898 Reuse and disposal

of typically 500°C (932°F). RP from ships con- 40.5.5 HEAT CLEANED REINFORCEMENTS
taining 40% fiberglass was used. The system Peninsula Copper Industries (PCI) has
produces hardly any smoke or gas. The resin obtained data on their heat-cleaned glass fiber
yields pyro-oil and fiberglass can be recovered incorporated into polyester, polypropylene
without loss of strength. Table 40.18 shows the and nylon matrix laminates (Hanson, 1991).
yield (Kitamura, 1993). The performance of recovered glass fiber rein-
forcement is comparable to virgin glass in
many respects in polyester and nylon. Table
Table 40.17 Yield from pyrolysis - SRI/Michmae 40.19 compares PCI recovered fiber with PPG
fiber with a polyester resin. Table 40.20 pre-
Materials Yield wt.%
sents polypropylene data, comparing the base
Gas (liters) 90.7 resin properties to those using 22 wt YO bare
Pyro-oil (g) 344 34.4 reclaimed glass and two formulations of 22 wt
Remainder (8) 524 52.4 % silane-treated glass. The difference between
Note: per 1000 g of RP Formula A and Formula B is not explained, but

Table 40.18 Yield from pyrolysis - GIRIS/MITI Table 40.19 Average mechanical properties of poly-
ester /PCI-Glass composites and PPG composite.
Materials wt.%
Property PCI PPG
Cas (CO) 18
Pyro-oil: Tensile strength, MPa 25.0 24.9
Styrene monomer 25 (psi) (3 626) (3 600)
Solids (phthalic) 11 Compressive 89.7 n/a
Remainder: strength, MPa (psi) (13 000) n/a
Fiberglass 40 Flexural strength, MPa 81.4 84.5
Carbon 6 (psi) (11 800) (12 300)
Note: per 1000 g of RP
Flber length, cm 10.2 6.4
(in) (0.4) (0.25)

Table 40.20 Average mechanical properties of polypropylene/PCI-

glass composites

Property Filled, Filled,

Unfilled PP untreated treated A/B
Tensile strength, MPa 24.70 26.68 27.20/31.67
(psi) (3 582) (3 869) (3 945/4 593)
Tensile modulus, MPa 873 2 120 2 540/1370
(psi x lo6) (0.127) 0.308) (0.369/0.199)
Yield stress at break, MPa 25 20.1 17.9/28.4
(psi) (3 630) (2 910) (2 602/4 121)
Strain at break 556 391 313/16.7
(YO,at 50 mm/min)
Glass content 0.0 22.0 22.0
(volume YO)
 Disposal of nonrecyclables 899

Table 40.21 Average mechanical properties of adding to landfill. Incineration leaves a

nylon 6/6 PCI-glass composites residue which normally is deposited in a land-
fill, but increasing legislature action as well as
Property WPCI public opinion is reducing the use of landfills.
glass fiber
The energy content in SMC can be recovered
Tensile strength, MPa 102.8 by incineration, but the relatively low energy
(psi) (14 905) content together with the high amount of ash
Flexural strength, MPa 184.2 residue from the incineration makes incinera-
(Psi) (26 690) tion of SMC quite unprofitable. The ash
Flexural modulus, MPa 5292 residues from incineration are not useful as
(psi x lo6) (0.77) fillers in new SMC since the high temperatures
when incinerating, together with the presence
b o d impact strength
of oxygen, converts the calcium carbonate to
(notched 1/8 in), kJ/m 0.04
calcium oxide and that will adversely influence
(ft lb/in) (0.8)
(unnotched), kJ/ m 0.36 the maturation process (chemically thickening)
(ft Ib/in) (6.7) when making new SMC. There are no disad-
vantages, however, either in the form of added
Elongation, YO 3.0
pollution or toxic emissions.
Mold shrinkage, (in/in, Yo) 0.006, 0.6% The important aspect that SMC consists of
Glass content (vol Yo) 14.8 only 20-30% organic materials makes inciner-
ation and chemical degradation less suitable
compared to particle recycling (regrinding)
both show improvement over the base resin and pyrolysis which are using the inorganic
and the bare reclaimed glass. The values over- part of the material as well.
all fall far short of most of the commercially The non-metal mixture that remains,
available glass filled PP, where tensile known as ’fluff’, after such items as automo-
strengths range from 29 MPa (4200 psi) to 82.5 biles and white goods (refrigerators, washing
MPa (12 000 psi) with a mean value of 44.7 machines, etc.) are processed in shredders, is
MPa (6500 psi.). normally disposed of in landfills. Seventy-five
The performance of reclaimed silane-treated percent of shredder plant feed is from cars.
glass fibers in nylon is closer to that obtained This feed mixture has a composition of
for commercial compounds than for approximately 15-25% plastics, 25-75% inerts
polypropylene. Properties obtained using PCI and 2-35% moisture.
glass are given in Table 40.21. Depending on Research by General Motors, Ford and
the resin formulation, manufacturer’s data Chrysler and the American Plastics Council is
show tensile strengths for virgin glass rein- being conducted on recovery, recycling and
forced nylon range between 75 MPa reuse of plastics from scrapped cars and
(11000 psi) and 151.8 MPa (22 000 psi). trucks. Although plastics residue from recy-
Flexural properties show a similar relationship. cling vehicles represents less than 1%of the
solid waste sent to landfills in the USA each
year, auto industry officialsestimate that it still
40.6 DISPOSAL OF NONRECYCLABLES
accounts for more than 1 million tons of the
nation’s solid landfill waste annually.
40.6.1 INCINERATION AND LANDFILL
Research efforts are focused on materials that
The more desirable forms of disposing of com- currently are not recovered, primarily plastics,
posites are described in the previous section, glass, fluids, sealers, fabric, adhesives, paint,
both for economic payback and avoiding and rubber (fluff). Fluff accounts for less than
900 Reuse and disposal
2 wt YO of municipal solid waste. The joint
effort targets the plastics portion of the fluff.
The recovery of plastics from shredder residue
is hampered by frequent contamination from
paint, other plastics, metals, and adhesives.
Thus another goal of the effort is to develop
better methods to purify scrapped plastics.
The Department of Energy’s Argonne
National Laboratory has developed a process
to separate plastics and other recyclable mate-
rials from the ’fluff’ of shredded automobiles.
The process utilizes a fluidized bed process
and yields PUR, fines, iron oxide and mixed
plastics.
Germany appears to be moving away from
its rules forbidding incineration of many kinds
of waste. The Environment Ministry report-
edly will introduce legislation that would
allow incineration of composites and certain
plastics if recycling proves too expensive
(Protzman, 1993).
40.7 DESIGN FOR REUSE
40.7.1 AUTOMOBILES
An obvious approach to assist in the economic
success of recycling of multi-material parts is to
design the item originally for ease of disassem-
bly. Of particular interest are automobiles and
white goods (e.g. refrigerators). The major auto
makers of the US Council for Automotive
Research (USCAR), through their Vehicle
Recycling Partnership, are studying ways to
enhance compatibility and dismantling of plas-
tic parts (Wigotsky, 1993). Some bumper parts
now need only four bolts instead of twelve.
Potential amendments to the US Resource
Conservation and Recovery Act, passed in
1976, may specifically name automobile solid
waste. Federal regulations could possibly
require certain car design features, if only by
excluding certain materials. The VRP is work-
ing to establish a strong infrastructure for
recycling plastic parts, starting with things
that are easy to get at, such as fender liners, fan
shrouds and radiator supports. A well-estab-
lished infrastructure for recycling could head
off severe government restrictions on plastics
use.
As with durables in general, aids for recy-
cling vehicles include design for easy
separation and collection, parts consolidation
to simplify separation, material identification
on parts, restriction of plastic parts to recy-
clable resins, and avoidance of paints, coatings
and heat sensitive additives. Automakers
worldwide have agreed on an identification
code for all plastic parts heavier than
100 g (3.5 oz). Ford Motor Company has
issued guidelines on design for for recyclabil-
ity (Miller, 1993)
Germany has been a leader in design for
reuse. Porsche, on assignment from the
Automotive Engineering Research
Association, investigated designs for medium-
priced autos in which plastic parts could be
readily dismantled and recycled. The best
designs for meeting these objectives were
those in which combinations of easily disman-
tled parts were manufactured from a single
recyclable resin. An example of such a combi-
nation is a PP bumper system with a PP
sheath, an expanded PP core and glass-mat-
reinforced PP beam (Nir, Miltz and Ram,
1993).Many reclamation projects focus on the
bumper system. Bumpers are collected in pilot
programs, ground into particles and blended
with virgin resins. Use of a single recyclable
resin has been practiced by Peugeot, Ope1 (sin-
gle resin bumpers) and BMW (body panels).
The use of one resin in different forms, as
described above, is also under development
by Reko and DSM in auto dashboards.
In Landshut, Germany, BMW has a facility
capable of dismantling 25 cars a day. Eighty
percent of the parts in the BMWs low end ‘3
series’ can be reutilized in some form. Plastic
bumpers are turned into interior wall panels.
Seat covers and PU foam are used as sound-
deadening material for the floor in the ’3
series’. BMW also has three dismantling plants
in the USA (New York City, Los Angeles and
Orlando) (Protzman, 1993).
 Applications and markets 901

40.7.2 APPLIANCES roof-rack module which uses recycled filler.

Design for recyclability, of appliances and Introduced in 1992, the rack may have been
other white goods, is underway at several the first use of recycled filler in new SMC.
companies. Such designs allow for easy disas- Germany’s ERCOM and the SMCAA have
sembly, e.g. snap fit assembly with no signed an agreement to ’enhance the use of
fasteners, with each part preferably manufac- SMC/BMC in automotive parts by providing
tured from a single, readily recycled resin and an organization in each country that will
labeled as to its composition. Polymer accept scrap parts for recycling’. SMC is well
Solutions, a joint venture of GE Plastics and ahead of thermoplastics in automotive recy-
Richardson Smith, has already designed an cling use for major parts. This is because SMC
easy-to-disassemble refrigerator and a circuit fillers appear to be continually reusable with-
breaker box (Nir, Miltz and Ram, 1993). out sacrificing physical properties; replacing
half the CaCO, with SMC filler reduces
part weight and cuts compound cost.
40.8 APPLICATIONS AND MARKETS
Thermoplastics have limitations on the
amounts or frequency of reprocessing permit-
40.8.1 AUTOMOTIVE
ted before significant mechanical property
degradation occurs. There is also concern
The automotive industry is evaluating many with possible mixing of incompatible resins.
applications of recycled composite materials, Plastic material suppliers are working to pro-
particularly SMC, in new auto parts. The tech- duce resins with recycled plastic content
nology to recycle SMC, as discussed earlier, is (Miller, 1993).
available and apparently viable. The major There has, however, been reported one
barrier to recycle SMC is the lack of an infra- successful application of a recycled thermo-
structure, i.e. collection, processing, and plastic composite. Chrysler will feature
distribution, but this network will develop recyclable fenders for all of its 1993 LH pas-
because of environmental pressures, etc. senger cars. The fenders are made of
The first production application of recy- DuPont’s Bexloy K, a new glass-reinforced
cled SMC filler in the USA was by General PET polyester based composite. They can
Motors on the 1993 Corvette, an inner panel either be reground and molded again or
for the rear panel assembly (Rusch, 1993).The returned to the two pure feedstock ingredi-
part does not require a Class A surface. ents through a patented DuPont
Corvette anticipates expansion of recycled methanolysis process (American Plastics
SMC to eight more underskin panels in ensu- Council, 1993).
ing models. General Motors spokesmen predict that
In other applications, the SMC Automotive within five years there will be the necessary
Alliance (SMCAA) reported Ford Motor Co. infrastructure for recycling such parts as
expected to start using SMC with recycled fender liners, HVAC ducts, fan shrouds, radia-
composite filler on the Econoline Van interior tor supports and many interior components
engine cover during the 1993 model year, and (Wigotsky, 1993).
Chrysler will use recycled SMC on interior
trim on the RAM Van, the first parts that are
40.8.2 BUILDING CONSTRUCTION
visible. And in Europe, the SMCAA listed
three production auto parts that contain recy- A Canadian company has developed a prod-
cled SMC as filler (Audi spare-tire well, VW uct Stratum (Stratum@ is a registered
Polo engine module and VW Passat front-end trademark for the recycled materials produced
panel). Japan’s Toyota Carib has an interior by Plastiglas Industries) composed of a plastic
902 Reuse and disposal
binder, usually polyester, filled with up to 85%
by volume of recycled composite scrap
(Darrah, 1993). One application encapsulates
the scrap-resin mixture between two FRP
skins. The resulting panel has passed the full
scale fire test for exterior panel systems.
Work in Japan has been done to develop a
gypsum filled with milled composite ther-
moset scrap and a mortar with milled
composite scrap, both with mechanical prop-
erties suitable for construction (Kitamura,
1993).
40.8.3 ELECTRICAL PARTS
In Germany, two parts made with new SMC
formulations containing 10-15% by weight
fiber rich recyclate are already in production
or approved for production. These are an elec-
trical distribution cabinet and a cable
distribution base (Schaefer and Plowgian,
1993). Strength and modulus can be main-
tained with a reduction in density.
40.8.4 OTHER APPLICATIONS
Peninsula Copper Industries has identified an
application for small chips of printed circuit
board in an epoxy/coal tar base (Hanson,
1991). This composite is used as a cushion
material between rails and the steel approach
plates at railroad crossings. Initial tests indi-
cate that this composite is an effective
replacement for rubber-based materials
presently used. Several parts from SMC, made
from recycled SMC, have gone into production
or are approved for production in Germany.
These include sinks, seats and chairs.
In the thermoplastic field, a commercial
application for ‘Nyrim’ nylon block copoly-
mer-based SRIM is a manhole cover (Reitz,
1992). It utilizes a 3.545% fiber reinforcement
package. The recycled SRIM composite
yielded properties comparable to virgin injec-
tion molded impact-modified nylon.
40.9 LEGAL AND ENVIRONMENTAL
ASPECTS
The major federal waste legislation in the USA
addressing solid waste issues is the Resource
Conservation and Recovery Act of 1976. It
requires the Environmental Protection Agency
(EPA) to set guidelines for government pro-
curement of recycled products and it
mandates Federal agencies and contractors to
implement affirmative procurement programs.
Most states and many local governments have
established programs to procure recycled
materials. The 1976 Act was reauthorised in
1988 and continues in effect (Donnelly, 1993).
An industry concern is that the federal reg-
ulations might venture into the areas of car
design, if only by excluding, within certain
time periods, certain materials and design
approaches.
In the meantime, Senator Baucus (D-MT),
Chairman of the Senate Environment-Public
Works Committee, unveiled in April, 1993, a
four-part blueprint for recycling to be part of a
recycling bill to be introduced later. Two parts
concern composites: the Federal Government
should take the lead in procuring goods made
from recycled materials and second, manufac-
turers should be responsible for their products
when they become waste.
In Germany, increasing concern for the
environment has led to proposed laws for the
reuse of post consumer and post industrial
waste. Legislation for recycling of consumer
goods packaging was enacted in 1992, setting
minimums for collection and recycling
through 1995. Now proposed is the German
Refuse Act for Car Recycling, with its priority
for material recycling (Schaefer and Plowgian,
1993).
Other proposed legislation would levy a tax
on new cars to pay for their eventual
disposal. Another proposal by Germany’s
Environmental Minister would make automo-
bile manufacturers responsible for the final
disposal of their cars. Still another stipulated
that by 1993, plastics in new cars produced in
 Organizations active in composites recycling 903

Germany would be required to contain 25% by and construction/furniture.

weight recycled materials. Legislators and The SMC Automotive Alliance, Southfield,
industry will be following Germany’s new MI, is an activity of the SPI’s Composites
environmental laws, expecting to learn from Institute, composed of 35 SMC plastics mater-
that country’s experience, especially since the ial molders and SMC raw material suppliers.
current Democratic administration has One of their objectives is to prove that pyroly-
expressed interest in a progressive environmen- sis and grinding are viable methods of
tal policy, i.e. one of reduce, reuse and recycle.recycling automotive components made of
Two new laws have been enacted in Japan SMC.
in 1991; one is ’Law Concerning the Utilization The Center of Excellence for Composites
of Recycled Resources’ and the second Manufacturing Technology is operated for the
’Amendment of Waste Processing and Navy by the Great Lakes Composites
Cleaning’. Earlier, the National Diet amended Consortium, Kenosha, WI. One of the first pro-
a part of the Marine Safety Act to address the jects undertaken was a prepreg (carbon/
problem of treatment for scrapped ships. epoxy) scrap reclamation project.
Research and development on dismantling, The Big Three Vehicle Recycling Partnership
cutting up, shredding and various recycling of the US Council for Automotive Research has
methods of other large items followed. Such teamed with the Automotive Group of the
items include bathtubs or bath units, tanks American Plastics Council to create an infra-
and automotive parts. These enactments made structure for plastics recycling of scrapped cars
people strongly aware that plastic waste recy- and trucks.
cling had become an important social Suppliers of Advanced Composite Materials
problem. Association (SACMA), Arlington, VA, is a
trade association of composite material suppli-
ers, parts fabricators and organizations that
40.10 ORGANIZATIONS ACTIVE IN
provide ancillary support. Waste management,
COMPOSITES RECYCLING
including recycling composite waste, is one of
The American Plastics Council, Washington, their areas of activity.
DC, is a joint initiative with the Society of the ERCOM Composite Recycling GmbH,
Plastics Industry Inc. (American Plastics Karlsruhe, Germany, is composed of SMC pro-
Council, 1993). It was earlier known as the ducers and processors, resin suppliers and
Council for Solid Waste Solutions. The Council glass fiber producers. It was founded to
mission is to develop and implement a pro- develop and prove the recyclability of SMC in
gram for the responsible use, recovery order to maintain SMC market share in light of
(including recycling and energy recovery) and the strict German attitude towards waste man-
conservation of plastics. The Council is com- agement.
posed of 25 of the leading plastic resin Reinforced Plastic Waste Recycling and
producers, downstream customers and repre- Treatment Council, Chuo-Ku, Tokyo, Japan, a
sentatives of the plastics processor committee of the Japanese Reinforced Plastics
community. One of its four task forces is Society was organized to seek technical and
Product Stewardship, devoted to advancing social solutions in disposal and reuse of large
all options of integrated waste management. composite items such as ships, tanks and bath
This task force, under the Durables Program, units.
has identified four program groups to receive The Swedish Institute of Composites, Pitea,
recycling (life-cycle management) attention. Sweden, is doing experimental work to show
They are automotive, major appliance, com- that reground SMC can be incorporated into
puter and business equipment, and building new SMC and BMC products.
904 Reuse and disposal
ACKNOWLEDGEMENTS
The author wishes to acknowledge Mrs Peggy
Renkel for her word processing expertise,
helpful suggestions, diligence and patience in
chapter preparation and Dr David Graham for
his careful review of the text.
REFERENCES
American Plastics Council. 1993. Private
Communication, T. Donnelly. What Industry Is
Doing?
Broudy, Phil. 1993. NIRS. Private Communication.
Butler, Kurt. 1991. 46th Annual Conference, SPI
Composites Institute, Session 18-B.
Darrah, Basil. 1993. 48th Annual Conference, SPI
Composites Institute, Session 15-B.
DeMaio, Anthony. 1991. 46th Annual Conference,
SPI Composites Institute, Session 18-C.
Diesenhouse, Susan, 1994. Polyester Becomes
Environmentally Correct. The New York Times,
February 1994, Sec 3.5.
Donnelly, Thomas 111. 1993. Status Report on
National Legislation. SPE Recycling
Conference,June 16. Chicago, Illinois.
Graham, W. David, Jutte R.B. and Shipp, D.L. 1993.
48th Annual Conference, SPI Composites
Institute, Session 15-H.
Hanson, David. 1991. 46th Annual Conference, SPI
Composites Institute, Session 18-E.
Jutte, Ralph and W. D. Graham. 1991. 46th Annual
Conference, SPI Composites Institute, Session
18-A.
Kitamura, Tatsundo. 1993.48thAnnual Conference,
SPI Composites Institute, Session 15-E.
Lause, John. 1993. GLCC. Private Communication.
McDermott, Joseph. 1992. Thermosets Recycled,
What Now? Reinforced Plastics, 36(11).
November.
Miller, B. 1993. Recycling: What the Big 3 say.
Plastics World, 51 (lo), 32-37
Nir, M., Miltz J. and Ram, A. 1993. Update on
Plastics and the Environment. Plastics
Engineering, 49,(3), 87-88.
Norris, Donald. 1990. Proc. 1990 ASME/ESD
Advanced Composites Conference.
Olson, Barbara and H. DeKeyser. 1992. Recycling
Cured Phenolic Material, Rogers Corporation,
Molding Materials Div No. 5215-022-1.5E.
Presented at SAE International Congress,
Session Code M25B (February).
Pettersson, Joakim and P. Nilsson. 1993. 48th
Annual Conference, SPI Composites Institute,
Session 15-E
Protzman, Ferdinand. 1993. Germany’s Push to
Expand the Scope of Recycling. The New York
Times. July 4, sec 3%.
Reitz, James. 1992. 47th Annual Conference, SPI
Composites Institute, Session 4-B.
Richter, Heinz and Jurgen Brandt. 1987. Recycling
Carbon Fiber Scrap, Engineered Materials
Handbook 7: Composites, pp. 153-156.
Rusch, Ken. 1993. 48th Annual Conference, SPI
Composites Institute, Session 15-G.
Sahut, Jan 1994 Reinforced Plastic Making Some Big
Fancy Parts. Plastic WorId, 52(10), 24
Schaefer, Peter and A. Plowgian. 1993.48thAnnual
Conference, SPI Composites Institute, Session
15-D.
SMC Automotive Alliance. 1991. 46th Annual
Conference, SPI Composites Institute, Session
18-D.
Tesoro, Guiliana et al. 1992. 47th Annual
Conference, SPI Composites Institute, Session 4-
C.
Tesoro, Guiliana and Y. Wu. 1993. Chemical
Products from Cured Unsaturated Polyesters.
Advances in Polymer Chemistry, 12(2), 185-196.
Wigotsky, Victor. 1993. Plastics In Automotive.
Plastics Engineering, 49(4), 36-38.
Wood, J. 1991. A Disposal/Recycling Model for
Composite Waste Materials. First International
SAMPE Environmental Conference. May 1.
pp. 388-390.
LAND TRANSPORTATION APPLICATIONS
Douglas L. Denton
41.1 INTRODUCTION
The use of polymer composite materials in
land transportation is steadily increasing
because of the cost and performance advan-
tages that composites offer over competing
materials. Today, composites are extensively
used in well-established passenger car, van
and truck applications. New applications
demanding higher structural performance lev-
els are under development. Railroad cars,
mass transit vehicles and a wide range of mil-
itary ground transportation systems offer
expanding opportunities for composite mate-
rials.
Driving forces for the use of polymer com-
posites in ground transportation applications
include low manufacturing investment cost,
cost reduction through parts consolidation,
weight savings, good mechanical properties,
'Class A' surface quality, excellent durability
characteristics, inherent dent and corrosion
resistance, good noise and vibration dampen-
ing, styling flexibility and dimensional
stability. Factors which tend to mitigate
against their use are high materials costs, low
modulus and the reluctance to use materials
perceived to be 'new and unproven'.
Only those materials and processes which
provide required performance at the lowest
cost achieve long-term commercial success in
transportation applications. For high-volume 41.2 ECONOMICS AND MARKET GROWTH
automobile and truck applications, high-speed
Handbook of Composites, Edited by S.T. Peters. Published the development and acceptance of new appli-
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
41
processes must be used to manufacture parts
rapidly enough to meet the production rates of
the assembly plants. As a result, injection and
compression molding processes are used
extensively for these applications. Composites
typically used in transportation applications
consist of low-cost grades of thermoplastic or
thermoset polymers reinforced with E-glass
fibers. Often these composites also contain
mineral particulate fillers. Composites con-
taining high-modulus fibers, such as carbon,
and higher-performance resins such as epox-
ies, are used only where the higher cost can be
justified to meet special product requirements.
Metal matrix composites are used very spar-
ingly in ground transportation.
Over the past 50 years, the use of polymer
composites generally has progressed from
low-performance applications towards more
demanding applications requiring excellent
surface appearance, high mechanical proper-
ties, increased temperature stability or
improved durability. With increasing
demands to reduce vehicle weight for
improved fuel economy, and to reduce invest-
ment costs for greater competitiveness,the use
of composites in ground transportation is
expected to increase for many decades to
come.
The steady growth in the use of composites for
land transportation is attributed primarily to
cations. From the late-1960s to the mid-1990s
906 Land transportation applications

composite usage in USA transportation more be equal to or lower than stamped steel parts.
than quadrupled (Fig. 41.1), and since the A primary factor offsetting high materials cost
early 1980s it has expanded at a faster rate is the lower investment needed to make parts
than the total composites market. Land trans- from composites compared to steel. To pro-
portation use of polymer composites duce a composite part generally only one
represents the largest segment (over 30%) of mold and one press is needed whereas most
the total market and reached 430 000 metric steel parts require multiple stamping tools and
tons in 1994 according to the SPI Composites presses to form the part. In addition, compos-
Institute. ites offer the opportunity to integrate several
parts formed in steel into one part. This fur-
ther reduces the number of tools and presses
needed, and eliminates the welding opera-
tions required to join the stampings.
The cost advantage achieved or cost penalty
incurred by composites depends upon the
total volume of an application. As the number
of parts produced becomes very high, the
reduced investment in tools and presses is off-
set by the higher materials cost for the
composite. In the automobile industry the use
of a composite part produced at a volume of
several hundred thousand units per year may
Year not be not cost effective. But production of the
Fig. 41.1 Growth in the shipments of polymer com- same composite part at volumes of tens of
posites for use in land transportation. (Source: SPI thousand units per year may be very competi-
Composites Institute.) tive. The specific cost 'cross-over' point
between composites and steel depends on a
large number of factors and must be deter-
Composites have generally displaced metal mined for each specific application.
alloys such as steel to gain new applications.
In order for a material substitution to be suc-
41.3 HISTORICAL DEVELOPMENT OF
cessful, composites must provide all of the
APPLICATIONS
functions required by the part at a competitive
cost. Because of strong competitive forces in Polymer composites began to appear on cars
the transportation industry original equip- shortly after World War I1 in small compo-
ment manufacturers (OEMs) seldom pay nents under the hood and inside the
higher cost for a new material to achieve desir- passenger compartment. The first major mile-
able functions beyond the part requirements. stone in exterior parts was the introduction of
Therefore, composites must achieve cost effec- the Corvette in 1953 which sported body pan-
tiveness for long-term use in transportation els made of glass fiber reinforced polyester
applications. (Fig. 41.2). The body panels were produced
On a price per unit weight basis, composite with open mold and preform molding
material costs are generally several times processes up to 1972, when the production
higher than the metals used in automobile and was converted to compression molded sheet
truck applications. However, when the total molding composite (SMC). The invention of
cost of component production and vehicle the SMC process and the development of 'low
assembly is considered, composite parts can profile' polyester resins, which provided
 Historical development of applications 907

Fig. 41.2 Glass fiber reinforced polyester body panels on the 1953 Corvette was the first major application
of compositesin the automotive industry. Other composite applications introduced on the Corvette include
bumper beams, leaf springs, radiator support, seat backs and rear floor pan. (Photo courtesy of General
Motors Corporation.)

improved surface appearance, allowed the Fuel Economy (CAFE) standards led to intense
proliferation of composites into higher vol- development of new composite applications
ume body applications. and a significant upswing in composite usage
SMC grille opening panels (GOP) were in the late 1970s (Fig. 41.1). Composites not
introduced in the late 1960s and rapidly only expanded into additional cosmetic parts,
spread throughout the industry because fiber but began to be seriously considered for use in
glass GOPs saved weight and reduced cost structural components. Intense programs to
through significant parts consolidation. With develop radiator supports, transmission sup-
the introduction of composite panels on auto- ports, leaf springs and wheels were initiated.
mobile assembly lines, the dimensional Efforts to find additional under-the-hood and
consistency of molded parts became well interior applications of composites were also
known. Manufacturers also recognized that intensified.
the SMC panels could not be deformed to Improvements in composite surface quality
adjust for variations in the steel body struc- and productivity lead to the introduction of
ture. Modification of assembly plant the 1984 Fiero, the second high-volume vehicle
procedures to accommodate the unique char- with all exterior body panels made of compos-
acteristics of composite parts continues to be ites. Using innovative body construction,
an issue with new part introduction. exterior panels produced by the SMC and
The need to reduce vehicle weight through RRIM (reinforced reaction injection molding)
materials substitution and downsizing to meet processes were mechanically fastened onto a
government mandated Corporate Average steel spaceframe. A similar design approach
908 Land transportation applications
was used for the construction of General
Motor’s all purpose vehicles (APV).
Introduced in 1989, these minivans used
approximately 120 kg (260 lb) of SMC per
vehicle (Fig. 41.3). With annual production
volumes ranging from 90 000 to 148 000 vehi-
cles per year this represented the largest single
application of composites in the automotive
industry.
The Dodge Viper was the first American
vehicle to have all body panels produced by the
resin transfer molding (RTM) process (Fig.
41.4). The low production volumes for the
Viper (under 5000 per year) made this an ideal
application for composites. The selection of an
RTM process with low cost molds resulted in
greater investment savings than could be
achieved with SMC and RRIM. This milestone
application was introduced in the early stages
of an industry-wide effort to develop the RTM
and SRIM (structural reaction injection mold-
ing) processes for the production of structural
and Class A parts for the transportation market.
Fig. 41.3 GM’s all purpose vehicle (APV) is the automotive industry’s largest application of composites.
Each vehicle uses approximately 120 kg (260 lb) of SMC in addition to other polymer composites. (Photo
courtesy of General Motors Corporation.)
41.4 CURRENT APPLICATIONS
41.4.1 AUTOMOTIVE APPLICATIONS
On average, cars produced in USA in 1994
contained about 50 kg (110 lb) of fiber rein-
forced composites. The broad usage of
composites in the automobiles and trucks is
illustrated by the list of applications in Table
41.1. Distinctions can be made between appli-
cations that are experimental, have been in
limited production or are well-established in
production. In many cases, breakthrough com-
posite applications are introduced by
manufacturers of low volume specialty vehi-
cles before they appear in high volume car
lines produced by larger companies such as
Chrysler, Ford or General Motors. These larger
companies often will evaluate a new applica-
tion on a low-volume specialty vehicle or on a
customized segment of a high-volume vehicle
before committing to high-volume production
with a composite part.
 Current applications 909
-
--
7-
--
- - I. ~ _ _. - - ~ ~

-----zm

Fig. 41.4 The Dodge Viper is the first American car to have ail Class A composite body panels produced
by the resin transfer molding (RTM)process. (Photocourtesy of Chrysler Corporation.)

Automotive body applications Newly developed composites made from com-

pression molded glass fiber mat thermoplastic
Composites have proven to be very successful sheet (GMT) or liquid molded (RTM/SRIM)
in a wide range of exterior body panels and thermoset resins may also compete with SMC
are used in hundreds of vehicle applications. for horizontal body panels.
Excellent surface finish, light weight, and a The broader use of composites in body pan-
thermal coefficient of expansion near that of els is restricted by their limited cost-
steel have made these applications successful. effectiveness at very high production volumes.
Customers appreciate the dent and corrosion Composite panels are well-suited for niche
resistance of composite panels. vehicles and for providing economical oppor-
SMC dominates composite applications in tunities to achieve styling differences within a
horizontal panels such as hoods, roof and deck body line, but they are seldom employed in
lids, and competes with RRIM for vertical pan- high-volume applications. Another factor that
els such as fenders, doors and quarter panels. precludes the use of some polymer composites
The use of unreinforced thermoplastic body in body panels is sensitivity to high tempera-
panels on vehicles such as G M s Saturn and ture. In most assembly operations all body
Chrysler 's Intrepid, Concorde, and Vision panels are subjected to a heat soak at
demonstrate the potential for the displacement 175-205°C (350400°F) for about 30 min fol-
of composites in some body applications. lowing the electrodeposition of a corrosion
910 Land transportation applications

coating (‘E-Coat’ or ’ELPO) to the steel body and extensive testing, a transverse rear leaf
structure. Only a limited number of low-cost spring was introduced on the 1981 Corvette.
polymer composites can resist dimensional This 3.6 kg (8 lb) filament wound E-glass/epoxy
change or surface distortion during this heat monoleaf spring replaced a ten-leaf steel spring
treatment. weighing 19 kg (421b). A front transverse
While composites are used in the body spring was added to the Corvette in 1984 and
structure for several low-volume sports cars, the first composite longitudinal spring
this opportunity remains essentially untapped appeared on the General Motors Astro van in
in the auto industry. The Lotus Esprit has an 1985. The use of composite springs rapidly
all-composite body produced by the VARI spread across GM car lines in the late 1980sand
process (vacuum assisted resin injection) that early 1990s. In less than a decade from its intro-
is mounted on a steel frame. Lotus uses a sim- duction, the Inland Division of GM (now
ilarly produced composite floor pan and body Delphi Chassis Systems) was manufacturing
panels in the Elan. Consulier manufactures more than one million Liteflex@composite
sports cars with all-composite monocoque springs per year (Fig. 41.5) to meet the demand.
bodies produced by vacuum bag molding of
epoxy prepregs with E-glass, Sglass, carbon
and KevlaP fibers. The entire body structure
weighs only 125 kg (275 lb) and takes all struc-
tural loads. Higher volume applications in
body structure includes the Corvette which
has used composites in the floor pan, rear
underbody and radiator support.
Since the early 1980s an evolving series of
composite materials and processes have been
used to produce front and rear bumper beams.
SMC containingrandom chopped and/or con-
tinuous unidirectional fibers was initially
used. Subsequently, stamped thermoplastic Fig. 41.5 Composite leaf springs reduce vehicle
composites and SRIM bumper beams have weight, resist corrosion and outlast traditional steel
been commercialized.Special design consider- leaf springs. (Photo courtesy of Delphi Chassis
ations and parts consolidationhave lead to the Systems.)
use of glass-reinforced polypropylene
(Azdel@)in the front bumper beams of
Chrysler minivans, which are produced in vol- The exceptional weight savings and outstand-
umes of more than 500 000 units per year. ing durability have been the keystones to the
success of composite springs in cars and more
Automotive chassis applications recently, in heavy trucks. Composite springs
last at least five times longer than steel coun-
While relatively few composite chassis compo- terparts in laboratory fatigue tests and in field
nents have been commercialized, notable service. Added advantages are improved
applications have provided evidence of the packaging due to smaller size, and improved
performance level and durability offered by ride and handling characteristics. Their long-
composites. term field success has also clearly
One of the most successful automotive stmc- demonstrated the survivability of polymer
tural applications to date is the composite composite materials in the harsh under-vehi-
leafspring. After decades of development work cle environment.

Another suspension application demon-
strating the durability and load carrying
capability of composites is wheels. The com-
mercial introduction of polymer composite
wheels was on the 1989 Shelby CSX modified
version of the Dodge Shadow. Developed by
the Motor Wheel Corporation, the Fiberide@
wheel uses a combination of structural SMC
and XMC. These materials provided a mix-
ture of chopped random and oriented
continuous E-glass in a vinyl ester resin. At
reduced weight, the composite wheel out-
performed both steel and aluminum wheels
in fatigue. The development of polymer com-
posites that retained acceptable lug nut
torque after wheel heating caused by extreme
braking conditions was a technical advance
that made this application possible.
A front suspension stabilizer link was
introduced on the 1994 Ford Taurus and
Mercury Sable. Made from a glass fiber rein-
forced copolymer polyacetal, this was the
first use of a structural thermoplastic com-
posites in such an application in North
America. This durable part does not require
painting and reportedly provides a 42%
weight reduction and 33% cost reduction
over the replaced steel part.
Automotive powertrain applications
The application of composites in the power-
train is extensive and is growing. In the past,
only metals were considered for use in the
demanding environment of the engine and
transmission. Increasingly, composites are
being selected to reduce weight and cost, and
to improve NVH (noise, vibration and harsh-
ness), engine efficiency, packaging and
corrosion resistance.
Air intake manifolds are rapidly being con-
verted from metal to injection molded
thermoplastics reinforced with short glass
fibers. Introduced on European cars in the
1970s, composite manifolds are predicted to
be used on most vehicles by the turn of the
century. Most intake manifolds are produced
Current applications 911
by the 'lost-core' process in which a low tem-
perature melting alloy such as tin-bismuth is
used as a form to mold the hollow sections.
The core is then melted away from the cured
part in a subsequent operation. An alternative
is to 'weld' two thermoplastic pieces to form
the manifold. To reduce cost, some fuel
intakes are being integrated with the air
intake manifold.
Injection molded phenolic compounds are
used in many engine and transmission appli-
cations because of dimensional stability and
creep resistance at higher temperatures.
Current applications include pulleys, torque
converter reactors, thrust washers, water out-
lets, valve covers, radiator end caps, motor
commutators and fuel rails (Fig. 41.6).
While the performance advantages of com-
posite drive shafts and propeller shafts (lower
weight, better NVH, increased durability) has
been established, cost remains a barrier to
their wide spread use. A composite drive shaft
has an economic advantage, however, when it
replaces two-piece metal shafts. The most suc-
cessful designs have used glass and/or carbon
fiber composite overwrapped on an alu-
minum tube using pultrusion or filament
winding processes.
Fig. 41.6 Powertrain applications of phenolic com-
posites include transmission torque converter
reactors and thrust washers, poly-V pulleys, and
water outlets. (Photo courtesy of Rogers
Corporation.)
912 Land transportation applications
Experimental engines made almost exclu-
sively of polymer composite materials,
including block, head, pistons and connecting
rods, have been tested, but commercialization
is in the near future. Many
matrix (MMC) parts have been
prototyped for engine applicationsf
few have gone into production
(Table 41.1). Aluminum reinforced with silicon
carbide, alumina or carbon fibers offers the
potential for good mechanical and thermal
properties with large weight savings.
However, factors such as high cost, low ductil-
ity and machining difficulties have retarded
the commercialization MMCs in transports-
tion components.
Automotive interior applications
manufacturers make extensive use
of polymeric materials on the interiors of cars
and trucks/ most do not require fiber rein-
to meet performancerequirements.
Some notable exceptions are seats, load floors,
knee and instrument Pane'
seat
were first introduced on the 1975 Corvette. In
addition to stamped polypropylene, ther-
mosetting Polyurethanes and Polyester are
used inboth seat back and seat pans. An injec-
tion seat with long fiber
reinforcement Premiered On the 1993 Dodge
sheet is cur-
rently preferred for load floors in station
wagons and extended pick-up truck cabs.
Stamped polypropylene has been used in
numerous knee bolsters. This structural part at
the bottom of the instrument panel helps to
control occupant movement during a frontal
crash. Composites and unreinforced thermo-
plastics are also being used in instrument
panel supports to provide lower cost through
parts integration and reduced weight. The use
of composites in the front of vehicle interiors is 41.4.3 RAILROAD APPLICATIONS
expected to expand.
41.4.2 TRUCK APPLICATIONS
Composites are widely used in the medium-
duty and heavy-duty truck industry to
decrease weight, reduce manufacturing and
maintenance costs, and extend the longevity of
the vehicles. Lighter trucks allow increased
payload capability and improved fuel econ-
omy. Since trucks are generally not produced
in high volumes, the lower tooling invesment
favors composite parts. The durability is
important since are used for many
years.
Composites are commercially used for
essentially all skin surfaces on truck cabs, air
deflectors, hoods, fenders, roofs, side closure
panels, sleeper box and doors. Mack Truck
introduced the first structural SMC door in
1978 and two years later GM Truck and Coach
made the first use of continuous fiber SMC in
the door of the Astro and General truck cabs.
In 1983 Mack Truck became the first manufac-
turer to introduce a cab with composites used
in all exterior surfaces. These panels covered a
frame made of steel, aluminum, and
structural composite beams. Several all-com-
posite truck cabs using monocoque structures
have been prototyped and shown to meet all
performance requirements.
Weight savings of 20% are achieved in truck
trailers when floor, wall and ceiling panels are
composite. In addition, refrigerated trailers
made from composites are 25-30y0 more ther-
mally efficient than metal trailers. In a recent
application, Trail King has introduced a flat
bed trailer with a fiber reinforced epoxy deck
to achieve lower weight, corrosion resistance
and lower cost.
One of the fastest growing application in
heavy truck is composite leaf springs for large
weight savings and greatly extended spring
life.
Durability and light weight make composites
attractive for railroad applications, yet few
 Current applications 913

Table 41.1 Composite applications in automobiles and trucks'

Experimental Limited production Well established

Body Front rails Radiator support Grille opening panel
A, B and C pillars Floor pan Grille opening
Roof frame Cowl panel reinforcement
Rockers Wheel housing Rear end panel
Rear underbody Windshield surround Hood
Pickup truck box Door surround Deck lid
Truck cab structure Center tunnel Lift gate
Truck trailer bed Tanker truck trailers Rear hatch
EV battery tray Roof panel
Hardtop cover
Fenders
Quarter panels
Doors outers
Door inners
Spoiler
Headlamp cover
Fuel filler doors
Front bumper beams
Rear bumper beams
Truck air defector
Truck trailer walls
Truck trailer roof
Chassis Front cross member Wheels Leaf spring
Transmission support Stabilizer bar links Disk brake pistons
Brake rotors'
Powertrain Throttle body Drive shaft Air intake manifold
Oil pump
- - Propeller shafts Battery tray
Transmission valve body Water pump housing Fan shroud
Hydraulic clutch actuator Water pump impeller Radiator end caps
Engine - Pistons, block, Fuel pump components Transmission torque
head, piston pins3 Fuel rail converter reactor/stator
connecting rods3 Fuel tank supports Transmission thrust washer
rocker arms2 Camshaft sprockets Motor commutators
bed plate2 Oil pan Diesel electronic unit injector
Flywheel4 Differential cover Valve cover
Drive shaft2 Valve lifter guides Timing chain covers
CNG storage cylinders5 Poly-V pulleys
Cylinder liners2 Idler pulley
Pistons2 Distributor cover
Interior Car jack Knee bolster Seat back
Steering wheel Instrument panel support Seat support
Window frame/trim Load floor
Plenum
Glove box

Polymer composite unless noted otherwise Electric powered vehicles

Metal matrix composites Natural gas vehicles
Metal matrix or polymer matrix composites
914 Land transportation applications
have been commercialized. Pultruded glass
fiber reinforced thermoplastic composite pan-
els are used to construct a 'Secured Modular
Automotive Rail Transport' (SMART) for
Union Pacific Railroad. Each three-tier struc-
ture serves as a 'car rack' to protect eighteen
automobiles from damage and theft during
transport to the dealer. The use of composites
also significantly reduces the maintenance cost
of the car rack.
Composite hopper car covers protect grain
and other dry materials that need protection
from moisture. The covers, which range from
9-15 m (3040 ft) in length, are fabricated by a
hand lay-up process. Two prototype
glass/polyester filament wound railroad cars
termed the 'Glasshopper' have been in service
since 1981 without failure. Produced in a joint
venture by ACF Industries, Cargill and
Southern Pacific, the corrosion resistant, light-
weight composite car can carry a greater
payload, but is significantly more expensive
than a steel hopper car.
41.4.4 MASS TRANSIT APPLICATIONS
Buses and passenger rail systems offer many
more opportunities for the application of com-
posites than are presently in service. Some
cosmetic and semi-structural applications
have been successfully implemented, but few
examples of structural components are found.
The durability of polymer composites has
lead to extensive use in seats for buses, sub-
ways, people movers and trains. Composite
sandwich panels with glass fiber-phenolic
skins over aramid or aluminum honeycomb
are used in walls, ceilings and floors of many
European mass transit cars. These rigid panels
are very lightweight and the use of phenolic
resins allows attainment of fire/emission stan-
dards. The end caps of transit cars are often
molded composites. Pultruded exterior panels
are being substituted for aluminum on buses
to reduce weight and decrease assembly cost.
The development of high speed rail sys-
tems, which attain speeds up to 480km/h
(300 miles per hour), may offer an opportunity
for composites because of the need to mini-
mize weight. Weight reduction is especially
important for magnetic levitation (MAGLEV)
systems where the vehicle is suspended above
the guideway to provide friction free move-
ment.
41.4.5 MILITARY APPLICATIONS
Limited applications of composites are found
in combat and non-combat ground vehicles in
the US military, but if current development
programs are successful, much greater use of
composites should result. Modern warfare
requires rapidly deployable, survivable vehi-
cle systems. Thus, weight reduction in all
vehicles, including armored vehicles, is desir-
able. In addition to weight savings,
composites can potentially offer increased
durability, improved signature management!
better personnel protection and lower produc-
tion cost.
The goal of an ongoing Army project, the
Composite Armored Vehicle Advanced
Technology Demonstrator (CAV ATD), is to
establish the feasibility of using polymer com-
posites in the primary structure of a 20 tonne
(22 ton) combat vehicle to achieve a 33%
weight saving over a traditional metal vehicle.
Composites are also being considered for com-
bat vehicle armor - used either alone or in
conjunction with ceramics and/or metals - to
provide significant weight savings over cur-
rent materials. The High Mobility
Multi-purpose Wheeled Vehicle (HMMWV),
which is currently in production, utilizes an
integrated hood/fender assembly molded
from SMC. In upgraded versions, composite
armor is attached to the HMMWV.
Phenolic spa11 liners containing Kevlar or
S-2 Glass@fibers are used in the M113A3
Armored Personnel Carrier and Bradley
Fighting Vehicle to provide troop protection.
Longer service life and chemical protection
were the motivation for the incorporation of
composite seats and side racks in 2.2 tonne
 Conclusions 915

(2.5 ton) and 4.4 tonne (5 ton) trucks. Other and technical expertise acquired in defense
potential composite applications such as M1 programs to the development of composite
Abrams Main Battle Tank components (dri- technology needed to improve the competi-
ver’s seat, air intake plenum, stowage box, tiveness of American industries with a
and power pack container), tactical vehicle particular emphasis on the automotive indus-
body, fuel tanker and HMMWV drive shaft try. Numerous federal programs are directing
are under consideration for production after dollars and technical expertise resident in the
the turn of the century. National Laboratories into ground transporta-
tion programs. A notable example is the
41.5 FUTURE DIRECTIONS
’Partnership for a New Generation of Vehicles’
program, which teams the government with
The growth of the transportation market is the automotive industry to produce the tech-
expected to continue, and potentially acceler- nology to make safe, comfortable, and
ate, into the 21st century. As composites affordable cars that achieve up to 30 km/l (82
become better understood by designers, and miles per gallon) of gasoline with low emis-
as the reliability and advantages of these mate- sions. Composite materials are expected to
rials are more clearly demonstrated, they will play a key role in meeting this challenging
be used increasingly in more demanding goal. Successful implementation of the tech-
structural applications. Body structure, chassis nologies developed in these cooperative
and powertrain offer tremendous opportuni- programs could have an enormous impact on
ties for the utilization of composite materials. the usage of composites in future vehicles.
Improved manufacturing capability to rapidly
produce composite parts will boost their eco-
41.6 CONCLUSIONS
nomic viability in high volume applications.
The development of a commercial infrastruc- Ground transportation is the largest and one
ture and market for the large scale recycling of the fastest growing segments of the polymer
and reuse of polymeric materials will also composites market. While transportation use
increase the growth opportunity for compos- of composites is expected to expand, the rate
ites. of growth depends on a number of factors.
The potential economic advantages and Improvements in technology are needed to
weight reductions afforded by the use of com- increase high volume production capability
posites in integrated body structure and and increase the cost competitiveness of com-
chassis components has driven development posites relative to other materials. The
programs since the 1980s. In 1988 Chrysler, performance and durability of composites in a
Ford and General Motors formed the wide range of structural applications must be
Automotive Composites Consortium (ACC) to demonstrated. More designers and engineers
conduct joint R&D on structural polymer com- need to become familiar with the unique char-
posites with a focus on these structural acteristics of composites and learn to develop
applications. Operating under the United States designs that use the full potential of these
Council on Automotive Research (USCAR),the materials. An economically viable infrastruc-
ACC works with supplier companies and uni- ture for dealing with post-consumer waste
versities to develop the processing, materials, must be established. With these advances,
design and joining technology needed to composites are expected to play an important
achieve production worthiness and cost effec- role as industry meets the increasing world-
tiveness of composite structures. Currently, the wide demand for safe, clean, energy efficient
US Federal Government is providing resources land transportation.
MARINE APPLICATIONS 42
Wayne C. Tucker and Thomas Juska

42.1 INTRODUCTION resins, but their superior resistance to hydrol-

Use of composites in marine applications is ysis and blistering aacquemet and LaGrange,
widespread. The two major advantages of fiber 1988) makes isophthalic polyester a better
reinforced dastics over metals are resistance to choice for applications requiring long term
the marine environment, particularly the elim- exposure to water.
ination of galvanic corrosion and the ease of Use of vinyl esters is becoming more com-
tailoring structures, which are fabricated by mon. Although they are more expensive than
molding processes. In addition, composites polyesters, vinyl ester laminates generally
have high strength-to-weightratios. have better properties. In addition, vinyl esters
This chapter is an overview of the materials have excellent resistance to matrix hydrolysis.
and fabrication processes used in marine appli- Also available are mixtures of vinyl ester and
cations of composites. More comprehensive polyester, which offer some of the benefits of
studies of the use of composites in marine con- vinyl ester but at intermediate cost.
struction have recently been published (Smith, Epoxy laminating resins, rarely used in
1990;Greene, 1990; Davies and Lemoine, 1992). marine applications due to cost and the need
for elevated temperature cure, are used by
some boat builders in high performance one-
42.2 MATERIALS off racing craft and some production boats.
Among the advantages of epoxy are extended
42.2.1 RESINS out-time compared to room temperature cur-
Resins used in marine applications generally ing resins and low volatile organic content.
cure at room temperature, both for the low The material form is wet epoxy prepreg
fabrication costs and because elevated temper- (sometimes referred to as a wet-preg to distin-
ature performance is not required. guish it from conventional prepreg) made by
General purpose polyester is the most com- the boat builder (Gougeon, 1992). Fabrication
mon laminating resin. These materials, based is normally by vacuum bag, room temperature
on orthophthalic acid (phthalic anhydride), cure followed by oven post-cure at about 50°C
are the least expensive, but long term immer- (122°F).
sion without a barrier coat will probably result
in blistering (Burrell, Herzog and McCabe, 42.2.2 REINFORCEMENTS
1987). Polyesters based on isophthalic acid are
slightly more expensive than general purpose E-glass fabric is the primary reinforcement in
marine construction, of which there are numer-
ous forms. There are two basic styles: woven
Handbook of Composites. Edited by S.T. Peters. Published and knitted. Woven fabrics are further subdi-
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 vided into woven roving and woven yarn.

Woven roving are the most common fabrics
due to their low cost. They are available in a
variety of weights and weave patterns, but a
800 g/m2 (24 oz/yd2) plain weave is probably
the most frequently used. In small boat con-
struction, the fabric is usually mat-backed, in
which a chopped strand mat has been stitched
or powder bound to one side of the fabric.
Woven yarn, also called textile fabric or
cloth, is more expensive and therefore used
infrequently. These materials are finer in tex-
ture than woven rovings and are used as
surfacing plys, particularly in tooling.
Knitted glass fabrics are becoming more
common. The rovings are stitched together,
which keeps the strands relatively parallel (no
crimp as in weaves) and stabilizes the fabric
against distortion during handling. The orien-
tations of the separate layers and the number
of separate layers, which compose knitted fab-
rics can be varied, although a 2-ply 0/90 is
most common. Knitted fabrics are currently
available up to 2500 g/m2 (72 oz/yd2).
Chopped strand mat is most commonly
used where a resin-rich layer is desired, such as
between the core and fabric in sandwich struc-
tures. Usually the first ply next to the gel coat
is a layer of mat, which reduces print-through
of the reinforcement as well as providing addi-
tional protection from water permeation.
S-2 glass is about six times the cost of E-
glass, so it is rarely used in marine structural
applications. S-2 made in the G filament is
sized for epoxy and when made with the K
filament is sized for polyesters and vinyl
esters.
Carbon fiber is also rarely used because of
cost. America’s Cup racing sailboats use car-
bon throughout the boat and some racing
powerboats use carbon as well. Carbon has an
additional problem in that it can corrode met-
als in contact with it in the presence of water
(Tucker, Brown and Russell, 1990; Aylor and
Murray, 1992).
Polymeric fibers, namely Kevlar and
Spectra, are sometimes used in marine appli-
cations where weight is critical (Sloan and
Materials 917
Nguyen, 1992).Their use is limited because of
cost and also because they cannot bear much
load in compression.
42.2.3 CORES
Linear PVC foam is used extensively in boat
hulls, at a density of 80 kg/m3 (5 lb/ft3). The
resilience of the material allows hull deforma-
tion during impact with no skin/core
debonding, skin damage or core shear failures.
Crosslinked PVC foam is used in decks, bulk-
heads and cabins because it has better
structural properties and will not creep at the
higher topside service temperatures. It is
available in a wide range of densities, but is
usually used at 80 and 100 kg/m3 (288 and
3601b/yd3). Both types of PVC foam are
closed cell, absorb very little water and are
moderately priced.
End grain balsa, also widely used as the
core in boat sandwich structures, is inexpen-
sive and has excellent structural properties.
Under some circumstances, however, balsa
can rot. If skin/core debonding occurs and
water is allowed to penetrate this interface, the
wood will eventually degrade. It has been
shown, however, that balsa will provide a long
marine service life with proper maintenance
(Baltek Corporation, 1986).
Composite core is also available. The mate-
rial is made in two forms, either sinusoidal
nested-wave, or in a closed cell configuration
where planar webs alternate with sinusoidal
webs (Plunkett et aI., 1992).This type of core is
essentially a collection of sine wave stiffeners
fused to skins with a laminating resin. It
appears to have great potential for marine and
civil engineering structures and has in fact
been used to make about 200 prototypes,
including deckhouses, storage tanks, build-
ings and parabolic solar energy concentrators.
42.2.4 SKIN/CORE BONDING
A good bond between skin and core is critical
to the performance of sandwich structures. In
918 Marine applications

boat building it is general practice to use

vacuum bag pressure to achieve the necessary
quality. There are two basic methods: one is to
use a paste adhesive between skin and core
and the other is to use the laminating resin as
the adhesive.
Paste adhesives for a polyester or vinyl ester
laminate are filled polyesters. The adhesive is
catalyzed and troweled onto the surface of pre-
cured laminate (normally the outer skin) and
the foam core is sprayed with catalyzed resin
(Johannsen, 1990). The core is then bedded into
the paste, the vacuum bag is positioned and
the assembly is allowed to cure at room tem-
perature. The core either has holes to allow air Fig. 42.1 Boat hull blisters. (Courtesy of Dr. Tom
to escape, or contour core is used. In both cases, Rockett, University of Rhode Island.)
observation of the paste seeping through the
spaces is evidence for a successful bonding
operation. The inner skin is laminated directly
3. More water is drawn into the laminate
onto the surface of the core, with the first ply
through osmosis, creating a localized pres-
normally a chopped strand mat.
sure. The solution in the osmotic center
Some sandwich structures are made by
hydrolyzes the resin, resulting in an
bonding the core with a resin rich layer. In this
increase in water-soluble materials, which
method, a wet-out ply of chopped strand mat
then draw more water into the laminate
is applied to the outer skin and used as a bed-
and increase the pressure.
ding for the core. In a recently discovered
variation of this approach, which appears to There are materials solutions to the blistering
offer some advantages, a ply of polyester mat problem of orthophthalic polyester laminates.
is used to bed the core (Lewit, 1990). One is to coat the hull below the waterline
with an epoxy paint formulated to reduce
water penetration (Interlux, 1993). Another is
42.3 ENVIRONMENTAL EFFECTS to use a permeation barrier between gelcoat
and laminate, as mentioned previously. A
42.3.1 BLISTERING more expensive solution to blistering is to
change to a vinyl ester laminating resin. Use of
Blistering can occur in gel coated marine lam-
isophthalic polyesters is another alternative,
inates (Fig. 42.1). The causes are complex and
which offers a compromise between cost and
blisters may occur due to the selection of mate-
resistance to hydrolysis.
rials or due to the process used in fabrication
Blistering of carbon fiber reinforced plastics
or both. The formation of blisters basically
involves three steps (Marino, Rockett and
(CFRP) in seawater can occur for another rea-
son. When galvanically coupled to a metal
Rose, 1985):
fitting, the CFRP becomes cathodic. The result-
1. Water permeates into the laminate. ing electro-chemical reaction produces
2. Water-soluble components in the resin are hydroxyl ions near the carbon fibers. To bal-
dissolved in this water and are concen- ance the charge, sodium ions are drawn in.
trated in cracks or voids in the laminate, The eventual result is blisters with high alka-
creating an osmotic center. linity (Tucker, 1991; Miriyala et al., 1993).
 Fabrication 919
42.3.2 MICROBIAL DEGRADATION production rates. These machines perform
All engineering materials become colonized three important functions: they wet out the
by microorganisms within hours after expo- fabric, meter the resin and place the wet out
sure in natural waters (Little and Wagner, fabric via an overhead crane or gantry
1986). Microorganisms grow and produce a (Venus-Gusmer, 1989). Laminators must still
viscoelastic layer or biofilm. The environment roll out the fabric after it is placed to remove
at the interface is radically different from the air. Resin contents are reduced to about 50
wt %.
bulk medium in terms of pH, dissolved oxy-
gen and organic and inorganic species (Little et Portable impregnators are also occasionally
ai., 1991).In addition to biofouling, the mater- used. Some high performance racing sailboats
ial properties may be adversely affected. are laminated with wet epoxy prepreg made
Epoxy and nylon coating on steel can be by the fabricator.
breached by mixed cultures of marine bacteria
(Jones, Walsh and Mansfield, 1991). Sulfate 42.4.3 RESIN TRANSFER MOLDING
reducing bacteria (SRB) degrade marine
caulks and polymeric coatings (Jones, Walsh Vacuum assisted resin transfer molding
and Mansfield 1991; Jones et ai., 1992a,b). (VARTM)has been shown to have great poten-
Organic surfactants on S-2 glass fibers have tial for the fabrication of ship hulls and
reportedly been attacked in the presence of secondary structures. The Naval Surface
SRB as well (Tucker et al., 1993). Warfare Center, Carderock Division, has had
Microorganisms can be a threat to material several prototype structures made with a
performance in the marine environment. VARTM method known as SCRIMP (Seemann,
1989), including deckhouse modules, masts
and a Swimmer Delivery Vehicle (NSWC
42.4 FABRICATION Carderock Division, 1993). The advantages of
VARTM over hand lay-up are that very low
42.4.1 HAND LAY-UP resin contents are achieved (30-35 wt YO), the
process is less labor intensive and styrene
Hand lay-up is the most common fabrication emissions are almost eliminated. Laminate
method in marine construction. Catalyzed mechanical properties of panels made by
resin is first applied to the gel coated mold VARTM show significant strength and stiff-
surface, usually by spraying. A layer of dry ness improvements over panels made by hand
mat or fabric is positioned onto the resin and lay-up (Juska,Mayes and Seemann, 1993).
by pressure of hand-held rollers, resin gradu-
ally soaks through the fabric and most of the
trapped air is forced out. This process is 42.4.4 VACUUM BAG PROCESSING
repeated until the desired number of plys is Vacuum bag processing is used extensively in
attained. The full thickness of the structure is the boat building industry to facilitate bonding
rarely built up all at once, but is usually done of the core onto pre-cured skins, as described
in several lay-up/cure stages. Resin contents earlier. Vacuum bags are rarely used to compact
are normally about 55 wt % and void contents polyester or vinyl ester wet lay-ups because
about 1%. there is little time to place the bag before gela-
tion. Vacuum bag consolidation is used,
however, to laminate wet epoxy resins and
42.4.2 IMPREGNATORS
oven-cured prepregs, but the practice is limited
Impregnators are sometimes used in the fabri- to the production of high performance boats
cation of large composite structures to increase such as the America’s Cup racing sailboat.
920 Marine applications

Autoclaves are rarely used in marine con- and can be used as a guide to the properties of
struction, mainly because the process is too typical marine laminates (made by hand lay-
expensive for marine structures. There are a up) with those attainable by alternative
few exceptions, however. Submarine sonar fabrication methods.
bow domes are autoclave cured, as are car- The properties of cored panels are becom-
bon/epoxy sailboat masts. ing increasingly important to the design of
marine structures, particularly boats. Recent
studies have indicated that cored panel prop-
42.4.5 FILAMENT WINDING
erties as determined with standard beam
Filament winding is very often used to make bending tests should be supplemented by
structures and machinery for marine applica- measuring the response of plate specimens
tions. It is inexpensive, largely automated and subjected to uniform pressure loading (Huss,
low resin contents are achieved. It is most 1990; Reichard, 1992; Gougeon and Bertelsen,
appropriate for parts with a circular cross sec- 1993).
tion, such as shafting, piping and pressure
bottles.
42.6 STRUCTURES

42.5 MECHANICAL PROPERTIES 42.6.1 MINE COUNTER MEASURE VESSELS

Materials with a wide variety of fibers, resins,
resin weight contents and void contents are
used in marine construction. Extensive testing
at NSWC, Carderock Division, has led to a
database of marine construction materials
made by hand lay-up, VARTM and vacuum
bag consolidated prepregs ouska, Ma yes and
Seemann, 1993; Juska 1993). The values in
Table 42.1 were abstracted from this database
Mine counter measure vessels are among the
largest GRP boats fabricated. These military
vessels are made of non-magnetic material
(GRP or wood) to reduce the threat from mag-
netic mines. Several foreign Navies have built
composite minehunters, including the Soviet,
British, Swedish, Italian, French and
Australian, usually 4548 m (150-160 ft) long
(Greene, 1990).

Table 42.1 Properties of marine laminates

Fabric Woven Woven Style 7781

resin roving roving epoxy
vinyl ester vinyl ester
Fabrication Hand lay-up VARTM Prepreg
Resin content (wt Yo) 50-60 30-35 35-40
Void content (%) 0.5-1.5 0-0.5 0.54
Compression strength, MPa 172-207 379414 379414
(psi x lo3) (25-30) (55-60) (55-60)
Tensile strength, MPa 172-207 379414 379414
(psi x lo3) (25-30) (55-60) (55-60)
Tensile modulus, GPa 11.7-13.8 21.4-22.8 21.4-22.8
(psi x lo6) (1.7-2.0) (3.1-3.3) (3.1-3.3)
Flexural strength, MPa 276-345 483-552 483-552
(psi x lo3) (40-50) (70-80) (70-80)
 Structures 921

The US Navy, whose Mine Counter 42.6.3 LARGE POWER YACHTS

Measure (MCM) ships have a wooden hull Large custom private power yachts, typically
construction, is currently building the MHC- 21-39m (70-130 ft) long but up to 48m
51 class coastal minehunter with GRP (160ft), are made with GRP by several boat
(Hepburn, Magliulo and Wright 1991). The builders. Most of the builders make hulls
Navy selected to modify the Italian Lerici class cored with linear PVC, with decks, bulkheads
design for the MHC-51, which has an unstiff- and superstructures cored with crosslinked
ened single skin hull. The resin is an PVC. The cores are bedded in paste adhesive
isophthalic polyester formulated to have a and vacuum bagged to the outer skin. Blister
long gel time (about four hours). The rein- protection is usually provided by several lay-
forcement for the hull, decks and transverse ers of epoxy paint applied to the gel coat after
bulkheads is DF1400 (1400 g/m2; 40 oz/yd2) the boat is demolded.
composed of spun roving in the fill direction. Westport Shipyard developed the concept
The superstructure is constructed of Rovimat of using the same (female)mold to make sev-
1200, an 800 g/m2 (24 oz/yd2) woven roving eral non-identical boats. They have pulled 35
stitched to a 400 g/mZ (12 oz/yd2) mat. The hulls from a single mold, which they alter in
reinforcement is wet-out and placed with an length and width to accommodate the design.
impregnator. Westport uses an overhead crane impregnator,
which they believe saves 50% in labor over
42.6.2 SMALLBOATS hand lay-up. They laminate with a general
purpose polyester resin and a 800g/m2
Small boats and craft are usually constructed (24 oz/yd2) woven roving (not mat backed).
from GRP and probably dominate the marine Other builders have also adopted the vari-
composites market. There are numerous styles able mold approach. The Christensen Motor
of power and sail boats. In spite of the diver- Yacht Company makes boats by hand lay-up
sity in hull shape and size there are fairly up to 43m (140 ft) long. They prefer knitted
standard fabrication techniques and materials reinforcement (2408) for its handling charac-
used in boat building. A comprehensive teristics and more uniform resin content and
review of the methods and materials used in use vinyl ester in the outer skin. North Coast
Navy craft fabrication and repair has recently Boats has a mold capable of producing boats
been published (Russell, 1992). up to 40 m (131 ft) long. They make boats by
Female molds are more common than male hand lay-up with a relatively heavy knitted
plugs in production boats due to the impor- reinforcement (3205) and a vinyl ester/poly-
tance of unvarying hull shape and ester resin mixture. The Nordlund Boat
appearance. After the mold surface is coated Company laminates with a 600 g/m2
with release agent, it is sprayed with several (18 oz/yd2)knitted reinforcement for the outer
layers of gel coat (usually an isophthalic acid, skin, for reduced print through and woven
neopentyl glycol polyester) until a roving in the inner skins.
0.5-0.76 mm (20-30 mil) wet thickness is Some builders of large yachts do not use a
achieved. The gel coat is allowed to harden variable mold. Admiral Marine specializes in
prior to lamination. The first ply of the lami- one-off female tooling. They used this concept
nate is usually a chopped strand mat to to fabricate a 48 m (160 ft) private motor yacht
reduce print-through of the subsequent layers (by hand lay-up). An E-glass/Kevlar hybrid
of woven or knitted reinforcement. Boats are fabric was used in the decks and cabin.
usually fabricated by hand lay-up, as Jones-Goodell Yachts also make a unique
described earlier. female tool for each boat, producing boats UP
to 33 m (110 ft) long.
922 Marine applications

Delta Marine produces displacement, semi- typical of marine construction, however; since
displacement and planing hulls using a the designs minimize weight and maximize
variety of techniques. The displacement hulls stiffness of structural components, the yachts
are built using a stiffened single skin, where use aerospace materials. For example, the
the semi-displacementhulls in the larger sizes boats built for America3Foundation's success-
utilize a balsa cored sandwich construction in ful defense of the 1992 Americas Cup had
the sides and a stiffened skin bottom. The pri- carbon/epoxy tape in the hull (cored with
mary materials used are a mat backed knitted aluminum honeycomb), frames, keel, mast,
fabric (3205) and a combination of vinyl ester pole and boom, carbon winch drums and
and general purpose polyester laminating shafting and pultruded Kevlar standing rig-
resin. In addition to private motor yachts, ging (Kramers, 1993). The design philosophy
Delta builds commercial fishing vessels and was to keep the weight as low as the IACC
small charter boats. rules allowed, while maximizing stiffness and
being just strong enough to avoid failure. The
processing conditions for the hull are limited
42.6.4 AMERICA'S CUP RACING SAILBOATS
to 1atmosphere pressure (i.e. vacuum bag) at
The America's Cup class yachts use compos- 95°C (203°F))while those for the mast are 3 x
ites more extensively than any other marine lo5 N/m2 (3 atm) and 135°C (275°F).
structure. The materials in the boats are not

RECOVERY STROBE MAIN THRUSTERS

LIGHT \ ELEVATORS

\RF BEACON
TITANIUM HEMISPHERE
RECOVERY
RETRACTABLE LIFTING

EMERGENCY

GRAPHITE COMPOSITE
PRESSUREHULL

\\
DESCE

E
!E
ZI:: /
FORWARD-
LOOKING
SONAR
OAS
CCD
CAMERA
\
FORWARD VERTICAL
THRUSTER
\
SIDE-LOOKING
SONAR
' I
DOPPLER
TRANSDUCERS

AFT VERTICAL
THRUSTER
NAVIGATION
TRANSPONDER

Fig. 42.2 Advanced Unmanned Search System. (Courtesy of Naval Command and Ocean Surveillance
Center, RDT & E Division.)
 Structures 923

42.6.5 PRESSURE HULLS 42.6.7 FAIRINGS

The potential for composites in pressure hulls
has been demonstrated (Garvey, 1990; Stachiw
and Frame, 1988).Actual use of composites in
these structures has been limited, however.
One exception is the Advanced Unmanned
Search System (AUSS), developed and oper-
ated by the Naval Command, Control and
Ocean Surveillance Center, RDT&E Division
(NRad, 1992). It consists of a vehicle, a control
van, a maintenance van, a launch and recovery
ramp and tow fish for acoustic communica-
tions. As shown in Fig. 42.2, the vehicle has a
graphite/epoxy cylindrical pressure hull with
titanium hemispherical endclosures. The
design depth is 6095m (20000 ft) and it has
had 134 successful operations, including dives
to 3557 m (12 000 ft). The AUSS locates and
inspects objects on the ocean bottom with
sonar and cameras and transmits the informa-
tion to the surface acoustically. It is an
untethered vehicle, receiving commands
through the acoustic link.
The submarine fairwater, or sail, (Fig. 42.3) is
an excellent example of a large complex com-
posite marine structure. A typical fairwater is
12m (40 ft) long, 73m (24 ft) tall and com-
posed of over 1000 component sections. These
massive structures were retrofitted on numer-
ous classes of submarines replacing steel
fairwaters. The composite fairwaters provide
the Navy with lighter weight and non-corro-
sive properties that steel could not match. The
construction of submarine fairwaters consists
of E-glass/polyester panels and secondary
stiffeners bolted to the metal superstructure.
Mast fairings on Navy submarines are fitted

42.6.6 SONAR DOMES

There are numerous submarine and surface
ship sonar domes. The largest sonar domes in !
service for the Navy are submarine bow
domes. All bow domes made to date were
fabricated at the Terminal Island facility of
Hitco’s Defense Products Division. The struc-
tures are fabricated with glass/epoxy
prepreg and are autoclave cured in one stage,
which is remarkable because of the size,
weight and thickness of the parts. The mater-
ial characteristics necessary to allow the
one-stage cure are stringent and only four
materials have been qualified for use in sonar
bow domes (Hitco, 1986). The mechanical
properties specified are also restrictive, par- :
ticularly the value of Mode I fracture
toughness, where an incipient value of
I
2627 J/m2 (15 in lb/in) is specified.
Fig. 42.3 Submarine fairwater. (Courtesy of Lunn
Industries, Inc. Wyandanch, NY.)
924 Marine applications
on periscope masts, antenna masts and
snorkel masts. The masts are constructed from
epoxy/fiberglass and some types are filament
wound.
Figure 42.4 illustrates a propulsion shaft
fairwater for the US Navy’s CG-47 class cruis-
ers. These hybrid-composite components were
filament wound with continuous carbon and
glass fibers on a six-axis filament winder. They
provide a 50% reduction in weight over their
metallic counterpart while exhibiting superior
stiffness and strength. These cantilevered
structures are subjected to large hydrody-
namic loads. The composite system resists
corrosion and biofouling due to a co-cured
external jacket which also improves acoustic
characteristics.
Fig. 42.4 Propulsion shaft fairwater. (Courtesy of B.F. Goodrich Aerospace, Engineered Polymer Products
Business Group, Jacksonville,FL.)
42.6.8 CONTROL SURFACES
The NR-1 nuclear powered research subma-
rine was targeted by NAVSEA and the David
Taylor Research Center as a test platform for
the first all-composite diving planes. The div-
ing planes are hybrid composite construction
with a syntactic foam core.
42.6.9 OILPLATFORMS
The offshore oil industry is making use of com-
posite materials on their platform structures.
Examples of applications are: composite drain
lines, composite cable trays, composite well
head access platforms (Fig. 42.5) and compos-
ite firewater systems (Fig. 42.6). The structures
 Machinery 925

42.6.11 DECKING
Aside from the application mentioned in the
section on oil platforms (Fig. 42.5), composite
decking is used where lightweight non-cor-
roding decking is needed. Examples are ship
superstructures, work platforms and catwalks.

42.6.12 SHIPBOARDARMOR
Composite deckhouse armor is used by the
Navy in the LHD class. LHD-1, the USS Wasp,
has panels composed of Kevlar reinforced
Fig. 42.5 Composite wellhead access platform. vinyl ester. For LHD-2, LHD-3 and LHD-4, the
(Courtesy of EXXON Production Research material was changed to S-2 fabric-reinforced
Company.) phenolic, each vessel of which carries
64 000 kg (140 000 lb) of armor plate (Owens
Corning Fiberglas, 1991). The change was
made to reduce cost without sacrificing ballis-
tics protection. The fiber/matrix adhesion in
the S-2 material was deliberately engineered to
I'
be poor, which results in superior resistance to
penetration by projectiles.

42.7 MACHINERY

42.7.1 PROPULSION SHAFTING

Fig. 42.6 Compositefirewater systems on EXXONs
BATT platform. (Courtesy of Ameron Inc.)
are fabricated from pultruded vinyl ester with
an outer scrim of continuous glass mat while
the pipelines are filament wound glass/epoxy.
42.6.10 CONCRETE FORMS
Repairs to bridges, piers, docks and other
structures with deteriorating pilings are
accomplished by pulling a fiberglass form
around the old piling underwater. The form is
set on a precast concrete footing which fits
around the old piling. The fiberglass form is
then pumped full of concrete. The form may
be stripped and re-used or left in place as
added protection from ice and floating debris.
Use of composites in propeller shafts is being
investigated at the Naval Surface Warfare
Center, Carderock Division (Wilhelmi,
Appleman and Loo, 1986). The advantages
over steel are reduced galvanic corrosion,
weight, cost and bearing loads, while allowing
an increase in fatigue stresses, flexibility and
vibration damping. A small diameter 63.5 mm
(2.5 in) filament wound propulsion shaft has
been evaluated in a 4-year t i a l aboard a Naval
Academy Yard Patrol Vessel (YP-654 Class).
Encouraging results from the YP trial, labora-
tory torsion and fatigue testing and analytical
studies employing finite element stress analy-
sis techniques have led to current R&D efforts
to develop a Navy-Standard composite shaft-
ing 'base laminate', design and procurement
specifications and a metal/composite cou-
pling technique suitable for the largest
diameter shafting systems.
926 Marine applications

42.7.2 PIPING SYSTEMS permit measurement of the radial thermal con-

ductivity of experimental candidate composite
Composite piping systems are gaining accep-
heat exchanger tubes (Korczynski, 1993).
tance in marine applications (Fig. 42.6). The
Installation of composite centrifugal pumps
components of piping systems, piping, fit-
tings, valves, heat exchangers and pumps, are (Suitt and Girona, 1993) and piping on Navy
all being investigated for replacement with ships has proven encouraging to date. There
fiberglass (Wilhelmi, 1988). The major reason are some unresolved issues involved with
for replacement is the elimination of corrosion more extensive utilization of composite piping
and galvanic effects, resulting in an increased components in Navy ships, namely, concerns
service life with less maintenance. In addition, about impact, shock and fire resistance.
composite pump components and valves have
improved erosion resistance compared with
42.7.3 DIVING EQUIPMENT
metallic counterparts. A fluid flow loop was
designed and built by NSWC Carderock Composite materials in the diving industry
Division to evaluate the performance of the have proven advantages in numerous applica-
composite components under typical operat- tions. Figure 42.7 illustrates a fundamental
ing flow rates, pressures and temperatures. shift from the standard Navy Deep Sea Diving
This facility also incorporates a single-tube dress consisting of a copper and brass helmet
counterflow heat exchanger configuration to and breast plate bolted to a canvas suit with

Fig. 42.7 Navy standard deep sea diving dress, old and new. (Courtesy of Coastal Systems Station,
Dahlgren Division, Naval Surface Warfare Center, Panama City, FL.)
 Machinery 927

lead shoes and lead weight belt. Out of water

the dress weighed over 90kg (200 lb). The
1
modern dress consists of a fiberglass helmet - %
with neoprene suit and weighs less than 45 kg
(100 Ib) on land. Many of the buckles and fas-
teners used to attach lifelines, hot water lines,
emergency backpacks and other accessories
are made of a thermoplastic with a chopped
fiber filler, replacing metal fittings which tend
to corrode. Surface supplied gas bottles for the
diver’s breathing air are made from fiberglass
overwrapped cylinders (Fig. 42.8). These gas
bottles can be charged to 20.6 Mpa (3000 psig)
and represent a 50% weight reduction over
conventional steel cylinders.
Figure 42.9 illustrates another type of div-
ing suit. The torso is a carbon fiber reinforced
vinyl ester. It is made by hand lay-up on a
mandrel and room temperature cured while
rotating on a spit. The diver inside the suit
remains at one atmosphere of pressure and
can dive to 610 m (2000 ft) remaining for sev-
eral hours without the need for
decompression.
Portable recompression chambers for trans-
porting divers iA need of treatment from
Fig. 42.9 Navy One Man One Atmosphere Diving
remote areas are made from filament wound
System (NOMOADS). (Courtesyof Coastal Systems
Once inside and pressur- Station, D d g r e n Division, Naval Surface Warfare
ized, the diver may be transported to a Center,panamacity,~~.)
medical recompression facility.

7----- 42.7.4 CABLES

Because carbon is conductive, some interest has
been generated in making light weight conduc-
tive cables for underwater instrumentation
using specially treated carbon fibers. Due to the
weight of copper or aluminum wire, towed
electronicsunderwater are difficult to engineer.

42.7.5 BUOYS AND FLOATS

h
Fig. 42.8 Special diver air support system.
(Courtesy of Structural Composites Industry, a
Harsco Company.)
Sophisticated buoys for oceanographic mea-
surement have been developed for long term
mooring of instruments at depths up to 914 m
(3000 ft) of sea water. The buoys are made of
Syntactic foam and are deployed in a SUbSUr-
face mode. They can provide over 680kg
928 Marine applications

(1500 lb) of buoyancy. In addition, buoyancy New marine applications of composites are
systems are used on risers for offshore oil rigs. also under development. A particularly chal-
Because drilling takes place in excess of 1.6 km lenging and intriguing application is deep
(1mi) deep on some rigs, the drill sections diving man-rated pressure hulls. The
become extremely heavy and require flotation Advanced Research Projects Agency (ARPA)
to offset the enormous weight. Syntactic foam is sponsoring the Thick Composites
with a tough outer composite skin is used for Technology Development program to design,
durable flotation. Many Coast Guard buoys fabricate and evaluate a Man-Rated
are now being deployed with syntactic foam Demonstration Article constructed of carbon
cores and composite skins. reinforced composite materials (Kelly, 1993).
The objective of this program is to develop the
technology, experience and confidence neces-
42.8 CURRENT AND FUTURE
sary to demonstrate the feasibility of using
DEVELOPMENTS
composites in primary structure in underwa-
Use of composites in the marine environment ter vehicles (Hoffman and Kelly, 1992; Leon
continues to evolve. There are several recently and Coffenberry, 1992; Camponeschi et al.,
developed resins, prepreg fabrics, cores and 1994).
fabrication processes whose implementation
will significantly change the industry. REFERENCES
Perhaps the most significant change is the
development of effective VARTM processes, Aylor, D. and Murray, J. 1992. The Effect of Seawater
Environment on the Galvanic Corrosion
most notably SCRIMP (Seemann, 1990).Using Behavior of Graphite/Epoxy Composites
conventional resins, fabrics, cores and tooling, Coupled to Metals. Carderock Division, Naval
VARTM increases fiber content over hand lay- Surface Warfare Center SME-92/32.
up and almost eliminates VOC emission. Baltek 1986. Baltek Data File 151.
Resin development efforts include the for- Burrell, P.P., Herzog, D.J. and McCabe, R.T. 1987. A
mulation of polyesters and vinyl esters which Study of Permeation Barriers to Prevent Blisters
cure upon exposure to ultraviolet light (Pfund, in Marine Composites and a Novel Technique
for Evaluating Blister Formation. Proc. 42nd
1992).The major advantage is that these mate- Annual SPI Conference.
rials cure at room temperature but have an Camponeschi, E.T., Jr., Bohlman, R.E., Hall, J. and
indefinite working life. Carr, T.T. 1994. The Effect of Assembly Fit-Up
The activity in prepreg development is low Gaps on the Compression Response of Thick-
temperature curing epoxies (Pfund, 1993). Section Carbon/Epoxy Composites. ASTM
Materials are available which cure at 85°C STP-Compression Response of Composite
(185°F) and have several weeks working life, Structures, 1994.
or cure at about 60°C (140°F) with a few days Davies, P. and Lemoine, L. 1992. Nautical
Construction with Composite Materials, Proc.
working life. Excellent properties can be International Conference Paris, France, 7-9
attained with vacuum bag consolidation December 1992.
(Juska, 1993). Garvey, R.E. 1990. Composite Hull for Full-Ocean
In core technology, low cost thermoplastic Depth. MTS Journal, 24(2):49-58.
honeycombs are being investigated to replace Gougeon 1992. Gougeon Laminating System.
PVC foam and balsa in some applications, Product Literature, Gougeon Brothers lnc.
Gougeon, M.A. and Bertelsen, W.D. 1993. The
particularly to reduce structure-borne noise.
Gougeon Hydromat Test System: Special
Use of composite core will probably gain Methods and Equipment For Investigating the
wider acceptance. In addition, new structural Effects of Various Pressure Loadings on
foams are being developed that are not PVC- Sandwich Composite Panels. Proc. 48th Ann. SPl
based. Conf. and Expo ‘93.

Greene, E. 1990. Use of Fiberglass Reinforced
Plastics in the Marine Industry. Ship Structure
Committee Report SSC 360.
Hepburn, LCDR R.D., Magliulo, G. and Wright,
T.W. 1991. The US Navy's New Coastal
Minehunter (MHC): Design, Material and
Construction Facilities. Naval Engineers J., May
1991.
Hitco 1986. Hitco Technical Report 20-04.16, Rev.C.
Hoffman, P. and Kelly, J.J. 1992. Manufacture of
Advanced Composite Submarine Structures
(MACSS).Proc. 37th Intern. S A M P E Symp.
Huss, J. Rowland. 1990. Structural Response of
Marine Sandwich Panels to Uniform Pressure
Loading. Naval Engineers Thesis, Massachusetts
Institute of Technology, Cambridge, MA.
Interlux 1993. Technical Bulletin 900B
Jacquemet, R. and LaGrange, A. 1988. Aging of
Laminated Polyester/Glass and Evolution of
Their Mechanical Characteristics in Marine
Media. Composites, 4:4046.
Johannsen, T.J., 1990. Correct Core Installation,
Bonding Techniques and a Repair Case History
of a 56 ft Sailboat and a 47 ft Sportfishing Yacht.
Paper read at the Atlantic Marine Surveyors
Conference on Newest Developments in
Boatbuilding and Repairing, 9-10 October 1990,
Annapolis, MD.
Jones, J.M., Walsh, M., Mansfield, F.B. 1991.
Microbial Electrochemical Studies of Coated
Steel Exposed to Mixed Microbial
Communities. Corrosion 91, Paper 108, NACE.
Jones, J.M., Vasanth, K.L., Conrad, T.K., Little, B.,
Ray, R. 1992a. Corrosion Resistance of Several
Conductive Caulks and Sealants From Marine
Field Tests and Laboratory Studies With Mixed
Communities Containing Sulfate Reducing
Bacteria. Intern. Symp. on Microbiologically
Influenced Corrosion (MIC) Testing ASTM.
Jones, J., Walsh, M., Little, B., Ray, R., Mansfield, F.
1992b. ESEM/EDS Studies of Coated 4140 Steel
Exposed to Marine, Mixed Microbial
Communities Including SRB. 8th Intern. Congr
on Marine Corrosion and Fouling, Taranto, Italy.
Juska, T., Mayes, J.S. and Seemann, W. 1993.
Mechanical Properties and Impact Damage
Resistance of Composites Fabricated by Low
Cost, Vacuum Assisted, Resin Transfer Molding.
Naval Surface Warfare Center, Carderock
Division, SSM-64-93/ 04.
Juska, T. 1993. An Evaluation of Low Temperature
Curing Prepregs. Naval Surface Warfare Center,
Carderock Division, SSM-64-93/07.
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Kelly, J.J. 1993. Thick Composites Technology
Development Program.
Kramers, S.D. Engineering for the Americas Cup.
Proc. 1993 Intern. SAMPE Conf., Philadelphia,
PA, 25-28 Oct 1993.
Korczynski, J.F. 1993. Development of Composite
Heat Exchangers For Seawater Applications.
Proc. 1993 Intern. SAMPE Conf., Philadelphia,
PA, 25-28 Oct 1993.
Leon, G.F. and Coffenberry, B. 1992. Proposed
Fabrication Process for Thick Composite
Submarine Structures. Proc. 37th Intern. S A M P E
Symp.
Lewit, S. 1990. Use of Polyester Mat as a Bedding
Material for Cross-linked PVC Foam Cored
Production Laminates. Proc. 3rd Intern. Conj on
Marine Applications of Composite Materials,
Florida Institute of Technology, Melborne, F1.
Little, BJ., Ray, R., Wagner, P., Lewandowski, Z.,
Lee, W.C., Characklis, W.G., Mansfield, F. 1991.
Biofouling, 3:45.
Little, B.J. and Wagner, P. 1986.J. Adhesion 20:187.
Marino, R., Rockett, T., Rose, V. 1985. Blistering of
Glass Reinforced Plastic Marine Materials: A
Review. NOAA/Seagrant Technical Report 88,
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Miriyala, S.K., Tucker, W.C., Brown, R. and Rockett,
T.J. 1993. The Mechanism of Galvanic Blistering
in Carbon Fiber Composites. Proc. ICCM/9
Madrid, Spain V.5 pp. 546-553.
NRaD 1992. Naval Command, Control and Ocean
Surveillance Center Technical Document 2348,
San Diego, CA 95152-5000.
NSWC, Carderock Division. 1993. Low Cost, High
Quality Composite Ship Structures Technology
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Model Basin, Bethesda, Maryland, 20084-5000,
May 1993.
Owens Corning Fiberglas 1991. 5-2 Glass Armour.
Case History. Landing Helicopter Deck (LHD)
Deckhouse Armor Application, Owens Corning
Fiberglas Corp., Pub. No. 15-ASP-16157-A., Jan
1991.
Pfund, 8. 1992. Light-Curing Resins. Professional
Boatbuilder Magazine, No. 18, August/
September 1992.
Pfund, B. 1993. Pre-preg Reinforcements.
Professional Boatbuilder Magazine, No. 24,
August/September 1993.
Plunkett, J.D., Cohen, R., Kunz, B.P. and Kunz, J.
1992. Light-weight, Volume-Produced
Industrial Honeycomb Composites For Marine
Structural Applications. MTS '92 Con& Proc.,
930 Marine applications
Marine Technology Society, Washington, D.C.,
October 19-21.
Reichard, R.P. 1992. Pressure Testing of FRP
Sandwich Panels. M A C M ‘92 Conf. Proc.,
Composites Education Association, Inc., March
22-24,1992.
Russell, M. 1992. Inspection and Repair Manual for
Fiber Reinforced Plastic Boats and Craft.
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Seemann, W. 1990. US Patent Number 4 902 215.
Sloan, F. and Nguyen, H. 1992. Applications of
Extended-Chain Polyethylene Fibers in the
Marine Composites Industry. MACM ’92 Con$
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March 22-24,1992.
Smith, C.S. 1990. Design of Marine Structures in
Composite Materials, London and New York
Elsevier Applied Science.
Stachiw, J.D. and Frame, B. 1988.
Graphite-Fiber-Reinforced Plastic Pressure
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Standard Family of Composite Material
Centrifugal Pumps for Naval Surface Ships.
Naval Engineers J., May 1993.
Tucker, W.C., Brown, R and Russell, L. 1990.
Corrosion Between a Graphite/Polymer
Composite and Metals. J. Composite Materials
24:92.
Tucker, W.C. 1991. Degradation of
Graphite/Polymer Composites in Seawater. J.
Energy Resources Technol. Trans. ASME 113 4:264-
268.
Tucker, W.C., Little, B.J., Ray, R., Wagner, P. 1993.
Microbial Degradation of Fiber Reinforced
Polymer Composites. Proc. ICCM/9, Madrid,
Spain, V.5, p. 554
Wilhelmi, G.F. 1988. Composites for Ship
Machinery Applications. Presented at the
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COMMERCIAL AND INDUSTRIAL 43
APPLICATIONS OF COMPOSITES
Stewart N.Loud

43.1 INTRODUCTION materials such as E-glass fiber reinforcements,

This chapter describes the use of composites and polyester, some of the low-temperature
for industrial and commercial applications, performing epoxies, or a variety of engineering
which perhaps is best described as thermoplastic resins, usually referred to as
'Miscellaneous' or 'All Other Applications'. It fiberglass-reinforced plastics or FRP (or in
is an overview of the myriad number of appli- Europe, GRP). Processes used have been
cations that cannot always be neatly grouped mainly the hand lay-up, compression, injec-
into major sectors as with transportation, tion, filament winding and pultrusion
marine, aerospace/defense, sports, and the methods. Most unit volumes for advanced
like. Briefly described are representative appli- composites range from the hundreds of units
cations, the benefits offered by composites, per year to a few thousand, unlike the tens of
highlights of the primary materials and thousands of units typical with automotive
processes, and some conclusions about the parts. Some of the most mature FRP applica-
approximate market size for this extremely tions (yet still with solid growth rates) include
diverse market sector. No attempt is made to electrical insulating sheet and sheet molding
define the technology of the materials and compound (SMC), bulk molding compound
processes, as these are well covered in other insulators, glass fabric reinforced electronic
printed circuit boards, pultruded items such as
chapters.
ladders, filament wound electrical tubing,
thermoset SMC and injection molded thermo-
43.2 HISTORICAL PERSPECTIVE plastic business equipment and appliance
housings, hand lay-up antennas, and others.
Advanced composites (typically produced
using high-performance fibers and/or resins) This base of
FRP applications has been used as
a launching platform for a huge diversity of
historically have been dominant in the aero-
new applications. Many now utilize the more
space and defense sectors and in many
sporting goods products. Hand lay-up with advanced fibers and resin systems or hybrids
of these material systems.
autoclave molding have been the major
processes used for part fabrication. Engineered
composites applications for several decades 43.3 PROGRESS
have been fabricated predominantly from
With the slowdown in worldwide defense
spending during the early 1990s, numerous
Handbook of Composites. Edited by S.T. Peters. Published producers have looked to new market oppor-
in 1998by Chapman & Hall, London. ISBN 0 412 54020 7 tunities for growth, especially for advanced
932 Commercial and industrial applications of composites
fiber and resin products, and increasingly to
hybrids of several materials. As a result,
advanced and hybrid fiber reinforced prod-
ucts are now moving into the application
sectors formerly dominated by metals and
even glass fiber products. Also, the focus on
’defense conversion’ has resulted in retarget-
ing of some governmental budgets to support
defense contractor conversion to civil applica-
tions. Many of these applications reside in the
commercial and industrial market sectors, the
focus of this chapter.
A vast diversification of composites has
occurred in this sector. From the 1960s and
1970s with many electrical, electronic, appli-
ance and business equipment applications,
the business has grown into pressure vessels,
laptop computers, centrifuges, flywheels, fuel
cells, railroad car components, drive shafts,
fuel pumps, loom components, musical
instruments, oil and gas riser pipe, power
lighting and distribution poles, industrial
process rolls, advanced wind turbines and
much more. The processes used here have
remained fairly constant: pultrusion, filament
winding, compression molding, injection
molding and hand lay-up, but the use of resin
transfer molding has increased dramatically
for many of these applications. Materials
applications that were almost exclusively
fiberglass and polyester, thermoplastics, or
low-temperature curing epoxies have evolved
into much more vinyl ester usage and
migrated to the use of more high-performance
fibers such as KevlaP and Twaron@aramids,
Spectra@high-molecular weight polyethylene
(HMWPE), and many types and forms of the
carbon fibers. Ceramic matrix composites
(CMCs)and metal matrix composites (MMCs)
are of increasing interest and are sometimes
competing with polymer-based fiber compos-
ites (PMCs), for example in automotive drive
shafts. Even carbon fiber reinforced carbon
matrix materials (C-C) are moving from the
aerospace sector into commercial use. The use
of ’advanced’ materials has now matured
enough that it is considered by many in the
industry to be counter productive to even use
the term ‘advanced composites’ anymore.
43.4 APPLICATIONS REVIEW
Following is an alphabetical review of applica-
tion segments of this market or of unique and
emerging material systems used broadly in
related industrial applications. Representative
organizations are cited as examples of the
types of companies and institutions active in
these market sectors so that the reader can
research further into the applications of inter-
est. Applications believed at this time to offer
the opportunity for significant growth are pre-
sented in the most depth. Some applications
covered also fit into other market sectors, but
their technology is unique or they are indus-
trial components sold into the other markets,
so they are described here. Throughout the
chapter, tables highlight many applications by
major market sector, some long established
and many in the emerging growth stage, to
stimulate the reader’s thinking on other poten-
tial applications that might benefit from
applying composites. Those applications in
the tables that tend toward more usage of the
highest performance materials are listed with
an asterisk (*).
43.4.1 ANTENNAS
Telescoping composite tubes are used to form
a lightweight antenna support intended for
military use and the ultimate in portability.
The tubes must be exceptionally light, so the
producer used woven Spectra UHMWPE fiber
in epoxy resin. They are fabricated using a
conventional roll-wrap process similar to that
used to produce composite fishing rods. The
total weight is only 1.8-2.2 kg (4-5 lb) includ-
ing 11 nested tubes that collapse to only 711
mm (28 in) for portability but can easily be
extended and locked to form a support pole
6.7 mm (22 ft) long.
Resin transfer molding is increasingly dis-
placing hand lay-up for fiberglass/polyester
 Applicafions review 933

communications antenna dishes. When the economics and performance versus conven-
new technologies for direct-broadcast satel- tional technologies of steel and concrete.
lites become more commercial, small Other organizations are working on a vari-
composite dish antennas, probably produced ety of bridge programs where composites are
using compression molded SMC, could the central enabling technology for improved
become a booming market. civil engineering structures. For example, FRP
and CFRP laminated plates are
adhesively/mechanically bonded to the
43.4.2 BRIDGES
underside of steel or concrete bridge beams to
Mostly small foot bridges or the railings, lad- extend their structural in-service life. In
ders and decking of structures in highly Scotland, in 1992, an all-composites cable-
corrosive environments typically have used stayed footbridge was installed between two
FRP components over the last few decades. portions of the Linksleader Golf Club and
However, in the last several years there has across the Tay River (Fig. 43.1). Installation
been a great increase in interest in the use of was accomplished using mostly on-site hand
fiber composites for civil engineering and labor. Much of the structure was constructed
infrastructure applications. One segment of
- -
particularly high interest is composite bridges
that offer great corrosion resistance and
weight savings. Composite tendons or rein-
forcing bars reinforced with fiberglass, carbon
fiber or aramid fiber are being studied aggres-
sively for use as rebar or for prestressing of
concrete bridge decks. Defense Advanced
Research Projects Agency (DARPA,Arlington,
VA) has funded a Technology Reinvestment
Project (TRP) at the University of California at
San Diego (UCSD) and with the Advanced I
Composites Technology Transfer/Bridge
Renewal Consortium for three technology I
)I

demonstration areas. First is the development

of low-cost fiberglass or carbon fiber rein-
forced plastic (CFRP) filament wound jackets
for the repair and upgrading of freeway
bridge or parking structure columns to make
them more earthquake resistant. Second is a
composite or hybrid composite/concrete
bridge deck technology that would allow
rapid replacement of bridges on highways
and interstates. Last is a plan for a 130 m (450
ft) cable-stayed all-composite vehicular
bridge to be built at UCSD over the Interstate
freeway at La Tolla, CA, in the late 1990s. All
Of the advanced with Fig. 43.1 All-composite cable-stayed bridge, assem-
fiber, are of high interest for these projects- bled from isopoIyester composites. The bridge’s
Also, high-speed, low-cost fabrication A-frame towers are 17.5 m (57 ft) high. (Courtesy of
processes will help to achieve competitive Amoco Chemical Co.)
934 Commercial and industrial applications of composites

Table 43.1 Construction/civilengineering/ infra- and internal components. For example,

structure Harbec Plastics (Ontario, NY) is a custom
injection molder for a compensating arm for a
Bridge grder upgrade plates* business machine printer housing using 30
Foot bridges* v / o fiberglass / polycarbonate compound.
Cable-stayed bridges*
Replacement bridge decks* They also mold a print head carriage using
Earthquake repair and upgrades/column wrap* carbon fiber/PC with Teflon added for wear
Bridge decking, panels, enclosures* resistance. Such parts are common to most
Pipeline rehabilitation liners* typewriters and printers. Carbon fiber pro-
Manhole covers vides electrostatic dissipation. Equally
Trench covers important is the dimensional stability they
Cables, tendons, rebar, dowel bars* obtain to meet a specification for precision-
Acoustic wall panels*
Marine piling molded inserts with a 0.025 mm (0.001 in)
Piers* concentricity on two critical shaft bearings.
Computer room flooring* Growth in this segment comes mainly from
Curtain walls* further displacement of other materials as
Glulam wood beams* composites gain market share. The benefit of
Mine roof bolts high value here is increased design freedom
Earth anchor rods offered by the light and strong FRP materials.
Residential ballistic wall panels
Coalescent grid/water treatment* This sector is dominated by the molding com-
Toxic waste disposal tanks* pounders and the custom molders such as
Chemical grating Premix (No. Kingsville, OH) and Rostone
Platforms (Lafayette, IN).
Walkways
Table 43.2 Appliances/businessequipment

from pultruded shapes. In mid-1994, in the Sanitaryware

UK, a 2720 kg (6000 lb) replacement lift bridge Dishwashers
deck for a road across a canal was constructed Oven door handles
from pultruded FRP and mounted on steel Frying pan components
beams attached to the lift mechanism. Bridge Phone/fax EM1 covers*
counterweights were reduced, offering cost Copier housings and components*
Computer cassette robotic system*
savings. The infrastructure business sector, Refrigerator liners
particularly roads and bridges, could become Business machine bases
one of the largest growth areas for composites Laptop computer cases*
to displace steel and concrete over the next Microphone booms*
decade or more. Development of appropriate Dishwashers
codes and standards along with strong Air conditioners
cost/performance demonstration projects are Office furniture*
Toasters
keys to success.

43.4.3 BUSINESS EQUIPMENT 43.4.4 CABLE CARS

This sector is one of the more mature and has Composite cabins were retrofitted to replace
been heavily dominated for many years by steel and aluminum at Chamonix, France to
compression molded or injection molded reduce the weight of the cable cars at a ski
reinforced thermoplastics for housings, bases, resort. Ingenex, a French engineering firm,

built new lightweight car bodies using sand-
wich construction with Kevlar/epoxy face
sheets and a Nomex@honeycomb core. The
supporting arm that holds each cable car is fab-
ricated from carbon fiber/epoxy over a Nomex
core. These replacement structures allow for
many more passengers to be carried on the
existing system. This avoided having to scrap
the existing system that was becoming over-
loaded, thus avoiding rebuilding the whole
system reportedly at a cost 10 times as much.
43.4.5 CARBON-CARBON COMPOSITES FOR
NON-AEROSPACE MARKETS
The vast majority of uses for C-C composites
are in aerospace and defense. However, many
potential industrial applications are emerg-
ing for this unique high-temperature resistant
material system. DOE has studied C-C com-
posites for fusion energy systems. One
project involved brazing C-C composites.
Another program studied development of
pitch-based carbon fiber (PBCF) reinforced
C-C composite tiles to line the inside walls of
future fusion devices such as the Compact
Ignition Tokamak (CIT). Perhaps such tiles
later will find application in commercial heat
exchangers. Kureha Chemical Industry Co.,
Ltd, and Osaka Gas Co., Ltd of Japan are
active in the USA market. Applications tar-
geted include C-C structures for
high-temperature furnaces and fuel cells, wet
and dry friction materials, plus brake disks
and self-lubricating bearings for automotive
and truck applications. C-C brakes and
clutches are used worldwide in some racing
car classes such as Formula 1 and for the
Indianapolis 500 race but are banned from
other classes due to the premium cost.
43.4.6 CERAMIC-MATRIX COMPOSITES (CMCS)
These materials have received a significant
boost in funding because of continuing inter-
est by the USA Department of Energy Office of
Applications review 935
Industrial Technologies. Their Continuous
Fiber Ceramic Composites (CFCC) Program
Plan (10-year plan) was an expansion of the
continuing support activity directed toward
'enabling technology' efforts since 1987. DOE
defines a CFCC as a long fiber (ceramic, glass
or carbon) embedded in a ceramic matrix.
Concerns about CMCs raised by potential
industrial users include material and process-
ing costs, long-term component fracture
toughness, general durability in a variety of
environments, the ability to join components
with different compositions and the availabil-
ity of near-net-shape fabrication methods with
3-D fiber architectures (preforms).A relatively
new type of ceramics, CFCCs offer the poten-
tial to meet the demands for a variety of
industrial applications. Some primary applica-
tions envisioned for these materials include:
burners/combustors, chemical reactors and
process equipment, heat recovery systems,
refractories and related products, separa-
tion/filtration systems, stationary engines,
waste incineration systems, tooling, structural
components, biomedical parts, wear parts in
machinery, and other specialty high-tempera-
ture products.
Hexcel Corp. (Pleasanton, CA) offers high-
performance ceramic materials for various
military components such as missile fins,
radomes, jet engine parts, and high-tempera-
ture tooling, but much larger potential
markets might develop in the commercial sec-
tor, especially for less-expensive CFCCs using
E-glass fiber or other low-cost reinforcements.
Examples cited by Hexcel include honeycomb
heat exchangers used in high-pressure coal-
fired gas turbine generators and feed tubes
(used to overcome corrosion and thermal
shock problems) for a toxic waste incinerator
operating at 870°C (1600°F).
Successful conversion of the applications
noted above could generate savings of 1.1
quads (a quadrillion BTUs) of thermal energy
per year, and reduce NOxemissions by 0.6 mil-
lion tons/year, according to the DOE.
936 Commercial and industrial applications of composifes

43.4.7 CONDUCTIVE FIBER FOR SHIELDING

BUSINESS EQUIPMENT
Cytec Industries sells a conductive fiber con-
centrate or intermediate containing carbon I1
fiber for electrical conductivity. In most of
these products, Cytec starts with continuous,
standard 33 msi, 12K carbon fiber that is elec-
troplated with nickel before being chopped
into 6.35 mm (0.25 in) lengths. The fiber load-
ing is typically 60-75%, even to 90% if sold to
a compounder who adds resin to make a spec-
ified injection molding compound.

43.4.8 CORROSION-RESISTANT SECONDARY

STRUCTURES - GRATING, LADDERS, PIPING
Composite products are offered by many com-
panies including Amalga, Brunswick,
Fibergrate, International Grating, Creative
Pultrusions and others. Strongwell takes pul-
truded structural fiberglass shapes
(tradename: Extren), fabricates them into use-
ful structures, and distributes to various
industrial customers. The material is available
in over 100 standard sizes and shapes, and is
produced in three series: general-purpose, fire-
retardant and a premium grade that is both fire
retardant and highly corrosion resistant. This
grade, called Extren 625, uses a vinyl ester
resin; the other two are made with polyester
formulations. Applications include handrails,
stairways, ladders, cable and channel trays,
platforms and walkways, troughs, weir and
baffle plates, racks, bridges, identification
signs, sump tanks, battery boxes, drain pipes,
etc. Besides the offshore drilling and produc-
tion industry, Strongwell serves a variety of
industries, including aquaculture, chemical
processing, food/beverage, marine, metal pro-
cessing, waste treatment, petrochemical,
power plants, pulp and paper mills, radar
installations, transportation and many special-
ized applications such as raised computer
floors. For static dissipation, carbon fibers can
be located at the surface of grating (Fig. 43.2).
Fig. 43.2 ConductiveFRP grating for static electric-
ity dissipation.(Courtesy of CI/SPI.)
43.4.9 D m SHAFTS - PICKUP TRUCKS AND
COOLING TOWERS
Strongwell continues to use substantial
amounts of carbon fiber for the hybrid drive
shafts they sell to Dana for shipment to
General Motors. At close to 226 800 kg (500 000
lb) per year of carbon fiber usage and esti-
mated to climb soon to one million lb, this is
said to be the largest industrial application for
carbon fiber reinforcements. The carbon fibers,
mainly from Hexcel, are pultruded with resin
along an aluminum tube and overwrapped
with fiberglass for damage tolerance.
Carbon fiber/epoxy is used for cooling
tower drive shafts as well. SpyroTech (Lincoln,
NE) is a major supplier of these shafts along
with Amalga Composites (W. Allis, WI),
Addax, Inc. (Lincoln, NE) and ACPT
(Huntington Beach, CA). A circumferential
wrap of E-glass/epoxy is added for debulking
and impact protection. These shafts exhibit up
to five times the durability at one-fifth the
weight of steel shafts and are far more corro-
sion resistant. Cooling tower shafts (as with
vehicular shafts) produced with carbon fibers
are stiffer and can be produced in lengths
twice as long as with steel without suffering
vibration damage in use, eliminating the need
for intermediate bearings and supports.
43.4.10 ELECTRICALAND ELECTRONICS insulating hardware, ladders and hotline tools
This sector of the market is composed of many for line installers, lighting poles, connectors,
applications that are maturing or have high microchip encapsulation and many more.
penetration compared with other materials. Fiberglass reinforcement predominates due to
Applications include motor and generator its insulating characteristics and low cost.
components, switch gear, insulating sheet, Sales are cyclical due to the high market share
molded insulators, subway third rail insulat- held by FRP, but there is still strong growth
ing cover board, FR-4 and G-10/11 glass fabric seen from penetration gains versus phenolic,
reinforced epoxy printed circuit boards porcelain, and other materials.
(PCBs), utility transmission and distribution
43.4.11 F ~ E ~ BREATHI~G
I ~ ~ APPARATUS
R

Table 43.3 E l ~ ~ c a l / e l e ~ r o ~ c s / e n e r g ~ The key component of firefighter breathing

systems/commu~cations apparatus is the air storage bottle that comes
in different sizes, materials, and pressure rat-
Electric motors ings. Structural Composites Industries
Fuse tubes (Pomona, CA) continues to be well ahead of all
Lighting poles competitors making small filament-wound
Dis~ibutionpoles composite pressure vessels. SCI supplies air
Cable tray bottles (all of their firefighter's bottles use S-2
Power tool cases
Motor control centers Glass) to Mine Safety Appliances. They report-
Printed circuit boards edly have never had a field failure. Many air
Circuit breakers breathing systems distributed by MSA are
Guy wire insulators used to escape smoke or other noxious materi-
Utility transmission towers als in mines, chemical plants, refineries, hotels,
Electrical bus bars aircraft, etc. SCI also is a major supplier for the
Dis~~bution transformer cores, cases escape-slide air bottles in use on transport air-
Shielding - RFI, ESD, EMI*
Battery boxes, casings
craft built by Boeing and Airbus. Many
Electron beam acceIerators* composite oxygen storage bottles are pro-
Electrical insulators duced for hospital and home care and for use
Electrified third rail cover board in highflying commercial and general-aviation
Electrical switchgear aircraft (for example, for escape slide inflation
Power hot-lie tools but using Kevlar 49/epoxy overwraps for
Electronic connectors decreased weight).
Outlet boxes Other composite bottles are used to inflate
Aerial lift truck booms
Electronics chassis* rafts, balloons and other flotation systems. EFI
Computer chip carriers* Corp. (San Jose, CA), a s ~ b s i d j a rof~ Racal
Electronic equipment racks" Electronics ii-i the UK, and Luxfer USA Ltd
Fuel cells* (Riverside, CA) continue to be SCI's main
Flywheel mechanical batteries* competitors as suppliers of firefighter air bot-
Superconducting magnetic energy siorage (SMES) tles. They sell air bottles to Scott, Survivair,
Wind turbine blades*
Telescopingportable antennas* North Safety and others in the USA and over-
C o ~ ~ i c a t i antenna
5 n ~ dishes seas. About 250 fire departments in American
Radio masts" cities have bought hundreds of thousands of
Satellite TV dish antmas composite bottles to replace the much heavier
Microwave guides steel bottles. Lighter bottles with longer last-
Fiber optic cable tension members ing air supplies give firefighters more time on
938 Commercial and industrial applications of composites
station in the heat of a fire fight. The bottles
must store air for long periods at 31 MPa
(4500 psig).
43.4.12 FLYWHEEL MECHANICALBATTERY
SYSTEMS
US Flywheel Systems, Inc. (Camarillo, CA),
Calstart (Burbank, CA), American Flywheel
Systems (Seattle, WA) and others all hope to
supply kinetic energy storage flywheel sys-
tems (now often called mechanical storage
batteries) for future electrical vehicles in
California and elsewhere (Fig. 43.3). Flywheel
batteries have an estimated 5-10 times the
watt hours per pound storage capacity of con-
ventional lead acid batteries. They are
impervious to temperature variations, may be
drained repeatedly of stored energy without
cyclic degradation, can be recharged in as little
as a few minutes, should last 3040 years with-
out requiring replacement or maintenance,
and create no toxic waste problems. Mileage
range in an electric car (such as GMs Impact)
could reach a projected 482-640 km (300400
miles) or more according to some developers,
as opposed to a practical range of only 95-128
km (60-80 miles) for today’s electric cars using
conventional battery systems.
Fig. 43.3 Flywheel battery components. (Courtesy
of American Flywheel Systems.)
Larger flywheels also show promise for
stationary energy storage and peak power
shaving applications, and the business
opportunity for such systems could be enor-
mous. Federal technology centers, such as the
Lawrence Livermore and Oak Ridge National
Laboratories, now are part of teaming
arrangements to enhance flywheel technol-
ogy transfer from defense and other
government programs to the private sector.
The rims of the rotating wheels in these sys-
tems are filament wound using advanced fiber
composites, including E glass, S-2 glass,
Kevlar and carbon fibers. At speeds attainable
by composite wheels, metal flywheels disinte-
grate. Use of this system is a good example of
technology transfer from aerospace to the
civilian sector.
An electric car with a flywheel storage sys-
tem on board (and perhaps with regenerative
braking through the flywheels) could
approach zero emissions and is expected to
meet the much tighter California air quality
standards set for early next century. California,
New York and Massachusetts, have mandated
that 2% of cars sold in those states in 1998
must be zero emission vehicles; the percent-
ages increase to 5% in 2001 and 10% in 2003.
The challenge is how to offer an affordable car
with desirable range and performance that can
meet those goals.
Lawrence Livermore National Laboratory
reported during a SAMPE seminar that the use
of composite flywheels in an electromechani-
cal battery ’would be ideal for use in electric
powered vehicles’. They found that a high-
strength carbon fiber (such as Toray’s T700 or
T1000) yielded the highest energy storage
capacity. Since then, Lawrence Livermore
National Laboratory and General Motors
Corp. have teamed on a three-year, $3 million
project to develop a new generation of more
efficient automobile flywheel batteries. The
GM vehicle project is part of the ’Partnership
for New Generation Vehicles program’
launched by President Clinton in September
1993.

43.4.13 FUEL TANKS FOR NATURAL GAS
VEHICLES (NGV)
Lincoln Composites (Lincoln, NE) and ED0
Corp. (Canada) introduced certified 'all-com-
posite' compressed natural gas (CNG)
pressure vessels under the 1993 US
ANSI/AGA standard called NGV2 for ultra-
light, nonmetallic natural gas vehicle fuel
tanks. The availability of these certified plas-
tic-lined, composite-overwrapped fuel tanks is
expected to accelerate the usage of advanced
composites into this potentially large alter-
nate-fuel marketplace for composites. Besides
weight savings of up to 70% (compared with
steel, aluminum, or metal-lined NGV tanks)
and greater durability, the new tanks offer
increased fuel capacity, extending driving
range.
The weight savings are achieved through
use of a hybrid composite, for example using a
30 msi modulus T650/35 carbon fiber from
Amoco Performance Products (Alpharetta,
GA) or a Toray T700S/12K carbon fiber.
Hybridized with the carbon fiber might be an
E-glass fiber roving from Owens-Corning,
PPG, or Vetrotex Certainteed to reinforce an
epoxy resin formulation. The composite is fila-
ment wound over a thermoplastic liner of
high-density polyethylene (HDPE). In the
hybrid, carbon fiber provides an extremely
high strength-to-weight ratio, with the ability
to withstand many pressure cycles along with
superior fatigue characteristics, while the
fiberglass enhances toughness. HDPE liners
are lighter weight than steel or aluminum and
more resistant than both to the highly corro-
sive elements sometimes found in natural gas
supplies around the USA. A minimum 15-year
life expectancy is set for the NGV2 tanks; after
that they are to be discarded.
Other pressure vessel programs are under-
way at Comdyne I, Compositek (Kaiser),Fiber
Dynamics, Amalga and Structural
Composites. Large customers for the older
fiberglass/epoxy overwrapped aluminum
NGV fuel tanks include General Motors and
Applications review 939
Chrysler and many city transit bus operators
such as Tacoma, Sacramento, Salt Lake City,
Reading, Binghamton and other Northeast
and Canadian cities. Recent failures of CNG
tanks during refueling (reportedly caused by
exposure to unexpected acid solutions) appear
to have been solved with an installation
redesign and protective coatings. Additional
interest comes from utilities such as Southern
California Gas & Electric and Columbia Gas
companies.
Carbon fiber priced today at about $5-6/kg
($ll-l3/lb) for high-strength 12K fiber is
about twice as expensive as S-2 glass fiber and
much higher than E glass but appears eco-
nomically competitive for this market. One of
the above supplier companies did a cost and
weight analysis to decide how much of a pre-
mium would have to be paid if
higher-strength fibers were used rather than E
glass. Using E-glass/epoxy overwrap, the
weight would be about 45 kg (100 lb). S-2 glass
reduces the weight to 36-38 kg (80-85 lb), and
a 12K carbon fiber/epoxy overwrap reduces
the weight to 18-20 kg ( 4 0 4 3 lb). Using fiber
costs of $2.20, 11-13.00 and 26.50/kg ($1, $5-6
and $12/lb) respectively, the estimated fiber
cost per NGV pressure vessel is $64 for E glass,
$300-315 for 5-2 glass, and $285-310 for car-
bon fiber. Combining the various cost
components brings the heaviest (E glass) tank
cost to $380-400, S-2 tank to $700-720, and the
carbon fiber tank to $600-620. Thus, to save
about 27.2 kg (60 lb) by switching from E glass
to carbon fiber reinforcement, the cost pre-
mium is about $220, or $3.6-3.7 per pound
saved. Auto designers in the past have sug-
gested that a $2 premium per pound saved
was acceptable, but they might be willing to
pay more now in view of the environmental
benefits gained by burning cleaner fuel.
The combined production of mid-size
pickup trucks in the USA by Chrysler, Ford
and General Motors is reported to be more
than 600 000 per year. If only 10% are built
with natural gas as the fuel and there are two
or three fuel tanks on each truck, there is a
940 Commercial and industrial applications of composites
very large potential market in the millions of
pounds of materials required. Transit buses
may be an even larger market.
Table 43.4 Transportation system equipment
Seats/frames
Monorail cars
Mobile storage modules - CNG*
CNG/NGV fuel tanks*
Rail freight car doors
Rail car knuckles
Hydrogen storage tanks*
Intermodal containers
Maglev train guideways*
High-speed train brakes*
Concept/show car chassis*
Electric vehicle frames/chassis*
Racing car brakes and clutches*
Solar-powered racing vehicles*
Highway reflecting markers
Airport approach light towers
Airport ticket counter tops
Drive shafts - pickup trucks*
Aircraft escape slide inflation bottles*
Ship propulsion shafts*
Cablecar cabins and support arms*
Shipboard crane components
43.4.14 GLULAM BEAMS
Composites are leading to revolutionary wood
beams for bridges; laminated beams benefit
dramatically from use of carbon and aramid
fibers and cost less. Wood structural building
materials have required only the highest qual-
ity wood to achieve necessary performance
levels. Wood (’the original composite’) has a
high strength-to-weight ratio; however, highly
engineered components such as beams have
had to allow for the inherent variability of
wood and wood types. The best woods have
come from ’old growth’ forests that today are
in decline or are in designated wilderness
areas. Logging practices and environmental
considerations (remember the spotted owl?)
have removed ’old growth’ as a source and
have driven producers to consider new tech-
nologies.
American Laminators (Drain, OR) and the
Wood Science & Technology Institute
(Corvalis, OR) have developed a superior line
of glued-laminated (glulam) wood beam
products based on Douglas fir and compos-
ites. Because these beams are a hybrid
material system, they marry the light weight
and high strength of aramid/carbon fiber
composites with the already light weight,
high strength nature of wood to make a prod-
uct that can compete favorably with steel,
concrete, and other wood beams. Of special
note is that these new composite/wood
beams for buildings or bridges outperform
conventional wood beam products and usu-
ally can be offered at a purchase price or first
cost of about 2545% less than conventional
glulam beams!
Dead weight design load is reduced by
40-60°/0 for large structures and long spans.
For structures where deflection is a major con-
sideration in design, the patented technology
takes advantage of the high modulus of Akzo
Nobel Fortafil carbon fiber with 33 msi modu-
lus and 550 ksi tensile to more than double the
design capacity in compression versus typical
unreinforced glulam products. Where
increased tensile performance is required,
Akzo Nobel Fibers’ Twaron or DuPont’s
Kevlar 49 aramid yarn is used. Some of these
beams can be massive; e.g. typically 24 m long
x 1200 mm deep x 254 mm wide (80 ft x 4 ft x
10 in) to much larger. The fibers reinforce pul-
truded plates that are adhesively laminated
during the standard beam forming and bond-
ing.
Many structures (100 as of this writing) are
already in place using the new composite glu-
lams, in California, Oregon, Wisconsin and
Hokkaido, Japan. More structures now are in
the design stages (ca. 100) including large
domed structures with over 164 m (500 ft) clear
spans, for Japan, USA and European clients.
Estimates by various participants suggest that
the global opportunity for this
composite/wood beam technology is in the
billions of dollars. In the USA, the conventional

glulam market is over $1.2 billion/year and is
supplied by 147beam manufacturers. Potential
requirements in the 45 million kg (100 million
lb) range for just the high strength carbon and
aramid fibers are seen about the year 2000. One
observer close to the project said that 'this has
to make a big splash in composites and could
be the biggest new composites application in
20 years!'
43.4.15 HIGH-PRESSURE TUBING AND
BATTERY CASINGS
Amalga Composites filament winds carbon
fiber/epoxy over battery casings for Johnson
Controls. The Inconel liner has a carbon
fiber/epoxy overwrap which is under 0.34
MPa (50 psi) stress when discharged and 5.86
MPa (850 psi) when fully charged. These bat-
teries are designed to be buried in the desert to
power instruments during the night and they
are recharged during the day. Amalga also
makes vessels for high-pressure applications,
including a filament wound carbon
fiber/epoxy-overwrapped steel tank to with-
stand 3.41 MPa (500psi) for use as an
emergency backup pressure cell for the F-22
fighter. Other interesting high-pressure prod-
ucts are carbon fiber/epoxy-reinforced
metallic cylinders that achieve 41-83 MPa
(6000-12 000 psi) of pressure capability. Lower
pressure pneumatic tubes are being made by
Amalga for service at 1.7 MPa (250 psi), and
these usually are reinforced with a fiber-
glass/epoxy overwrap.
43.4.16 HIGH-SPEED TRAIN BRAKES -
CARBON-CARBON
Carbone Industrie in France has been testing
carbon-carbon brakes on the French TGV
Atlantique line. Two similar but slightly differ-
ent applications are being tested; for the drive
wheels and for the bogey. The C-C brakes
must qualify on cars being stopped from
300-350 km/h (to 215 mph) before they can be
considered for regular service. Alsthom, the
Applications review 941
TGV car designer and builder, must decide
whether the weight savings, lack of fade and
projected longer life (as with similar C-C air-
craft brakes systems) justify a change in the
steel brakes now in service. With plans to
build similar high-speed rail systems in Texas
and other parts of the USA, there is growing
interest in the results of the tests. Several com-
panies in Japan have similar interest in using
C-C brakes on proposed advanced bullet
trains, which also might reach speeds of 350
km/h. Later magnetic levitation (maglev)
trains which will approach 500 km/h may be
assessed for use of these ultra-high-perfor-
mance brakes.
43.4.17 HYDROGEN FUEL STORAGE
Hydrogen storage tanks may offer potential
for filament-wound pressure vessels, but it
will be several years before this can possibly
occur. Syracuse University received a grant
from the Department of Energy to prove a
novel approach to hydrogen storage. The
hydrogen would be stored in a filament-
wound tank in which activated carbon
granules are closely packed. After being
cooled in a liquid nitrogen heat exchanger to
the desired storage temperature, the hydro-
gen is passed through the activated carbon
where some is adsorbed. It is then stored at
low temperature (150K) and relatively low
pressure 5.51 MPa (800 psig) before being
released via slight heating of the granular
carbon while opening a valve for controlled
release into the nearby hydrogen-oxygen fuel
cell. A design engineer predicts that a car
powered by an electric motor energized with
a hydrogen-oxygen fuel cell will be able to
outperform a similar vehicle powered by a
gasoline engine. Since hydrogen as a fuel
requires a massive change to the fueling
infrastructure, the timing for this market sec-
tor is hard to predict. If such an infrastructure
is installed, there will likely emerge many
more composites applications such as large
tanks and pipelines.
942 Commercial and industrial applications of conqposites

Table 43.5 Miscellaneous molded with nonwoven-fabric are 20-50%

~~
"JurassicPark dinosaurs
High-altitude balloon gondolas*
Aquaculture cages for fish farming
Telescope tubes*
Helmets*
Superconductingsupercollider*
Firefighter air bottles*
Oxygen storage bottles*
Life raft inflation bottles*
Flag poles
Deep-submergencecapsules*
Riot control body armor/shields*
43.4.18 LAPTOP COMPUTERS
Lightweight laptop computers with carbon
fiber reinforced plastic cases were first intro-
duced in the USA in the early 1990s at the giant
Comdex computer show in Las Vegas. Toshiba
America Information Systems (Irvine, CA)
introduced three models, reporting that their
light weight 2.5-3.6 kg (5.5-7.9 lb) and porta-
bility were partially due to the use of a carbon
fiber molded case (Fig. 43.4). The new cases
Fig. 43.4 Lightweight computer case with nonwo- fiber/epoxy, high-speed loom frame compo-
ven fiber reinforcement. (Courtesy of Toshiba nent for a USA equipment producer, using
America InformationSystems, Inc.)
lighter than older, thicker plastic cases and
have a wall thickness of only 3.04 mm (0.12 in)
without sacrificing ruggedness. The carbon
fiber/thermoplastic is supplied by Kobe Steel
Ltd. and Mitsubishi Rayon Co., Ltd of Japan.
In a related competitive development,
Advanced Logic Research, Inc. (ALR - Irvine,
CA), introduced the world's first modular
notebook PCs offering processor chip
upgrades. The ALR notebooks are ergonomi-
cally designed with a thin carbon fiber
reinforced, lightweight case that fits into a
standard-size briefcase. Other notebook com-
puter producers have composite development
programs underway.
Based on market share estimates provided
by Stanford Resources, Inc. in PC Magazine
(August 1994), Compaq has the largest market
share today at 14.1% of shipments in 1993,
Apple is second at 13.6?'0, Toshiba is third at
11.1%, IBM is fourth at 7.1%, followed by
dozens of other producers.
43.4.19 LOOM COMPONENTS
DFI Pultruded Composites, Inc. (Erlanger, KY)
was one of the first to successfully pultrude car-
bon fiber/epoxy, once quick-curing epoxies of
the proper viscosity became available. One of
their better customers is in Europe for DFI's
pultruded lightweight, low inertia, carbon fiber
shuttle arms that rapidly reciprocate in the
older style but updated rapier looms still being
used by many industrial fabric weavers. The
shuttle arms are delivered in six lengths rang-
ing from approximately 1.3 to 2.1 m. DFI used
34 msi modulus carbon fibers as the reinforce-
ment. [Incidently, one of their unique products
is a pultruded rod using carbon fiber/epoxy
with a diameter as small as 0.25 mm (0.010 in).]
Polygon Company Div. of Plas/Steel Industries
(Walkerton, IN) pultrudes a carbon
Akzo Nobel Fortafil's 50K filament fiber.

43.4.20 MAGLEV TRAIN GUIDEWAYS
Magnetic levitation or maglev train system con-
cept definition contracts are funded by the
DOT-Federal Railway Administration under
the $151 billion Intermodal Surface
Transportation Act which was passed in 1991
and included $750 million to be used specifi-
cally to complete the design and construction of
a USA demonstration maglev line about 32 km
(20 mile) long. The German Transrapid maglev
system design is planned for the 20km (13
mile) demonstration system to be built in
Orlando, FL. USA and Canadian companies
competing for future maglev system contracts
include Northrop Grumman, Foster-Miller,
Magneplane, Boeing, Bombardier and
Morrison-Knudsen (the latter three are propos-
ing the most extensive use of composites on the
‘rolling’ stock, perhaps including the outer
skins of the maglev cars plus the interiors).
On the maglev vehicles, General Electric is
developing shielded superconducting mag-
nets and their coil design, shielding, motors,
levitation and carbon fiber/epoxy cryostats.
To employ the latest methods of producing
low-cost composite train vehicle structures
and to keep costs down, carbon fiber will be
used selectively, with high-performance fiber-
glass the main reinforcement for sandwich
panels, possible low-FST (fire, smoke toxicity)
materials for the vehicle interiors.
Regarding the guideway, they favor a U-
shaped configuration and either reinforced
concrete throughout or with a composite
grille at the center of each guideway beam. To
reinforce the concrete, they recommend using
post-tensioned FRP tendons in the magnetic
field and closest to the path of the cars and
more conventional steel rebar prestressing in
the lower regions of the supporting columns,
well away from the high magnetic field to
avoid raising the maglev drag coefficient sig-
nificantly. Magneplane International predicts
that the guideway will be the dominant cost
component, so it has first design priority.
Their target is not to exceed $6.2 million per
Applications review 943
km ($10 million per mile) for a dual track
guideway. Their design includes a concrete
box beam for the guideway with the bottom
of the vehicle ’wrapped’ around the beam for
safety. The guideway might use a hybrid of
fiberglass and carbon fiber rebar rather than
steel rebar reinforcement. Foster-Miller is
focused on high-performance, low-cost guide-
ways. Most of their current emphasis is on
using high-strength FRP post-tensioning
members (both transverse and longitudinal)
in the upper areas of the guideway. West
Virginia University is working on a DOT-FRA
contract titled: ’Assessment of Maglev
Guideway Systems’. Imbedded fiber optic
systems may be used to monitor entire guide-
way systems and to detect potential trouble
spots such as joints. West Virginia University
data show that if FRP rebar or tendons are
used, the load-carrying capacity is about
twice that achieved with steel. Although the
initial cost might be five times greater, the
weight reduction can be 80%, so on a perfor-
mance-per-pound basis, FRP would be lower
in installed cost than steel rebar reinforced
concrete. WVU also is looking at more
advanced composite materials, including car-
bon fiber and hybrids. Another option is to
use an aramid fiber tendon, and candidates
include Teijin’s Technora, Akzo Nobel Fiber’s
Twaron and Du Pont’s Kevlar.
43.4.21 MEDICAL, HEALTH AND SAFETY
PRODUCTS (SEE CHAPTER 44)
BioMechanical Materials Corp. (Camarillo,
CA) and Composiflex (Erie, PA) are among
those selling carbon fiber/acrylic and carbon
fiber/urethane sheet stock to orthotic equip-
ment distributors. They in turn sell this
material to hundreds of small local laboratories
that fabricate components tailored by ortho-
tists for each patient, including such items as
arch supports, knee braces and custom sports
braces. BioMechanical Materials among others
also sells large quantities of composite sheet
944 Commercia2 and industrial app2ications of composites
and fabricated parts to sports shoe manufac-
turers, such as Brooks and L.A. Gear, for
enhancing performance and the marketability
of the top-end shoes. Hexcel supplies a unique
hybrid E-glass and carbon fiber fabric rein-
forced epoxy 'chip' for arch supports in Reebok
sports shoes. For electrical hazard protection,
Composiflex produces a hybrid composite of
fiberglass/carbon fiber/epoxy to fabricate
lightweight toe plates for safety boots and
puncture-resistant insoles, replacing the tradi-
tional steel inserts. This company gets its name
from their product with multiple plies of ori-
ented fiber composite which can control
bending to certain directions.
Table 43.6 Medical products
MRI scanner cryogenic tubes*
X-ray tables*
Underwater therapy treadmill
Wheelchairs*
Orthotics - shoe arch, neck & knee braces*
Prostheses - artificial limbs*
External fixaters - orthopaedics*
Rehabilitation baths
Medical centrifuges*
Hip implants*
Heart valves*
Dental/prosthetic cements
X-ray file cassettes*
Medical sensors*
Walking canes*
Artificial ligaments*
43.4.22 METAL-MATRIX COMPOSITES (MMCS)
Duralcan USA (Novi, MI) markets low-cost
MMCs reinforced with alumina or silicon car-
bide particulate reinforcement. One of their
most successful applications is the use of rein-
forced aluminum wire for tire studs. Finland
and Sweden (and many USA states) banned
the older steel-jacketed tungsten carbide studs
from all-weather/snow tires due to road wear.
Many people assumed that studs degrade
highways prematurely because they wear
away road surface. The real culprit is centrifu-
gal force acting on the studs that causes the
older heavy tungsten studs to impact (rather
than scrape) the road surface. A Duralcan
MMC with 15 v/o alumina in 6061 aluminum
is being substituted to limit road damage
because of its lower weight. MMC wire is
being shipped at the rate of 'several tons per
month' for this application. Another interest-
ing wire application is for flame spraying
where the MMC adds to service life; alumina-
reinforced aluminum wire is sprayed onto
steel as an antiskid surface in marine environ-
ments such as ships, piers and oil platforms.
Previously, pure aluminum was flame sprayed
onto a steel surface before painting, serving as
a corrosion barrier.
Among the many other applications in
work or which have been tested to date are the
following: extruded truck frame channels [C-
channels of about 304 x 76 x 7620 mm (12 x 3 x
25 in)], motorcycle drive sprockets, a propor-
tional valve for a truck lift gate, compressor
piston-ring inserts, sporting goods such as golf
clubs and brake components for standard and
high-speed rail cars. Other promising applica-
tions are automobile brake rotors (initial
orders are now being used for early produc-
tion at this time) to reduce weight by replacing
cast iron. Further component applications
likely to emerge include pickup truck drive
shafts, engine cylinder liners, automotive sus-
pension arms, aircraft camera mounts,
electrical housings, and pistons for automotive
engines, piston inserts that reduce the energy
required for high-speed reciprocating motion
in large gas compressors, and tubing and forks
for high-performance racing and mountain
bicycles.
Recyclability is a major market issue for
high-tonnage applications of many materials,
especially now in Europe. Duralcan claims
that their MMCs have a potential advantage
over many other materials, including poly-
mer-matrix composites, since MMCs can be
recycled as a composite material or easily
reclaimed into high-quality aluminum by
melting and removing the reinforcing parti-
cles. Whether recycled or reclaimed, Duralcan
 Applications review 945

USA can achieve virgin material properties in Composite trailers could haul more fuel or
new parts. For example, they have recycled would be allowed on roads with weight
pickup truck drive shaft extrusions up to four restrictions or service pads not capable of han-
times, while retaining original property per- dling the heavier steel trailers. Manufacturers
formance in subsequent parts. In the of the current steel tube trailers include Christi
aluminum casting process, 30-40% of the Park Industries in McKeesport (PA) and Trend
process metal is not in the part but in the gates Fuels in Austin (TX). Certification by the
and risers, and all of this material is now being Department of Transportation (DOT) is
recycled. required to allow use of large composite stor-
Duralcan USA's parent company is Alcan age tanks on highways if loaded with
Aluminium Ltd in Canada (Jonquiere, compressed natural gas to 25 MPa (3600 psi) or
Quebec), and their plant has an ultimate higher. Projections for the composites poten-
capacity for these products of around 11-16 tial in this one application range from 3645
million kg (25-36 million Ib) per year. In some million kg (80-100 million lb).
applications (bikes and drive shafts, for exam-
ple) these MMCs could readily displace some
43.4.24 MOLDING COMPOUNDS FOR
growth opportunities now seen for polymer
INJECTION MOLDING
composites.
MMCs from other producers also show A steadily growing segment of the advanced
great promise in the field of electronics. Multi-composites market is a variety of injection
chip modules (MCMs) require high molded parts made with carbon fiber, or
dimensional stability, thermal conductivity hybrids with fiberglass or aramid reinforce-
and thermal shock resistance. Mounting them ments. LNP Engineering Plastics, Inc. (a unit
on MMC provides these benefits, especially of Kawasaki Steel based in Exton, PA) partici-
for high-density avionics applications on air- pates in many current applications in the
craft or for radar and other systems on board commercial and industrial sectors. (See
ships. For maximum thermal conductivity in Section 43.4.3.) There is a trend toward
electronic backplanes, Amoco Performance increased use of the higher-temperature ther-
Products's K-1100 pitch-based carbon fiber moplastics, and at LNP these include
might be used. polyethersulfone (PES), polyarylsulfone
(PAS), polyetheretherketone (PEEK),
polyphenylene sulfide (PPS) and polyetherim-
43.4.23 MOBILE STORAGE MODULES FOR CNG
ide (PEI, or Ultem). Their long fiber
Aerojet and Pacific Gas & Electric have teamed compounds called Verton offer performance at
to demonstrate a low-cost, lightweight com- the high end of the mechanical performance
posite Mobile Storage Module that is a large spectrum for compounds.
NGV fuel tank made of carbon fiber or fiber- RTP Company (Winona, MN), Comalloy
glass composite overwrapped aluminum used International (Nashville, TN) and
to transport CNG from the utility to the user. Compounding Technology, Inc. (Corona, CA)
These tubes are currently 381 mm (15 in) manufacture molding compounds made with
diameter by 6096 mm (20 ft) long, and several the high-performance thermoplastic resins
of these would be mounted in a truck trailer listed above plus large amounts of polycar-
that can be used to transport, store, and bonates and nylons/polyamides, much of
deliver natural gas fuel to fixed loading areas. these for electrical and electronic insulating
These modules would be moved between fleet components. A smaller part of the business is
refueling stations, thereby avoiding the neces- nickel-coated carbon fiber for added conduc-
sity of installing a costly pumping system. tivity, and they also use some stainless steel
946 Commercial and industrial applications of composites
fiber to make compounds suitable for
EMI/RFI Shielding. DSM Engineering
Plastics, Inc. (Evansville, IN) and others report
a noticeable trend toward using higher-tem-
perature glass-filled thermoplastics for
components used in the electronics industry,
mainly for connectors. Currently, the liquid
crystal polymers (mainly Vectra from Hoechst
Celanese and Xydar from Amoco) are widely
used for electronics applications. Having been
part of the Akzo organization for several years
(and before that, Fiberfil), they have worked
closely with Akzo Nobel Fortafil Fibers
(Rockwood, TN) to develop special grades of
chopped and milled carbon fibers with suit-
able finishes. Other suppliers include Toho
Carbon Fibers and Hexel. Heavy-tow fiber
(50K filament count and greater) made from
commercial-grade PAN precursor is well
suited to making lower-cost chopped fiber.
Usage of carbon fiber has been going up every
year and has reportedly passed annual con-
sumption of 2.25 million kg (5 million lb) per
year that would translate into compound vol-
umes five to ten times that.
43.4.25 MUSICAL INSTRUMENTS
Kaman Aerospace (Bloomfield, CT) offers the
Ovation Instruments guitar. The top of the
Ovation series is called the Adamas and its
excellent tone is attributed to the use of a com-
posite sandwich construction for the top. The
outer and inner plies are single layers of 5-mil
unidirectional carbon fiber/epoxy tape, while
the core is 0.762 mm (0.030 in) thick birch
veneer. Fiberglass composites are also used for
other Adamas components, including the
bowl. These are mostly handmade guitars so
annual production is small. A producer of clas-
sical guitars is Kuau Technology (Maui,
Hawaii) with carbon fiber/epoxy and the RTM
process is their preference. The Luthier’s
Mercantile (Healdsburg, CA) catalog for
stringed musical instrument producers gener-
ates 99% of their business via mail order. They
offer carbon fiber/epoxy bar and sheet stock in
various sizes for reinforcing the necks of gui-
tars or banjos, plus for making bridge blanks,
fingerboard underlays, stiffening braces and
other components requiring extra strength,
stiffness and/or creep resistance. Other instru-
ments now offered in carbon fiber and other
composite materials, all claiming better tone
and clarity, are violins and bows, bases, drums
and sticks, sousaphones/tubas (an old applica-
tion in FRP), harps, pianos and more.
Table 43.7 Consumer products
Camera tripods*
SCUBA tanks*
Banjos*
Sousaphones/ tubas
Harps*
Pianos
Umbrellas*
Attache/brief cases*
Cassette tape/CD player cases*
Exercise equipment*
Art work bracing systems*
Guitars*
Violins and bows*
Bases*
Camera cases*
Eyeglass frames*
Caskets
Binocular /monocular bodies*
Running shoe arches*
Audio earphones*
Drums and sticks*
43.4.26 OIL AND GAS APPLICATIONS
Conoco, Inc. (Ponca City, OK), Shell (Houston,
TX) and others are involved in oil and gas
exploration to production depths typically to
619-928 m (2000-3000 ft) and to even more than
4 km (15 000 ft). Conoco is the first company
with one of the new tension-leg platforms
(TLP) in use. Shell is building such a platform
and planning several more in partnership with
Exxon and British Petroleum. The oil industry
has a ’steel and concrete bias’ which is the result

of many years of experience, relatively low ini-
tial cost, ample supply, current design codes,
etc. However, new materials are the major tech-
nology thrust needed in offshore structures
because the industry is forced to spend too
much money fighting corrosion of steel.
Current offshore structural applications of
composites include low-pressure pipe, grat-
ings, handrails, equipment covers or
enclosures and ladders. Future application
development is likely to focus on FRP for
high-pressure piping, pressure vessels, accom-
modation modules and blast walls. FRP
products (mainly E-glass reinforced) provide
installation savings ranging from 10-70%,
improved life-cycle costs, enhanced safety,
30-70% weight savings and environmental
advantages, according to studies by Conoco. It
is expected that a variety of composite materi-
als will be used for offshore structures, with
carbon fiber, aramid and fiberglass reinforce-
ments, thermosets and thermoplastic matrix
resins and some hybrids.
The Institute Franfais du Petrole supported
development of advanced composite tubes
developed by Aerospatiale for risers on off-
shore stationary drilling platforms and tension
leg platforms. These tubes are hybrids of high-
strength fiberglass and carbon fiber and are
offered in diameters ranging from 76 to 300 mm
(3 to 12 in) and in lengths up to 24 m (80 ft).
Internal working pressures are in the 34-103
MPa (5000-15 000 psi) range, tensile loads to
90 000 kg (100 tons) will be accommodated by
a special high-strength threaded steel alloy
coupling, and the design life can be as high as
20 years. Typical drilling risers will be up to 10
times the height of the Eiffel Tower [up to 3000
m (9800 ft)] and weigh over 2.2 x lo6 kg (2500
tons). Syntactic foams control buoyancy and
reduce the effects of sea loads from waves,
currents and storms. The case for composites
is clear, as weight savings could exceed
544 000 kg (600 tons). A 900 kg (one ton)
reduction in the offshore superstructure or the
risers results in a savings of 272 kg (3 tons) of
displacement load on the platform. Working
Applications review 947
closely with IFP and Aerospatiale Space &
Strategic Systems are Lincoln Composites
(Lincoln, NE and teamed with Aarding BV in
The Netherlands) plus Coflexip & Services,
Inc. (Paris). Coflexip is reportedly the leading
producer of sub-sea pipelines and risers to
transport oil and gas products at offshore pro-
duction facilities. The initial product of the
Lincoln-French joint venture was a composite
TLP riser pipe that connects well-heads to
tethered floating platforms. Risers provide a
casing to protect the well bore and to carry the
oil to the surface. Tethers will be 244.5mm
(9.60 in) diameter tubes, with a wall thickness
of about 13.5mm (0.53 in) and 12-17m
(40-55 ft) long.
Table 43.8 Oil and gas exploration
Tension leg platform tethers*
Fire shields - drilling rigs
Drilling tubes*
Sucker rods/slides
Oil well logging probes*
Tribological bushings, seals, ' 0 rings*
Drilling motor shaft
Drill casing
Longer-term commercial application growth
in this sector for advanced composites should
include moorings and tendons, drilling and
production risers, drill pipe and tubing and
some pressure vessels. With platform construc-
tion costs exceeding $1.5 billion per unit, there
could be a substantial dollar potential for the
various composite applications. One producer
estimates the current usage of steel to be as high
as 1.5-1.8 x lo9kg (1.7-2.0 million tons) used for
oil- and gas-well downhole tubulars. Much of
that could be displaced by composites (at one
fifth the weight) because of their advantages in
high specific strength, fatigue resistance, corro-
sion resistance, lighter weight, low coefficient
of thermal expansion and reduced installation
cost (due to lighter weight)
948 Commercial and industrial applications of composites

43.4.27 PIPELINE REHABILITATION 43.4.28 POLES - POWER DISTRIBUTION AND

A high-volume application for Kevlar 49 and
other aramid fiber reinforcement has been
developed by Insituform of North America,
Inc. (Memphis, TN) with the help of Du Pont.
A patented product called Insituform has been
used extensively for years in repairing and
generally 'rehabilitating' old large-diameter,
gravity-flow and pressure pipes. Insituform
can repair or replace a damaged pipe very
rapidly to minimize downtime. The process
was developed in the UK many years ago but
most of the recent progress has reportedly
been made in the USA. A special needled poly-
ester felt reconstruction tube (called
Insitutube) is coated on the outside (typically
with a thin layer of polyurethane), and is cus-
tom engineered and manufactured to fit the
damaged pipe exactly. It is impregnated with a
liquid thermosetting resin (polyester, vinyl
ester, or epoxy as appropriate for the chemical
environment to be experienced) and lowered
into a manhole through an inversion tube. One
end of the Insitutube is attached to the lower
end of the inversion tube elbow. The resin-
impregnated tube is turned inside out using
cool water so that the smooth coated felt exte-
rior then becomes the new interior surface of
LIGHTING
Shakespeare (Newberry, SC) developed fila-
ment wound distribution poles that were
installed by Montana Power Co. These fiber-
glass/polyester poles weigh half as much as
wood; material efficiency is improved through
the use of stitched fabric reinforcements as
well. Weight savings enhance the ease of
installation in remote areas through use of
smaller helicopters than required for wood
poles (Fig. 43.5). The 355 mm (14 in) diameter
poles are generally 12-14 m (40-45 ft) tall.
Another major advantage of FRP poles is the
elimination of chemical treatments required to
preserve wood poles. An 80-year service life is
. ... .
'
.,
.4.

the pipe. Circulation of hot water through the

tube then cures the resin-impregnated felt.
This repair process typically is performed
on an old water or sewage pipe that has been
buried for many years and which is starting to
leak. The whole procedure can be done with-
out digging up or otherwise disrupting the old
pipe. Kevlar 49 is used to reinforce the poly-
ester felt in the hoop direction. This reduces
the felt thickness and the total weight, increas-
ing the inside diameter of the repaired pipe,
and generally adds both structural strength
and rigidity. Also involved is Shell Chemical
(Houston, TX) where a special quick-curing
epoxy is being developed for this application.
Dow Plastics (Midland, MI) supplies resins to
another company in this business, In-Liner Fig. 43.5 Installing lightweight composite utility
Corp., with their cured-in-place-pipe (CIPP) poles by helicopter. (Courtesy of Amoco Chemical
process, among many users. CO.)
 Applications review 949

targeted. In a related development, Composite fiberglass knitted multiaxial fabrics from

Power Co. (Las Vegas, NV)fabricates FRP util- Brunswick Technologies, Inc. (Brunswick,ME)
ity poles using pultrusion. Prospects for both and vinyl ester resin from Dow Plastics
companies are enhanced because of the envi- (Midland, MI). The process is called Seemann
ronmental concerns when using treated wood Composite Resin Infusion Molding System or
poles and the cost escalation of older products SCRIMP. Co-owners of the process technology
that bring them closer to the current premium that can infuse preforms of 6 m by 2 m (20 ft by
costs of composite poles. 7 ft) in only 35 mm (1.4 in) are Hardcore,
The California DOT (Sacramento, CA) is Seemann Fiberglass and TPI (also see rail item
potentially interested in the use of composites above). They license this process technology to
to build 53 m (175 ft) tall light standards for others. The USA Navy has been assessing this
highway interchanges. Caltrans currently uses technology for years in the development of
galvanized steel but these must be replaced major ship structures, including masts.
periodically and are difficult to erect and Composites sheet pile from companies such as
maintain. Among the firms that have built tall Creative Pultrusions and others are also likely
steel light standards are Ameron, Union Steel, to experience a major growth trend.
Valmont and Shakespeare. The hope is that
current composite technology for lighting and
43.4.30 RAILROAD ROLLING STOCK
power poles and for sailboat spars to 55 m (180
COMPONENTS
ft) height can be expanded into such highway
infrastructure applications. Burlington Northern Santa Fe Railroad (Ft.
Worth, TX) is a very innovative company and
plans use of composite overwrapped air bot-
43.4.29 PORTS AND HARBORS
tles for use on locomotives. They favor the
A potentially significant new application with lightest version that would use a plastic liner
major potential for tonnage of FRP is that of and a carbon fiber/epoxy overwrap to replace
dock and wharf pile fenders. Du Pont fabri- heavy steel tanks for improved corrosion resis-
cated composite fenders for a systems tance and easier/safer installation by work
company. Six developmental fenders were crews. Weight saved on railroad rolling stock
installed in mid-1994 in the Chesapeake Bay also increases the capacity for revenue genera-
area. They replaced multiple sets of fender pil- tion from hauling increased cargo. Lincoln
ings in 10-pile clusters that had steel fender Composites and Compositek fabricate such air
surfaces. The treated wood pilings only last bottles while Dresser Industries’ Nil-Cor
about seven years on average, the steel plates Operations makes a variety of composite
are drastically deformed and rust relatively valves. Most use fiberglass/vinyl ester con-
quickly. struction; others are made of carbon
The FRP fenders with UHMW polyethylene fiber/vinyl ester, fiberglass/polysulfone and
skinned impact surfaces to date have better fiberglass/polyphenylene sulfide composite.
withstood the impact of a 159 000 kg BNSF also seeks to introduce composites on
(350 000 lb) ferry boat (eight to ten times/day) existing or new freight cars. A prototype com-
than did the wood/steel system, with no dam- posite knuckle is in the design stage for
age reported in over two months as of this extended field tests. This is likely to be a
writing. The lightweight composite fenders hybrid featuring carbon fiber/epoxy with
were installed in only 3.5 h with a cherry steel inserts to protect the high-wear areas.
picker while the steel and wood system Another industry program is development of
require a barge crane at much greater expense. an FRP cargo door to be produced using a
Composite fenders are fabricated using resin infusion process called SCRIMP offered
950 Commercial and industrial applications of composites
by Hardcore Composites (New Castle, DE),
Seemann Fiberglass (Hanrahan, LA), and TPI
(Warren, RI).
Composite auto hauler composite cars with
all-pultruded components of fiberglass/poly-
ester have been developed by W. Brandt
Goldsworthy & Assocs. (Torrance, CA) along
with Alcoa Composites and Stoughton
Composites (Brodhead, WI) for the Union
Pacific. Many other freight car development
programs are under way at Trinity Industries
and elsewhere. Corrosion resistance and light
weight are the two primary benefits of com-
posites that are sparking this interest.
43.4.31 RAILWAYS AND TUNNELS
Besides pultruded and filament wound com-
posite cableways, ducts and piping, there is a
vast array of associated molded parts for
trackside, station equipment and furniture.
Development of fiberglass reinforced pheno-
lic-matrix composites, with their superior FST
properties, has become an important contribu-
tor to the increasing acceptance of composites
for interior components. European countries
now virtually mandate using phenolic resin
composites for underground railcar and sta-
tion components. Some of ICI’s Modar
acrylic-modified polyester and also the less
flammable phenolic-based composites were
used in the Channel Tunnel, mainly for electri-
cal cable tray. The market for composites in
railways and tunnels could double during the
next few years due mainly to the greater atten-
tion being paid to safety, including improved
fire, smoke, and toxicity performance (reduced
FST).
43.4.32 ROLLS AND AIR SHAFTS
Industrial rolls and expanding air shafts used
inside cardboard core tubes on winders to take
up paper, films and foils will be major growth
applications in the industrial composites sec-
tor. Tidland Corp. is said to be the world’s
leading supplier of core shafts of all types and
reportedly buy most of their carbon
fiber/epoxy rolls from Lincoln Composites.
Shafts from about 2-10 m (6-33 ft) long are
fabricated using hybrid carbon fiber and fiber-
glass in epoxy which are about one-fifth the
weight, operate at faster speeds and use less
energy than the conventional steel rolls.
Fiberite (Wilmington, DE), Epoch Industries
(Garland, TX), Addax (Lincoln, NE), and
Quality Composite, Inc. (Sandy, UT) are
among others that fabricate such products.
Amalga Composites, Inc. (Milwaukee, WI) is a
more recent entry into the filament winding of
carbon fiber/epoxy tubes for the industrial
rolls used in paper and plastic film converting
machinery and reportedly is a major supplier
to American Roller (Bannockburn, IL). They
use Grafil’s 33 msi carbon fiber but leave the
finishing and coating operations to American
Roller. According to ARC, there are many
potential applications for composite rolls.
These include replacing the steel rolls com-
monly used in winder core, winder shaft, idler,
layon and dancer/ transducer positions to
manufacture film, flexible packaging, foils,
magnetic audio and video tape and photo-
and pressure-sensitive papers on printing
presses, laminators, coaters and blown film
lines. However, selecting the right composite
for each of these positions is not quite as sim-
ple as ordering an off-the-shelf product. ARC
technical and marketing people make a special
point of explaining why each composite roll
should be customized to the end-user’s spe-
cific application and operating parameters,
especially because of the many types of com-
posite materials and structural designs
available on the market today.
Another filament wound tube fabricator for
this application is SpyroTech Corp. (Lincoln,
NE). Also, TPI (Warren, RI, and formerly
called Tillotson Pearson) has been using fila-
ment winding to make fiberglass/epoxy and
carbon fiber/epoxy tubes for paper mill rolls.
It is noteworthy that Mitsubishi Rayon in
Japan is one of the largest suppliers of such
rolls in the world. These suppliers market the
 Applications review 951

major benefit of hybrid carbon fiber-fiberglass Table 43.9 Industrial equipment

and 120°C (250°F) cure epoxy composite rolls
and shafts compared to steel and aluminum Coordinate measurement/3-D gaging*
shafts, namely a 50% weight reduction. Magnet support rings*
Torque tubes*
Precision balancing allows higher operating Paper folding plates*
speeds than with metal rolls. Advanced com- Coating doctor blades*
posite rolls exhibit 20% less deflection under Textile bobbins*
loads. Also, composite rolls offer superior Instrument housings
fatigue resistance for increased service life and Pump impellers*
improved damage tolerance versus steel or Crane components
Backhoe components
aluminum. Forklift components
Polygon (Walkerton, IN) is a pultruder and Mixer drive shafts*
braider active in fabrication of such industrial Containers
rolls. Composite Development Corp. (West Chemical mixer paddles*
Wareham, MA) also supplies to the converting Liquid level measuring sticks
industry that wants to use thinner gage Surveying transit tipod
Industrial rolls - paper, film,foil, printing*
paper/film/foils yet process at higher speeds, Water tanks
so the lightweight, low-inertia rolls produced Chemical filtedframes
using carbon fiber composites with the fabric Radio-controlledvehicles
roll-wrap process are rolls that offer improved Mirrors*
handling characteristics (Fig. 43.6). Heavier Cryogenic vessels*
rolls such as plate cylinder rolls (used to Core tube air shafts*
Generator housings
mount printing plates) offer excellent weight Welding robot arms*
savings that are important in a process with Laser resonator spacer tubes*
constant and many job changeovers. Some Pump casings
producers of rolls use braided reinforcement Speaker housings*
preforms from companies such as A&P Signage
Textile looms - rapiers, heddles, shuttle cocks,
Technology (Covington, KY). picker sticks*
Ball and butterflv valves
Conveyor belt sGpport shafts
High-pressure hydraulic pipe*
Pneumatic piping'
Uranium enrichment centrifuges*

-
Cooling tower drive shafts*
Tote trays/Storage bins
I Tooling*
Optical benches*
~ PCB conveyor components
Coil springs*
Underwater light housings
Light bulb sockets
Propellers
Fan blades
Ladders

' -
Fig. 43.6 Composite industrial rolls. (Courtesy of
Safety shoe toe guards
Industrial shaft couplings
Broomhandles
W i d o w cleaning squeegee handles
Cherry picker lifts
Composite Development Corporation.)
952 Commercial and industrial applications of composites

The considerable weight reduction com- Institute of Standards and Technology (NIST)
pared with steel rolls means less strain and in Boulder, CO, and the Phillips Laboratory at
fatigue and reduced injuries for the operators. Edwards AFB, CA, assist by conducting the
For example, a steel roll that is slightly over low-temperature testing work. Competing
2489 mm (98 in) long, 152 mm (6 in) O.D., and technologies for SMES include pumped water
127 mm (5 in) I.D. would weigh approximately storage, batteries, and potentially, flywheels.
188 kg (239 lb). A fiberglass-reinforced compos- Recent work has been focused on develop-
ites roll of the same dimensions would weigh ing and testing the prototype of a full-size
27 kg (61 lb), while a carbon fiber composites mockup of a SMES unit. E-glass fiber rein-
roll of this size weighs only 22 kg (49 lb). forced plastic curved, pultruded vinyl ester
resin beams were developed to simultane-
ously provide essential electrical insulation
43.4.33 SMC - TOUGH, HIGH-PERFORMANCE
(between conductor coils and between the
Premix, Inc. (No. Kingsville, OH) and their conductor and the ground) and the conductor
Quantum Composites division (Midland, MI), support structure.
focus on 'ultra-high strength and toughness' Pultruded FRP was chosen because it pro-
Lytex SMC that is offered with carbon fiber or vides reasonable structural performance and
fiberglass reinforced epoxy or vinyl ester the required electrical insulation capabilities at
resins. Present nonaerospace uses for this cryogenic temperatures for an affordable cost.
unique SMC include a prosthetic foot, an auto- Test articles were fabricated and then the
mobile brake component, an electrical mechanical, thermal, and electrical properties
connector and more. Projected applications were measured over the temperature range of
include automotive suspension and structural 4-295K. FRP beams, pultruded by Compositek
chassis components, recreational-vehicle high- (of Brea, CA and now part of Kaiser
impact parts and other applications Aerospace),met the goal of comparable perfor-
demanding toughness and excellent dynamic mance to currently used and more expensive
fatigue resistance (including aerospace). materials such as G-10 laminate produced with
fiberglass fabric and epoxy resin. The tensile
failure strains for the materials tested using liq-
43.4.34 SUPERCONDUCTING MAGNETIC
uid helium ranged from 1.2% at 295K to 1.9%
ENERGY STORAGE SYSTEMS (SMES)
at 4K. The pultrusion machine was built by
Composites play a key role in the insulation Pultrex Ltd (Clacton-on-Sea, UK). Johnson
and structural systems of the SMES Program Industries Composite Textile Reinforcements,
at General Dynamics Space Magnetics, now a Inc. (of Phenix City, AL) supplied the stitched
unit of Martin Marietta. Years of development fiberglass preform materials, which ranged
may now offer dramatic potential for carbon from 9 to 18 plies in thickness.
fiber and glass fiber composites in the future. SMES develops large radial loads when
The purpose of SMES is to economically store charging. This requires strong coil support
electrical energy from power production late straps, which are integrated by General
at night and then to retrieve it during peak Atomics (San Diego) and which were filament
demand periods during the day. wound by Lincoln Composites (Lincoln, NE).
Heading the team is Bechtel National, Inc. The short straps look like a fan belt about
as system integrator. General Atomics is 127 mm (5 in) wide and 762 mm (2.5 ft) long
responsible for the coil supports and was the and are wound with S-2 glass fiber prepreg.
designer and fabricator of the first SMES unit Larger straps, about 89-1200 mm (3.54 ft)
to be operated successfully (1983) by an elec- long and 100 mm (4 in) wide, are wound using
tric utility, Bonneville Power System. National carbon fiber prepreg.
 Applications review 953

The SMES Engineering Test Model (SMES- and is produced using 68 w/o AS4 carbon fiber
ETM) consists of a two layer, radial, helically filament wound in PEEK thermoplastic matrix.
wound, 96 m (315 ft) diameter solenoid coil They have reportedly produced well over 45
that has been designed to store a minimum of 360 kg (100 000 lb) of parts with this material
20 MWh of electrical energy in its magnetic ’under production conditions, to aerospace
field. The coil stack requires 66 layers of FRP requirements’. Also offered are parts molded
curved beams for the support structure or 825 from their injection-molding grade. Polygon
24 m (80 ft) sections weighing 907 kg (2000 lb) offers a line of ’Poly Lube’ composite bearing
each. A full-sized, 20 MWh ETM demonstra- materials, hybrids of fiberglass and Teflon. Bal-
tion unit will require about 725 000 kg (1.6 Seal Engineering Company (Santa Ana, CA)
million lb) of FRP composite. A full-scale test markets carbon fiber and graphite-filled Teflon
model of SMES will consist of a large, cylin- fluid seals and ’0’-rings. The primary benefits
drical coil 91 m (300 ft) in diameter sunk into a are dimensional stability and a low coefficient
9 m (30 ft) deep trench in the ground. Stored of friction under elevated temperature and
energy can be retrieved slowly or almost pressure, with no ’extrusion’ of the resin
instantaneously, and the technology is consid- matrix. Carbon fiber adds to the tribological
ered a promising method of storing electrical value of the rings through prevention of adhe-
energy for peak load demands. sion of the Teflon to the bearing surface.
Bechtel estimates that the potential SMES Tiodize (Huntington Beach, CA) sells self-
market in the USA alone could be as high as $3 lubricating composites based on carbon fiber in
billion/yr. The Electric Power Research a high-temperature resin used for bushings,
Institute in Palo Alto (CA) and the SMES thrust bearings, rod-end bearings and ball-
Utility Interest Group (SUIG, Dallas, TX) are bearing retainer rings. They emphasize the
promoting the commercial development of the advantage of using these materials compared
SMES technology because it looks promising to aluminum in retaining specific modulus at
for electrical load leveling, increasing electrical temperatures to 316°C (600°F).
system reliability, savings in fossil fuels,
reduced air pollution, emergency backup
43.4.36 URANIUM ENRICHMENT
power, virtually instantaneous response and
CENTRIFUGES
the ability to store energy from intermittent
sources such as solar and wind generation of Louisiana Energy Services is a joint effort of
electricity. EPRI estimates that by 2010, storagethree USA electric utilities, Duke Power Co.,
could usefully provide as much as 10% of the Louisiana Power & Light Co. and Northern
nation’s generating capacity. Using storage to States Power Co. Along with the internation-
save power generated at night when power ally known engineering firm of Fluor Daniel,
plants normally run at very low rates some Inc., Urenco will build and help operate a ura-
day could potentially save the cost of building nium fuel enrichment plant for these utilities.
many new generating plants at far higher cost Urenco is a European organization with close
than adding SMES storage capacity. to 15 years of experience operating commer-
cial uranium enrichment plants in Germany,
the UK and The Netherlands. Together, the
43.4.35 TRIBOLOGICAL APPLICATIONS - SEALS
three utilities own and operate 11commercial
AND ‘O-RINGS
nuclear power plants. In the enrichment
EGC Corporation (Houston, TX) is a custom plant, high-speed ultracentrifuges will be
fabricator of molded components for oil field used to enrich the uranium and hopefully can
and refinery applications. Their ‘wear-resistant supply nuclear plant fuel at a price lower than
composite’ is called XC-2 tribological material is being projected by DOE, according to the
954 Commercial and industrial applications of composites
program planners. Carbon fiber/epoxy fila-
ment wound composite tubes are to be used
for the high-speed rotors but most of the tech-
nology details remain proprietary to Urenco.
At this writing, Louisiana Energy Services
continues with the approval process for the
required environmental impact report in sup-
port of their license application. They hope to
start construction soon, and have the new
plant in full operation in the late 1990s.
Similar composite centrifuge rotors are
believed to be standard design for European
and Japanese uranium enrichment work.
43.4.37 VALVES
Dresser Valve & Controls Division, Nil-Cor
Operations, (Alliance, Ohio), sells several
types of composite valves to the chemical
industry. Over 100 000 Nil-Cor advanced com-
posite valves are currently in service at over
100 USA paper mills. Their current valve prod-
uct line includes fiberglass and carbon fiber
reinforced PPS, polysulfone and vinyl ester in
several sizes and types. Fiberglass reinforce-
ment and Dow Chemical's Derakane 470 vinyl
ester resin (among others) are used in ball and
butterfly valves for the chemical industry.
43.4.38 WIND TURBINE BLADES
TPI, Inc. located their composite wind turbine
blade production in Portsmouth, RI. TPI
makes fiberglass/vinyl ester blades regularly
for large operators of wind energy farms in the
USA. The size of the individual generating
units has gradually increased from the 50 and
100 kW sizes with 8 m (27 ft) composite blades
that were most common several years ago to
the larger 300-kW units that are now in
demand. Each of the three new size blades is
17 m (56 ft) long and uses a sizable quantity of
material. Production rates have reached as
high as 5000-6000 blades per year. Among the
critical aspects of making large windmill
blades is the need for proper balance. This is
one reason that the TPI product has succeeded
while other blade manufacturers had to fold
when the market started to collapse several
years ago.
Sandia National Laboratories (of
Albuquerque, NM) developed advanced wind
turbine technology using the vertical axis
approach and signed a technology agreement
with Flo-Wind Corp. (Pleasanton, CA). Flo-
Wind has used extruded aluminum blades but
plans use of composite blades. Flo-Wind cur-
rently operates 'over 500' such turbines with
aluminum blades currently in operation on
two California windfarms, likely candidates
for retrofit with composite blades. Glasforms
(San Jose, CA ) is one of their prime suppliers
for composite parts.
Competition continues to develop overseas.
Japan's Tomen Corp. has joined with
American and British firms to build several
large wind power farms in Wales and
Cornwall, UK, operated by a company called
British Wind Farms, based in London.
Included in their plans was the construction of
300 windmills with a total generating capacity
of 77 000 kW. Many European countries are
making sizable commitments to increased use
of windpower, including Denmark, Germany,
Holland and Spain.
The National Renewable Energy
Laboratory, a unit of the Department of
Energy (formerly called the Solar Energy
Research Institute), is in Golden, CO. They are
interested in all types of alternate energy sys-
tems, including battery-operated vehicles,
engines that can use different types of fuels,
including hybrids and biofuels. NREL spon-
sored an effort called the 'Advanced Wind
Turbine Next Generation Preliminary Design
Project', with the goal of bringing wind power
generation costs down from the current 7-84
to below the P 5 4 per kwh with coal genera-
tion. Wind generators must be made of
materials likely to last at least 30 years, so the
additional cost of using carbon or aramid
fibers to reduce rotor blade weight and/or
improve performance might be amortized
over a long period.
 Market data 955

Today there are over 15 000 windmills in at twice the growth rate of the Gross Domestic
California alone, with a total electrical generat-Product (GDP).
ing capacity of 1300 megawatts. To date, they Sectors that fall mainly into the commercial
have generated a total of over two billion kwh, and industrial applications arena, the focus of
replacing 3.5 million barrels of oil. However, this chapter, are noted next. The corrosion-
this is only 1.7% of the total power requirement resistant application sector for chemical
of the state of California during the same storage, process tanks, pipe systems, cooling
period. There are more windmills overseas tower components, wastewater treatment,
where about 70% of the total has been installed. pressure vessels, and pollution control equip-
ment grew 5.9% in 1993. This is because of
43.5 MARKET DATA
their ties to capital spending and substitution
for other materials, and another 3.7% gain is
A frame of reference on market size is useful in likely in 1994.Electrical and electronic applica-
assessing composites growth prospects. The tion usage grew at 5.7% in 1993 (plus 5.5%
Composites Institute of the Society of the more in 1994). Power poles and fiber optic
Plastics Industry issued a news release cable splice boxes are examples of growing
February 8,1994 stating that USA shipments of areas here. The appliance, business equip-
fiber reinforced plastics (FRP) reached an esti- ment, and consumer product markets gained
mated 1.23x lo9kg (2.73billion lb) in 1993. This only 3.0% (plus 3.7% more in 1994) and 2.2%
was an increase of 6.9% over 1992 (thisis almost (with another 4.2% in 1994) respectively,
entirely fiberglass-reinforced polyester, vinyl mainly from material substitution. Lastly, the
ester, and epoxy material but includes 'other' category grew at 7.1% in medical
advanced fibers composites). Projected 1994 equipment such as orthopaedic appliances
growth to 1.32 x lo9 kg (2.90 billion lb) of com- and dental materials. The Composites Institute
posites represents an increase of another 6.2%. (CI) represents over 415 firms in the compos-
Overall growth in sales of composites continues ites industry and is the SPI's largest division.

Table 43.10 USA composites shipments: 1984-1994 (in million Ib)

Markets 1984 1985 1986 1987 1988 1989 2990 1991 1992 1993 1994
projected
(revised)
Aircraft/aerospace/ 29 32 37 36 39 41 39 38.7 32.3 25.4 24.6
military
Appliance/business 123 133 137 141 150 151 153 135.2 143.2 147.5 153.0
equipment
Construction 430 445 456 506 495 470 468 420.0 483.0 530.0 575.0
Consumerproducts 143 142 149 167 169 158 165 148.7 162.2 165.7 171.2
Corrosion-resistant 310 295 291 329 349 335 350 355.0 332.3 352.0 365.0
equipment
Electrical/ 189 191 201 214 230 229 241 231.1 260.0 274.9 290.0
electronic
Marine 309 335 340 413 452 405 375 275.0 304.4 319.3 332.8
Transportation 540 563 585 656 695 677 705 682.2 750.0 822.1 890.0
Other 80 82 83 75 80 76 79 73.8 83.4 89.3 93.9
Total 2153 2218 2279 2537 2659 2542 2575 2360 2551 2726 2895.5
Includes reinforced thermoset and thermoplastic resin composites, reinforcements, and fillers.
Source: SPI Composites Institute, 1994 Semi-annual statistical report, February 8,1994
956 Commercial and industrial applications of composites
43.6 PREDICTIONS
Much of the long-term growth for composites is
likely to come from this miscellaneous sector of
the business. The most likely segments to expe-
rience large unit growth rates are CNG tanks,
flywheels, industrial rolls, distribution and
lighting poles, civil structures, consumer and
medical products and some other oil and gas or
transportation components. Composites have a
low market share in many industries, and com-
mercial and industrial applications should
continue to experience well above average
growth compared with other composites, other
material systems, and the total economic
growth rate on a worldwide basis. Such growth
over the long term is believed likely to exceed
the 5-8% growth rate expected for 1994 over
1993 shipments for these composites markets.
43.7 CONCLUSIONS
Because these sectors of business and technol-
ogy are highly fragmented many smaller
producers are likely to participate. The scale of
production is often not well suited to large
producers. Also, the cost for large producers to
pursue such fragmented businesses, pieces of
which may not be very large, could be higher
per unit or unit weight than for their huge
composites commodity businesses such as
automotive, marine and others. Much of the
innovation in material forms and process tech-
nology also resides in this group of markets.
Thus, one should look to these markets not
only for growth but also for technology and
new ideas.
REFERENCES
Most of the information provided in this
chapter was generated through attendance at
trade shows, interviews with industry partici-
pants, review of press releases, other
extensive reading of publications, and the
experience of the author over 30 years.
Therefore, since most paragraphs would have
required almost a reference per sentence, we
elected to list below the best generic and reli-
able USA-based sources available to research
these applications and markets or to track
their future activities, participants and
prospects.
Composites Institute of the Society of the Plastics
Industry, New York, NY.
Composites News: Infrastructure and Advanced
Material newsletters. Loud, Steve, (ed.) Solana
Beach, CA: Composites Worldwide, Inc.
Composites Industry Monthly and ACM Monthly
newsletters. Burg, Martin, (ed.) San Diego, CA:
Composite Market Surveys.
Composites Technology and High-Performance
Composites magazine. Hazen, Judith Ray, (pub-
lisher), Denver, C O Ray Publishing, Inc.
Performance Materials and Fleets t? Fuels newsletters.
Piellisch, Richard, (ed.) San Francisco, CA:
August Pacific Press.
plasticsBRlEF Reinforced Plastics Newsletter. Best,
James R., (ed.) Toledo, OH: Market Search, Inc.
COMPOSITE BIOMATERIALS 44
Shalaby W. Shalaby and Robert A. Latour

44.1 COMPOSITES AS A FAMILY OF phosphate-based fiber showed large increases

BIOMATERIALS in both strength and stiffness (Casper et al.,
Although the use of high modulus metallic 1985; Lin, 1986). However, these families of
devices for internal bone fixation has been suc- composites lose a substantial fraction of their
cessful, there is a call to develop nonabsorbable, strength while retaining greater proportion of
their stiffness after short term exposure to an
polymeric, composite substitutes having elas-
aqueous physiological environment. Attempts
tic modulus approaching or slightly higher
to improve the strength retention have
than those of bones. This is to alleviate the
included coating the composite material to
problem of stress-shielding and consequent
bone resorption as well as any concerns related retard the transport of fluids to the
to toxicity of metallic ions as corrosion prod- polymer/fiber interface (Kelley et al., 1988;
Andriano, Daniels and Heller, 1991) and sur-
ucts. (Gillett et al., 1984; Tonino and Folmer,
face modification of the phosphate fibers with
1987). Furthermore, to avoid a second surgery
a siloxane film barrier (Andriano, Daniels, and
to remove a non-absorbable device and to
Heller, 1992).Growing interest in the inorganic
allow for gradual load transfer to healing
phosphate-based fillers led Andriano and
bones, completely absorbable composites were
coworkers to compare the biocompatibility of
proposed and evaluated by many investigators
several phosphate, fiber-reinforced polymers
(Casper et al., 1985; Daniels et al., 1990; Lin,
in a preliminary study (Andriano et al., 1993).
1986; Tormala et al., 1991; Vainionpaa, 1987).
Thus, phosphate fibers of calcium-sodium
Among the key types of totally absorbable
metaphosphate (CSM), sodium-calcium-alu-
composites are those based on polyesters or
minum-polyphosphate (NCAP) and
polyorthoesters, reinforced with organic fibers
potassium metaphosphate (PMS),with copoly-
(Tormala et al., 1991; Vainionpaa et al., 1987) or
mers of E-caprolactone and lactide or
calcium or sodium/calcium polymetaphos-
polyorthoesters have been used as organic
phates (Casper et al., 1985, Andriano et d.,
matrices. The CSM and NCAP fibers were
1993). A family of composites having organic
found to be acutely nontoxic in cellular tissue
polyester fibers as fillers (e.g. poly-L-lactide
and whole animal evaluation.
reinforced with polyglycolide fibers, displayed
large increases in strength and modest
increases in stiffness (Tormala et al., 1991; 44.2 COMPOSITE BIOMATERIALS: GENERAL
Vainionpaa et al., 1987). On the other hand,
polylactide reinforced with inorganic calcium Like the more traditional composites, those
classified as composite biomaterials contain
two or more distinct constituent materials or
Handbook of Composites. Edited by S.T. Peters. Published phases on a microscopic or macroscopic size
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 scale but not on the atomic level. Thus, fiber-
958 Composite biomaterials
glass-reinforced polymeric composites and
other reinforced resins are composites while
metal alloys are not. Interest in the former sys-
tems was associated with the need to replace
or augment biological tissues which are com-
posites in their own rights. For instance bone,
skin and blood vessels are typical natural com-
posites. In both natural and man-made
composites (or composite biomaterials) the
strength and modulus of the matrix are depen-
dent on the shape, stiffness and orientation of
the reinforcing materials as well as their adhe-
sion to the matrix. High modulus fibers
uniaxially oriented in a low modulus matrix
can produce stiff solid composites with maxi-
mum strength and modulus along the fiber
direction as in carbon fiber-reinforced epoxy
resins. Complex high density natural compos-
ites include cortical bones, dentin, cartilage as
well as wood. Should air be a distinct phase of
the composite, a foam is produced, as in syn-
thetic sponges or lung tissues and cancellous
bone (Park and Lakes, 1992).
Early application of hard or dense synthetic
composites as biomaterials includes the use of
reinforced acrylics as dental fillings. The com-
posite resins consist of a polymer matrix such
as crosslinked methacrylate resin and a stiff,
inorganic filler including barium glass or silica.
The methacrylate resin can be based primarily
on the glycidyl methacrylate derivations of
bisphenol A. The choice of such components is
consistent with the repair site, i.e. dentin,
which in turn is a composite, made primarily
of collagen and microscopic inorganic crystals
of an apatite of calcium and phosphate. In gen-
eral, the primary tissue of the teeth such as
dentin is denoted as mineralized tissue where
the primary function is load-bearing. A closely
related tissue to dentin, both positionally and
functionally is bone, which is a complex min-
eralized collagen. The composition and
orientation of the bone components as load-
bearing composites vary in different bones.
Thus, in designing synthetic devices for repair-
ing bone, one has to take into account the
properties of the hard tissue in question. These
include strength, creep stiffness, and fatigue
characteristics. For example, for anchoring a
metallic hip prosthesis a high modulus
crosslinked, filled methacylate 'grouting' or
bone cement is usually sought. For cementless
hip prostheses, carbon-fiber reinforced high
performance thermoplastic polymers, such as
poly(ether-ether ketone), PEEK, or aromatic
poly sulfones (PS) are being explored.
Cartilage is a low-load bearing, natural
composite and its synthetic substitutes can be
made of reinforced elastomers. Elastomeric
tissues such as skin and blood vessels are
made primarily of collagen and other biopoly-
mers which impart compliance and elasticity.
Synthetic substitutes of these tissues are far
from being perfected. However, a key consid-
eration is the use of an elastomeric polymer or
design to provide inherent or engineering
elasticity, respectively.
Bioceramics and particularly hydroxyap-
atite (HA) have been used or proposed for use
in many orthopedic and dental applications
(Heimke, 1989, 1990). However, the mechani-
cal properties of HA were not sufficient for
demanding load bearing applications, such as
fracture fixation or spinal fusion, and this led
to its limited use in this area (Bostman et al.,
1989). To address this issue, Knowles and
Bonfield (1993) developed a glass-reinforced
HA with enhanced mechanical properties.
Utilizing glasses of the types xNa,O-(l-x)
P,O, and xCaO-(l-x) P,O, (where x = 0.2, 0.3
and 0.5), a systematic study was conducted on
the effect of increasing network-modifying
oxides in the glasses on the mechanical prop-
erties of composites containing 2.5 and 5 wt Yo
filler. The results indicate that HA reinforced
with CaO-P,O, glass at about 2.5 wt Yo is of
significant benefit to both the stabilization of
HA and production of high flexural bend
strength composites. This is illustrated in Fig.
44.1. for three types of CaO-P,O, glasses
where that mole ratio CaO/P,O, was 20/80,
30/70 and 50/50 for composites designated as
C,P, C,P and C,P, respectively.
 Orthopedic implant applications 959

160 nents for joint arthroplasty. Each of these

applications has a unique set of material and
140
-x-
. 2.5YOC3P
2.5YG5P mechanical requirements which are addressed
120

-
P
a
100
in this section.
FRP composite materials can be consid-
z 80
u)
ered to be composed of at least three, and
ftl 60 possibly four, distinct components: the fiber
which reinforces the matrix; the polymer
40
matrix which provides three-dimensional
20 support to the fiber; and the fiber/matrix
o i interface which serves as the agent of load
1150 1203 1250 1303 1350 1403 transfer between the fiber and polymer
Flrlng Temperature (C) matrix. In certain formulations, a fourth com-
ponent, the fiber/ matrix interphase, must
Fig. 44.1 Effect of glass composition on flexural
bend strength for three different glasses at 2.5% also be considered. The interphase represents
wt YO additions (from Knowles and Bonefield, the volume of matrix immediately adjacent to
1993). each fiber which is influenced by the fiber,
causing the matrix in this area to have mor-
phological differences (i.e. crystallinity)
44.3 ORTHOPEDIC IMPLANT APPLICATIONS
and/or compositional differences (i.e. mix-
The incentive for use of fiber reinforced poly- ture of matrix and sizing agent from fiber)
mer (FRP) composite materials in most compared to the bulk matrix material. The
nonmedical applications is provided by their site-specific biologic environment can poten-
superior specific mechanical properties (i.e. tially influence each of these components of
strength/weight, stiffness/weight ratios). the composite differently. Fortunately, experi-
However, this offers very little benefit for ence has shown that the in vivo environment
orthopedic implant applications. Implants are can often be suitably represented by simple
typically sufficiently small such that weight is physiologic saline solutions at 37°C (99°F)
not an important design requirement. and pH = 7.4 for in vitro biomaterials perfor-
However, there are other very important med- mance investigations. However, it must be
ically related incentives for the development recognized that exceptions to this are not
of these materials for the treatment of muscu- uncommon, and site-specific in vivo testing is
loskeletal problems. essential prior to clinical evaluation of new
While there are numerous potential ortho- composite material formulations; not only for
pedic applications for FPR composite implant biocompatibility assessment, but also to
materials, most work has been concentrated in ensure materials response to the biologic
four specific areas. FRP composite materials environment has been properly understood.
are being investigated for the design of FRP composites are uniquely different com-
femoral components for total hip arthroplasty pared to metals in that they are permeable to
and for pins, plates, screws, and nails for frac- moisture and salt ions. Therefore, if environ-
ture fixation as alternatives to metal alloys. mental durability is to be properly
Fiber reinforcement is also being investigated investigated, test samples ideally should be
as a means of improving the fatigue resistance fully saturated in their test environment prior
of polymethylmethacrylate (PMMA) bone to testing. The American Society for Testing
cement and the wear, creep, and fatigue resis- and Materials (ASTM) F04 Subcommittee on
tance of ultrahigh molecular weight Composite Materials is currently developing
polyethylene (UHMWPE)articulation compo- standards for environmental conditioning
960 Composite biomaterials
prior to materials performance evaluations to
address this issue.
The biologic response to an implant mater-
ial is as important as the material response to
the environment. Biologic response to an
implant material has been found to be strongly
dependent upon whether the material in ques-
tion can be internalized (phagocytosed)by the
cells of the body which regulate the body’s for-
eign body response. Thus, a material which is
very well tolerated in bulk form when
implanted in the body (i.e. too large to be
ingested by cells) may elicit a strong inflam-
matory response when in particulate form if
the material particles are sufficiently small (i.e.
< 10 mm (0.4 in)) to be phagocytosed by cells
which mediate inflammatory response
(Goldring, Clark and Wright, 1993; Black,
1992). Thus, in the development of composite
biomaterials, it is important to not only assess
the biocompatibility of the device in question,
but to also assess biologic response to wear
debris and degradation products of the fiber
and polymer matrix materials.
44.3.1 FEMORAL COMPONENTS FOR TOTAL
HIP ARTHROPLASTY
Femoral components are permanent implants
ideally intended to last the entire life time of
the patient. Current day metallic devices for
this application have reported life expectan-
cies of 90% survival out to 10-15 years in the
elderly patient population, lower survival
rates in younger patients (Callaghan, 1990).
While this is considered good performance for
an orthopaedic implant, certainly 90% sur-
vival at 30 years would be much preferred.
Metallic components have the draw-back of
being so stiff that much of the applied joint
load is bypassed around the normally highly
stressed proximal-medial region of the femur
(calcar). This condition has been documented
to lead to stress-shielding induced bone
resorption (Sumner et al., 1992). In severe
cases, this may not only contribute to compo-
nent failure through loosening, but may also
severely complicate revision surgery (Engh
and Bobyn, 1988).
Several theoretical and experimental
investigations have indicated that more com-
pliant femoral components result in higher
stress levels in the calcar area of the femur,
thereby reducing stress shielding and main-
taining greater levels of bone stock mass and
quality (Bobyn et aI., 1992; Huiskes, 1992).
While this is true, a widely reported miscon-
ception concerning this point is that an
optimal condition would be reached if a
femoral component could be designed to
match the longitudinal elastic modulus or
stiffness of cortical bone. This idea is com-
pletely erroneous and represents a failure to
understand the mechanics of femoral compo-
nent/femur load transfer. As long as a
femoral component relies on intramedullary
fixation, non-physiologic load transfer will
occur, leading to some degree of stress shield-
ing in the proximal femur. However, as a
general concept, the degree of stress shield-
ing should decrease proportionately to stem
bending compliance.
Three mechanical factors must be consid-
ered for the successful design of FRP
composite femoral components. These are: (1)
increased stem compliance to reduce calcar
stress shielding; (2) fixation to bone and main-
tenance of acceptably low stem/bone
interfacial stresses to prevent loosening; and
(3) maintenance of acceptable stress levels
within the femoral component to prevent
fatigue failure. These factors are not indepen-
dent; both interfacial stress level and
component fatigue strength will be influenced
by implant compliance. An optimal design
may exist which can satisfy all three mechani-
cal requirements and provide a superior hip
joint replacement over current day metallic
devices. Because of low bending stiffness, FRP
composite stems cannot be properly evaluated
by test methods developed for stiff metallic
stems. The ASTM is currently developing a
standard practice for fatigue testing of compli-
ant FRP composite stems.

Two FRP material systems are primarily
being considered for femoral component
development: carbon fiber-reinforced polysul-
fone (CF/PSF), and carbon fiber-reinforced
polyether etherketones (CF/PEEK) (Davidson,
1987; Skinner, 1988). Several studies have
addressed the effect of the biologic environ-
ment upon the mechanical material properties
of these two composite materials with mixed
results. CF/PEEK has been demonstrated to be
very durable in physiologic saline environ-
ments when PEEK was APC2 grade (ICI,
Tempe, AZ) (Strait et al., 1991; D’Ariano et al.,
1994;Zhang et al., 1994),while 380 grade PEEK
(IC1 Films Inc., Wilmington, DE) has been
found to be sensitive to hydrolytic degradation
of the fiber/matrix interface (Meyer and
Latour, 1993). CF/PSF strength has been
reported in separate studies to be both very
stable (Overland et al., 1993) and significantly
degraded by exposure to physiologic saline
and exudate environments (Strait et al., 1991;
Latour and Black, 1992,1993).Biocompatibility
studies of both CF/PSF and CF/PEEK com-
posite materials have suggested that, in bulk
form, these materials should provide accept-
able biocompatibility for use in femoral
component applications (Wen et al., 1990).
However, the generation of wear debris from
implant/bone abrasion, and subsequent
potential inflammatory reactions, is an impor-
tant concern.
44.3.2 FRACTURE FIXATION DEVICES
FRP composite material devices are being
developed for the replacement of metallic
plates, screws, pins, and nails for fracture fixa-
tion. In contrast to joint replacement, these
applications require only temporary implants.
The ideal fracture fixation device would be
sufficiently rigid initially to provide adequate
fracture stabilization, then gradually decrease
in stiffness over time to transfer stress to bone
after fracture union to avoid stress shielding,
and then eventually disappear to eliminate the
need for retrieval surgery.
Orthopedic implant applications 961
Two classes of FRP composite fracture fixa-
tion devices have been primarily considered:
nonabsorbable and fully absorbable. Compliant
nonabsorbable plates and nails have been
investigated as a means of avoiding stress
shielding associated with the use of stiff metal-
lic components (Woo et al., 1976).
Unfortunately, clinical results have indicated
that, in high load bearing applications such as
the tibia, compliant fracture fixation plates
allow excessive motion at the fracture site caus-
ing unacceptable levels of pain upon weight
bearing (Tayton et al., 1982; Tayton and Bradley
1983). This presents a ’Catch-22’ situation in
which compliant bone plates may only be able
to be utilized in very low load bearing applica-
tions, however, without high load bearing,
stress shielding is not a serious concern and
compliant plates are then no longer needed.
Whde the advantages of nonabsorbable com-
posite fracture fixation devices are therefore
questionable, fully absorbable composite frac-
ture fixation devices offer significant potential
advantages over currently used metallic
devices. These materials have the potential to
be developed into components with sufficient
initial stiffness and strength for load bearing
fixation, which are then slowly degraded and
absorbed by the body following healing such
that implant retrieval is unnecessary.
Two types of fully bioabsorbable compos-
ites have been investigated: (1) polymer fiber
reinforced polymer, and (2) ceramic reinforced
polymer. Bioabsorbable polymeric materials
for both fiber and/or matrix which have been
widely investigated are polyglycolic acid
(PGA), polylactic acid (PLA), polydioxanone
(PDS) (Tormala et al., 1991; Bostman et al.,
1991), poly-e-caprolactone (PCL) (in’t Veld,
1993), and polyhydroxybutyrate (PHB)
(Knowles et al., 1992). More recently, bioab-
sorbable polycarbonates and ’pseudo’-
polyamino acids have also been developed as
well (Pulapura and Kohn, 1992). Types of
ceramic fibers which have been investigated
are phosphate glasses and calcium phosphate
based ceramics (Andriano, Daniels and Heller,
962 Composite biomaterials

1992). Implant designs have utilized both con- devices typically occurs by loosening via com-
tinuous and discontinuous fiber reinforcement bined fatigue fracture of the cement and the
of the polymer. bone/cement or cement/implant interfaces.
The main obstacle to widespread applica- Fiber reinforcement is a potential means of
tion in these materials is their rapid loss of improving the fatigue strength of bone
strength and stiffness in vivo. This currently cement. Several investigations have
restricts their use to only low load bearing addressed this issue with the use of short
applications. This behavior has primarily been fiber reinforcements of carbon (Pilliar et al.,
attributed to rapid hydrolysis of the 1976), polyaramid (Wright and Trent, 1979),
fiber/matrix interface (Andriano, Daniels and ultrahigh molecular weight polyethylene
Heller, 1992). The development of more (Wagner and Cohn, 1989), titanium
durable fiber/matrix interfacial bonding in (Topoleski et al., 1992)) stainless steel
absorbable composites is essential if these (Fishbane and Pond, 1977), and PMMA
materials are to be successfully developed for (Buckley, 1991), to name a few. In general,
load bearing applications. these studies have demonstrated the
The biocompatibility of bioabsorbable poly- expected result that short fiber reinforcement
mers and fibers being developed for can increase both strength and toughness of
orthopaedic applications is considered to be bone cement. Problems with fiber wetting,
good, however, clinical use of self-reinforced fiber distribution, void content, and increased
PGA pins has demonstrated an 8% rate of viscosity are cited as the major problems
aseptic sinus tract development in patients which have prevented clinical implementa-
(Hofmann, 1992). While not compromising tion. Bulk bone cement is actually a
fracture union, this may require surgical inter- self-reinforced particulate filled composite
vention. Experience suggests this may occur material. The composite formulation with
when implant degradation product generation greatest potential may therefore be the
exceeds the local tissue clearance capability. replacement of the PMMA microspheres with
The balance between degradation product similar quantities of PMMA fibers. This may
release and tissue clearance ability raises a enable mechanical properties to be improved
concern for the development of larger while not causing significant increases in
implants of these materials. This problem may cement viscosity during cure.
potentially be overcome with the development
of more slowly degrading implants.
44.3.4 ARTICULATION COMPONENTS
Ultrahigh molecular weight polyethylene
44.3.3 BONE CEMENT
(UHMWPE) is extensively utilized in total
Polymethylmethacrylate (PMMA) is utilized joint replacement prostheses to provide a low
extensively in orthopedic surgery as a friction surface for articulation against a
method of prosthesis fixation in joint replace- matched metallic or ceramic component. Wear,
ment. Bone cement is prepared in the creep, and fatigue resistance are the major
operating room by the surgical team by mix- problems associated with the use of plain
ing methylmethacrylate monomer with UHMWPE in these application, especially for
polymethylmethacrylate microbeads. The knee joint prostheses (Connelly et al., 1984).
mixture is first allowed to partially polymer- Fiber reinforcement offers a mechanism of
ize, and then is placed in a prepared surgical potentially improving these properties.
site within a bone cavity. PMMA is a brittle Reinforcement with carbon fibers was ini-
polymer and can be considered the weak link tially considered for this application, and even
in joint replacement. The failure of cemented utilized clinically for both knee joint and hip

joint replacement (Wright et al., 1988). This,
however, proved to be a very poor choice of
reinforcement. Wear resistance studies with
this material provided mixed reports ranging
from significantly decreased to significantly
increased wear rates (McKellop et al., 1981),
while fatigue resistance was found to be actu-
ally decreased by an order of magnitude
compared to the unreinforced UHMWPE
(Connelly et al., 1984). This behavior can be
explained by the very brittle nature of carbon
fiber and the very low interfacial bond
strength between the fiber and matrix (Meyer
and Latour, 1991). This combination leads to
rapid crack initiation and propagation and
third body wear during articulation via fiber
fragment release. This incident in the history
of implant design provides a clear example of
the complexities of composite materials
behavior, and demonstrates the fact that fiber
reinforcement of a polymer does not necessar-
ily improve mechanical performance.
Although carbon fiber was not a good
choice for the reinforcement of UHMWPE, as
the old saying goes, ‘the baby should not be
thrown out with the bath water’. Potential
improvement of wear, creep, and fatigue resis-
tance of UHMWPE may still be achieved using
other types of reinforcement. In particular, a
reinforcement is required which has properties
of high strength, high strain to failure, high
bond strength to UHMWPE, high wear resis-
tance, and which is as biocompatible as
UHMWPE in both bulk and particulate form.
While UHMWPE is the most commonly
used polymer for articulation, other composite
systems have been investigated such as carbon
fiber reinforced triacine resin and polymer
fiber reinforced elastomeric composites
(Harms, 1984; Sutphin et al., 1993). Despite the
failure of CF/UHMWPE articulation compo-
nents, the reinforcement of polymeric
articulation surfaces is still an active area of
research for the development of improved
prostheses.
Composites for soft tissues 963
44.4 COMPOSITES FOR SOFT TISSUES
Composite biomaterials have been mostly
associated with their use in conjunction with
hard tissues. However, composites for repair-
ing or replacing soft tissues can potentially
become quite important due to the growing
interest in vascular and skin grafts, as well as
bioartifical organs. Simple devices such as
sutures for soft tissue repair have been
patented in composite forms. For instance,
composite silk sutures with compliant copoly-
ester matrix have been described as having
lower tissue reactivity, and higher strength
retention in the biologic environment as com-
pared with wax-coated silk sutures (Shalaby,
Stephenson and Schaap, 1984). Composite,
woven vascular prosthesis with absorbable
[10/90 poly(^-lactide-coglycolide)] and non-
absorbable (polyethylene terephthalate)
segments, were made and used as model sys-
tems for studying the derivation of neointima
in vascular grafts (Greisler et al., 1988).
Composite artificial blood vessels were pre-
pared by injecting water-soluble chitosan
derivatives (e.g. hydroxypropylchitosan) and
heparin into a microporous polytetrafluo-
roethylene tube followed by freeze-drying
(Yamamura et al., 1992).What may be consid-
ered as a bioartificial vascular graft is the one
prepared by endothelial cell seeding of a
woven synthetic graft using filtration tech-
nique (Idezuki, 1993). Thus, canine venous
endothelial cells which were seeded onto a
low porosity vascular prosthesis were
allowed to grow around the fibers in early
periods. They then formed a monolayer on
the internal surface of the tube at later periods
in vitro. Properties of polyester fiber blends
were evaluated as totally (Greisler, et al.,
1988a) or partially (Yu and Chu, 1993)
absorbable vascular grafts.
Melt-blended absorbable polymers made of
lactide and glycolide having the proper chem-
ical composition to provide controlled
miscibility in the liquid state were molded into
components of surgical staples having the
964 Composite biomaterials

desired in vivo strength retention profile Casper, R.A., Kelley, B.S., Dunn, R.L., Potter, A.G.
(Smith et al., 1988;Jamiolkowski et al., 1989).In and Ellis, D.N. 1985. Fiber-reinforced
the solid state the molded articles exhibited a absorbable composites for orthopedic surgery.
Polymer Mater. Sci. Eng. 53: 497-501.
two-phase morphology. The texture of the dis- Connelly, G.M., Rimnac, C.M., Wright, T.M.,
persed phase m a y allow one to denote these Hertszberg, R.W. and Manson, J.A. 1984.
systems a s microcomposites. Fatigue crack propagation behavior of ultrahigh
molecular weight polyethylene. J. Orthop. Res. 2:
119-125.
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Shalaby, S.W. and Newman Jr., H.D. 1988. Higk
Glycolide Blends for Absorbable Staples. US Patent
(to Ethicon Inc.) 4 741 337.
Strait L.H., Jamison R.D., and Gavens, A. 1991.
Effect of environment on the flexural and com-
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carbon/polyetheretherketone composites.
Trans. SOC.Biomater., 14: 286.
Sumner, D.R., Turner, T.M., Urban, R.M. and
Galante, J.O. 1992. Experimental studies of bone
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Sutphin, C.M., LaBerge, M., Drews, M.J., Lickfield,
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SCIENTIFIC APPLICATIONS OF COMPOSITES 45
Vicki P. McConnell
45.1 INTRODUCTION
Science may be seen as a journey, encompass-
ing both inner and outer space on the quest for
greater understanding of the universe. This
can take literal form, such as the journey
toward ever farther, faster flight regimes of
experimental aircraft like the X-30, or here on
Earth aboard a high-speed train that levitates
on magnetic rails. Or the journey can take the-
oretical form in scientific instruments that
measure the smallest particles of matter on
Earth and peer into the black holes‘ of space.
From the human eye to ’eye in the sky’ space
telescopes, science continually extends our
vision of the universe.
Science and composites have always inter-
sected in the R&D laboratory with new
materials and process discoveries, and in the
fabrication of actual structures used in scien-
tific applications. The material selected for the
Hubble Space Telescope metering truss, for
example, and the process used to build the
components of that structure are directly
related to its ability to accomplish a unique sci-
entific mission.
As one might expect, pure science is rarely
accomplished in a vacuum; helpful data are
drawn from commercial, industrial and mili-
tary programs and may return to those venues
if the scientific application involves technol-
ogy transfer. Government and private sector
sources may team up to make the scientific
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
research possible. And while national technol-
ogy agendas are largely determined by the
presiding political administration, there is
nothing temporary or partisan about the expo-
nential growth of global competition.
Government agencies in the USA have
worked over the years to form a long-term
national technology strategy that integrates
materials science. These have included the
National Critical Materials Council (estab-
lished by Congress in 1984), the White House
Office of Science and Technology (which coor-
dinated President Bush’s National Materials
Initiative and the $1.8 billion Advanced
Materials and Processing Program), the
National Center for Advanced Technologies
(NCAT) formed in 1989 by the Aerospace
Industries Association, the Department of
Commerce’s Advanced Technology Program
administered by the National Institute of
Standards and Technology (NIST), and the
Defense Advanced Research Projects Agency
(DARPA) within the Department of Defense.
Grants totalling nearly $500 million were
awarded under President Clinton’s
Technology Reinvestment Project (TRP) in this
program’s first year, 1993. TRP channels
defense department funds to projects that
emphasize dual-use technology for both com-
mercial and military applications, with the
ultimate goal of enhancing cost and informa-
tion sharing and ensuring that key USA
industries stay on the technological leading
edge (Lynch, 1993). The variety of composite-
related TRP projects have ranged from rapid
densification of carbon-carbon components,
968 Scientific applications of composites
infusion-molded infrastructure products,
marine craft and dockside structure develop-
ment to electric vehicle body and propulsion
systems.
45.2 APPLICATIONS
For the scientific applications described in
this chapter, carbon fiber-reinforced ther-
mosets and thermoplastics offer a superior
strength-to-weight ratio over metal and other
materials, as well as extremely close fabrica-
tion tolerances, complex contours and load
tailorability, part consolidation through inte-
gral design, and resistance to multiple
degradation factors. In some cases, parts and
structure simply could not be made to meet
performance parameters without the use of
advanced composite materials.
45.2.1 SCIENCE-MISSIONSPACECRAFT
For composites, the hard vacuum of space pre-
sents a rigorous environment which may
include atomic radiation, thermal cycling, UV
ionizing radiation and micrometeroid impacts.
In answering the challenges of these synergis-
tic effects on spacecraft, advanced composites
provide crucial payload weight savings, near-
zero CTE, and good dimensional stability
when material formulation or design takes
hygroscopy and outgassing into effect.
Composites are commonly used in optical
benches, precision mounts (including struc-
tural trusses), solar arrays and booms (Lubin
and Dastin, 1982).
Spacecraft truss structure
Carbon fiber/epoxy tubes joined into truss
structures are commonly used for supporting
instruments on science spacecraft, such as the
propulsion subsystems and upper-stage
assembly for the radar-mapping Venus probe
Magellan. Some 60 tubes in the truss range in
diameter from 25-100 mm ( 1 4 in) and in
length from 180-1830 mm (7 in-6 ft). They
were designed for compression load capabili-
ties from 860-6000 kg (1900-13 230 lb). The
same thermoset prepreg used for Magellan
parts worked well in the science and
radioisotrope thermal-generator booms and
low-gain antenna struts and mast on the
Galileo Jupiter observer.
Originally envisioned as one of four 'great
observatories' in the sky, NASA's Hubble
Space Telescope (HST)took its place in 1990 as
the largest optical system in orbit - the size of
a railroad boxcar weighing 11 567 kg (25 500
lb) (McConnell, 1989). Capable of studying
wave lengths from far UV to far IR, the focal
length of this 'eye in the sky' is 607 mm (189
ft). Pointing accuracy and stability are critical
- the telescope may hold direction for as long
as 24 h at a time depending on the object of
focus (Fig. 45.1).
Supporting the secondary mirror in precise
alignment with the primary mirror is a carbon
fiber /epoxy metering truss, engineered to
maintain stability of the nominal 5080 mm
(200 in) spacing between the mirrors within
+15 x lo4 mm ( 6 0 microinches) in the pres-
ence of A1"C (e0"F) excursions at mean
temperature of -73°C (-100°F). The truss was
fabricated by Boeing Defense & Space Group
(Huntsville, AL), along with a carbon
fiber/epoxy focal-plane structure that sup-
ports five primary science instruments and
three fine-guidance sensors.
Additional composite HST parts include a
support-systems module equipment shelf that
holds three positioning gyros, and the fine-
guidance keel. Discrete internal ribs direct load
paths out the main core members and prevent
curvature in these parts. Shelf and keel were
designed by Perkin-Elmer (Danbury, CT) and
fabricated at Composite Optics Inc. (San Diego,
CA). COI has developed a proprietary mois-
ture-barrier plating technology to seal epoxies
from the effects of moisture prior to launch.
Both COI and Jet Propulsion Laboratory
(Pasadena, CA) have built spacecraft test arti-
cles using a carbon fiber/cyanate ester
(McConnell, 1992b) composite that shows less

Fig. 45.1 Composite structural truss (a) aboard Hubble Space Telescope (b)aligns primary and secondary
mirrors. (Sources:NASA, Perkin Elmer.)
moisture absorption than epoxies and greater
toughness than either epoxies or BMIs. Lastly,
HST’s high-resolution spectrograph optical
bench was manufactured by Hercules
Aerospace Co. (Magna, UT) to specifications
from Ball Aerospace Systems Group (Boulder,
CO). Carbon fiber/epoxy offers CTE equal to
quartz and maintains 2 m (6.5 ft) of optical sur-
faces to within 0.0254 mm (0.001 in).
Launched in December 1995, the Solar and
Heliospheric Observatory (SOHO) was
designed to be pointed directly at the Sun to
study the interactions between the Sun and
Earth’s environment. The largest moving
instrument aboard SOHO is the Ultraviolet
Applications 969
Coronograph Spectrometer (UVCS), designed
as an occulted telescope to focus on solar
winds (McConnell, 1993~).As with HST, opti-
cal mechanisms require accurate and
repeatable positioning, so UVCS’s design cen-
tralized upon a three-segment carbon
fiber/epoxy structure. Ball Aerospace Systems
Group and COI built the seven-sided truss of
flat panels that result in cylindrical shape.
Some 80 separate stability requirements had to
be met, along with strict mass requirements
(the structure weighs 21.7 kg (48 lb) but sup-
ports 91.6 kg (202 lb) of instrumentation), and
the ability to survive launch loads of 18G.
High-modulus pitch-based carbon fiber /epoxy
970 Scientific applications of composites
prepreg met weight, mass and optical stabil-
ity parameters with no outgassing or
microcracking. Especially thin prepreg
(0.063 mm (0.0025 in) cured ply thickness)
also enhanced the thermal conductivity of the
fiber, an added stability factor (Kilpatrick,
1992).
AXAF orbiting observatory
Slated for launch from the Space Shuttle in
August 1998, the Advanced X-Ray
Astrophysics Facility spacecraft will bridge
the gap between the two Great Observatories
currently in orbit: Hubble Space Telescope and
Compton Gamma Ray Observatory.
TRW (Redondo Beach, CA) is prime con-
tractor for AXAF and the spacecraft will
contain four sets of unique cylindrical, grazing
incidence mirrors. These are mounted concen-
trically in a nested array. Carbon fiber/epoxy
is used in equipment compartments attached
to the central cylinder, large curved and coni-
cal shell structure, mirror support sleeves, and
solar array panels. Eastman Kodak built the
2643 long optical bench that forms the main
structural element, with carbon fiber skins
over honeycomb core.
LDEF composite specimen testbed
Proof positive of the hostile effects of space
startled cosmonauts on the Mir space station
in 1992 when they found not a shred
remained of the Soviet flag after a year in
orbit on the station's exterior. Further proof
comes in data retrieved from NASA's Long
Duration Exposure Facility (or LDEF), a 12-
sided circular spacecraft launched into low
Earth orbit (LEO) from the Challenger shuttle
in April 1984 and retrieved in 1990 (Fig. 45.2).
By 1993, postflight analysis of the 86 experi-
ment trays containing more than 10 000
different material specimens has been carried
Fig. 45.2 End panel of LDEF
spacecraft shows effects of space
exposure on materials speci-
mens. (Source:NASA.)

out by a team of international scientists.
Research on LDEF's composites specimens
has provided a benchmark for next-genera-
tion space materials, such as those that make
their way onto the international space station
(Stein, 1993).
The six-year duration of LDEF's exposure
to the LEO space environment provided the
longest term flight data ever retrieved for
analysis at that time. Post-retrieval sympo-
siums have shared analytical conclusions,
and NASA selected M/Vision software from
PDA Engineering (Costa Mesa, CA) as one
format for the sizeable LDEF Materials
Database which contained research informa-
tion on about 35% of the LDEF materials by
the end of 1994.
An important conclusion drawn from LDEF
specimen analysis is that environmental
effects are dependent upon the location of
composite hardware on a spacecraft - leading
or trailing edge, shielded or unshielded from
degradation factors (only metal matrix com-
posites with aluminum matrices showed no
location-dependent degradation; magnesium-
matrix composites oxidized on sample edges)
Fig. 45.3 LDEF orientation in orbit. (Reprinted with permission of Bland A. Stein, NASA Langley Research
Center.)
Applications 971
(Fig. 45.3). Atomic oxygen is identified as the
most detrimental factor to polymer-matrix
composites, especially on uncoated surfaces
(George, 1992). Erosion has been observed to
0.127 mm (0.005in) (about one ply of laminate)
on leading edge components made from car-
bon fiber with epoxy, polyimide and
polysulfone matrices.
Micrometeroid damage was not cata-
strophic on any LDEF specimens, but can
compromise surfaces and lead to substrate
erosion (Blair, 1992) (Fig. 45.4).Another con-
clusion drawn based on post-flight analysis
was that predicting erosion rates and formu-
lating material with enhanced A 0 resistance
should key on fiber resistance as the dominant
factor. A prediction model for A 0 erosion
yield in polymer materials has been developed
(Tennyson, 1993), based on the repeatable
atomic composition of the polymer.
An LDEF follow-on spacecraft, the
European Retrievable Carrier (EURECA) was
retrieved by the shuttle Endeavor in June, 1993
after 11 months in a 370 km (230 mile) orbit.
EURECA's mission focused on materials and
fluids in low microgravity and LEO exposure
972 Scientific applications of composites

45.2.2 THE X-30 NATIONAL AEROSPACE

PLANE (NASP)
This NASA/ Air Force single-stage-to-orbit
technology demonstrator program begun in
1986 generated significant advanced research
into aerothermodynamics, propulsion, and
new enabling materials (Fig. 45.5). These
accomplishments were due in great part to
unprecedented teaming among competitive
aerospace companies contracted for the pro-
ject. NASP was designed as a piloted vehicle
capable of horizontal takeoff and landing on
conventional runways (with an airbreathing,
hydrogen slush-fueled engine), hypersonic
cruise (speed range to Mach 25), low Earth
orbit, and operation at temperature extremes

Fig. 45.4 Two LDEF composite samples show

micrometeroid damage in center. A 0 erosion
affected only epoxy in E-glass/epoxy sample (a)
but uniformly degraded matrix and fiber in carbon
fiber/epoxy sample (b). (Source: Christopher
Bland, Lockheed Missiles & Space Co.)

on solar array components. Shorter duration

experiments (from 11 to 40 h of exposure)
flown aboard the shuttle Atlantis in July 1992
focused on further analysis of atomic oxygen
effects (particularly flux reaction and erosion
rates) upon nearly 1500 material and coating
samples. These experiments included NASA’s Fig. 45.5 Materials science results in technology
EOIM-3, and payloads sponsored by the transfer from NASP demonstrator vehicle research
University of Alabama and Case-Western (a) to a computer part that speeds up data access
Reserve University (Friebele, 1992). (b). (Source: NASk/Air Forch.)
 Applications 973
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974 Scientifi'c applications of composites
(cryogenic to 2760°C (5000°F)). R&D efforts
resulted in innovative materials science
among five composite categories (Mcconnell,
1990), with more than 2000 airframe and
scramjet propulsion components, structure,
and systems built (Table 45.1).
Until October 1994, NASP represented the
hypersonic flagship program of the USA. At
that time, the initial program goals transitioned
into the hypersonic system technology pro-
gram (HYSTP), funded jointly by the US Air
Force and NASA and which will focus on
development of hypersonic scramjet propul-
sion. Yet resulting scientific R&D from the
NASA program generated considerable tech-
nology transfer to a broad range of commercial
applications, including oilfield pipe, auto
engines and hip joint implants. One of the tita-
nium MMCs developed did not exist before the
NASP program and is 100 times more resistant
to corrosion than standard aircraft titanium.
An aluminum/beryllium alloy tested in NASP
heat exchanger prototypes has since found
application in computer actuator arms, provid-
ing a 20% increase in data access speed. Big
Three automakers have studied NASP-devel-
oped titanium MMCs and alloys to cut weight
by 50% in valves, piston rings, cam shafts, con-
Fig. 45.6 Composite aeroshell
and nose cone enabled DC-X
single-stage-to-orbit prototype
launch vehicle to fly nose-first
takeoff and tail-sitter landing.
(Source: McDonnell Douglas
Aerospace.)
necting rods and other engine parts. Thin-
gauge titanium aluminide foil has been tested
in heart valve assemblies and pacemaker cases.
Adaptation of computational fluid dynamics
(CFD) - the study of high-speed laminar air
flow developed to maximize NASP's body con-
figuration - has proven useful in analyzing
aircraft and automotive aerodynamics, as well
as blood flow in artificial hearts. Dr. Steve
Charles of the Center for Retina Vitreous
Surgery (Memphis, TN) began work with the
Rockwell Science Center (Thousand Oaks, CA)
in February 1992 to apply NASP-developed
CFD to modeling fluid flow inside the eye. CFD
will help analyze the role played by rapid eye
motion (up to 600"/s) in retinal detachment,
and possibly enhance the precision of surgical
procedures. Dr. Charles performs some 15 000
vitreous retinal surgeries annually and ulti-
mately expects to use CFD to design a new
suite of surgical tools, 'applying hard science
rather than guesswork to the entire tool set'.
45.2.3 DELTA CLIPPER EXPEFUMENTAL
LAUNCH VEHICLE (DC-X SSTO)
Under a $60 million contract from the Ballistic
Missile Defense Organization, McDonnell

Douglas Aerospace (Huntington Beach, CA)
developed its Delta Clipper experimental pro-
totype (DC-X) to prove the practicality,
reliability, operatability and cost efficiency of a
reusable single-stage-to-orbit (SSTO) flight
vehicle. Comparative figures suggest that
reusable rockets like a full-scale DC-X could
reduce commercial/military payload delivery
costs to under $500/lb - an attractive alterna-
tive to the $10 OOO/lb for the Space Shuttle
(1993 figures).
The one-third scale DC-X prototype had
completed five suborbital flight tests before
being grounded by an on-board explosion that
damaged the composite aeroshell. Despite this
accident, DC-X landed safely and the shell
was repairable. Data collected in the first flight
test series formed the advanced technology
backbone for an upgraded DC-XA vehicle,
developed jointly by McDonnell Douglas
(now the Boeing Co.) and NASA (with some
$43 million in NASA funding) in 1995. The
DCX-A was renamed the Clipper Graham in
1996, and completed several milestone flights
that year: altitude of 10 300 ft with 550 ft lat-
eral movement, and a second flight 26 hours
after the first to demonstrate rapid turn-
around.
Rapid prototyping played an essential role
in the cost effectiveness of building the DC-X
prototype, including construction of compos-
ite aeroshell, nose cone, and base heat shield
components (McConnell, 1993~). The aeroshell
and nose cones were fabricated by Scaled
Composites (Mojave, CA); five aerodynamic
composite flaps on the carbon fiber/epoxy
aeroshell provided the ability to ascend nose
first and return to Earth for a 'tail sitter' land-
ing. Composites accommodated the program's
ambitious scheduling with rapid aeroshell
construction (nine months) and by allowing
continuing modifications without huge cost
overruns. Lay-up of woven fabric composite
skins over foam core resulted in aeroshell wall
thickness range of 12.7-38.1 mm (0.5-1.5 in).
Besides enduring external temperatures to
149°C (300°F) and internal temperatures to
Applications 975
-73°C (-100"F), the aeroshell incorporated
built-in longitudinal longerons to handle
engine/truss, parachute deployment and
landing gear loads.
Glass fiber/epoxy was used in the 762 mm
(2.5 ft) tall nose cone since it required signal
transparency for antennae. McDonnell
Douglas decided that carbon fiber/epoxy
skins over syntactic foam in the DC-X base
heat shield provided the best material system
for meeting weight, price, and scheduling
demands. The shield (about 396 mm (13 ft) on
a side) featured a unique 'super circle' sec-
tional design, joined with titanium fasteners.
Both the prime and subcontractor worked to
the philosophy of building real structures to
collect and prove data before moving on to
more expensive program goals, something of a
first in such R&D efforts.
The durability of composite aeroshell mate-
rials and overall system design was proven in
the June 1994 explosion; according to the pro-
gram director, the 1220by 4570 mm (4 by 15 ft)
vertical tear would probably have demolished
other launch vehicles. McDonnell Douglas
developed and fabricated a robust carbon
fiber/epoxy liquid hydrogen tank for DCX-A
in 1996,8 ft in diameter and 16 ft tall, but 33%
lighter than previous aluminium alloy tanks.
45.2.4 GROUND-BASED SCIENTIFIC
INSTRUMENTS
Wind tunnel blade
While CFD places air-flow analysis within the
domain of computer mathematics, there is
nothing quite like proving an aerodynamic
concept in a wind tunnel. At NASA's Ames
Research Center (Moffett Field, CA), different-
sized wind tunnels can accommodate small
models of experimental structures and shapes
as well as full-scale vehicles (such as tractor
trailers and an F/A-18 aircraft). Compressors
generate high-speed air flow with rotating
blades, usually constructed of aluminum or
laminated wood. In the Ames tunnel with a
976 Scientific applications of composites

3352 mm (11ft) test section, composite design sandwich structure of syntactic foam core
and prototyping work supported by Dr. Clem covered with hybrid glass and carbon
Hiel, a former NASA senior design engineer, fiber/epoxy skins laid up at 0/+30/-30 ori-
and his associates has examined the potential entation. Though syntactic foam can typically
of using composite blades in the compressor, be four to eight times higher in weight than
which is capable of speeds to 711 rev/min. traditional foams, mechanical properties are
These blades would offer the advantages of several orders of magnitude higher. This is
improved damage tolerance, longer fatigue due to the energy-absorbing capacity of glass
life, higher damping and improved safety in microspheres inside the foam core, which
the event of catastrophic failure. also localize damage when they are crushed.
Design of a prototype composite blade in In addition, local regions of skin failure are
1995 (Fig. 45.7) (which is 1067 mm (42 in) clearly visible to the unaided eye by an exter-
long, 406 mm (16 in) wide at the root, taper- nal imprint. Carbon fiber skins served as the
ing to 241 mm (9.5 in) at the tip) featured a structural backbone by providing high spe-
cific strength and stiffness, while the foam
core supported skins against impact. Glass
fiber skins acted as sacrificial protective coat-
ing and visual enhancement of impact
damage during residual strength assessment.
Dr. Hiel reports that the prototype composite
blade tested to seven times the expected com-
bination of centrifugal and air loads, and was
clearly capable of carrying higher loads when
the test fixture failed. Manufacturing the
blade through resin transfer molding (RTM)
could result in a blade that would compete
with aluminum in acquisition costs while
reducing weight significantly (Hiel, 1993).

Particle accelerators
To study the exotic mixture of protons, neu-
trons, nuclei and the smallest particles of
matter - quarks - inside the atom, physicists
have turned to complex scientific instruments
that generate enough voltage and acceleration
to create high-energy particle collision.
Analysis of the collisions in this 'quark soup'
could reveal mysteries among the building
blocks of matter.
At Newport News, VA, the Southeastern
University Research Association oversees
operation of the Continuous Electron Beam
Fig. 45.7 Wind tunnel blade made of carbon Accelerator Facility (CEBAF). Here a continu-
fiber/epoxy skins over syntactic foam core (left) ous electron beam with up to 4 billion eV of
weighs 50% less than aluminum counterpart. energy is steered by superconducting magnets
(Source:NASA Ames Research Center.) through up to four orbits of an underground
978 Scientific applications of composites
ground tunnel in Ellis County, TX. The SSC
design was based on a dual ring of 10 000 elec-
tromagnets accelerating needle-thin proton
beams at 20 trillion eV cryogenic temperature
and ultrahigh vacuum. After a decade of work
and investment of $2 billion, however,
Congress cancelled the program. While much
was made in the national press about the
wasted effort (and the huge hole in the
ground), SSC composites research has yielded
unprecedented results that were directly
applicable to other ongoing high-energy
physics applications (such as the Relativistic
Heavy Ion Collider at Brookhaven National
Laboratory in Upton, NY, the Tevatron
Collider at Fermi National Accelerator
Laboratory in Batavia, IL, the Tokomak
Physics Experiment in Princeton, NJ, and the
European International Thermonuclear
Experimental Reactor).
For SSC dipole magnets (each nearly 18 288
mm (60 ft) long and weighing 11 340 kg (12.5
tons)) and smaller quadrupole magnets, com-
Fig. 45.9 Glass fiber/epoxy end saddles were fabricated and tested for Superconducting Supercollider
magnets. (Source:Brookhaven National Laboratory.)
posite prototype support post tubes were fab-
ricated to test various designs to balance
multiple performance parameters with cost
constraints (Sondericker 1991; Nicol 1992,
1993; Hiller, 1991, 1992, 1993). Material and
process systems examined included continu-
ous carbon fiber/epoxy laminates,
injection-molded chopped glass fiber/PEI,
and RTMd glass fiber/bismaleimide.
Machine-woven near-net shape preforms were
also considered, along with RTMd phenolic
triazine (McConnell, 1991a) (Fig.45.9). In other
components, such as coil spacers and end
parts, the predominant prototyping method
was machining glass fiber/epoxy, though
options considered included highly
crosslinked BMI doughs and other polyimide
resins with chopped glass, fabricated by low-
pressure techniques such as structural RTM.
'Magnets were built for SSC that were never
seen before in the world', recounts John
Morena, who served as the primary compos-
ites materials and processes advisor on the
 Applications 979

project. ’There were many “lessons learned” as Under the National Maglev Initiative in
a result of the years of composite materials 1992, four maglev teams developed concept
development and applications,’ he adds. ’This definitions with funding from the Intermodal
initial work has provided the composites com- Surface Transportation Efficiency Act (ISTEA).
munity with the ability to predict the All concepts were geared toward transport
performance of advanced composites and vehicles capable of 482 km/h (300 mph)
other polymer materials in cryogenic and high speeds and incorporated some utilization of
energy physics applications. These original composites. Among team members in the
materials are now used in MRI, superconduct- early ‘90s were aerospace companies Beech
ing magnet energy storage, magnetic Aircraft and Grumman Corp. Drawing on its
levitation systems, fusion, power transmission extensive aerospace design/fabrication exper-
and space applications.’ Others involved in tise, Grumman Corp. - Aerostructures Div.
magnet prototyping were General Dynamics, (Bethpage, NY), began development of a 2/3-
Westinghouse Electric, Babcock & Wilcox, as scale electromagnetic system, based on
well as the Fermi and Brookhaven laboratories superconducting iron core magnets spaced
and the SSC on-site laboratory. Morena notes a50 mm (2 in) from guideway rails. According
particular materials characterization study to Richard Gran, Director of Advanced
conducted as part of Supercollider R&D: sub- Concepts at Grumman, ‘the advantage of this
jecting thermoset and thermoplastic resin design as compared to a repulsive magnet sys-
systems to high proton irradiation at cryogenic
tem is that no secondary suspension system is
temperatures (lo9rads at 4.2K). One intriguingrequired; passenger compartment acceleration
result: undercuring some thermoset compos- is monitored (Shaw, 1993).Though Grumman
ites can increase their longevity in the cold intended to finish construction and testing of
irradiation environment without sacrificing its first magnet by April, 1994, funding issues
performance (Morena, 1994). precluded completion: The company merged
with Northrop Corp. (Los Angeles) and then
with Lockhead Martin by 1997, no maglev
45.2.5 MAGLEV TRANSPORT SYSTEMS OF THE
development existed within the newly framed
FUTURE
business entities.
One potential application of SSC research on Also intent upon prototyping a maglev sys-
superconducting magnets could be magnetic tem is Maglev 2000 of Florida Corp. (Stuart,
levitation (or maglev) of high-speed trains EL.) formed by SSC materials/processes con-
over elevated guideways. Maglev is consid- sultant and co-inventor John Morena with
ered by many to be the transportatiodfreight physicist Dr. John Danby and nuclear engi-
solution of the future. Composites offer a neer/rocket scientist Dr. James Powell. Danby
whole list of attributes in vehicle/guideway and Powell are considered the pioneers of USA
structure and in superconducting coils and maglev technology. Prior to publishing their
electromagnetic shielding: high strength and first papers on magnetic levitation (Powell,
stiffness with low weight, nonconductivity, 1996), Danby reports that concepts of electro-
nonpermeability, corrosion resistance, low dynamic levitation and propulsion had
thermal conductivity and high heat capability surfaced periodically but were not considered
at low temperature. Overall weight savings of practical. Early in his career, he worked on
carbon fiber/epoxy or phenolic vehicle floor building particle accelerators while Powell was
beams and shell structure (sandwich panels of involved in advanced reactors. ’Fixed field
honeycomb core with carbon fiber/epoxy magnets on a moving vehicle can induce cur-
skins) could better aluminum by 15%of body rents underneath or around the vehicle
weight (Cope, 1993). sufficient to levitate it,’ explains Danby. ’This
980 Scientific applications of composites
requires a strong force to keep the vehicle sep-
arated from the guideway in a stable way. We
formulated the geometries to accomplish that
strong stability with efficient inductive,
shorted metal-loop elements on the guideway
and superconducting magnets on the vehicles.’
The highly successful Japanese maglev devel-
opment is based on the ideas of Powell and
Danby (McConnell, 1993a).
In 1990, they came together with Morena to
build a proposed 32-80 km (20-50 mile) route
in Florida with inital design featuring a unique
guideway with 8 inch spacing that dampens
noise and vibration, and completely enclosing
electromagnetic and dynamic fields. It will
demonstrate full speed (300 mph) nonmechan-
ical switching capability. Unique to the Maglev
2000 design is the ability to carry and individ-
ually deliver heavy freight (such as tractor
trailors) to stations on major highways.
Specific utilization of composites will likely
draw upon Morena’s SSC experience with low-
cost fabrication processes such as RTM and
resin film infiltration. Guideway and vehicle
test articles are being built in 1997. The cost of
Phase 1is estimated at $4 million with comple-
tion slated for June 1998; in Phase 11, a full
scale 120 ft long advanced transport freight
and passenger vehicle would be constructed
with composite outer secondary shell.
45.3 CONCLUSIONS
The scientific journey continues, surviving
budget cuts, continual goal assessments, and a
changing global culture. Composites are
intrinsic to reaching any progressive destina-
tion, whether that be in space or moving
people and goods over this planet. Science-
based programs have proven invaluable in Lynch, Ted. 1993. The Technology Reinvestment
generating technology transfer for new prod-
ucts that enhance essential quality of life, such
as medical care. Advanced materials are key McConnell, Vicki P. 1989. Advanced composites
enablers, then, for both public and private
enterprise, and for the ultimate science of
shaping the future.
REFERENCES
Blair, Christopher and Petrie, Brian C. 1992. Low
earth orbit environmental effects on composite
materials: results from LDEF. Intern. SAMPE
Tech. Conf. Proc., October 20-22, Toronto, (24):
T186-T200.
Cope, David B. 1993. Why does maglev need com-
posite materials?Intern. SAMPE Tech. Conf. PYOC.,
October 26-28, Philadelphia, (25): 141-151.
Friebele, Elaine. 1992. The ghost of LDEF-future:
EOIM-3 continues the quest. LDEF Newsletter,
PO Box 10518, Silver Spring, MD 20914. May 15:
19-22.
George, Peter and Dursch, Harry W. 1992. Low
earth orbit effects on organic composite materi-
als flown on LDEF. Paper read at
NASA-sponsored 2nd LDEF Materials work-
shop in October, Huntsville, AL.
Hiel, Clement, Dittman, Dan and Ishai, Ori. 1993.
Designer’s comer: composite sandwich con-
struction with syntactic foam core. Composites
24(5):447450.
Hiller, M.W. et al. 1991. SSC quadrupole magnet
cryostat design alternatives. Adv. Cryogenic
Engineering 37A, New York: Plenum Press, pp.
535-542.
Hiller, M.W. and Waynert, J.A. 1992. A cryogenic
support post for SSC quadrupole magnets. Proc.
IISSC 4, New York Plenum Press, pp. 297-300.
Hiller, M.W. et al. 1993. A low-cost support post for
SSC quadrupole magnets and other cryogenic
applications. Paper read at International
Materials Conference July 12-16, in
Albuquerque, NM.
Kilpatrick, Mark C., Girard, Joseph D. and Dodson,
Kelly J. 1992. Design of a precise and stable
composite telescope structure for the UVCS,
April SPIE conference proceedings, Design of
Optical Instruments, (1690):196-215.
Lubin, George and Dastin, Sam 1982. Aerospace
Applications of Composites. Chap. 28 of
Handbook of Composites, (ed. George Lubin),
New York: Van Nostrand Reinhold, pp.
722-743.
Project - the government and industry as part-
ners. Advanced Composites, July/August: 36-42.
make a case in space. Adv. Comp., Sept/Oct: 34-
45. 1990. National Aerospace Plane: a new
regime in flight. Adv. Comp., Nov/Dec: 3745.
1991a. Superconducting supercollider: design
changes. Composites l n d u s t y Monthly 19, item 3.

1991b. Progress report: composites in space-
craft. Adv. Comp., July/Aug: 26-34.1992a. Flight
vehicles of the future. Adv. Comp., Jan/Feb:
28-34. 1992b. Tough promises from cyanate
esters. Adv. Comp., May/June: 28-37. 1993a.
Composites ride the rails. Adv. Comp.,
March/April: 28-37. 199310. Surviving space: a
program and materials quandary. Higk-
Performance Composites, Nov/Dec: 22-28. 1993c:
Focus on design: telescope structure. Higk-
Performance Composites, Nov/Dec: 54-56.
Morena, John. 1994. Invaluable materials science
from Super Collider. High-Performance
Composites, Jan/ Feb: 12-1 3.
Nicol, Thomas H. 1992. SSC 50mm collider dipole
cryostat single tube support post conceptual
design and analysis. Proc. IISSC 4, New York:
Plenum Press, pp. 747-755..
Nicol, Thomas H. 1993. Single tube support post
thermal analysis and test results. Paper read at
IISSC 5, May 6-8, in San Francisco, CA.
Peterson, Ivars. 1992. Flash tracks-building an eye-
piece for a particle accelerator. Science News 142,
July 4: 8-9.
Powell, James and Danby, Gordon. 1966. High
speed transport by magnetically suspended
References 981
trains. Paper 66-WA/RR-5 read at ASME
Winter Annual Meeting Nov. 27-Dec. 1,in New
York City.
Shaw, P.1993. Overview of maglev vehicle struc-
tural design philosophy, material selection, and
manufacturing approach. Paper read at Maglev
93 conference May 19-21, at Argonne National
Laboratory.
Sondericker, J.H. 1991. Alternate concepts for struc-
turally supporting the cold mass of a
superconducting accelerator magnet. Proc.
IlSSC 3, New York, Plenum Press, pp. 175-189.
Stein, Bland A. 1993. LDEF materials overview.
Second Post-Retrieval Symposium, LDEF-69
Months in Space, NASA Conference Publication
3194, (ed. Arlene S. Levine), Vol. 3, pp. 741-789.
Tennyson, R.C. and Manuelpillai, G. 1993. Analysis
of LDEF micrometeroid/debris data and dam-
age to composite materials. Second
Post-Retrieval Symposium, LDEF-69 Months in
Space, NASA Conference Publication 3194, (ed.
Arlene S. Levine), Vol3, pp. 493-512.
CONSTRUCTION
Ever J. Barber0
46.1 INTRODUCTION
Composite materials are used by the construc-
tion industry to replace or complement
conventional materials such as steel and con-
crete. The main reasons for the use of
composite materials are corrosion resistance,
electromagnetic transparency and weight sav-
ings. Frequently, structural engineers take
advantage of more than one salient feature of
composites to formulate a design that is com-
petitive with an alternate design based on
conventional materials.
Corrosion resistance is the most important
advantage of composites with respect to steel
for construction applications. The selection of
a composite material usually begins with the
selection of a resin that is capable of resisting
the attack of a corrosive substance. The corro-
sive agent can be anything from spring water
to sulfuric acid. Most composite manufactur-
ers provide corrosion resistance guides for
their products. For example, a table listing the
maximum operating temperature of isoph-
thalic polyester and vinylester resins as a
function of the chemical type and concentra-
tion is given by TUFSPAN Technical Data and
Design Guide (1991). Chemical resistance of
common resins used in pultrusion to various
chemical and concentrations as function of
operating temperature is given by Pletcher
(1991). Fibergrate (1992) supplies a Chemical
Resistance Guide for their molded fiberglass
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
46
and pultruded products listing concentration,
operating temperature, and frequency of
exposure for a variety of chemicals. Most fiber
reinforcements are usually corrosion resistant.
Unlike metals, composites do not produce
interference with electromagnetic radiation.
The resin system can be selected to obtain very
low loss factors, but standard resin systems
are adequate for most structural applications.
Buildings for electromagnetic interference
(EMI) testing must be non-magnetic to avoid
attenuation and interference with the phenom-
enon that is being measured. All computer
equipment, for example, must be tested in an
EM1 facility. Imaging equipment such as
nuclear magnetic resonance (NMR) in hospi-
tals must be mounted in a magnetically free
environment. An electromagnetically trans-
parent cover for communications equipment
allows for the use of less-expensive, non-envi-
ronmentally protected electronic hardware
and reduced maintenance costs. Antennae
structures that do not interfere with the signals
being relayed or received by the antennae
increase the efficiency of the system.
While weight saving is the main driving
force behind the application of composites in
aerospace, it is not so critical in construction
projects. However, reduction of structural
weight can be exploited as a secondary advan-
tage to help offset the higher cost of
composites as compared to conventional
materials. Lightweight structures require less
foundation and supporting structure. In the
case of bridges, a noncorrosive bridge deck
can be built to replace existing steel reinforced

concrete decks that corrode rapidly under the
attack from de-icing chemicals. For example, a
pultruded deck was used to construct the
Wick Wire Run vehicular bridge on public
road 26, in Taylor County, West Virginia (com-
pleted August 1996).An added advantage of a
composite deck would be the weight reduc-
tion that supposedly would allow the user
(highway department) to re-rate some bridges
for a higher live load without major modifica-
tions to the existing superstructure. The live
load could be increased by approximately the
same amount of dead load saved with the use
of the composite deck minus adjustments for
dynamic effects. Other applications where
weight savings are important are cladding of
buildings, rehabilitation of chimneys, etc.
46.2 CURRENT APPLICATIONS
Current applications of composites in con-
struction can be classified by the major
advantage of the composite material that is
exploited. The main ones are corrosion resis-
tance and magnetic transparency. An
alternative classification may be based on the
type of construction. Composites are used in
the form of structural shapes (similar to steel
construction), as reinforcement for concrete,
cables, and for rehabilitation of existing struc-
tures. Reinforcement of concrete may be in the
form of conventional reinforcement, pre-
stressed concrete, or post-tensioned structures.
Rehabilitation applications include repairing
deteriorated structures as well as increasing
the load carrying capacity of sound structures
to re-rate them for higher load capacity.
Some of the recent applications of compos-
ites in construction of civil infrastructure will
be described in the next section. Further exam-
ples of applications can be found in previous
reviews (Barbero and GangaRao, 1991,
GangaRao and Barbero, 1991), professional
journals ( e g SAMPE Journal, ASCE Journal)
and edited books (Mufti, Erki and Jaeger,
1991a, 1991b; Iyer, 1991, Neale and Labossiere,
1992).Applications to pipes and tanks in ser-
Current applications 983
vice for more than twenty years atest the excel-
lent corrosion resistance of fiberglass
reinforced composites. The following exam-
ples of fiberglass reinforced isopolyester resin
applications, described extensively in the
excellent review by Adams and Bogner (1993),
illustrate the feasibility of constructing com-
posite structures and using them for many
years. A three mile pipe of diameter 254 mm
(10 in) is reported in service since 1971. Fifteen
miles of piping, carrying saline water with
temperature up to 50°C (112"F),pressure up to
lo6 N/m2 (10 bar), and exposed to sunlight has
been in operation in Saudi Arabia since 1983
without problems. An old sewage duct was
lined in 1971, then inspected in 1991 showing
no sign of deterioration. More than 300 000
underground fuel tanks are in use in North
America alone. Some of these have been in
operation for more than 26 years without
problems. Internal or external lining of steel
tanks has been common practice for more than
twenty years in the oil industry to protect and
reinforce the bottom of steel tanks that are cor-
roded internally because of corrosive
substances in the oil or externally because of
contact with soil. Wine tanks have been in
operation for more than 20 years without
problems. Ducts carrying chlorine gases and
sulphur dioxide, in use since 1962, and tanks
holding hydrochloric acid, in use since 1964,
remain in perfect condition. A chimney
exposed to organic chemicals, water vapor,
and temperature up to 60"C, in operation since
1968 is reported. Chimneys are important con-
struction applications because they are load
carrying structures designed for large wind
loads. A detailed account of recent applica-
tions of composites in construction, classified
by the type of construction, follows.
46.2.1 REINFORCEMENT OF CONCRETE
Concrete can be reinforced with fiber rein-
forced composites, with fibers mixed in the
concrete, or by polymers added to the concrete
mix. This article will concentrate on the use of
984 Construction

fiber reinforced composites, i.e. a combination Rebars

of fiber and polymer matrix, to substitute or
Reinforcing bars (rebars) have been used for
complement the traditional use of steel rein-
reinforcing concrete structures that require
forcing bars (rebars) in concrete. The addition magnetic transparency, such as imaging
of polymer or fibers to cementitious materials, equipment at hospitals (Fig. 46.2). The major
sometimes better classified as a ceramics, bear- expected application is to replace steel rebars
ing limited resemblance to regular, low cost in concrete bridge decks exposed to de-icing
concrete, falls beyond the scope of this article.
chemicals. The first use of composite rebars for
The interested reader may wish to consult a vehicular, public bridge is the McKinleyville
Mufty, Erki, and Jaeger (1991b, Chap. 2). Use Bridge, located in West Virginia, USA.
of fiberglass and carbon fibers mixed directly
Construction was completed August 1, 1996,
into concrete has been reported (Mufty, Erki
by Orders Construction Co., of St. Albans, WV.
and Jaeger, 1991a).Seibu Construction Co. Ltd. The bridge is a 54 m (177 ft) long concrete deck
used carbon fibers, produced by Mitsubishi
over steel stringer accommodating two lanes
Kasei Co., for the exterior walls of the
of vehicular traffic. The reinforcement of the
Kitakyushu Prince Hotel in Japan. Kajima Co.
concrete is exclusively made of composite
also used carbon fiber reinforced concrete pan-
rebars with E-glass fibers. It was designed by
els for the exterior of its head office building in
the West Virginia Department of
Japan. Polymer concrete is used in a variety of Transportation - Division of Highways (pro-
applications, such as in highway parapet walls
ject S305-27/4-0.03) and the Constructed
developed by Morrison Molded Fiber Glass
Facilities Center at West Virginia University.
(Fig. 46.1). The installation of the lightweight
The project was supported by the Federal
polymer concrete panels reduces to anchoring
Highway Administration, composite rebar
the panels to an existing parapet, then pouring
concrete into the panel that act as a stay-in-
place concrete form. Composite reinforcement
of regular, low cost concrete can be done using
rebars, grids, pre-stressing tendons and post-
tensioning cables.
F 1

Fig. 46.2 Fiberglass reinforced composite rebars

Fig. 46.1 Installation of polymer concrete panels as during construction of reinforced concrete struc-
highway parapets. (Courtesy of the Quazite ture. (Courtesyof Reynolds, Schlattner,Chetter, and
Division o~MMFG.) Roll Inc.)
 Current applications 985

manufacturers, and the Corps of Engineers. sion strength and, for most practical pur-
E-glass polyester rods are cost competitiveposes, negligible tensile strength it is
with steel rebars at the present time. These advantageous to pre-stress concrete so that a
rebars have evolved from smooth pultruded state of compressive stress is created before
rods to engineered rebars with improved bond the actual load is applied. (The American
strength to concrete. Further improvements in Concrete Institute recommendation ACI 363 R
bond strength, tensile strength, and durability
suggests a value for the modulus of rupture of
are certain to occur in the near future. concrete f, = 11.7 cfc)1/2which is a very low
E-glass composite tanks have been in ser- value of tensile strength in relation to the
vice for over 20 years, in permanent contact compression strength of concrete, f,.)Then,
with highly acid environments and under con- applied loads only reduce the amount of com-
stant stress. The use of the SPI liner (ASTM pressive stress without producing tensile
D-3299 and D-4097) proved very successful to stresses. In this way, concrete cracks are pre-
protect glass fibers from attack by chemicals in
vented, which in turn reduces moisture intake
storage tanks. Also, composites have been in and degradation. High strength steel tendons
contact with concrete for many years without are currently used for pre-stressing concrete.
deterioration. Investigation of the possible Even though cracks are arrested by the pre-
degradation of fiberglass rebars in concrete is
stress, concrete is porous and water and
under way. The possibility of moisture intake chemicals may reach the prestressing tendons.
of Aramid fibers may be a problem for rebars Composite tendons may replace the steel ten-
expected to be in service for at least 50 years.
dons for added durability. Pre-stressed
Carbon fibers have superior properties but concrete is usually pre-cast at a factory, then
transported to the site. The tendons are pre-
their cost limits their potential as a replace-
ment for construction steel. stressed by a hydraulic jack, the concrete is
Rebars are placed in the form-work to pro- poured and left to cure. After the concrete is
vide for reinforcement of concrete in the sameset, the tendons are cut to remove the chucks
way as fibers are used to reinforce polymers. used to apply the pre-stressing load. Some of
Usually, two perpendicular orientations are the pre-stress is lost because of the compres-
used, with more rebar area in one direction, sion, creep, and shrinkage of concrete. The
higher the elastic modulus of the tendon, the
according to the requirements of the structure.
Placement of rebars requires relatively inex- higher the pre-stress loss. For this reason, low
modulus glass fiber tendons experience less
pensive labor. The grid-like structure necessary
to reinforce concrete can be obtained pre- pre-stress loss than steel or carbon fiber ten-
assembled in the form of grids. Grids are dons. Pre-stress loads are high and induce
rectangular networks of rebars produced with large strains in the tendons, which may accel-
continuous fibers. Although more expensive erate degradation if the tendons are exposed
than rebars, they may be convenient if the to highly alkaline environment (Sen, 1992).
Two important requirements for pre-stress-
labor cost is high or the installation difficult, as
in the case of tunnels. Grids can also be pro-ing applications are a good bond strength
between the tendon and the concrete and
duced at or near the construction site by tying
rebars into a grid. The light weight of the availability of an effective temporary anchor-
age system. The anchor is not very critical
resulting grid makes transportation to the site
and installation simple. because it is temporary. Therefore, it does not
have requirements of non-corrosiveness, cost,
size, etc., but it must be able to transfer the
Prestressing load and sustain it until the concrete sets.
Since concrete has a relatively high compres- Anchorage systems are reported by Noritake
986 Construction
et aZ. (1992), Mochida, Tanaka and Yagi (1992),
Kakihara et al. (1991), etc. for various types of
tendons based on glass, aramid, and carbon
reinforcement. Sen (1992) used the anchorage
developed by Iyer at South Dakota School of
Mines and Technology. Efficient utilization of
composite tendons calls for large pre-stressing
forces to be applied. Permanent levels of stress
in the tendons should be under the stress rup-
ture limit of the composite (see Section 46.3.4).
The pre-stress forces applied to composite ten-
dons may induce cracking of the polymer
matrix. Matrix cracking;may be detrimental to
" d
the fatigue life of the composite. Also, cracking
facilitates the ingress of moisture that may
cause degradation of organic fibers or precipi-
tate alkaline reaction of glass (see Section
46.3.4).
Pre-stressing has been successfully used
by Iyer (1993) in a bridge deck (Fig. 46.3) pre-
cast and pre-stressed, then transported to the
bridge site. The bridge construction was
sponsored by Owens-Corning, AMOCO,
South Dakota Office of Economic
Development and South Dakota Cement
Plant; with the participation of Clark
Engineering, Glenn C. Barber and Associates,
FMG Engineering, Polygon, Shell, Central
Mix, Carlon/Ace Hardware and South
Dakota Concrete Products. A 180 mm (7 in)
concrete deck was post-tensioned with glass
and carbon fiber tendons which were subse-
quently grouted with epoxy based mortar.
The deck is supported by steel girders 2.6 m
(8.5 ft) apart and the bridge spans 9 m (30 ft).
Aramid bars were used in a standard pre-
stress pre-cast concrete factory to build
concrete barges (Noritake et aZ., 1992). At least
10 concrete bridges have been constructed in
Japan with some kind of composite reinforce-
ment (Mufti, Erki and Jaeger, 1991a). The
Shinmiya bridge is a pre-tensioned concrete
bridge built in 1988 in a coastal area. The pre-
cast concrete girders were pre-stressed with
seven strand, carbon composite tendons pro-
duced by Tokyo Rope Manufacturing Co.
Epoxy coated steel rebars were used for the
- -'*----
I
J. I
I
r,_
Fig. 46.3 Post-tensioned concrete-deck bridge over
steel stringers. (Courtesyof Owens Coming.)
stirrups. The Sumimoto Construction Co. built
a demonstration bridge in 1990 in Oyama
using three concrete box girders pre-tensioned
with aramid composite rods, produced by
Teijin Co. Grouted anchorages were used to
pre-stress the rods at a permanent stress of
70% of their static tensile strength. While the
stirrups were also aramid composite rods,
epoxy coated steel rebars were used as shear
connectors between the girders and the rein-
forced concrete deck, which was reinforced
with epoxy coated steel rebars. The deck was
post-tensioned with aramid composite rods
which were then permanently grouted in the
deck. The Birdie bridge was built by Kajima
Co. in 1990 at the Ibaragi Prefecture using a
variety of composite materials. Carbon fiber
composite rods, produced by Mitsubishi
Kasei, were used to anchor the abutments. Pre-
cast concrete panels reinforced with vinylon
short fibers are connected with a grid of car-
bon fiber composite cables produced by Tokyo
Rope Manufacturing Co. The bridge is pre-
stressed with aramid composite flat bars
commercialized by Nippon Aramid Limited.
Half of the aramid bars are used as pre-ten-
sioning tendons and the remaining act as
post-tensioning tendons,with a permanent

stress of one third the static tensile strength.
Post-tensioning
Post-tensioning of concrete with steel or com-
posite tendons is performed to induce a state
of compressive stress in the concrete similarly
to pre-stressing, but post-tensioning is per-
formed at the construction site. A hole or
some kind of access is left in the concrete to
thread the post-tensioning cables through.
Tensile force is applied to the tendons against
the concrete structure before the structure is
loaded by the service loads. The anchorage
system is subject to severe requirements. First,
it must sustain the tension load for the whole
life of the structure, which requires very care-
ful design against creep in the anchor. Second,
the anchor should be resistant to corrosion as
the tendon itself if the non-corrosive proper-
ties of the system are the objective of replacing
steel tendons. The reduced weight of the ten-
dons is not very important because the heavy
weight of the concrete structure. While the
stress losses of fiberglass tendons are smaller
than those of steel cables, it is difficult to jus-
tify the use of more expensive and novel
composite tendons for this reason alone.
Therefore, corrosion resistance is the main
objective of using composite tendons. In this
case the anchorages should be resistant to cor-
rosion. Also, the structure to be post-
tensioned is usually made of reinforced con-
crete (although the reinforcement is not
sufficient to carry all the load). If corrosion is
a problem, the conventional reinforcement
(not pre-stressed or post-tensioned) may also
have to be made of composite material rebars.
Anchors for post-tension applications are
still being developed and evaluated.
Meisseler and Preis (1989) report on an
anchor developed to hold glass reinforced
tendons. The anchor is of the potted type, in
which the tendons comprising a cable are
spread at each end and potted in a steel
anchor with some grouting material, usually
a polymer. The potted type anchors are based
Current applications 987
on the transfer of the axial load in the cable,
by shear in the grouting material, to the
anchor. Attaching the anchor to the tendons is
a labor intensive process. The resin used to
bond the tendons to the anchor may creep,
leading to loss of pre-stress. This anchor was
used to partially post-tension several bridges.
Cases have been reported where individual
tendons slipped and broke at the anchor dur-
ing post-tensioning at the bridge site. Porter
and Barnes (1991) report several anchorage
systems. To avoid the problems that all pot-
ted type anchors have, Ahmed and Plecnik
(1989) developed a filament wound cable
where continuous fibers are wound around
the end eyes of the cable. Each cable must be
custom made for the required length, but the
problems of potted type anchors are elimi-
nated.
The Bachigawa-Minami-Bashi bridge (Koga
et al., 1992) uses both pre-stressing and post-
tensioning carbon fiber tendons. The
Schiessbergstrasse bridge in Germany and the
Notch bridge in Austria (Wolf and Miesseler,
1992), use partial post-tensioning with fiber-
glass cables. Some of the tendons that form a
cable contain sensors (copper wire or fiber
optical gauges) to monitor the strain level,
integrity of the tendon, and location of even-
tual damage. A demonstration bridge was
built in 1990 by the Sumimoto Construction
Co. in Oyama, Japan, using a single concrete
box girder, post-tensioned with aramid com-
posite rods produced by Teijin Co. The
internal tendons are placed in a parabolic
housing in each web and post-tensioned with
steel grouted anchorages to a permanent stress
of 25% of the static tensile strength of the ten-
dons. The external tendons are placed at the
bottom of the box girder and post-tensioned,
with grouted anchorages built with composite
casings for added corrosion protection, to a
permanent stress of 10% of the static strength.
Besides the composite post-tension cables, the
regular reinforcement of the girder uses epoxy
coated rebars. Further details are given by
Mufti, Erki and Jaeger (1991a).
988 Construction
Rehabilitation
There is significant interest in using compos-
ite materials for rehabilitation and upgrading
of existing structures. These structures may
have been damaged as a result of corrosion of
the steel reinforcement or they may need
upgrading to new seismic standards, larger
traffic loads and volume, etc. Interest in com-
posites is motivated by the ease of
installation of the reinforcement, its corrosion
resistance (mainly at the bond surface), and
the possibility of selecting from a variety of
elastic modulii which improves the compati-
bility between the reinforcement and the
existing structure Meier et al. (1992),
Saadatmanesh and Ehsani (1991), and others
have demonstrated the feasibility of rehabili-
tating concrete, steel, and wood structures by
reinforcement with composite plates. Meier et
al. report a variety of failure modes that may
be encountered in concrete beams reinforced
with composite plates. The reinforcement
may be a cured composite plate bonded to
the beam (Munipalle, 1992), or a room-tem-
perature cure prepreg directly applied to the
structure. The reinforced plates can be
applied with or without pre-stressing. While
pre-stressing the composite plate increases
the efficiency of the reinforcement, it also
complicates the rehabilitation process. Since
delamination of the reinforcing element is of
major concern, special reinforcement details
are used at the ends of the reinforcement.
Composite materials can also be bonded to
the sides of beams to improve the shear
strength. While using prepreg materials, both
shear strengthening and resistance to delami-
nations can be obtained by partially or
completely wrapping the beam with the rein-
forcement. Meier et al. (1992) reports on the
rehabilitation of two bridges in Switzerland.
The Ibach bridge was repaired using carbon
fiber reinforced plates bonded to the concrete
bridge. The rehabilitation of the timber
bridge in Sins involved replacement of the
wood pavement with transversely pre-
stressed and glued laminated deck (Davalos
and Salim, 1992). Some of the timber beams
were reinforced with carbon reinforced epoxy
plates. Rostasy, Hankers and Ranish (1992)
report on the reinforcement of the
Kattenbusch bridge (Germany) using steel
and glass reinforced composite plates. The
main reason cited for the selection of com-
posite plates is the documented corrosion of
the steel plates at the bonded interface.
Composite jackets have been proposed to
retrofit columns for seismic solicitations. Scale
samples (40%) were tested (Priestley, Seible
and Fyfe, 1992) and promising results were
found. A fiberglass epoxy jacket is built
around the hinge region of the column. On an
active confinement jacket, hoop stress is
induced by pressure grouting the space
between the concrete column and the compos-
ite jacket with either epoxy or concrete. A
passive confinement is obtained when no
pressure grouting is used. Passive confine-
ment is used in regions of high compression
stress, over the region of lap-spliced longitudi-
nal bars, or for regions of high shear stress.
Significant concrete dilation and consequent
longitudinal microcracking is necessary to
activate the confinement effect in passively
encased concrete. Active confinement has the
advantage that the confinement effect is
always available.
Chimneys have been rehabilitated in Japan
by Mitsubishi Kasei using carbon composite
tape and strands (Mufti, Erki and Jaeger,
1991a). The composite tape is applied along
the length of the chimney to provide addi-
tional bending strength. The strand is wound
around the chimney to provide hoop rein-
forcement. A fire protection mortar is finally
applied to protect the polymer composite from
fire, to limit the heat gain, and to avoid degra-
dation of the polymer matrix that otherwise
would occur if the carbon composite were
exposed to the environment.

46.2.2 STRUCTURAL SHAPES
Composite structural shapes resemble steel
hot- and cold-rolled structural sections.
Composite shapes are produced by pultrusion
in a variety of sizes and shapes (Creative
Pultrusions, 1989; MMFG, 1992). The rein-
forcement of choice is E-glass mainly because
of low cost. Most shapes are produced with
isophthalic polyester and vinylester, but some
pultrusions using epoxy, phenolic, and even
thermoplastics are available at higher cost.
Even for the most common polyester and
vinylester, there is a wide variety of resins sys-
tems, differentiated by mechanical properties,
thermal behavior, and cost. While vinylesters
are considered to have superior corrosion
resistance and mechanical properties than
polyesters, high grade polyesters may match
the mechanical properties of vinylesters.
Structural shapes are used primarily
because of their excellent resistance to chemical
degradation. In the case of electromagnetically
transparent structures, structural shapes are
routinely used for building construction in
very much the same way as steel shapes.
However, E-glass reinforced shapes have a
much lower modulus of elasticity than steel,
which causes design problems when direct
replacement of steel shapes by composite
shapes is attempted. Specialized sections, with
cross sections different from steel shapes, are
available for use in building systems with con-
struction characteristics (e.g. joist spacing)
very similar to steel frame buildings
(Composite Technology, 1992). Unlike steel
shapes, the mechanical properties of compos-
ite structural shapes largely depend on the
internal reinforcement, and the thermal and
corrosion response varies drastically with the
resin system used. Since the reinforcement
and the resin systems used are not standard-
ized, very different set of properties are
possible for identical cross sections, from dif-
ferent manufacturers.
Current applications 989
Platforms
Industrial platforms built entirely of pul-
truded fiberglass reinforced plastics are
widely used because of their corrosion resis-
tance. An area of application of special interest
is offshore platforms for oil production. Two
views, from above and below, of a fiberglass
well bay platform are shown in Figs 46.4(a)
and (b). Steel well bay platforms corrode
quickly in the marine environment. Painting
jobs are difficult because sand blasting may
release paint into the ocean unless costly pre-
cautions, such as scaffolding, are taken. Old
paint may be lead-based and cannot be
stripped unless it is completely captured and
dumped at a hazardous waste site. Well bay
platforms are installed after the production
wells are in operation. The area is usually clut-
tered with equipment, which makes difficult
the access of heavy lifting equipment needed
for installing heavy steel platforms, and weld-
ing cannot be done without shutting down oil
production. Fiberglass platforms weigh typi-
cally 30% of their steel counterpart, allowing
for installation by a smaller crew, in less time,
with less demand for space for lifting equip-
ment, and reduced transportation costs to the
site. The composite platforms are assembled
with mechanical connections eliminating the
need for welding and they are virtually main-
tenance free in the corrosive marine
environment, without need of painting. A 6 m
x 12 m (20 ft x 40 ft) well bay platform was
installed in 1986 on Shell’s Southpass 62 pro-
duction platform in the Gulf of Mexico by a
crew of four in two days and it is estimated
that a similar steel platform would have
required five days by a crew of eight because
of the lack of room for heavy lift equipment.
Building systems
Complete building systems, including the
structural frame, cladding and roofing are
available in fiberglass reinforced composites
(Composite Technology, 1992).Electromagnetic
990 Construction

Fig. 46.4 Well bay platform in an off-shore oil production facility (a) seen from above, @) seen from below.
Composite materials manufactured by MMFG. (Courtesy of MMFG.)
 Current applications 991

Interference ( E M ) testing buildings must be

built of materials free of magnetic interference,
with all metals ruled out and the use of timber
limited by the need to use steel connectors.
Pultruded structural shapes, fiberglass
cladding, and foam core panels offer an attrac-
tive alternative since all components can be
connected with fiberglass bolts and or glued
together to form an electromagnetically trans-
parent structure. Innovative combinations of
glued laminated timber (GLULAM)with com-
posites have also been exploited. A computer
testing facility (Fig. 46.5) was built for IBM in
Poughkeepsie, NY, by Corflex International Inc.
of Warren, OH, and Haines Lundberg Waehler
of New York, NY, using pultruded structural
shapes from Creative Pultrusions Inc. (1989).

Fig. 46.6 Fiberglass spire installed atop the 55-story

Nations Bank in Atlanta, GA. Comuosite materials
manufactured by MMFG. (Courtes; of MMFG.)

Fig. 46.5 Computer testing facility using pultruded Pedestrian bridges

structural shapes and fiberglass reinforced panels.
(Courtesy of Creative Pultrusions, Inc.)
The Nations Bank building in Atlanta, GA,
shown in Fig. 46.6 features a 11m (36 ft) tall,
all fiberglass spire at its top. Electromagnetic
transparency of the composite material used
allows the spire to house valuable communi-
cation antennae. Light weight, molded-in
color, and timely delivery were cited as advan-
tages of composite materials for this highly
visible application. The spire is mounted
312m (1023ft) above ground, and it is
designed to sustain a wind pressure of 550 kPa
(BO psi).
A number of pedestrian bridges have been
built with composite materials. Early bridges
are reported by Meier (1991), Barber0 and
GangaRao (1991) and others. While a few
bridges have been built by hand lay-up, the
majority are built with pultruded sections.
Concrete bridges partially reinforced with
composite tendons are discussed in previous
sections on concrete reinforcement. In this sec-
tion, we concentrate on bridges where most of
the materials used in the construction of the
bridges are composites. Because of cost, E-glass
reinforcement has been used most.
Johansen et al., from E. T. Techtonics of
Philadelphia, PA, report on the construction of
992 Construction
shapes. (Courtesyof E.T. Tcchtonics.)
three bridges of 6.1 m (20 ft), 9.75 m (32 ft),
and 15.24m (50 ft) (Fig. 46.7) using their
design and construction method, called
PRESTEK. Given the low stiffness of E-glass
reinforced pultruded composites when com-
pared to steel, conventional steel or concrete
designs are not efficient when implemented
with composites. The PRESTEK system uses a
beam-truss geometry of pultruded tubes pre-
stressed with aramid or steel cables. The three
bridges are a king-post truss, a queen-post
truss and a bow-string truss respectively.
Maunsell Structural Plastics in Beckenham,
Kent, England, with the participation of GEC
Reinforced Plastics (pultrusion manufactur-
ing), Scott Bader Co. Ltd (resin supplier),
Vetrotex UK (glass reinforcement), Ciba Geigy
Plastics (adhesives), Linear Composites
(Parafil cable stays), R. O'Rourke and Sons
(construction management), and University
of Dundee, constructed a pedestrian bridge
over the river Tay in Aberfeldy, Scotland. The
pultruded deck is cable stayed from two A-
frame towers, 17.5m (57 ft) high, to provide
for adequate stiffness despite the low stiffness
of the pultruded glass-polyester deck (Fig.
46.8). The bridge is 113m (370ft) long and
2.23 m (7.3 ft) wide, with a main span of 63 m
(206 ft). The deck and towers are constructed
with Maunsell's interlocking panels (ACCS
System by Designer Composites Technology
Ltd), pultruded with 70% volume of fiberglass
reinforcement and isophthalic polyester resin,
then bonded together with an epoxy adhe-
sive. The cable stays are Parafil ropes, a
Kevlar fiber core in a polyethylene sheath.
The bridge deck was designed to be modular
so that every component could be handled by
hand. The heaviest module, a 6 m (19.7 ft) by
0.6 m (2 ft) plank weighed only 66 kg (145 lb).
The weight of the deck is only 150kg/m
(lOOlb/ft) and each tower weighs only
2500 kg (5511 lb), facilitating erection and
reducing the cost of the foundation. The com-
posite system has class 2 fire resistance rating.
Bridge enclosures
The A19 Tees Viaduct in Middlesbrough, UK, is
a steel-concrete bridge with 117 m (383 ft) span

Fig. 46.8 Pedestrian bridge across the river Tay in Aberfeldy, Scotland, features an all-composite deck cable
stayed with Parafil cables from two composite A-frame towers. (Courtesyof Maunsell Structural Plastics
Ltd.)
(Head, 1988) where rapid deterioration of the
steel plate girders was taking place.
Maintenance (e.g. painting) and rehabilitation
work are difficult since the viaduct spans over
railroad tracks. A composite material enclosure
was built in 1989 to prevent further deteriora-
tion by isolating the bridge from the
environment and to facilitate maintenance and
rehabilitation. A floor area of 16000m2
(172 200 ft2)using 250 metric tons (275 US tons)
of composite material was created under the
bridge by interlocking pultruded panels
wrapped around the steel girders of the bridge
to create a box. The enclosure system was
designed by Maunsell StructuralPlastics Ltd, of
Beckenham, Kent, UK. The system uses inter-
locking panels designed by Maunsell and
fabricated by GEC Reinforced Plastics Ltd,
while the main contractor was Fairclough
Construction Ltd. The enclosure system has
been also used in the construction in 1992 of the
enclosure to the Bromley South Bridge, seen in
Current applications 993
Fig. 46.9, over the railway station. Pultruded
plank and connector sections are joined to form
a floor system suspended from the steel girders
of the bridge. Pleasant appearance was
required since the bridge is located in a resi-
dential area and over the railway station. Light
weight and low maintenance costs were cited
as additional advantages of composites for this
application.
Cooling towers
The resistance of composite materials to
humidity and creep under sustained loads has
been demonstrated by their successful appli-
cation to cooling towers, in operation for more
than twelve years (Fig. 46.10). Cooling towers
are permanently loaded with the heavy
weight of the ceramic filling used for cooling.
These towers are built by Ceramic Cooling
Towers of Forth Worth, TX, entirely of com-
posites except for the ceramic filling. The
994 Construction
Fig. 46.9 Enclosure of the Bromley South bridge is accomplished with interlocking pultruded panels
bonded together into a floor system and suspended from the steel girders of the bridge. (Courtesy of
Maunsell Structural Plastics Ltd.)
composite material is in permanent contact
with hot water and humid hot air circulating
through the tower. Reduced maintenance of
the tower is cited as an important advantage of
using composites. Light weight of the struc-
ture of the tower is an additional advantage
when the towers must be located on top of
buildings. Construction of large industrial
cooling towers motivated the development of
the UNILITE Modular System which takes
advantage of modular construction to reduce
cost. Composites facilitate modular construc-
tion because of the variety of shapes that can
be easily produced.
Marine construction
Potential applications for composites in the
construction and rehabilitation of marine and
waterfront constructed facilities include
docks, piers, harbors, etc. An all-composite
pontoon designed by Maunsell Structural
Plastics Ltd, of Beckenham, Kent, UK and dis-
tributed by Designer Composites Technology
Ltd, UK, is shown in Fig. 46.11. Finger piers of
up to 15 m (49 ft) are built with cellular inter-
locking pultruded panels, joined to foam filled
flotation units. The surface of the pontoon is
covered with a non-slip polyurethane coating
which is acid, solvent, and heat resistant.
46.3 DESIGN CONSIDERATIONS
Current composite design practice emphasizes
simultaneous design of the structure (beams,
plates, frames, etc.) and the material (compos-
ite) for optimum performance. Design practice
for composites used in construction differs
from aerospace applications in the sense that
standardization of components is required
because of cost and safety. Therefore, design is
divided into member design, usually per-
formed by the manufacturer, and system
design, carried out by the structural engineer.
Codes of practice do not yet exist for structural
design with composites, but they are being
 Design considerations 995
. .. ... ._... .
deflections are controlled by the bending stiff-
ness D, equivalent to EI for steel beams. Since
composite beams have different values for
modulus of elasticity at various points in the
cross section, it is not possible to completely
define the stiffness with respect to both axis of
bending by the product of the modulus and
the corresponding moment of inertia (€1 and
€Ixx ) Instead, two bending stiffnesses and <
Dx are defined, with respect to the strong axis
and weak axis respectively. Shear deforma-
tions are neglected for steel beams because the
shear stiffness of steel is high ( G / E = 0.4) while
for composites is low ( G / E < 0.1). The shear
stiffnesses of a composite beam with respect to
the two axis of bending are denoted F y and Fx.
The values of the bending, shear, and axial
stiffness (Dy, K F ~ A,)
, can be obtained from
tables supplied by the beam manufacturer,
k
obtained experimentally (Bank, 1989), or com-
puted if detailed information about the
constituent materials is known (Barbero,
1998). Maximum deflections can be computed
using the formulae in Fig. 46.12. Experimental
values of shear stiffness usually refer to the
Fig. 46.10 All-composite cooling towers like this, product of K F where
~ K is the shear correction
developed and manufactured by Ceramic Cooling factor.
Tower, have been in operation for more than twelve
years.
c
developed. Some methods of analysis and
design recently developed are described in
this section.

46.3.1 BEAMS
Beams are the most common structural com-
ponent in civil engineering applications. Both . -+-----
deflection and strength are equally important
in the design of composite beams. Composite
beams are thin-walled and composed of an
assembly of flat panels. Most beams are pris-
matic but they can have taper. They are
Fig. 46.11 The pontoon pier shown is built of inter-
produced by pultrusion, filament winding, locking pultruded panels and foam filled flotation
hand lay-up, automated lay-up, etc. devices. A polyurethane coatingprotects the surface
Deflection of composite beams has two from acid, solvents, and heat. (Courtesy of
components, bending and shear. Bending Maunsell Structural Plastics Ltd.)
996 Construction

W
4
5 W L + 1 WLZ
n s%=384% 8 KF~
I

Fig. 46.12 Center deflection of composite beams including bending and shear effects.

The sigruficance of the shear deflection with
respect to the bending deflection varies with
the span, the larger the span the lesser the influ-
ence of shear. Sometimes, properties of beams
are reported without distinction between the
bending and shear components, using an
apparent value of modulus Eapp= Dy/lyy,where
D,, is the bending stiffness with respect to the
strong axis. The bending stiffness with respect
to the weak axis Dx cannot be accurately
obtained as Dx = EapIxx. The apparent stiffness
Eappis then used in &e classical deflection for-
mulas (for steel) that do not account for shear
deformations. The reported values are usually
based on three-point bending tests, performed
at the factory with a specific span, which is sel-
dom reported. The results of using the classical
(steel) deflection formulas for spans or loading
other than that of the test are only approximate.
The main modes of failure of beams in
bending are: (a) compression crushing of the
compression flange; (b) local buckling of the
compression flange; (c) tensile rupture of the
tension flange; (d) shear failure of the web;
and (e) web buckling. Since each part (panel)
of the cross section can be built with different
materials, the failure mode can be controlled
by design. Local buckling modes can be elimi-
nated by increasing the thickness and
choosing the fiber orientations properly
(Barber0 and Raftoyiannis, 1993). The com-
pression strength of composites is lower than
the tensile strength. Therefore, a symmetric
section is not the most efficient cross section.
Symmetric sections fail in the compression
flange first. Tensile failure may occur in
unsymmetric sections, when the compression
flange works with composite action with a
deck, etc. Shear failure is less likely to occur in
sections with multiple webs. Incorporation of
off-axis fibers (cloth, mats, etc.) increases the
shear strength.
46.3.2 COLUMNS
Columns are structural members subjected
primarily to compression forces acting along
Design considerations 997
the length of the member. Lateral forces (e.g.
wind forces) and bending moments (e.g.
eccentric loading) are considered secondary
forces, which are dealt with separately.
Column performance is limited by one of two
failure mechanisms, crushing and buckling.
Crushing is the failure of the material because
of excessive compressive stress, similar to
yield of steel. Buckling is more frequent in
composite columns because thin-walled sec-
tions are preferred. A thin-walled section may
experience at least three different types of
buckling, which are described next.
Long and slender columns fail in a global
sense when the axial load reaches a critical
value P,, For load values lower that the criti-
cal load the column remains straight. When
the load reaches critical value, the column
experiences sudden lateral deflection. The
axial stiffness after buckling is much lower
than the stiffness before buckling. Therefore,
the lateral deflections are quite large and they
usually precipitate another mode of failure
like crushing of parts of the cross section, lead-
ing to collapse.
The concept of slenderness allows us to
compare members of different cross sections
and column lengths for their tendency to
buckle. For a composite column, the slender-
ness is defined as
= L&) (46.1)
where P, is the local buckling load, D is the
bending stiffness, and Le is the effective
length of the column, which is used to
account for different end conditions (Gere
and Timoshenko, 1990, p. 589).
Short and stubby columns, which have a
low Slenderness value, are less likely to buckle
in a global mode as described previously.
However, individual parts (flange or web) of
the cross section may buckle locally. Local
buckling is very likely to occur in composite
columns because they are commonly thin
walled. The compressive stress required to trig-
ger local buckling increases with the thickness
998 Construction
of the cross section and the local stiffness of the
material. The narrower the flange or web
under consideration, the higher the local buck-
ling load P,. The wavelength of local buckling
is independent of the length of the column for
columns of practical lengths.
Flange buckling of open section members is
triggered by pure compression.It occurs during
compression of columns and on the compres-
sion flange of beams in bending. Web buckling
is initiated by shear and it occurs during bend-
ing of beams. Web buckling of open section
columns is not common because most open sec-
tions have wide flanges that buckle first. There
is of course no distinction between flanges and
webs in closed section columns. Unlike steel
structural shapes, composite closed sections are
easier to produce and structurally more effi-
cient than open section members.
Local buckling can be prevented by choos-
ing the section geometry and material
properties. Global buckling can be prevented
by a combination of section geometry, material
properties and bracing. If all buckling modes
are prevented, the strength of the member is
limited by the crushing strength of the mater-
ial itself, which plays a role similar to the yield
strength of metals. The crushing strength is a
material property which is independent of the
thickness of the flange or web and the geome-
try of the section. As for any composite
property, it depends of the constituents (fiber
and resin) and the arrangements of the fibers
inside the material (orientation, fiber volume
fraction, stacking sequence). The crushing
strength is usually determined experimentally
but the main factors that influence its value
can be highlighted by predictive equations
(Tomblin, 1994; Barbero, 1998).
A slender column buckles in a global
(Euler) mode. A not-so-slender column may
fail in a local buckling mode. A thick-walled
stubby column may fail due to crushing.
Columns with a slenderness ratio less than 0.5
fail in a local buckling mode. For slenderness
larger than 1.5 the mode is purely global
(Euler). Columns with slenderness between
0.5 and 1.5 show some type of interactive phe-
nomenon. The interaction occurs between the
local mode, the global mode, and crushing.
Interaction results in lower buckling loads
than those predicted by any of the modes act-
ing alone.
There are many situations of practical inter-
est for which the buckling loads required to
produce two or more failure modes (Euler,
local, crushing) may be very close. In this case
the failure modes interact. That is, the proxim-
ity of the stresses to more than one mode of
failure causes the structure to fail at a lower
stress value that predicted by either of the
modes involved should they be acting sepa-
rately. Euler and local modes interact to give
an overall strength deterioration. Interaction
must be taken into account because the
strength values predicted by either isolated
mode fit are not conservative. The failure load
of a column (Po) taking into account local,
global, and interaction phenomena simultane-
ously can be obtained from the following
design equation (Barbero and Tomblin, 1993)
The column properties needed to use this
design equation are: the local buckling load PL;
the interaction constant c; and the bending
stiffness D, which along with the length of the
column enter in the computation of the slen-
derness 1 (46.1). All these properties can be
determined experimentally or predicted ana-
lytically. The bending stiffness D and the local
buckling load P,, can be predicted analytically,
while an analytical study of the interaction
phenomenon is presented by Raftoyiannis
(1993). The design equation does not have any
safety factor included. Typical properties of
wide-flange pultruded structural shapes are
given in Table 46.1 where the interaction con-
stant is c = 0.84 for all sections reported.The
length at which maximum interaction occurs
is denoted by L‘.
 Design considerations 999

Table 46.1 Column properties obtain the Euler buckling load P,,, as the
inverse of the slope in the A/€' vi: A plot,
Section PL (kN) D (kN cm2) L x (cm) where A is the lateral deflection and P is the
102 x 102 x 6.4 223.25 6094.67 105.9 load.
152 x 152 x 6.4 175.12 20954.42 221.5 Interaction testing can be performed with
the same setup described for global (Euler)
testing. The objective is to determine the inter-
action constant c in (46.2). Once two or more
modes of failure interact, the Southwell
method cannot be used. Therefore, only the
Testing of short columns is performed to iden- maximum collapse load is reported for tests
tify the local buckling load P, in the column performed on columns having slenderness
design (46.2).Buckling of the flanges is seldom values between 0.5 and 1.5. The collapse load
a sudden phenomenon as described by the is lower than the critical load that would occur
theory because of the imperfections of the should any of the modes involved act isolated
material. Therefore, flange lateral deflections from the others, as the experimental data
are observed from the onset of the test and clearly indicates. The test is conducted with a
they grow as the load is applied. The buckling column length that exhibits maximum interac-
load P,, to be used in the design corresponds tion (L*), which occurs for a column
to the asymptote of the hyperbolic curve of slenderness 1= 1. The interaction constant is
load vs. deflection. Since it is not practical to computed as c = (q + s - l)/qs, where q = P/P,,
conduct the test up to the large deflections s = P/P,,, P is the collapse load, P, is the local
needed to realize the asymptotic value of load, buckling load (predicted or previously mea-
a data reduction technique (Tomblin, 1991) is sured on short columns) and P,, is the Euler
used. buckling load (predicted or previously mea-
Columns having slenderness larger than 1.5 sured.)
will buckle in a global mode (Euler).The Euler
buckling load is controlled by the bending
46.3.3 REINFORCEMENT OF CONCRETE
stiffness D. A column with pinned-pinned end
conditions is subjected to an axial load (prefer- Reinforcement of Portland cement concrete
ably under axial displacement control).Pinned can be accomplished with composite reinforc-
end conditions are the only conditions that can ing bars (rebars) instead of steel bars to
be achieved with any degree of certainty. A minimize the corrosion of steel and cracking of
100% degree of fixity required by a clamped concrete caused by the expansion of the cor-
end condition is not achievable on composite roding steel rebars. Composite rebars should
columns because of the difficulties associated have good bond with concrete and adequate
with connecting composites. Data from corrosion resistance. Pultruded rebars are the
pinned-pinned columns can be used for other most common and least expensive alternative
end conditions by using the effective length for the reinforcement (not pre-stressed) of con-
concept (46.1). Weak axis tests are simpler to crete. Pultruded rebars have an angle
perform, since strong axis tests require the use overwrap and/or a sand coating to improve
of lateral support. Because of the imperfec- the bond with concrete. Fiberglass rebars,
tions in the material and loading fixture, the aramid rebars, seven-wire carbon cables,
load deflection plot has an hyperbolic shape, grids, and even gratings have been used in
the buckling load being given by the asymp- research studies as reinforcements of concrete.
tote of the plot. A data reduction technique Fiberglass rebars have lower modulus of
known as the Southwell method is used to elasticity than steel rebars, causing larger
1000 Construction

deflections than in steel reinforced concrete Creep is observed as increasing elongation

beams. Typically, the deflection of reinforced under constant load. Relaxation is the reduction
concrete (RC) beams is controlled by two fac- of stress over time for a constant elongation.
tors: the amount of concrete that remains Permanent levels of stress in the composite
un-cracked (essentially in compression); and should be under the stress rupture limit (also
the modulus of elasticity of the reinforcement. called static fatigue) of the composite. Martine
The extension of cracking in the tension side of (1993) reported stress rupture of E-glass rein-
RC beams depends largely on the strength and forced composite at 10 000 h at 58% of the initial
uniformity of the bond between the rebar and strength. Glaser, Moore and Chiao (1983) report
concrete. Good bond translates into uniformly survival of S-glass reinforced epoxy specimen
spaced cracks in the tension side of the beams. to a 10 year sustained load test: 90% of the spec-
Therefore, a larger area of concrete remains imens survived at 50% of static strength; 98%
un-cracked, thus contributing to the bending survived a 40% loading; and 100% survived a
stiffness and limiting deflections. Fiber rein- 35% loading. To account for stress rupture and
forced composite rebars have a linear other factors in the design of fully overwrapped
stress-strain behavior up to failure, thus they pressure vessels for compressed natural gas,
experience a brittle behavior when compared stress ratios (burst over service fiber stress) of
to steel rebars that have a yield plateau (i.e. 3.5 for fiberglass, 3 for aramid, and 2.25 for car-
plasticity) before they rupture. Brittle behavior bon reinforced composite were proposed by the
is not convenient from a safety point of view American National Standards Institute (AGA
because of possible catastrophic RC member NGV2 1992).These are indications that the sta-
failure. However, concrete reinforced with tic strength of fiber reinforcements cannot be
fiberglass rebars experiences very large deflec- utilized for long duration loads like those
tions up to failure, larger than comparable encountered in construction applications.
steel reinforced beams in their plastic regime, Glass fibers, if unprotected, deteriorate
because of a combination of low modulus of when exposed to an alkaline environment.
elasticity and high tensile strength of the fiber-Therefore, glass reinforced composites rely on
glass rebars. the protection provided by the resin to resist
No code or standard regulating the design the attack of alkaline environments. Alkaline
of RC beams, reinforced with fiberglass com- degradation is of particular concern in con-
posite reinforcing bars (rebars) is in place at crete reinforced with fiberglass composites
the time of this publication. Faza and since the concrete mix is alkaline. While con-
GangaRao (1993) suggest that it is possible to crete alkalinity is well documented at the time
proceed along the lines of the American concrete is poured, only now are studies being
Concrete Institute guidelines ACI 318-89 com- conducted to investigate the level of alkalinity
plemented by the recommendations ACI 363 of concrete with time. Water is needed to
R, properly modified to account for the prop- establish a link between the glass fibers and
erties of the fiberglass rebars. the alkaline concrete environment. If water is
present, the link can be established through
46.3.4 ENVIRONMENTAL EFFECTS
cracks in the resin. Permeability of the poly-
mer matrix resulting from voids or moisture
Dead loads (e.g. the weight of the structure) diffusivity of the polymer are being consid-
will be applied to the composite material for the ered as possible additional mechanisms that
life of the structure. Sustained loads induce two may place the alkaline concrete environment
major effects in composites, creep and stress in contact with the glass fibers.
rupture. Creep and relaxation are two altema- S2-glass reinforced Shell Epon 9310 com-
tive descriptions of the same phenomenon. posite rods produced by pultrusion were used

by Sen, Issa, and Mariscal (1992) to pre-stress
concrete piles. Seven 3 mm (0.125in) diameter
rods were twisted with one turn every 30 cm
(12 in) to create a seven wire strand. The
strands were used to pre-stress concrete piles
to be used in marine environment. To simulate
marine environment, the piles were subjected
to wet and dry seven-day cycles in a 15%
sodium chloride solution, then tested to failure
in bending. To facilitate the moisture ingress,
four out of eight glass composite reinforced
piles were pre-cracked at the mid-span prior
to testing. The bending strength of specimens
subjected to the wetting cycles, specially those
pre-cracked, reduced significantly over time.
From the pre-stressing force applied, it is pre-
dicted that 1.6% strain was induced in the rod,
while larger values of strain may have been
induced during the precracking of the beams.
Additionally, radial stresses produced by the
twist of the rods in the strand and by the mois-
ture ingress in the resin may have caused
cracking. Although the neat resin failure strain
is reported at 4%, the strain applied to the
composite rods may have produced cracking
of the matrix, thus facilitating the ingress of
moisture carrying the alkaline solution to the
glass fibers. Scanning electron microscopy
micro-photographs clearly show degradation
of the glass fibers along with some cracking of
the matrix. An additional pile was fabricated
with pultruded fiberglass rods for which an
additional coating resin was added to provide
a smooth finish. This pile performed signifi-
cantly better than the other four after a nine
month exposure, perhaps because of the
added protection of the finishing resin. It is
concluded that the alkalinity of the environ-
ment (eg. concrete), the availability of water
or other solvent, and the protection provided
by the resin must be evaluated for each spe-
cific application.
46.4 CONCLUSIONS
Composite materials have been used for many
structures that have performed well over
References 1001
many years of service, mostly in adverse con-
ditions. Composites are being used
extensively for applications where the advan-
tages significantly justify their higher initial
cost. Composites have been successful when
the design and manufacturing of a product
was performed by a single company or group
of companies, using the integrated design
approach typical of the aerospace industry.
The use of composites in the traditional civil
engineering environment, where individuals
create unique structures from standard com-
ponents, has been slow, with the exception of
markets where corrosion resistance offsets
higher costs and less than optimum perfor-
mance. Large markets have not developed
partly because of lack of design codes and
specifications and lack of awareness of com-
posites advantages by structural engineers. A
number of factors, including the decline of
military industry and the need for rehabilita-
tion of USA infrastructure, have produced a
flurry of activity in this area, which undoubt-
edly will produce significant progress in the
application of composites in construction.
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AGA NGV2. 1992. Proposed American National
Standard, basic requirements for compressed
natural gas vehicle (NGV) fuel containers. Draft
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Ahmed, S.H. and Plecnik, J.M. 1989. Transfer of
composite technology to design and construc-
tion of bridges. Washington, DC: US
Department of Transportation, Federal
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Bank, L.C. 1989. Flexural and shear modulii of full-
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Barbero, E.J. and GangaRao, H.V.S. 1991. SAMPE J.
Part I(12) 1991. Part II(1) 1992
Barbero, E.J. 1998. Introduction to Composite Materials
1002 construction
Design. Washington, DC: Taylor and Francis.
Barbero E.J. and Raftoyiannis, I. 1993. Local buck-
ling of FRP beams and columns. ASCE J. Mater.
Civil Engng, 5(3), 339-355.
Barbero, E.J. and Tomblin, J. 1992. A phenomeno-
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Davalos, J.F. and Salim, H A. 1992. Design of stress-
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Faza, S and GangaRao, H.V.S. 1993. Pultruded fiber
reinforced plastic bars, an alternative to steel
reinforcement of concrete, Section 13-D, Proc.
48th A n n . Conf, pp. 1C-5C. New York:
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Fibergrate. 1992. Structural Fiberglass Products and
Systems. Dallas, TX: Fibergrate.
GangaRao, H.V.S. and Barbero, E.J. 1991.
Construction: structural applications, in
Encyclopedia of Composites (6), (ed. S. Lee). New
York VCH Publishers.
Glaser, R.E., Moore, R. and Chiao, T.T. 1983. Life
estimation of an E-glass epoxy composite under
sustained tensile loading. Composites Technology
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Head, P. 1988. Use of fiber reinforced plastics in
bridge structures. Helsinki: XI11 International
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(IABSE),pp. 123-128.
Iyer, S.L. 1993. First composite cable pre-stressed
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Iyer, S.L. (ed). 1991. Advanced Composite Materials in
Civil Engineering Structures, (ed. S.L. Iyer). New
York American Society of Civil Engineers.
Kakihara, R., Kamiyoshi, M., Kumagai, S. and
Noritake, K. 1991. A new aramid rod for the
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Koga, M., Okano, M., Kawamoto, Y., Sakai, H. and
Yagi, K. 1992. Application of a tendon made of
CFRP rods to a post-tensioned pre-stressed con-
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Bridges and Structures, (eds. K.W. Neale and P.
Labossiere).Montreal: The Canadian Society for
Civil Engineering, pp. 405-414.
Martine, E.A. 1993. Long-term tensile creep and
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glass-reinforced composites. Proc. Composites
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glass fiber composite bars as reinforcements, in
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MMFG. 1992. EXTREN Fiberglass Structural Shapes
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533-541.
Pletcher, D. 1991. Consider structural composites,
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Iyer). New York American Society Of Civil
Engineers, pp. 123-131.

Priestley, M.J.N., Seible, F. and Fyfe, E. 1992.
Column seismic retrofit using fiberglass-epoxy
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Bridges and Structures, (eds. K.W. Neale And P.
Labossiere). Montreal: The Canadian Society
For Civil Engineering, pp. 287-298.
Raftoyiannis, L. 1993. Buckling Mode Interaction in
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WV.
Rostasy, F.S., Hankers, C. and Ranisch, E-H. 1992.
Strengthening of R/C- and P/C-structures with
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Neale and P. Labossiere). Montreal: The
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Fiberglass Pretensioned Piles in a Marine
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Materials, 3rd Edn. Boston: PWS-KENT
Publishing Co.
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ACKNOWLEDGEMENTS
My sincere gratitude to Prof. G. Turvey for his help
researching applications in Europe, to all the con-
tributors of information for this article, and to West
Virginia University for the support of this project.
AEROSPACE EQUIPMENT AND 47
INSTRUMENT STRUCTURE
G a y C. Krumweide and E d d y A. Derby

47.1 INTRODUCTION aluminum, or very expensive beryllium fur-

It is necessary to discuss GFRP (graphite fiber ther justified the material selection.
reinforced plastics) thoroughly in order to Consequently, numerous mirror bezels,
understand the importance of composites in telescopes, optical benches and reflectors were
the manufacture of aerospace equipment and designed and built from GFRP in the early
instrument structures. Before composite mate- 1970s. As a result of these efforts, today more
rials such as GFRP became viable candidate and more structures are being fabricated from
materials for aerospace primary structures, or GFRP materials, principally because specific
even for sporting equipment, they were first materials matching specific property require-
used for aerospace equipment and instrument ments are now available.
structures. Because composites exhibited both Although GFRP has dominated composite
unique and superior properties, designers materials applications, DuPont's Kevlar-49
were willing to pay the prevailing high prices has been found to be ideal for antenna reflec-
to achieve their design goals. For space hard- tors because of its extremely light weight and
ware, where a pound of weight saved was RF transparency. Many communication satel-
worth thousands of dollars, designers were lites utilize this type of Kevlar reflector, such
motivated to characterize composite materials as the SatCom-F, Telstar, ANIK-E, SpaceNET,
suitable to their applications. Understandably, and Superbird SCS (Fig. 47.1).
composites for primary and secondary struc-
ture (e.g. launch vehicles, aircraft frames, wing
spars and skins, etc.) were a 'hard sell', and
temperature extremes were too severe for
'thermosetting' GFRP to be used on missiles.
The quantity of GFRP required for a particular
piece of aerospace equipment or instrument
structure was usually minimal, so relative
costs were low, and composite materials' supe-
rior properties compared to heavy Invar, or
high coefficient of thermal expansion (CTE)

Handbook of Composites.Edited by S.T. Peters. Published

in 1998 by Chapman & Hall,London. ISBN 0 412 54020 7 Fig. 47.1 SuDerbird SCS Kevlar dual-shell reflector.

For aerospace equipment and instrument
structures, generally, thermoplastic versions of
GFRP have not seen as much application as
the thermosets due to high investment costs in
tooling and facilities. Considering the rela-
tively small quantities that are usually bought,
thermoplastic applications are not often cost
effective. Also, the required high temperature
cures subject the laminate to microcracking
instabilities.
Metal matrix composite applications have
been limited, and knowledge of material prop-
erties and processes has been restricted due to
their use on classified programs. Materials like
silicon carbides and carbon-carbon find lim-
ited, but important, use in aerospace
structures, particularly mirrors. Design selec-
tion criteria plays an extremely important role
in determining what type of material is used
on any particular component of aerospace
equipment and instrument structures. The pri-
mary reasons for choosing a composite
material, rather than a metal, are weight,
dynamic stability and thermal stability.
Table 47.1 categorizes some of the desirable
and undesirable characteristics that con-
fronted the early users of GFRP. Table 47.2
addresses the undesirable properties listed in
Table 47.1 and indicates how the aerospace
equipment and instrument designers have rec-
ognized the barriers or problems with GFRP
and found work-around techniques to allow
their usage. Table 47.3 illustrates several struc-
tural applications where GFRP have been used
Table 47.1 GFRP properties
Desirable
Low density
Coefficient of thermal expansion(CTE near
zero)
High specific strength
High specific stiffness
Readily formable
Crack growth resistant
Adaptable laminate properties
Easily repairable
Historical perspective and progress 1005
and/or are going to be used for aerospace
equipment and instrument structures.
Table 47.4 compares the mechanical and
thermal properties of candidate materials for
aerospace equipment and instrument struc-
tures. One could ask, from the obvious
property advantage of beryllium, why all such
structures are not made from beryllium? If not
beryllium, why not metal matrix composites
or carbon-carbon (C/C) or silicon carbide
(Sic)? The answer is that raw material cost,
fabrication cost, practical size, and other criti-
cal properties all come into play for any
specific application. Table 47.5 shows typical
design requirements for various applications
and indicates which materials typically satisfy
the critical requirement.
The primary reason that GFRP is a material
candidate for most applications is the wide
range of material systems that are currently
available that can compare with Kevlar, alu-
minum, Invar, beryllium, metal matrix
composites, silicon carbide, and carbon-car-
bon.
47.2 HISTORICAL PERSPECTIVE AND
PROGRESS
From a historical perspective, and to illustrate
where significant progress has been made in
the use of composites for aerospace structure,
the following areas of interest will be
addressed:
Undesirable
Low short transverse properties
Hygroscopic
High material cost
High fabrication cost
Low impact strength
Subject to microcracks (translaminarstress
relief)
Low peel strength
1006 Aerospace equipment and instrument structure

Table 47.2 GFRP design barriers and work-around techniques

Undesirable properties Barrier to design Work-around techniques Reference

Anisotropic Low strength in 1. Radius blocks Stumm,1981

behavior angles 2. Substitute material Campbell, 1981
(metals)locally Krumweide, 1988
3. Use mortise and
tenon joints
Thermal instability 1. Use mortise and Stumm, 1981
of angles tenon joints Campbell, 1981
2. Butt edges/insert Krumweide, 1988
3. Back-to-back splice
High through- 1. Egg crate joint Stumm, 1981
thickness expansion 2. Mortise and tenon Krumweide, 1988
of laminate 3. Add local Krumweide, 1991
compensation
4. Maximize in-plane
material orientation
5. Fitting Boss through
Skin
Hygroscopic nature Expansion/distortion 1. Moisture barrier Hertz, 1977; Stumm, 1979
2. Define exposure/ Walrath, 1979; Levy, 1984
drying scenario Krumweide, 1989
3. Cyanate ester Telkamp, 1990
Krumweide, 1991; Brand, 1992
Material cost/ High basic part cost 1. Proper material Krumweide, 1977
fabrication cost selection Krumweide, 1988
2. Tooling/fabrication
techniques
3. Assess cost/weight
ratio
4. Ovencure
5 . Minimize pieces
6. Eliminate molded
parts
7. Tailor joints/load
Susceptibility to Micro properties 1. Uselow Stumm, 1981
microcracks affected temperature Krumweide, 1991
curing resin systems Brand, 1992
2. Low stacking angle
3. Small ply thickness
4. Reduce fiber modulus
5 . Thermal cycle parts
6. Cyanate ester
Susceptibility to Low impact strength 1. Protect surface with Dunbar, 1978
impact damage Kevlar/honeycomb Herrick, 1984
2. Material design
(thickness, orientation)
Low peel strength Low joint allowables 1. Use mortise and Dunbar, 1978
tenon joints Krumweide, 1979
2. Fasteners and angle Stumm, 1981
clips

0 problems encountered/work-around
techniques;
0 construction methods;
0 tooling development;
0 major milestones.
47.2.1 PROBLEMS ENCOUNTERED/WORK-
AROUND TECHNIQUES
Aerospace designers have constantly been
seeking the ideal material - the one material
which meets design requirements with the
fewest compromises. Of course, few materials
are completely ideal for a given set of require-
ments and design trade-offs are almost always
necessary.
Table 47.2, above, summarizes typical prob-
lems, presents some design concerns, and/or
'barriers to design' associated with compos-
Table 47.3 GFRP Applications for aerospace structures
Equipment structures
RF Systems:
-Reflectors (Viking, Nimbus-G, ACTS)
-Feed horns and waveguides (INTELSAT)
-MUX cavities
-Diplexers
-Phased arrays
Large segmented reflectors
Solar panel (substrates) (BS-3, RADARSAT,
Mars Observer)
Booms, Stardust (Shuttle RMAB, M-SAT)
Bus (Mighty Sat M I , SMEX/WIRE, Indostar Forte)
Electronic chassis (EO1, SMTS-OBC, MARS 98,
Stardust)
CCA cardguides (NAWC Coldplate)
Solar Concentrators
Historical perspective and progress 1007
ites, principally GFRP, and indicates a variety
of work-around techniques which have been
implemented successfully to address these
design concerns. To help explain and clarify
these techniques, some examples of specific
design solutions are discussed below.
Moisture effects
For GFRP, it has been determined that the pre-
dominant mechanism of water penetration
into the laminate is through the resin by a dif-
fusional process. The moisture diffusion is
governed by Fick's second law which is simi-
lar to Fourier's equation for thermal
conductivity:
6C 6%
(47.1)
sf = Dzsz'
Instrument structures
Metering structures (LANDSAT, Thematic
mapper; SOHO, UVCS; HEAO-B, COSTAR and
Hubble Telescopes)
Camera housings (Mars Observer Camera (MOC),
Hubble WFOV Camera)
Optical benches (MAGSAT, UARS HRDI, Hubble
FGS Optical Benches)
FPA or relay optics (Hubble Telescope;
THEMATIC MAPPER)
Mirror bezel
Mirrors (Microwave Limb Sounder, NGST, INM
Scan Mirror)
Lens holders
Support benches (Hubble FGS)
Startrackers (Hubble Equipment Shelf)
Submillimeter reflector
Helicopter mast mounts
Laser comm gimbals
1008 Aerospace equipment and instrument structure

where c = moisture concentration; t = time; Dz
= moisture diffusivity; and z = thickness coor-
dinate.
Diffusivity is dependent on resin type and
temperature but is independent of moisture
concentration or laminate orientation.
Figure 47.2 illustrates the importance of
temperature in determining the diffusivity of a
laminate. Figure 47.3 illustrates the moisture
absorption behavior as a function of tempera-
ture for this same laminate. Note that this is
for a 100% relative humidity (RH) exposure.
Typical moisture absorption values (primarily
by the resin) are 3 . 5 4 % by weight for epoxy
and 1-1.3% by weight for cyanate ester. The
maximum moisture pick-up for the composite
(Mcm)may
be calculated by the following equa-
tion:
MCm= (Mrn)[x wr (47.2)
where Wr = resin weight YOand (MJr is the
maximum moisture pick-up for the neat resin
for a given relative humidity condition.
The moisture content as a function, Iw,can
be represented by:
Mcm= A (WB (47.3)
where A and B are coefficients obtained from
empirical data. Figure 47.4 depicts the per-
cent of moisture pick-up for various levels of

Table 47.4 Typical mechanical and thermal properties of isotropic/quasi-isotropic materials

~~ ~

Material Modulus E Density CTE CP K

(GPa) (Mg/m3) ( X 1O-6/K) (kJhgK) (WImK)
Copper 117 8.86 16.6 0.38 398
Beryllium 289 1.83 11.5 1.88 179-207
Aluminum 70.3 2.68 23.8 0.96 138-237
Titanium 113.7 4.43 9 0.54 16.9-20.8
Stainless steel 193 8.03 16.5 0.50 16.26
Super Invar 144.7 8.03 0.18 0.50 13.8
Fused silica 73 2.19 0.5 0.71 1.33
Ule fused silica 67.5 2.19 0.029 0.75 0.86
Zerodur 90.3 2.54 0.108 0.92 1.7
P75S/EP 103.3 1.72 -0.14 0.88 55.3
P100S/EP 143.3 1.80 -0.72 0.88 116
P120S/EP 170.9 1.83 -0.85 0.88 190
PlSOS/EP 186 1.83 -1.08 0.88 334
T300/EP 55.1 1.58 2.7 0.88 2.4
T50/EP 82.7 1.58 0.72 0.88 20.8
AS-4/EP 51.7 1.58 2.52 0.88 5.2
XN50A/EP 103.4 1.80 -0.072 0.88 48.4
XN70A/EP 144.7 1.83 -0.54 0.88 98.6
M55J/EP 103.4 1.66 -0.27 0.88 20.8
M60J/EP 120.6 1.69 -0.45 0.88 24.2
FT500/EP 82.7 1.77 0.36 0.88 41.5
FT/ 700/EP 137.8 1.80 -0.72 0.88 81.3
GY70/EP 110.2 1.66 -0.18 0.88 NA
Boron/EP 89.6 2.05 5.4 0.88 NA
S-GL/EP 26.9 2.02 9.7 0.71 0.34
KV49/EP 29.6 1.38 6.3 NA 1.04
KV-149 40.6 1.38 1.8 NA 1.04
NA = Not Available
 Historical perspective and progress 1009

Table 47.5 Material selection criteria

Aerospace application
Critical Equipment structure Instrument structure
-
requirements
RF Solar panel Bus Booms Stable Mirrors
reflectors substrates structures structures
Mass GFRP (1) GFRP(1) GFRP GFRP GFRP (5) GFRP (6)
Kevlar Kevlar Aluminum Aluminum Beryllium Beryllium
M/M Beryllium Si/C, C/C
M/M
Dynamic GFRP (1) GFRP (1) GFRP GFRP GFRP (5) GFRP (6)
stability Kevlar Kevlar Aluminum Aluminum Beryllium Beryllium
Aluminum M/M Beryllium Invar Si/C, C/C
M/M Aluminum
Thermal GFRP GFRP (1) GFRP (5) GFRP GFRP (5) GFRP (6)
stability Kevlar Invar Beryllium Invar Invar
M/M Beryllium Beryllium
Si/C, C/C
Dynamic GFRP (1) GFRP (1) GFRP GFRP GFRP (5) GFRP (6)
loads (Gs) Kevlar Kevlar Aluminum Beryllium Beryllium Invar
Aluminum M/M M/M Invar Beryllium
Aluminum Aluminum
Temperature GFRP (2) GFRP (2) GFRP (2) GFRP (2) GFRP (2) GFRP (2x6)
extremes Kevlar Kevlar Aluminum Beryllium Invar Si/C, C/C
Aluminum M/M M/M Beryllium Beryllium
Aluminum Aluminum
Hygrostability GFRP (2) GFRP (2) GFRP (2) GFRP (2) GFRP (2) GFRP (2)(6)
Aluminum Aluminum Beryllium Beryllium Invar
M/M M/M Invar Beryllium
Aluminum Aluminum
Si/C, C/C
High thermal GFRP (3) GFRP (3) GFRP (3) GFRP (3) GFRP (3) GFRP (3x6)
conductivity Aluminum Aluminum Beryllium Beryllium Invar
M/M M/M Invar Beryllium
Aluminum Aluminum
Si/C, C / C )
Low thermal GFRP (4) GFRP (4) GFRP (4) GFRP (4) GFRP (4) GFRP (4x6)
conductivity Kevlar
RF transmissibility Kevlar Kevlar - - - -

cost GFRP GFRP (1) GFRP GFRP GFRP Aluminum

Kevlar Kevlar Aluminum Aluminum Invar Invar
Aluminum
~

(1)Combinations of Kevlar and GFRP is used when mass and dynamic stability is important.
(2) Cyanate resins have been shown to handle temperature extremes (T, high, no microcrackhg).
(3) Pitch fibers (especially ultra, ultra high modulus have high thermal conductivity).
(4)PAN fibers have low thermal conductivity.
(5)Metals shown may be applicable if a small size structure.
(6) GFRP has been used successfully as mirror substratesand for some submillimeter reflectors core and skin.
1010 Aerospace equipment and instrument structure

or
A L / L = PAM
Once /3 is known, the expected strain can be
E calculated for a given percent moisture con-
tent in the laminate.
The significance of Fig. 47.4 cannot be over-
emphasized. Up until 1989 designers of aero-
space structures had to utilize the
work-around techniques 1and 2 mentioned in
Table 47.2 in order to handle the excessive

I.WOE4 '-
4- -
j
Ii
j
I
0.0024
l
j
*l ~

0.00211 0.0032 O.WJ6 0 . W

TEMPERATURE( 1 I K )
Fig. 47.2 Diffusivity against temperature for
P75S/cyanate; P75S/epoxy system.
relative humidity and shows the significance
between an epoxy and cyanate ester resin.
Table 47.6 provides values for the swelling
coefficient @) for typical GFRP materials
used to fabricate aerospace structures, where
p is calculated from:
p =
expansion and the corresponding distortion
associated with the hygroscopic nature of
epoxy based GFRP material systems. Table
47.7 indicates work-around techniques uti-
lized on various programs before cyanates
were introduced. Cyanate ester resin systems
now being used (Brand et al., 1992) in GFRP
materials offer increased stability at reduced
cost for aerospace structures, primarily due to
the possible elimination of expensive mois-
ture barriers (10% of manufacturing costs)
and the even greater cost of facilities for dry-
out processing.
(E&) (47.4)

IW

0 40
- rm ERLWW RES4N
( worn I
E
0 30
g
w
080 P76S I ERLISBZ
(EwxIl

5 080

I P
s
z
URE '
J
L
P765 I ERLlOsO
I CYUUTE I

0 10 020

OW
0 00
0 00 2 00 4 00 8 00 8 00 1000 RELATIVE HUMIDITY I X )
TIME ( H O U R S ~ 7 I P )

Fig. 47.3 Percentage moisture change against time Fig. 47.4 Percentage moisture pick-up against rela-
(h1Iz)for 0 . 5 m thick P75S/cyanate at 100% RH tive humidity (Yo). (a) ERL1999 epoxy resin; (b)
exposure. P75S/ERL1962 epoxy; (c) P75/ERL1999 cyanate.
 Historical perspective and progress 1011

Table 47.6 Typical material CMEs for pseudoisotropic laminates

Material p (PPM/%M) M , @ 100% RH

T300/EP 400 1.13
T50/EP 215 1.13
P75S/EP 162 1.03
P100s / EP 103 1.03
P120S/EP 86 1.03
P75S/CY 105 0.32

Microcracking Figure 47.5 illustrates the effect of composite

microcracking. As the temperature is lowered
Microcracking of a composite which causes
and reaches the threshold of microcracking, as
dimensional instability should no longer be an
evidenced by an abrupt strain change, the
issue if the proper material selections are
curve changes to a new slope. Dimensional
made. A need to thermal cycle to gain dimen-
instability manifests itself in the following
sional stability (causing translaminar cracking
ways:
or microcracking to progress to completion)
was a requirement in the past, e.g. in Hubble 0 A hysteresis effect is produced in the struc-
Telescope tube components. This was due, pri- ture.
marily, to of the relative brittleness 0 Changes in CTE occur (CTE becomes more
(non-toughened) of the resins and the unavail- negative with increased thermal cycling).
ability of thin cure ply thickness prepregs. 0 Moisture response rates and moisture levels
Also, at the time, the phenomenon was not increase.
fully understood. 0 Irreversible expansion of the GFRP material.

Table 47.7 Prior work-around technique for addressing the hygroscopic nature of graphite/epoxy

Instrument Work-around technique Annotations (Ref.)

(from Table 47.2 -
Hygroscopic nature)
Teal ruby 1 Stumm, 1979. Cryogenic application,
indium/bismuth deposited metal-type moisture
barrier - space application
Thematic Mapper 2 Walrath, 1979. Two flight units operational,
bake-out and environmental controls during
assembly and test very well controlled and
monitored - space application
Mars Observer camera 2 Telkamp, 1990. Pre-flight unit test provides
dimensional change data, compensated for by
preset of optics - space application
HRMA Cylinders HEAO-B 1 Hertz, 1977. Aluminum foil-type moisture
barrier; space application
1012 Aerospace equipment and instrument structure

I 2%
Anisotropic behavior
The anisotropic behavior of GFRP offers a
challenge in the design of aerospace struc-
tures. Some typical areas of concern are joints,
springback, cutouts in cylinders and bowing
of panels and assemblies.

Joints
Early in the 1970s, designers discovered that
the through-the-thickness (translaminar)
properties exhibited by GFRP reduced
strength and increased CTE values for joints,
Fig. 47.5 Interpretation of common events occur- i.e. the CTE in-plane may be 0.10X10-6/oCand
ring during measurements illustrating 34X104/"C through the thickness. In the fol-
microcracking of pseudoisotropic GY-70/930 lowing years, however, improved
(0"/45" /90° / 135")%.
12mm/ply. mechanical/ thermal joint designs have
evolved which optimize joint characteristics
relative to thermal distortion/ cost/weight
requirements. Figure 47.6 illustrates this evo-
lution for both fixed and removable joints with
the development path moving from A to D.
Today the following procedures can be used
by designers to select appropriate fiber and
resin systems to eliminate or minimize micro-
cracking.
0 Establish the thermal range of the exposure
environment.
0 Determine the stiffness, CTE, and weight
requirements of the application.
0 Use a thinner cure ply thickness (CPT)
prepreg, if high modulus materials are
required (e.g. 0.0063 mm or less CPT) or a
woven fabric. @ WAL OCUBLE CLIP @ MllY 6 TENON

0 Select a resin system compatible with the

thermal and mechanical requirement (e.g.
cyanate esters such as Fiberite 954-3 or YLA
RS-3 do not microcrack when used with
UHM pitch fibers (Amoco P75S) even at
cryogenic temperatures).
0 Establish the optimal fiber orientation (e.g.
(0"/45°/900/1350)s).
Of course, adequate testing of the material
laminates before they are employed in the
structure will ensure that correct material
selections have been made. Fig. 47.6 GFRP joint design evolution.
 Historical perspective and progress 1013

Springback Flat panel bowing/warping

Springback occurs when composite laminates
are formed into angles during processing.
Springback, or angle closure, occurs to the
extent of about 1.5" upon removal of the lami-
nate from the tool (General Dynamics
Corporation, 1985). Exposure to moisture con-
ditions will open this angle (via moisture
absorption) to return to, or even exceed, the
original angle. Through-the-thickness expan-
sion of the laminate is the source of this
dimensional instability. Using flat laminates
and butt bonding at right angles is the work-
around technique. Very thin clips can be used
at the joint.
Thermally, structures can be very sensitive
to this problem as was discovered in the late
1970s in the testing of the GEMS Forward
Mirror Support (Campbell et al., 1981). This
problem has often been overlooked by design-
ers over the years and needs to be considered
whenever composites are utilized on dimen-
sionally stable structures. Back-to-back angles
or more simply mortise/tenon joints have
been the work-around technique.
When laying up a flat panel, the typical fiber
angle tolerance from the desired angle is O G o .
This manufacturing tolerance is a major con-
tributor to the bowing or warping of a panel.
The thicker the laminate, the more a problem
these variations are, in that substantial forces
are required to make the panel flat. The lami-
nate can straighten upon moisture absorption,
and drying the laminate to its original cured
state will bring back the prior laminate geom-
etry.
The best solution for e h i n a t i n g bowed or
warped panels is to use a 'rotate and fold' lam-
inate technique, specifically developed, to
produce essentially balanced laminates. This
technique is depicted in Fig. 47.7. In essence,
ply lay-up tolerances are canceled by becom-
ing symmetrical, with the resulting laminate
properties truly isotropic throughout the lami-
nate. Note that this process is only applicable
to pseudoisotropic laminate configurations.

Cut-outs in curved surfaces (cylinders)

Some design approaches require holes in
cylinders. The degree of distortion when a
large hole is cut in a cylinder is surprisingly
extensive and the stresses generated can force
the cylinder to take a different shape (oval or
hour-glass). Even the ends of a cylinder that
has a large hole in it will not be flat or parallel
to each other. The thicker the cylinder wall, the
more difficult it is to correct this condition.
Stiffening rings usually correct the problem on
thin walled cylinders. Springback and cutouts,
in formed parts, may reduce the benefit gained
by a reduced number of piece parts if tight
dimensional control is necessary. Parts may
not fit together. Again, through-the-thickness
expansion of the laminate is the source of this
dimensional instability.
Fig. 47.7 The rotate and fold laminate construction
technique.
1014 Aerospace equipment and instrument structure

Assembly bowing
By maximizing the use of flat stock and mak-
ing dual skin, eggcrate core structures, very
stable assemblies are possible. This brings
about an additional concern with through-the-
thickness expansion in that when an egg-crate
core is used in a structure, severe bending is to
be expected unless a specific design technique
is employed. Since through-the-thickness
expansion is 1000-times the basic in-plane
expansion of the laminate, bending of the
structural assembly occurs. Figure 47.8 illus-
trates the correct and incorrect slotting
method. If done correctly the structure (Fig.
47.9) stays relatively straight through thermal
Fig. 47.9 FGS keel. The structure remains stable
cycling and moisture absorption. because the correct slotting method was employed.
Mortise and tenon joints, used instead of clips, also
promote stability.
INCORRECT SLOTTING METHOD
47.2.2 CONSTRUCTION METHODS
I 1
1 n n
WET OR T
n
R.T.
n I Some important design options for aerospace
equipment and instrument structure are:

lnnnnl ORY OR T = R.T.

0
0
truss (tubes) or cylinders (for telescopes);
monocoque skins or honeycomb sandwich
(for reflectors);
0 bonded, or bonded and bolted (for typical
joints);
CORRECT SLOTTING METHOD
0 molded unibody or flat laminate/bond
I U n U n
assemblies (for typical structures).

WET OR T R.T.
Truss compared with cylinder (telescopes)
Material availability, size, weight, interface,
DRY OR T : R.T.
loads and stiffness requirements or considera-
tions may drive the designer to a particular
configuration for a particular application.
Designers who favored tubular truss struc-
tures in the 1970s might not choose such an
approach today. Design techniques are differ-
ent, material choices are many, and
manufacturing methods have changed. Today,
for example, the Hubble Telescope could be
CROSSING RIB THICKNESS
ADHESIVE designed as a faceted, dual-shell structure
with a ribbed core. The faceted dual-shell
Fig. 47.8 Correct and incorrect slotting methods. (skins) could have water-jet cutouts with a
 Hisforical perspective and progress 1015

latticework appearance. Then, again, the tele- a molded part is excessive on a particular
scope might look the same but be fabricated design, a molded part may not be better. Then
from a non-microcracking, low moisture again, flat laminate construction may mean
absorbing, thin-prepreg, cyanate ester prepreg that more parts have to be made, inspected
system material. and handled, and if this cannot be done effi-
ciently by the manufacturer, then it may not
be the best approach. Some manufacturers
Monocoque skins compared with
can handle flat laminate construction very
honeycomb sandwich (reflectors)
efficiently, if they have experience of assess-
Large GFRP honeycomb reflectors were suc- ment of cost, weight, risk. Many flat laminate
cessfully fabricated in the mid-1980s for the 100% bonded assemblies for aerospace equip-
Advanced Communication Technology ment and instrument structure have been
Satellite (ACTS) spacecraft reflector. At the fabricated and successfully flown, both on
same time that large membrane reflectors aircraft and spacecraft. Apparently the previ-
were made for a Direct Broadcast Satellite ous high risk, thought to exist with this
(DBS) spacecraft reflector. They both met the approach, has not been proven true in prac-
desired design requirements. The tie-down tice. Here again, designer experience and
configurations and weight constraints, in part, preference will determine the course to fol-
dictated which approach was utilized. Here low.
again the requirements of size, weight, inter-
face, loads, stiffness and material availability
47.2.3 TOOLING DEVELOPMENT
will influence the design. Designer experience
and preference will also determine what con- The number of cures, the size of the part and
cept is used in the future. facilities available influence the choice of tool-
ing to such a degree that each product
fabricated must be thought-out thoroughly to
Bonded joints compared with bonded and
select the proper tooling.
bolted joints
An advantage of flat laminate construction
Experience with all bonded structures, cost is that it eliminates a need for fabricating pro-
considerations, and successful application (i.e. duction molds. A designer may want to look at
hardware on-orbit) are driving designers of this approach first in order to cut costs, if expe-
aerospace structures away from fasteners alto- rience and fabrication techniques support this
gether. The short cyclic load duration for method of fabrication.
spacecraft today are such that little, if any, ben- The high cost of production molds can be
efit is gained from bolts or fasteners and their significantly reduced through the use of alter-
use should be minimized. Aircraft applica- nate techniques. For example, for cylinders,
tions for equipment and instruments may be thin-walled rolled and welded aluminum
another story and each application needs to be molds create dramatic savings as their light
reviewed thoroughly, assessing cost, weight, weight permits envelope bagging which elim-
risk and so on. inates the need to withstand autoclave
pressures.
Monolithic (bulk graphite) molds are
Molded (unibody) compared with flat expensive and heavy (storage and heat-up
laminate bondedassemblies rate concerns), but their CTE match to GFRP
The use of fewer parts may not be beneficial or Kevlar/epoxy is a great advantage.
if they do not match up well at assembly. Greater accuracy and better replication of
Also, if the cost of tooling and touch labor for parts is possible.
1016 Aerospace equipment and insfvument structure

The tooling concept and materials used to ment and their application to aerospace equip-
ment and instrument structures (Tables 47.8
fabricate the tooling can be as important to the
success of the hardware as the hardware and 47.9). The photograph of the Hubble Space
Telescope (Fig. 47.10) only shows the metering
design itself. The aerospace structural designer
truss structure for the telescope; substantially
must stay in touch with technological develop-
ments in tooling and tooling materials. more GRFP was used in the fabrication of the
Ford Plane Assembly (FPA) and the many
other components. The milestones cited repre-
47.2.4 MAJOR MILESTONES
sent major advances and point the way for
Milestones in the use of composite materials continued use of composites for a wide variety
have been in the areas of materials develop- of aerospace structures.

Table 47.8 Milestones for GFRP materials

Material Achievement
Thin prepregs Reduced weight of hardware components
Minimized microcracking
Supported mirror technology
Increased thermal stability of laminates
Toughened epoxies Increase impact resistance of laminate
Increase bond strength (interlaminear) of joints
Increase compressions strength of laminate
High modulus PAN fibers Reduce hardware weight
Allow high stiffness, thermal stable, cyanate laminate
Allow high strength application
Ultra-ultra high modulus pitch fibers Increase thermal conductivity
Minimum weight, stiff structures
Increased EM1 capability
Cyanate ester resins Reduced moisture levels
Reduced strain response to moisture level
Reduced microcracking
Increased use temperature (high TE)

Table 47.9 Milestones for GFRP applications

Application Date Achievement

Hubble telescope 1970-1980 Design and fabrication of a very large
(2.4 m diameter x 5.2 m length) and
thermally stable structure
Nimbus-G 1970-1980 No fasteners - membrane shell 100%
bonded microwave reflector; Qual
unit qual-tested twice. Flown in 1990
as TOPEX.
Shuttle RMAB 1970-1980 Reusable structure. Multiple shuttle
missions.
 Current applications 1017
-

Fig. 47.11 ACTS reflector.

Fig. 47.10 Hubble space telescope metering truss

assembly.
47.3.2 HRDI OPTICAL BENCH (UARS)
This 1.24 x 1.8 x 0.11 m thick, 49.9 kg optical
bench for NASA's Upper Atmosphere
Research Satellite (UARS) mission was nearly
47.3 CURRENT APPLICATIONS
100% bonded (Fig. 47.12). The only fasteners
were anti-peel fasteners at the four comers
47.3.1 ACTS REFLECTORS
where graphite/epoxy (T50/ERL1962) panel
The Advanced Communications Technology sides terminate at titanium fittings. The bench
Satellite (ACTS) reflectors were manufactured carried 3.2 times its own mass and had a CTE
by Composite Optics, Inc. (COI), for General of 0.36 X 10-6/oC(Dodson, 1989).
Electric/Astro-Space Division under contract
with NASA Lewis Research Center (Fig. 47.11).
47.3.3 WCS(SOH0)
These large reflectors (2.2 and 3.3 m aper-
ture) had measured surface RMS accuracies of The Ultraviolet Coronagraph Spectrometer
approximately 0.071 mm over their entire sur- (WCS) for the European Space Agency's Solar
face after thermal cycling. These reflectors and Helospheric Observation (WHO) space-
were launched into orbit in September 1993 craft (1995 launch) is 100% bonded
and are functioning well. Their GFRP skins graphite/epoxy (P75S/ERL 1962) (Fig. 47.13).
(P75S/ERL1962) and Kevlar honeycomb core This truss structure is the first of its kind in that
(Kevlar 49/934) resulted in a 3.44 kg/m2 the basic truss panels are bonded assemblies
weight for the completed reflector (Rule, 1989). that have an I beam cross section. Eighty
1018 Aerospace equipment and instrument structure

ophcalstabilitynquktnmts(CTE-0.09 X lW/OC)
had to be satisfied along with strength and fre-
quency (70 Hz) requirements. The structure
will hold 90.7 kg of equipment and only weighs
21.8 kg itself (Kilpatrick et al., 1990).Most of the
surfaces on the structure were clearable and
inspectable (minimal closed areas).

47.3.4 COSTAR (HUBBLE TELESCOPE

Fig. 47.12 HRDI bench (UARS).
CORRECTIVE OrrrCS)
The Corrective Optics Space Telescope Axial
Replacement (COSTAR) was developed by
Ball Corporation by NASA/GSFC. This struc-
ture (Fig. 47.14) supports a Deployable Optical
Bench (DOB)that serves as the corrective optic
for the Hubble Space Telescope. Built by
Hercules Aerospace Company, this composite
structure has to have a low CTE (<0.15) and

:ig. 47.13 W Coronagraph Spectrometer (UVCS) telescope structure assembly (SOHO).


Fig. 47.14 Corrective Optics Space Telescope Axial Replacement (COSTAR).
high resonant frequency (100 Hz for the DOB).
The long-term stability effects due to moisture
absorption (ground) and desorption (space)
were addressed by optimizing the composite
laminate orientation. The long-term CTE con-
cerns were more important in meeting
line-of-sight requirements (>15 arc-sec) than
was a need to optimize CTE. A removable
cover and mounting of aluminum electronic
box required very unique design solutions
(Neam and Gerber, 1992).
47.4 PREDICTIONS
The dominance of GFRP as the preferred
choice composite material in the fabrication of
aerospace equipment and instrument struc-
tures will continue into the next century
because of a number of reasons:
Predictions 1019
0 new materials;
0 new manufacturing processes;
0 new applications;
0 economics.
This, of course, does not mean other composite
materials will not be used, but their use will be
in similar proportion as is the current practice.
47.4.1 NEW MATERIALS
GFRP is a constant evolution of material varia-
tions. Fiber makers continue to change their
fiber manufacturing processes to create a new
fiber to satisfy the needs of the user. Properties
like fiber strength, modulus, and thermal/elec-
trical conductivity are continuing to be
adjusted for various application requirements.
The demand for properties changes also are
requested of the resin manufacturers and/or
1020 Aerospace equipment and instrument structure

prepreg suppliers. Cyanate ester resin formula- 47.4.2 ECONOMICS

tions are in their infancy, current GFRP A 1993 conference held in Logan, UT, spon-
cyanates have levels of moisture absorption sored by the AIAA and Utah State University,
less than one-third the GFRP/epoxies. Soon had a basic theme for small satellite structures
moisture absorption for GFRP/cyanate may be of ‘cheaper, faster, better’. The ’better’ was in
one-tenth that of GFRP epoxies. In the future, some cases interpreted as lighter for better
we may have thermoset resins that will have performance.
no moisture absorption and their operating One of the primary messages to the indus-
temperatures may be over 240°C (464°F). try from that conference was that economics
dictates that satellites become smaller and
New manufacturing processes lighter so that the ’on-orbit’ cost for a particu-
lar satellite is much less, can be launched by a
It is hard to imagine new manufacturing meth- small, low-cost launch vehicle (e.g. OSC
ods for processing GFRP that are not in use Pegasus or Lockheed LLV1). GFRP is currently
today, but the demand for less expensive the most logical choice to satisfy the require-
materials, and hardware may bring develop- ment of cheaper, faster, and better.
ments. One method currently being developed Manufacturing processes are developed that
by Composite Optics, Inc. in San Diego, CA, will allow lightweight GFRP to be utilized for
called SNAPSAF is predicted to reduce the bus structures, solar panel substrates, reflectors
manufacturing cost to less than half current and instruments. Weight reductions of 5040%
levels. are possible with GFRP. Package size may be
the only limitation to allowing three or four
New applications satellites to be launched rather than one or two.
Creative packaging and miniaturization will
New applications stimulate the need for new solve this problem and launch booster cost will
materials, and new materials, in turn, create then be minimal (25-35% of the current cost
new applications. Future applications for level of a single satellite).
GFRP are mirrors of all sizes, surface figure This same idea (cheaper, faster, better) can
and accuracies in the IR and visible range, also apply to aircraft equipment and instru-
large antenna reflectors (9.1-27.4 m diameter), ments, namely, airborne avionics, tracking
electronic chassis and cardguides, plated RF
and targeting instruments, and phased
components (MUX Cavities, Diplexers),
arrays. Today, a military or commercial air-
phased arrays, to name a few. The list is on-
craft maker may not be able to sell a new
going but it is hard to tell whether new GFRP
aircraft but he could redesign the avionics
materials bring about these applications or the
(lightweight) to improve the performance of
applications bring about the material. For
that aircraft (including helicopters).
instance, Amoco’s KllOOX fiber is being exper-
imented with for electronic chassis, but the
original demand was for high thermal conduc- 47.5 CONCLUSIONS
tive material for heat sinks (thermal straps). Ln
The technology of composite materials, espe-
another example, thin prepregs were devel-
cially GFRP, is constantly evolving to allow
oped to make lighter skins for honeycomb
increased aerospace application. This
panel structures, but in the future mirrors for
increased use of GFRP is for both current type
visible range optics will also mostly use these
applications as well as genuinely new applica-
thinner prepregs.
tions where GFRP was not previously used.
The future for composites, in general, looks
 References 1021

promising because of the need for aerospace Krumweide, G.C., Brand, R.A. 1991. Attacking
equipment and instrument structures to be Dimensional Instability Problems in
lighter which increases performance and saves Graphite/Epoxy Structures. Composite Design,
costs. Manufacturing methods are being Manufacture and Application. ICCM/8.
Honolulu. July 15-19.
developed that allow GFRP hardware, in par- Krumweide, G.C. 1977. Development of a graphite/
ticular, to be processed less expensively with Epoxy Reflector: A design-to-cost project.
reduced cycle times. It is not hard to imagine SAMPE Quarterly. 8(3).
GFRP material replacing most metallic mater- Krumweide, G.C., Chamberlin, D.N., Rule, J.E.
ial applications for aerospace equipment and 1988.Adaptation and innovation in high-modu-
instrument structure once 'old paradigms' are lus graphite/epoxy composite design: Notes on
given up and awareness of new GFRP mater- Recent Developments. SPIE 0 - E LASIE 1988.
Los Angeles.
ial technology is the norm. Krumweide, Derby, E.A., Chamberlin, D.N. 1989.
The performance of effective moisture barriers
for graphite/epoxy instrument structures.
REFERENCES
SAMPE. Atlantic City, NJ.
Brand, R.A., Derby, EA., Chamberlin, D.N. 1992. Krumweide, G.C., Hoste, J.H. and Staats, J.R. 1979.
Evaluation of high-modulus pitch/cyanate Structural Development of the Thematic
material systems for dimensionally stable struc- Mapper Optical Metering Structure. The
tures. Design of Optical Instruments, Orlando, FL: Enigma of the Eighties: Environment,
SPIE. Economics, Energy. S A M P E J. 24(2), 1343-1355.
Campbell, M.P., Hoste, J.H., Kedward, K.T., Levy, D.J. and Arnold, C.R. 1984. Metal Moisture
Krumweide, G.C. 1981. Designing Composite Barriers for Composites. 29th Nat. SAMPE
Structures for Thermally Stable Applications. Symp. April 3-5.
Fifth DOD/NASA. Conf. Fibrous Composites in Rule, J.E. 1989. Thermal Stability and Surface
Structural Design. New Orleans, LA. January Accuracy Considerations for Space-based
1981. Single-and-Dual Shell Antenna Reflectors. E S A
Dodson, DJ., Rule, J.E. 1989. Thermal Stability ESTEC. Noordwijk, Netherlands.
Considerations for Space Flight Optic Benches. Stumm, J.E., Pynchon, G.E. Krumweide, G.C. 1981.
TomorrowS Materials Today. Vol. 34. Graphite/Epoxy Materials Characteristics and
Dunbar, D.R., Robertson, A.R., Kenison, R. 1978. Design Techniques for Airborne Instrument
Graphite/Epoxy Booms for the Space Shuttle Applications. 309. Airborne Reconnaissance. V,
Remote Manipulation. ICCM 11, Toronto, Canada. SPIE.
General Dynamics Corporation (GDC Manual). Stumm, J.E., Pynchon, G.E., Pepi, J.W. and Bovenzi,
1985. Design for Cost and Quality Manual. F.G. 1979. Low Temperature/High Stability
Herrick, J.W. Multi-Directional Advance Applications of Composites. The Teal Ruby
Composites for Improved Damage Tolerance. Experiment. Conf. Advanced Composites. El
Composites in Manufacturing 3. Anaheim. Segundo, CA.
January 10-12,1984. Telkamp, A.R., and Derby, E.A. 1990. Design
Hertz, J. Moisture Effects on Spacecraft Structures. Considerations for Composite Materials used in
1977. The Enigma of the Eighties Environment: the Mars Observer Camera. Advances in Optical
Environment, Economics, Energy. SAMPE, 24(2). Structure Systems. 1303. Orlando, FL: SPIE.
Kilpatrick, M.C., Girard, J.D., Dodson, K.J. 1990. Walrath, D.E. and Adams, D.F. 1979. Moisture
Design of a Precise and Stable Composite Absorption Analysis of the Thematic Mapper
Telescope Structure for the Ultraviolet Graphite/Epoxy Composite Structure. Modern
Coronagraph Spectrometer (UVCS).Advances in Developments in Composite Materials and
Optical Structure Systems. Vol. 1303. Orlando, FL: Structure. ASME Winter Meeting.
SPIE.
AIRCRAFT APPLICATIONS
Richard N . Hadcock
48.1 INTRODUCTION
Advanced composites, composed of high-
strength, high modulus, low density
continuous fibers embedded in polymer
matrices, first became available some 30 years
ago. Since then, composite aircraft structures
have transitioned from laboratory curiosities
into low-risk, light-weight alternatives to
metal structures. Thousands of safety-of-flight
composite components are flying in regular
service on military and civil aircraft.
Major advantages of high-performance
composite structures include weight savings,
material tailorability, improved fatigue and
corrosion resistance. Disadvantages are pri-
marily cost related. Almost all the composite
structures currently in production and service
have thermoset matrices. A few aircraft parts
are currently being made from thermoplastic
matrix composites. Metal matrix composites
are still in the development stage.
'Conventional' aircraft structural materials
now include polymer matrix composites in
addition to aluminum, titanium and steel. The
chronology of utilization of different rein-
forced plastics is shown in Fig. 48.1.
48.2 DESIGN AND CERTIFICATION
REQUIREMENTS
The general structural design and certification
requirements apply to both composite and
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
48
metal aircraft structures. However, there are
some basic differences between the generic
civil and military requirements and further
variations associated with the intrinsic differ-
ences between the structural behavior of
metals and composites.
The US Federal Aviation Regulations (FAR)
for civil aircraft and the US Air Force (USAF)
and US Navy (USN) military aircraft require-
ments have differences. The European Joint
Airworthiness Requirements (JAR) are similar
to the FAR and have a similar numbering sys-
tem, but, again, there are some differences.
FAR sections related to design and certifica-
tion of aircraft, aero engines and propellers
contain more than 600 pages'. The equivalent
USAF documents contain almost 400 pages
and distribution is restricted.
Although the requirements are applicable
to both metal and composite structures, certifi-
cation of composite structures is very much
more extensive and requires many more tests.
The contractor must fabricate and test thou-
sands of specimens and hundreds of
subcomponents to qualify a single new car-
bon/epoxy system and associated structural
details.
As an example, the material qualification
program for the all-composite Beech Starship
included collection and analysis of thousands
of data points from element, panel and sub-
component tests. Finally, fatigue and residual
strength tests were made of a complete air-
frame2f3. A similar test -program
- was used by
CASA to certify the Airbus A320
carbon/epoxy stabilizefl.

Colton/ x- -.- x P r o p e l l e r s
8.lUllt.
FbuPhenolk x - - - x
Fig. 48.1 Aircraft structural reinforced plastics. (01994 RNH Associates.)
Certification of military aircraft composite
structures also requires a major test program.
The ’Building Block‘ approach, which starts
with static, fatigue and damage tolerance
tests of elements, followed by tests of sub-
components and full-scale components, has
been very successful in identifying and solv-
ing design and manufacturing problems
before the design is finalized and frozen. Live
fire tests are also required for US military air-
craft certification. The ’Building Block’
approach was for certification of the
Grumman/US Air Force B-1A composite hor-
izontal stabilizer and for the McDonnell
Douglas/US Navy F-18 and AV-8B composite
wings5r6.
Advanced composite materials 1023
Composite M a t e r i a l x--RhD.-x Development
Winp Spar, Fuselage Produdlon
48.3 ADVANCER COMPOSITE MATERIALS
Boron fiber reinforced plastics (BFRP) and car-
bon fiber reinforced plastics (CFRP) advanced
composite materials were first used for aircraft
structures in 1966. Epoxy matrices were used
for these materials, which were produced as
prepregs in the form of unidirectional prepreg
tape.
Use of BFRP has been limited by the very
high material price (more than $900/kg in
1993).
Since the early 1970s, CFRP prepregs have
become available in the form of unidirectional
tape, woven broadgoods and other forms with
many different types of carbon fibers and with
many different epoxy, polyimide and bis-
maleimide (BMI) thermoset matrices. CFRPs
have also been available with PEEK and other
thermoplastic (TP) matrices.
1024 Aircraft applications

Almost all CFRP aircraft structural compo- Because the price of aviation fuel has
nents have been made with thermoset dropped dramatically since 1978 relative to
matrices (1993 prices ranged from $60/kg for material and labor costs, aircraft prices have
epoxy matrix unidirectional tape to $250/kg now become far more important a design
for BMI matrix materials). Thermoplastic requirement than weight savings. As such, it
matrix applications have been limited by the should now be assumed that the customer will
high price (about $250/kg) and low compres- pay very little premium for weight savings
sion strength of these materials. and the prices of composite components
Glass fiber reinforced plastics (GFRP) con-should be comparable to their metal counter-
sisting of E-glass, and the higher strength parts. Early in the design phase, weight
S-glass fibers in epoxy, polyimide and pheno- savings can be transformed into cost savings
by reconfiguring the airplane, but this is not
lic matrices are being used for helicopter rotor
blades, for many secondary structures such as possible once the overall design is frozen.
radomes and fairings. Glass/phenolic ther- Weight savings are most valuable early in the
moset and glass/polyethersulfone and other design phase, but the value of weight savings
thermoplastic matrix composites are used for diminishes as the design becomes finalized.
fire-resistant cabin and freight hold panels and The design of the structure is primarily
liners because of their low heat and smoke dictated by production costs and by main-
release properties. Prices of glass /epoxy tainability and repair considerations.
prepreg range from $5/kg to $10/kg. Composite material prices are very high and
DuPont introduced KevlaP 49 aramid fiber costs of design, certification testing, tooling,
in 1971. Aramid fiber reinforced plastics inspection, material storage, waste material
(AFRP) have low density, high tension disposal and repair are all higher than for alu-
strength and excellent impact damage resis- minum structures. However, these higher
tance, but low compression strength. AFRP costs can be offset by designing large integral
materials are being used for radomes, leading composite components which reduce part
edges, fairings, floors and other secondary count, the number of joints and assembly
structure applications. AFRP has also been costs.
used with some local CFRP reinforcement for Most aerospace companies are using the
the complete airframe of the Avtek 400A busi- 'Concurrent Engineering' approach, where
ness aircraft. engineering, manufacturing, quality control,
Most of the composite primary and safety- logistics support and cost estimating person-
of-flight structure components (wings, nel are formed into collocated teams. The more
fuselages, empennage and control surfaces) important interfaces are listed in Fig. 48.2.
currently in service are made from The costs and prices of aircraft components
carbon/epoxy prepreg unidirectional tape or vary considerably with the type of aircraft and
woven broadgoods. Some light aircraft are the type, construction, size and materials used
made almost entirely from GFRP woven for the component.
broadgoods. Current (19924) civil aircraft prices vary
from $70/kg ($30/lb) for a small private air-
48.4 THE DESIGN PROCESS
craft to between $800/kg and $lOOO/kg for
airliners and business aircraft. Military aircraft
Composites Structure design involves many costs are very much higher and are very
different disciplines and is far more complex dependent on the total numbers of aircraft pro-
than metal structures design because of the duced. These range from a cumulative average
anisotropic strength and behavior of the com- cost of $2100/kg for 3000 General Dynamic
posite material7. F-16 fighters to more than $12 OOO/kg for 20
 The design process 1025

Requirements I
External geometry
Interface geometry
External loads
Structural requirements
Interface requirements
Operational environment
Weight & cost targets

Design engineering
Internal loads (from stress)
Materials selection
(with M&P and stress)
Cost/weight tradeoffs
Detail design
Joints and attachments
Detail drawings
(Paper/computer)

I Engineering Production Other

Loads & dynamics Materials & processes Quality control
Loads Material specifications Material control
Stiffness requirements Process specifications NDI equipment
Flutter analysis, etc. M&P standards NDI/DI requirements
Accept/reject criteria
Stress Manufacturing (with stress and M&P)
Finite element models Manufacturing engineering Dimensional inspection
Design allowables Manufacturing methods MRR action/damage repair
(with M&P) Shop instructions (with stress, design and M&P)
Structural optimization Subassembly
(with weights) Assembly Cost estimatingkontrol
Stress analysis Manufacturing
Facilities/equipment Materials (including costs of
Test requirements
Stress reports Autoclaves/presses/ovens waste and waste disposal)
Refrigerators Engineering
Weights ATMs/TPMs Quality control
Weight targets NC ply cutters MRR actions
Weight control RTM/RIM equipment IE, facilities and equipment
Machining/ drilling/ trimming Rates and overheads
Structural test
Element tests Tooling Product support
Subcomponent tests Tool design Maintenance & repair manu LS
Static and fatigue tests Moldform tooling Inspection requirements
Environmental tests Bonding tooling Repair mater& and processes
Flight test support Assembly tooling Special repairs

Fig. 48.2 Design/manufacturing interfaces. (0

1994 RNH Associates.)
1026 Aircraft applications

v)
Z

1
7
1000
100
i”’
MILITARY TRANSPORTS

AIRLINERS

BUSINESSNC

tff PRIVATE AIC

w- 1
0
U
a
0.1

0.01
1000 10000 100000 1000000
OPERATING EMPTY WEIGHT, kg
a

CIVIL

v)
Z
0
i
1
7
te
W-
0
a
a

b OPERATING EMPTY WEIGHT, kg

Fig. 48.3 Aircraft costs and prices. (a) Fixed wing aircraft; (b) helicopters. (01994 RNH Associates.)
 Structural applications 1027

48.5 STRUCTURAL APPLICATIONS grown during the past 30 years. Published

During the past 30 years, structural applica-
tions of composite materials have grown from
a few radomes and fairings to the entire air-
frame. Many hundreds of CFRP wings,
stabilizers and flight control surfaces are cur-
rently flying in regular service.
The composites weight fraction has also
weight fractions are based on either airframe
weight, structure weight (airframeplus landing
gear), or operating empty weight; and in some
cases the base is not defined at all. Because of
these differences, the structural composite
material weight fractions shown in Fig. 48.4
have been normalized in terms of per cent
structure weight (airframe plus landing gear).

40-
xi---------- AV-88 Rafale DGripen
1
\ \ I
30
25
20
15
10

0
YEAR (FIRST FLIGHT)

Fig. 48.4 Composite material weights. (a) Tactical aircraft; (b) civil transports. (01994 RNH Associates.)
1028 Aircraft applications
The composites weight fraction for tactical
aircraft, Fig. 48.4(a), appears to have leveled
between 22% and 26%. The Lockheed F-22A
airframe is composed of 26% composites, 30%
titanium and 14% aluminum; the McDonnell
Douglas F/A-l8E structural weight is 22%
composites, 15%titanium, 29% aluminum and
14%steeP.
Composite weight fractions for other pro-
duction and technology demonstrator military
aircraft, such as the Grumman A-6E (which
has a CFRP wing designed and manufactured
by Boeing), Northrop B-2A bomber and YF-
23A fighter, General Dynamics F-16XL,
Grumman X-29A, Rockwell/MBB X-31A, IAI
Lavi, the British Aerospace EAP, the
Eurofighter 2000 and the Mitsubishi FS-X, are
not included because of space limitations or
availability of weight data.
The composites weight fraction for civil
transports, Fig. 48.4(b), has two branches: the
I-
10 20
COMPOSITES, % STRUCTURE WEIGHT
Fig. 48.5 Composite weight savings. (01994 RNH Associates.)
upper branch includes most of the Western
European airliners and the Boeing 777; the
lower branch includes the McDonnell MD-11,
Ilushin 11-96 and the Boeing 737X. The latter
aircraft is reported to have less composites
than the Boeing 737-300 because many of the
operators will be the smaller airlines which do
not have composite maintenance and repair
facilities12.
Weight savings provided by composites
vary considerably with the type of aircraft and
component. Weight savings, in terms of com-
posite weight fraction, are shown in Fig. 48.5.
These tend to decrease as the overall compos-
ite weight fraction increases. These data were
obtained from different sources, primarily
References 7, 9 and 12-18. It should be noted
that the weight savings for the AV-8B are
based on a weight estimate for comparable
aluminum wing, and not the AV-8A aluminum
wing, which is smaller15.
A
TACTICAL AIRCRAFT
I
TRANSPORT AIRCRAFT
30
 Structural components 1029

48.6 STRUCTURAL COMPONENTS combat and technology demonstrator aircraft

Many composite components are currently
being produced in the US and overseas for
military and civil aircraft. Most of the major
commercial aircraft primes subcontract out the
production of more composite components
than they build in-house.
Composite structural and semi-structural
components which are currently being pro-
duced are listed in Table 48.1. Some specific
aircraft components are described later in this
section.
Different forms of construction have been
used for many of these components. Some
Table 48.1 Aircraft composite structural components
wings have composite skins which are bolted
to metal substructure (e.g. the McDonnell
Douglas F/A-18, Grumman X-29, Rockwell
X-31, General Dynamics F-l6XL, IAI Lavi),
other wings have composite skins which are
bolted to composite substructure (e.g.
McDonnell Douglas AV-8B, Bell/Boeing V-22,
SAAB Gripen, Grumman/Boeing A-6E,
Dassault Rafale, British Aerospace EAP,
Eurofighter 2000)6,9,12,14,15,17.
At least three different forms of construc-
tion have been used for stabilizers: composite
skins bonded to metal/honeycomb substruc-
ture (Grumman F-14, McDonnell Douglas F-15

Wings: Fuselages: Propulsion systems:

Box beam skins Radomes Engine fan blades
Box beam substructure Forward fuselage Engine casings
Winglets Canopy frames (helicopters) Nozzle flaps
Leading edge flaps/slats Mid fuselage Thrust reversers
Ailerons/Flaperons Rear fuselage Engine nacelles and cowlings
Flaps Speedbrakes Fan cowls
Flap vanes Tailcone Engine doors
Spoilers Floor beams Fences
Fixed leading edges Floors Transcowls
Fixed trailing edge panels Rotordomes Firewalls
Flap track fairings Crew compartment armor Turbine blade containment
Actuator fairinns Rotary launchers rings
Cabin doors (helicopters) Drive shafts
Empennage: Cabin and freight hold Pylon fairings
Horizontal stabilizerslcanards: linings and partitions Fuel tanks
Skins Overhead baggage Drop tanks
Substructure compartments Propeller blades
Elevators Air ducts
Miscellaneous:
Leading edges Flight refuelling probes
Fixed trailing edge panels Crew seats
He1icopter/Rotorcraft:
Tips Toilet waste tanks
Main rotor blades Filament-wound air bottles
Vertical stabilizers: Tail rotor blades Cargo containers
Skins Rotor drive shafts Cabin door balance springs
Substructure Tooling
Doors and fairings: - moldforms
Rudders
Leading edges Landing gear doors - assembly/bonding fixtures
Fixed trailing edge panels Landing gear fairings - checking fixtures
Ventral fins Landing gear pods Honeycomb core (GFRP and
Tips Wing-fuselage fairings CFRP)
Antenna housings Stabilizer fairings Damage repair (metal and
EauiDment access doors composites)
1030 Aircraft applications

and F-18, Mikoyan Mig-29), composite skins stabilizer of the Grumman F-l4A, Fig. 48.6.
bolted to metal substructure (General The Navy requirement that the stabilizer
Dynamics F-16), and composite skins bolted to should be fully qualified by full-scale static
composite substructure (McDonnell Douglas and fatigue tests one year before the first flight
AV-8B, Bell/Boeing V-22)9,15*17,20J1. was satisfied by successful tests in 1969. More
Elevators, rudders, ailerons and other con- than 1500 stabilizers had been built when F-14
trol surfaces have generally been made by production ended in 1991l'.
bonding composite skins to substructure com-

spars.
All composite sheet-stiffened construction
is used for the forward fuselage of the
McDonnell Douglas AV-8B and the complete
fuselage of the Bell/Boeing V-229J4,16.
There are also many variations in the con-
struction of composite components used for
civil aircraft and helicopters.

48.6.1 MILITARY AIRCRAFT COMPONENTS

Development of advanced composites tech-
nology was initiated in 1964 by General
Bernard Schriever of the US Air Force who
tasked the Air Force Materials Laboratory
(AFML) at Wright Patterson Air Force Base,
Ohio, to contract some US aircraft companies
to design, fabricate and test various structural
components made from boron/epoxy.
McDonnell made 45 rudders which were
installed on F-4 fighters for service evaluation;
Fig. 48.6 (a) Grumman F-14; (b) F-14 borodepoxy
General Dynamics was awarded a major con- horizontal stabiliser.The stripes on the lower cover
tract to develop a boron/epoxy horizontal are aluminium foil for lightning protection.
stabilizer for the F-111 in 1966; and Grumman (Courtesyof Grumman Corporation.)
won a contract to design and fabricate a wing
box beam for a conceptual advanced fighter in
1968. The US Navy awarded a contract to Boron/epoxy covers were utilized for the
Douglas to develop a carbon/epoxy horizon- McDonnell F-15 horizontal and vertical stabi-
tal stabilizer for the A 4 in 1971. Douglas had lizers and rudders. The large speed brake,
previously made and flown a carbon/epoxy which is located on the fuselage behind the
wing flap on an A-4. By May 1971, more than canopy, is carbon/epoxy-aluminum honey-
80 different advanced composite aircraft com- comb sandwich. The F-15 was still being
ponent programs had been initiatedzJ3. produced in 1994,20 years after the first flight.
The first production application of The principal production use of
advanced composites for a safety-of-flight boron/epoxy was for the F-14 and F-15 stabi-
component was the boron/epoxy horizontal lizer covers. Boron/epoxy was selected

because a comprehensive design database was
available for the material from Air Force
development programs and was less expen-
sive than carbon/epoxy. During the
intervening years, this situation has changed.
Extensive design data have been generated for
many different carbon/epoxy systems and
prices are now significantly lower than for
boron/epoxy,
Carbonlepoxy was selected for the hori-
zontal and vertical stabilizers covers of the
General Dynamics F-16. These covers are
bolted to aluminum substructure. More than
3000 F-16s have been produced between since
1976.
McDonnell Douglas, with Northrop as the
major subcontractor, was awarded the Navy
Air Combat Fighter contract in 1976 with the
F/A-l8A, an enlarged and extensively modi-
fied version of the Northrop YF-17. To save
weight and offset the increased weight of the
landing gear and other components required
for carrier operation, carbon/epoxy materials
were used for the wing, tail, control surfaces
Percent of Structural Weight
FIA-18CID FlA-18UF
UAlurninurn 49 ________ 31
HSteel ___________ 15________ 14
NUilTitaniurn 13 ________ 22
Carbon EDOXV.--10 ________
Fig. 48.7 McDonnell Douglas F/A-l8E/F material usage. (Courtesy of McDonnell Douglas.)
Structural components 1031
and access panels. The aircraft is currently
being extensively redesigned and enlarged.
Designated the F/ A-1 8E / F, carbon / epoxy
accounts for 18%of the structure weight com-
pared to 10% for the F/A-18A. Because of its
higher strength and stiffness, the new
IM7/977-3 carbon/epoxy system is being
used for the wing and empennage skins
instead of AS4/3501-6’J2. F/A-l8E/F material
usage is shown in Fig. 48.721.
In 197677, McDonnell Douglas extensively
redesigned the British Aerospace AV-8A
Harrier vertical take off and landing (VTOL)
fighter/attack aircraft for the US Marine Corps
to improve range/payload capability.
Carbon/epoxy was utilized for the complete
wing, horizontal stabilizer and forward fuse-
lage. Designated the AV-8B Harrier 11, the
composite wing weight is about the same as the
aluminum wing of the AV-8A but has 19%more
area, a 50% increase in internal fuel capacity
and a supercritical airfoil. Range-payload capa-
bility was increased by 100%. Because of high
temperatures from the exhaust in the VTOL
18
1032 Aircraft applications
mode, carbon/bismaleimide is used for the
skins of the inboard flaps and the strakes,
which are mounted under the fuselage9J2.
Usage of composites, which account for 26% of
the airframe weight, is shown in Fig. 48.8.2l
Composites are also used on other US tacti-
cal aircraft. The Navy funded Boeing to design
a CFRP wing for the Grumman A-6E in 1987
because fatigue of the aluminum wings lim-
ited the life of the aircraft. Boeing built 179
composite wings in Seattle, which were
installed on the last batches of 21 A-6 aircraft.
An additional 158 aircraft were retrofitted
with CFRP wings. A follow-on program for
120 wings was canceled by the Navy in
September 1993.
The first production application of car-
bon/thermoplastic composites was the
stabilizers of the Lockheed F-117A interdictor.
The complete fleet of F-117A aircraft are being
filled with these stabilizers to extend the flight
envelope9J2.
The wing, fuselage, tail and the rotors of the
Bell/Boeing V-22 Osprey multi-mission VTOL
tilt-rotor aircraft are almost entirely made
from CFRP and GFRP. Composites, which
Fig. 48.8 McDonnell Douglas/BAe AV-8B material usage. (Courtesy of McDonnell Douglas.)
account for 44% and 7% respectively of the
structure and rotor weight of the aircraft, are
estimated to have provided a 25% weight sav-
ing relative to a comparable metal airframe1*J4.
Because weight is so critical to performance of
this aircraft, much of the structure is currently
being redesigned to further reduce weight and
costs'*.
The outer skin and much of the substruc-
ture of the large Northrop B-2A bomber is
made from carbon/epoxy. The B-2A was
designed and produced by a team composed
of Northrop, Vought and Boeing. The B-2A,
which has a wing span of 52 m (172 ft), a wing
area of 464 m2 (5000 ft') and a gross weight of
180 metric tomes (4000001b), first flew on
July 17,1989 and is by far the largest 'compos-
ite' aircraft to fly to date9J2.
McDonnell Douglas is using 6800 kg
(15 000 lb) of composite materials for control
surfaces, stabilizer leading edges, the tail cone,
landing gear doors and pod, engine nacelles,
and the wing-fuselage fairing of the US Air
Force C-17A transport.
These components, shown shaded in Fig.
48.9, account for 8% of the structure weight

and are made by McDonnell Douglas and
many different American and European sub-
contractors including Grumman (ailerons,
elevators, rudders), Heath Techna (fairings),
Beechcraft (landing gear doors),
Aerostructures Hamble (flap hinge fairings
and trailing edge panels) and Northwest
Composites (main landing gear pods).
Since 1970, more than 7500 fixed wing US
military aircraft have been produced which
utilized composites for safety-of-flight compo-
nents, such as horizontal stabilizers, wings
and control surfacess.
Composite materials have also been used
for many structural components of European
and other military aircraft. In France, Avion
Marcel Dassault-Breguet Aviation and
Aerospatiale have been involved in composite
structures development programs with the
French government support since 1972. A
boron/epoxy rudder was flown on a Dassault
Mirage I11 in 1975; horizontal stabilizers were
flown on the Mirage F I in 1976 and composites
first entered production in 1978 with CFRP
ailerons for the Mirage F I, which provided
NONSTRUCTURALPARTS,
LINERS, TROOP SEATS
7
Fig. 48.9 McDonnellDouglas C-17A composite applications.(Unpublished:all rights reserved under copy-
right law by McDonnell Douglas. Reprinted with permission.)
Structural components 1033
26% weight saving26. The Dassault Mirage
2000, which first flew in 1978, has a CFRP fin
designed and built by Aerospatiale, a
CFRP/BFRP hybrid rudder, and CFRP
elevons, nose landing gear doors and some
equipment doors. Composites account for
about 12% of the structure weight and provide
a 25% weight savings of that total. About 350
Mirage 2000 had been delivered by the end of
1993133.
Dassault Rafale C and M tactical combat air-
craft are now in production with CFRP wings,
forward fuselage, vertical stabilizer, fin, and
control surfaces with an AFRP radome and jet
pipe fairings, accounting for about 25% of the
structure. Other advanced materials include
superplastic formed-diffusion bonded tita-
nium leading edge flaps and canards and
aluminum-lithium fuselage panels9J3.
British Aerospace (BAe) designed and built
a CFRP wing for the SEPECAT Jaguar and
teamed with MBB, in Germany, to design,
build and fly a CFRP taileron for the Panavia
Tornado in the early 1980s. The British gov-
ernment authorized BAe to go-ahead by with
. .
GFRPlNomex Core
KevladFoam Core
Kevlar/Nomex
1034 Aircraft applications

development of the EAP (Experimental

Aircraft Programme) in 1982. The EAP had a
carbon/epoxy wing with carbon/epoxy sub-
structure co-bonded to the lower cover. BAe
made the right wing and Aeritalia, who con-
tributed about 15% of the costs of the program,
made the left wing9J3.The EAP flew in 1986
and the CFRP wings provided much of the
technology and background of experience
used currently by BAe Aeritalia (now Alenia),
CASA and MBB-Dornier (now DASA) for
Eurofighter 2000 (EFA) carbon/epoxy wings,
fin,rudder and control surfaces. The first EFA
flew in 19939.
The EAP wing also provided BAe with the
experience to assist SAAB in the design of the
CFRP wing for the Swedish JAS 39 Gripen
multi-mission fighter. The first three and a half
wing sets were manufactured by BAe, subse-
quent wings and all other CFRP components
are manufactured by SAAB in Sweden. CFRP
components include the wings, canards, fin,
outboard elevons, landing gear doors, fuse-
lage and fin fairings and some fuselage access
doors, shown in Fig. 48.10. The Gripen first
flew in 1988 and entered service with the
Swedish Air Force in 19939,'3J7.
Other military aircraft which have
AIRFRAME
advanced composite components and are cur- The airframe S ~ N C ~ I Cis~deslgned for hlgh durablilty and lo modern
rently being produced include the Russian damage tolerancecdteda. To keep the welght low, abaut 25 %of the
s t i c h m Is made lmm carbon flbre CompoGltes.
Mikoyan MiG-29 fighter and the Ukrainian
Antonov An-124 heavy transport. The rear
portions of the horizontal stabilizers, fins, md-
ders, ailerons and flaps of the MiG-29 have
carbon/epoxy covers, which account for about
7% of the airframe weight. Mixed composites
are used for many secondary structure appli-
cations on the An-124 stabilizer including
trailing edge panels, landing gear pods, wing-
fuselage and flap track fairings, floor beam
caps, and nacelles. About 5500 kg (12 125 lb) of (c) Carbon Fibre CompositesContent
CFRP, AFRP and GFRP are used on the An-
124, saving 1800 kg (3968 lb)9,13.
Many technology development and flight
demonstration programs which have incorpo- Fig. 48.10 SAAB JAS39 Gripen (a) Composite wing
rated CFRP wings and other components. assembly; (b), (c) composite applications. (Courtesy
These include the Rockwell International of SAAB Military Aircraft.)
 Structural components 1035

HiMAT, Grumman X-29A, Israeli Aircraft structures. Lockheed designed and made 18
Industries Lavi (the CFRP wing and vertical AFRP fairing panels and 8 AFRP ailerons for
stabilizer were designed and built by L-1011 Tristars. Lockheed changed many
Grumman), the General Dynamics F-16XL and glass/epoxy panels and fairings to
the Rockwell International/MBB X-31A9. Kevlar /epoxy for the extended-rangeTristars3I.
Aeroelastic tailoring was used on the The experiences gained from the ACEE pro-
HiMAT and X-29A to improve maneuver capa- grams provided the confidence needed by
bility and, in the case of the X-29A, prevent Boeing to select CFRP for the Boeing 757, 767
divergence of the forward-swept wing2s,29. and 737-300 control surfaces in the late 1970s.
Dornier designed, built and ground tested a Boeing uses about 1500 kg (3300 lb) of
CFRP wing for the Alpha Jet in 198630. advanced composites in the 757 and 767 and
680 kg (1500 lb) in the 737-300. CFRP compo-
48.6.2 CIVIL AIRCRAFT APPLICATIONS
nents include elevators, rudders and many
secondary structure components made from
Prior to 1972, the major US aerospace compa- CFRP, GFRP and CFRP/GFRP hybrids. By the
nies advanced composite development end of 1988, composite components on Boeing
programs were primarily directed toward mil- airplanes had accumulated more than 9-mil-
itary applications of these materials. Boeing lion flight hours3*.Most of the 757 and 767
flew a boron/epoxy fore-flap on a 707 in 1970, fairings and fixed panels were originally
but commercial aircraft advanced composites aramid / epoxy or aramid / carbon/epoxy
development essentially began when the hybrid-honeycomb sandwich construction.
ACEE (Aircraft Energy Efficiency) Program Because of surface and matrix cracking, much
was initiated by NASA in 1972. The program of the aramid/epoxy was replaced with
determined properties of different carbon/ glass/epoxy, to improve surface p r ~ t e c t i o n ~ ~ .
epoxy material systems after long-term world- Following definition in 1990 of the 777, the
wide environmental exposure and spectrum world’s largest twin-engined jet, Boeing
fatigue loading equivalent to 20 years or 36 000 formed design/build teams to develop the air-
flights of airline service. The program also frame and systems. About 15 000 kg
included flight service of numerous composite (33 000 lb) of composite materials are used on
components to obtain confidence in the long- the 777. The empennage, produced by Boeing
term durability of advanced composite at the new Composites Manufacturing Center
structures and materials3*. at Fredrickson, Washington, is made from a
The Boeing carbon/epoxy flight service new toughened-matrix carbon/epoxy com-
program, which began in 1973, included 108 posite prepreg, manufactured by Toray in a
Boeing 737 spoilers, ten 727 elevators and four plant next to the Fredrickson facility. The same
737 horizontal stabilizers. The McDonnell material is used for the floor beams, which are
Douglas carbon/epoxy program included 20 produced by Rockwell International. Other
DC-10 carbon/epoxy rudders and a single composite components are supplied by com-
vertical stabilizer. By 1991, one of the DC-10 panies in the USA, Canada, Europe, Australia,
rudders and the vertical stabilizer, which was Singapore, Brazil and Korea. The first 777 flew
installed on a Finnair DC-10, had respectively in June 1994 and deliveries began in July 1995.
accumulated 58 300 and 17 580 h o ~ r s l * , ~As ~ .of September 1996, Boeing had delivered 35
Lockheed made a carbon/epoxy vertical stabi- aircraft and had 281 orders from fourteen air-
lizer for the L-1011, which was tested but not lines8J2. Composite structure on the 777 is
flown. shown in Fig. 48.11.
The Lockheed flight service program was The stabilizers have laminated skins with
primarily directed to Kevlar/epoxy (AFRP) cocured stringers, solid laminate spars, simple
1036 Aircraft applications
m composite materlais
Toughenedmaterial for Improved damage reslstaneaand damagetolerance,
- and parts are deslgnedfor slmple, bolted or bondedIwairS
Corroslon andfatlgue reslsmt
* Welght savings
ITwghened graphite
I Glsphlte
1 HYbm
6 Flb.wb
Wlng fixed leading
Trailing edge panel
Nose
radome
Fig. 48.11 Boeing 777 composite structure. (Courtesyof the Boeing Company.)
honeycomb sandwich ribs and non-structural
forward torque boxes. They are designed for
simple repair. The horizontal stabilizer has a
span of 21.3m (70 ft) and the projected tail
area is 101 m2 (1090 ft2),about twice the span
and four-times the area of the AV-8B ~ i n g ~
Following successful airline service of the
DC-10 CFRP rudders and fin, deployed under
the ACEE program, and production experi-
ence from composite components on the
MD-80, McDonnell Douglas extended use of
composites on the MD-11 wide-body airlineP.
Almost 5000 kg (11000 lb) of composite
materials are used on the MD-11 of which
4400 kg (9700 lb) is structural (primarily car-
bon/epoxy). Weight savings of 20-30% have
been achieved after trading some weight sav-
ings for improved reliability, maintainability,
durability and producibility. Most of the com-
posite structure is solid-skin or Rohracell foam
sandwich construction. Honeycomb sandwich
construction has been avoided because of sus-
ceptability to impact damage and moisture
penetration into the core1*.MD-11 composite
components are shown in Fig. 48.12.
As a result of the very successful French
Dassault-Aerospatiale composites develop-
Outboard alleron fln torque box
Stablllzertorque box
leading and trailing
ment programs, which included components
for military aircraft and a complete CFRP wing
for the Falcon 10, Airbus Industrie began
using carbon/epoxy for the A-300-600 spoilers
in 1983 and for the complete vertical stabilizer,
, rudder,
~ ~ . elevators and spoilers of the A310-300
in 1985. The vertical stabilizer is used as a fuel
tank on extended range aircraft26.
The entire tail, control surfaces, and cabin
floor of the A320, A321, A330 and A340 are car-
bon/epoxy. The A300 medium-range narrow-
body airliner entered airline service in 1988 the
larger A330 and A340 wide-body airliners
entered service in 1993 and 1991 respectively.
Composite applications on the A320 are
shown in Fig. 48.1326.
The Airbus CFRP horizontal stabilizers are
designed and manufactured by CASA in Spain
and the vertical stabilizers are manufactured
by Deutsche Airbus in germ an^^,^^.
Avions de Transportation Regionale (ATR),
the Aerospatiale/ Alenia consortium, uses car-
bon/epoxy for all the control surfaces and
Kevlar/epoxy for many components of the
ATR 42 regional airliner which was certifi-
cated in 1985.

Winglet Trailing Edge No. 2 Engine inlet
Access Panels
Outboard Ailerons
Fig. 48.12 McDonnell Douglas MD-11 composite structure. (01991 by McDonnell Douglas Corporation.
All rights reserved. Reprinted by permission.)
ATR utilizes carbon/epoxy for the complete
outer wing boxes of the ATR 72, a stretched
version of the ATR 42, the first airliner with a
CFRP wing box to be fully certificated in
Europe and the USA. It first flew in 1988 and
was certificated and entered airline service in
1989. The wing box, which is a fuel tank, is
made by Aerospatiale at Nantes. The weight of
the wing box was reduced by 130 kg (286 lb)
using CFRP instead of a l u m i n ~ m ' ~ , ~ ~ .
Composite materials used on the ATR 72
and details of the CFRP wing box are shown in
Fig. 48.14.
Domier chose CFRP for the complete tail
and rear fuselage of the Domier 328 regional
airliner, which also has an AFRP pressure bulk-
head. The 328 was fully certificated and
entered airline service in 1993. Material distrib-
ution and details of the CFRP rear fuselage/fh
box structure are shown in Fig. 48.15.
The de Havilland Canada Dash 8, Embraer
Brizilia, SAAB 340 and other regional airliners
are using AFRP or CFRP for many secondary
structure components.
Structural components 1037
Maln Landing Gear
Door and Struts
OF-*
Many thousands of structural components
made from composites are currently in airline
service. Damage assessment and repair has
been a major problem to the airlines. Too many
different fiber-matrix systems are currently
being used, even by the same OEM; prepreg
materials are expensive and have a limited life;
damage assessment requires special non-
destructive test equipment and experienced
technicians; minor repairs need special skilled
mechanics; major repairs must be made in an
autoclave and take many days to complete;
cost of replacement parts or leasing spares are
much higher than metal part^^^,^^.
IATA sent a questionnaire to the airlines to
obtain information on composites maintain-
ability in December 1991. The ATA/IATA/SAE
Commercial Aircraft Composite Repair
Committee (CACRC) was formed the follow-
ing year. Committee members include
representatives from the FAA, airlines, OEMs,
NASA and material s ~ p p l i e r s ~ ~ .
1038 Aircraft applications

m CFRP Ailerons
IAFRP
CFRPIAFRP Spoile
GFRP shroud

j H o r c o n t al
stabi
. Iize r s
and elevators

Landing gear doors trailing edge

Fairings access
panels

Fig. 48.13 Airbus A320 composite applications.

corbcn 1 nomex sandwich

c o k n rnonolimic structure
kwhr 1 n o m u sandwich
kevlar 1 nornex sandwich
wifh stiffening carbon plies
A fib-lair I nomex sandwich A

dsm cobin floor an& : kevlar / nomex sandwich

propeller plader : fibreglorr / polyurethane foorn / d ~ r n i n i ~spar
m
broker : carbon
5,.Ib,II 91

CARBON SPARS
(FRONT AND RFAR )

(b)

CARBON PANELS
(TOP AND BOTTOM)

Fig. 48.14 ATR72 (a) composite applications; (b) CFRP wing box. (Courtesyof ATR.)
 Structural components 1039

Domier 328 CFC Components of the Rear Fuselage , ,u ,

653515.11
1,~ ~
and the Vertical Stabllirer Box

(b)

Fig. 48.15 Domier 328 (a) composite applications; (b) rear fuselage and fin. (Courtesy of Domier.)

48.6.3 GENERAL AVIATION APPLICATIONS The Starship and the one-piece CFRP wing,
The Windecker Eagle, which flew in 1967, was which has a span of 16.6 m (54 ft) are shown in
the first all-composite (GFRP) airplane to Fig. 48.16.
obtain full FAA certification. The Eagle was The complete rear fuselage, tail, and canard
followed by the Lear Avia Lear Fan 2100, of the Italian Rinaldo Piaggio P.180 Avanti is
which had an airframe made from CFRP with carbon/epoxy; the Avanti was granted full
some AFFW secondary ~tructure'~. The Lear certification in 1990, but only 20 aircraft had
Fan program was terminated in 1985 because been sold by the end of 1993. Piaggio was
of certification problems and costs. planning to build 10 aircraft in 1994.
The Beech Starship 2000, which is almost Most of the airframe of the Avtek 400A is
entirely made from carbon/epoxy-faced hon- Kevlar/epoxy with carbon/epoxy reinforce-
eycomb sandwich construction, received full ment. Avtek was initiating the FAA
FAA certification in 198837.By December 1993, certification program in 199338.
Beech had produced 50 Starships and produc- Some European all-composite (primarily
tion was put on hold because of slow sales. GFRP with carbon/epoxy reinforcement)
1040 Aircraft applications
Fig.48.16 (a) Beech starship 2100; (b) starship wing
upper cover. (Courtesyof Raytheon Aircraft Co.)
aircraft include the British Slingsby T67 Firefly
trainer (USAF T-3A), the German Grob G115
and FFT Eurotrainer. The Russian Sukhoi Su-
26 and Su-31 aerobatic competition aircraft
have carbon/epoxy wings and tails.
CFRP and GFRP materials have been used
for many experimental and home-built and kit
aircraft. These include the Voyager, designed
by Burt Rutan and built by Scaled Composites,
which made the first unrefuelled non-stop
flight around the world in December 1986.
48.6.4 HELICOPTER APPLICATIONS
Glass/epoxy main helicopter rotor blades
were initially developed in the late 1960s by
Messerschmitt-Elkow-Blom(MBB) in Germany,
Sud-Aviation (later Aerospatiale) in France
and Kaman in the United States. The MBB
80.105, which has GFRP blades, was first pro-
duced in 1967.
With the exception of Sikorsky, almost all of
the helicopters currently in production world-
wide have composite blades.
Aerospatiale (now part of Eurocopter
International, which was formed in 1991 with
the merger of the helicopter divisions of
Aerospatiale and DASA/MBB) began GFRP
composites in the mid-1950s for cowls and
fairings. About 25% of the structure weight of
the AS 365 is made from composites26.
Sikorsky used GFRP for the canopy frame
of the S-61 helicopter in 1959, and by 1967
composites use had been extended to the rear
fuselage skins, doors, the horizontal stabilizer
and the engine cowlings of the Sikorsky S-76.
Sikorsky and Bell produced composite compo-
nents for the ACEE program and complete
fuselages for US Army Advanced Composite
Aircraft Program (ACAP).
Composites are used extensively for the
rotor blades and much of the airframes of the
new Boeing/Sikorsky RAH-66 Comanche.
Compared to the UH-60 Black Hawk, compos-
ite usage in the airframe has grown from 9% to
51%; has shifted from 50% titanium to 67%
composites for the rotor system; and has
shifted from 22% magnesium to 28% compos-
ites for the drive system. Carbon/epoxy
accounts for 44% of the airframe weight; the
rotor blades are made from carbon/epoxy-
glass/epoxy broadgoods; the main gear box
housings are made from carbon/bismaleimide
using resin transfer molding (RTM);and the
tail drive shaft is filament-wound
carbon/ epoxf9.
Composites are being used extensively for
rotor blades and airframes many other new
American, Western European and Russian heli-
copters including the McDonnell Douglas
Explorer, Eurocopter BO 108 and the Kamov
Ka-62 g.
 Structural components 1041

48.6.5 PROPULSION SYSTEM APPLICATIONS

In addition to engine cowlings, cowl doors
and nacelles, advanced composites are being
utilized for engine casings, thrust reversers,
translating cowls, fan blades and propeller
blades.
A Grumman-developed carbon/bis-
maleimide aft cowl assembly and thrust
reverser for the Fokker 100 is shown in Fig.
48.17(a). This is 25% lighter and far less
expensive than the current titanium cowl
assembly. A production CFRP transcowl for
the General Electric CF6-80C2 engine is
shown in Fig. 48.17(b). The transcowl assem-
bly weighs 86 kg (180 Ib). Grumman has been
contracted to build 600 units for the CF6-
80C2, which are used on the Boeing 747 and
767, the MD-11 and the A320.

48.6.6 CONCLUSIONS
The weights of composite structures pro-
duced annually for airliners and military
aircraft, based on five-year averages, are listed
in Table 48.2.
Twenty years ago, advanced composite
structures were only being produced for com-
ponents of military aircraft. This situation has
changed dramatically during the intervening
years: the total annual production weight has
increased by two orders of magnitude and
most of the composite structure (66%)is being
produced for European airliners (Airbus, ATR, ~ assembly; (b) transcowl.
Fig. 48.17 (a) C F cowl
Dornier). (Courtesy of Grumman Corporation.)

Table 48.2 Composite structure production (five-year averages)

Period 1975-1979 1980-1 984 1985-2989 1990-1994

Total fly weight: 27 180 905 2620
metric tonnes/vear
Distribution:
US military aircraft 21 (78%) 56 (31%) 158 (18%) 172 (7%)
US airliners 3 (llY0) 97 (54%) 334 (37%) 582 (22%)
Other military aircraft 3 (11Yo) 21 (12%) 93 (loo/,) 126 (5%)
Other airliners - 6 (3%) 320 (35%) 1740 (66%)
1042 Aircraft applications
During the past 20 years, advanced corn-
posite structures have become light-weight,
reliable, low-risk alternatives to conventional
aluminum and titanium structures. Their use
will continue to grow.
REFERENCES
1. Federal Aviation Regulations (FAR), Subchapter C
- Aircraft. 14 CFR Chapter 1, US Department of
Transportation, Federal Aviation
Administration, Washington DC.
2. Abbott, Ric, Design and Certification of the All-
Composite Airframe. SAE paper 892210, SAE
Tech. C o d , September 1989.
3. The All-Composite Airframe Design and
Certification.Aerospace Engrzg, April 1990.
4. A. Barrio Cardaba, et al., Design and Fabrication
of the Carbon Fiber/Epoxy A-320 Horizontal
Tailplane. SAMPE J., Jan./Feb. 1990.
5. Waggoner, Gary and Erbacher, Herman,
Damage Tolerance Program for the B-1
Composite Stabilizer. AlAA Paper 77-464,
AIAA/ASME 18th Structures, Structural
Dynamics and Materials Conf., March 1977.
6. Weinberger, Robert A. et al., US Navy
Certification of Composite Wings for the F-18
and Advanced Harrier Aircraft. AlAA Paper 77-
466, AIAA/ASME 18th Structures, Structural
Dynamics and Materials Conference, March
1977.
7. Hadcock, Richard N. Design and Analysis of
Advanced Composite Structures. Handbook of
Composites, (ed. George Lubin), Chap 20, New
York Van Nostrand Reinhold, 1982.
8. Aerospace Facts and Figures 1992-2993(and many
previous editions). Aerospace Industries
Association of America, Washington, D.C.
9. Jane’s AI1 The World’s Aircraft, 1993-94 (and pre-
vious editions), (ed. Mark Lambert). Coulsdon,
England: Jane’s Information Group Ltd.
10. Ted G. Nicholas. US Military Aircraft Data Book.
Various editions. Data Search Associates.
11. Current Aircraft Prices ’88 (and other editions)
Interavia Publishing.
12. Aviation Week and Space Technology: Various
issues.
13. Defense News, Flight International, Aerospace,
Aeronautics B Astronautics, Aerospace
Engineering, Air International: Various Issues.
14. Aerospace Composites B Materials, 1988-1991 and
Aerospace Materials, 1992-1993, Burnham,
England: The Shephard Press.
15. Schier,J.F. and Juergens,R.J., They Force a Fresh
Look at the Design Process. Aeronautics b
&ptember 1983.
16. Watson, James C., AV-8B Composite Fuselage
Design. Aircraft, March 1982.
17. Lubin, George and Dastin, Samuel J. Aerospace
Applications of Composites. Handbook of
Cimposites, (ed. George Lubin), Chap 20, New
York Van Nostrand Reinhold, 1982.
18. Ashizawa, Moto, Composite Technology
Growth Leading to the MD-11 Application and
to the Civil Transport Aircraft of Tomorrow.
Proc. SAMPE Meeting, Japan, 1991.
19. Brenner, Lothar and Johst, Eberhard, The
Airframe of the Dornier 328 - Proven Progress.
DGLR Jahrbuch 1989 I.
20. Hadcock, Richard N. and Huber, John. Specific
Examples of Aerospace Applications of
Composites. Lecture Series No. 124, Advisory
Group for Aerospace Research and Development
(AGARD), October 1982.
21. Information supplied by the author by
McDonnell Douglas Aerospace, St. Louis,
Missouri. Reproduced with permission.
22. Rosato, Dominic V. and Lubin, George, Plastics
in Aircraft and Aerospace. Handbook of Fiberglass
and Advanced Plastics Composites, (ed. George
Lubin), Chap 29, New York: Van Nostrand
Reinhold, 1969.
23. Hadcock, Richard N., Boron/Epoxy Aircraft
Structures. Handbook of Fiberglass and Advanced
Plastics Composites, (ed. George Lubin), Chap 24,
New York Van Nostrand Reinhold, 1969.
24. Hadcock, Richard N., Status and Analysis of
Advanced Composite Aerospace Structures
Programs. Composites Technical Note No. CTN-
466-35. G m a n Aerospace Corp. May 1971.
25. Chaumette, D. Flight Qualification of
Composite Structures at Avions Marcel
Dassault - BrCguet Aviation. AlAA Paper 82-
0755,1982.
26. Information supplied to the author by Avions
de Transport Regional, Blagnac Cedex, France.
Used with permission.
27. Information supplied to the author by SAAB
Military Aircraft, Scania AB, Linkoping,
Sweden. Used with permission.
28. DeAngelis, V. Michael, In-Flight Deflection
Measurement of the HiMat Aeroelastically
Tailored Wing. J. Aircraft, December 1982.
29. Hadcock, Richard N., X-29 Composite Wing.
Evolution of Aircraft/Aerospace Structures and
Materials Con5 Air Force Museum/AIAA, April
1985.
 References 1043

30. Rose D. et al., Design of a Carbon-Fiber- Commercial Aircraft Group, Seattle,

Reinforced Wing for the Alpha-Jet Major Panel Washington.Used with permission.
Tests. 1.Aircraft, June 1986. 35. The Cost of Composites. Air Transport World,
31. ACEE Composite Structures Technology: July 1992.
Review of Selected NASA Research on 36. Harris, Charles, Assessment of Practices in
Composite Materials and Structures. NASA Supporting Composite Structures in the
Conf. Pubn 2321,1984. Current Transport Fleet. 4th NASADoD
32. Harradine, Peter J. and Quinlivan, John T., Advanced Composites Technology Conf., Salt Lake
Composites and the Commercial Jet - A Boeing City, Utah, June 1993.
Viewpoint. Paper No. AIAA-89-2126. 37. Information and photographs supplied to the
AIAA/AHS/ASEE Aircraft Design, Systems author by Beech Aircraft Corporation, Wichita,
and Operations Conference, Seattle, 1989. Kansas, 1993. Used with permission.
33. Hyatt, M. Caton, R. and Lovell, D., Advanced 38. Information and photographs supplied to the
Materials Development in Commercial Aircraft. author by Avtek Corporation, Camarillo
Paper No. AIAA-89-2127. AIAA/AHS/ASEE California, 1993. Used with permission.
Aircraft Design, Systems and Operations 39. Garbo, Samuel P. and Rosen, Kenneth M.,
Conference, Seattle, 1989. Composites Usage on the RAH-66 Comanche.
34. Information supplied to the author by Boeing Vertifite, March/April 1992.
COMPOSITES IN THE SPORTING GOODS 49
INDUSTRY
Brian E. Spencer

49.1 INTRODUCTION went into sport and recreation applications.

Worldwide sport and recreation applications
In 1990 Frost & Sullivan reported that over $800
are the third largest user of advanced compos-
million dollars were spent by domestic
ites behind defense/aerospace and elastomer
defense/aerospace contractors for advanced
reinforcement (tires, hose and belts)'. In the
composites. In the same period, $70 million
USA as well, sport and recreation applications
worth of advanced composites were purchased
are the third largest users of advanced compos-
from domestic producers for sporting goods.
ites. One of the major growth markets for
Advanced composites are usually defined as
advanced composites over the past several
those composites that use either carbon,
years has been the sporting goods industry.
aramid, Sglass, ceramic, polyethylene, boron,
Although there was a total decline in USA
or other high strength or high stiffness fiber. In
defense spending of only 14% from 1990 to
1991, the total worldwide consumption of
1994, the procurement decline was 45%' (Fig.
advanced fibers was estimated to be 27200
49.1). The defense procurement decline was
metric tons1. Approximately 10% of this fiber

300

",250 Manpower, R&D

ln
c logistics, other
=E0 200
c

7
(I)

m
150 Procurement

100

50

Fiscal year
Fig. 49.1 Defense budget declines. (Courtesy of
Handbook of Composites. Edited by S.T. Peters. Published Westinghouse ESG news and department of
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 defense budget.)

disastrous for the composites industry and
resulted in severe upheavals. Although no seg-
ment of the composites market could offset the
defense-induced decline, the sporting
goods/recreation composite segment along
with most other segments is predicted to show
positive growth in the near future3(Table 49.1).
This growth trend is expected to continue into
the 21st century. Advances in materials and
processes have reduced consumer prices for the
recreational composite while providing
improved performance for the athlete.
Some of the first applications for compos-
ites in sport and recreation were fiberglass
boat hulls and fishing poles. Now the list of
products using composites includes almost
every sporting and recreation activity.
Products in golf, tennis, and bicycle racing
have brought attention to the superior perfor-
mance of composites in sports and recreation.
Hand lay-up and roll-wrapping have been
the processes generally used for most sporting
goods applications. There has been an
increased interest in filament winding as a pre-
ferred process for tubular products such as
golf shafts, sail masts, ski poles, softball bats
and bicycle frame tubing, because filament
winding can lower labor costs and add a new
level of design flexibility, product consistency,
and quality for these products.
Table 49.1 Annual growth rate of selected materials by region, 1993-2003
_ _ _ _ ~
Productlend use US average
annual
growth %
Advanced polymer composites
Aircraft 6.5
Missiles/ space 1.0
Recreation 6.0
Armor 6.0
Automotive 50.0
Industrial/other 4.0
Total 7.1
Introduction 1045
49.2 MANUFACTURING TECHNIQUES
Composite products may be manufactured by
several processes, depending on the shape and
physical properties required. Common
processes are hand lay-up, machine lay-up,
roll wrapping, filament winding, pultrusion,
compression molding, platen molding,
chopped fiber spray-up, resin transfer mold-
ing and braiding. Not all of these processes are
efficient for manufacturing sport and recre-
ation products.
Virtually all fishing poles and most golf
shafts are fabricated by the roll wrap process,
which consists of placing pre-cut sheets of
prepreg unidirectional tape or cloth on a man-
drel, then rolling the mandrel between platens
to consolidate the composite. Fly fishing rod
lay-ups have in the past had all unidirectional
0" plies of one material but golf shafts may
have two fibers, such as carbon and boron,
and some angle plies. A release cloth or tape is
usually wrapped around the composite to
apply pressure during the required heat cure
process and hold the composite in place. After
curing, the composite part is pulled from the
mandrel and can be machined as necessary to
the final shape. The part is then painted and
graphics are added.
Braiding and pultrusion have been used
successfully for some applications. Tennis
Rest of world World average
average annual annual growth
growth YO %
8.5 7.45
4.0 2.2
3.5 5.0
4.5 5.4
2.0 26.7
5.0 4.6
5.4 6.4
1046 Composites in the sporting goods industry
rackets have been fabricated by braiding. The
braiding process for composites is identical to
braiding textiles, except that the fiber is usu-
ally braided as a prepreg. Prince introduced
the Vortex tennis racket, braided with co-min-
gled nylon and carbon fibers, in the late 1980s.
Ski poles, kite tubes, arrow shafts, and similar
hollow or solid shafts are made by the pultru-
sion process. Pultrusion of composites is
similar to extruding metals. The resin and
fiber material are pulled through a heated die
that forms the composite to shape and cures
the resin in one continuous process. Since the
fibers are essentially all aligned down the axis
of the part there is little transverse or hoop
strength unless hoop fibers or other off-axis
reinforcement such as mats are added during
the process. Arrow shafts have shattered on
impact because of this lack of strength in the
hoop direction.
Resin transfer molding (RTM) consists of
injecting resin into a mold containing fiber in a
preform pattern. Resin transfer molding is
usually used in conjunction with a fiber place-
ment technique such as hand lay-up, braiding
or filament winding. Some tennis rackets are
fabricated using the resin transfer molding
process4.
The filament winding process is the
machine controlled technique of applying a
controlled amount of resin and oriented fiber
on a mandrel that provides the finished com-
ponent shape. The mechanics of filament
winding are illustrated in Fig. 49.2 The ten-
sioned fiber bands are accurately placed on
the mandrel using numerically computer
controlled or chain and gear mechanical
winding machines. Fig. 49.2 shows the fiber
being pulled from tensioned spools through
the delivery eye onto the rotating mandrel.
The resin can either be pre-applied on the fiber
in an off-line operation (pre-impregnation, or
wet prepreg) or applied during the winding
operation (wet winding). Prepregging usually
requires storing the material at low tempera-
ture until required for winding to retard the
curing process. Wet winding uses a resin
bath, along the fiber path between the ten-
sioning system and the delivery eye, through
which the dry fibers are pulled. Both wet
winding and prepreg winding are widely
used. The choice of technique depends on the
application, cost and quality requirements.
Composites that have directionally oriented
continuous fibers are analyzed by techniques
such as netting analysis, rule of mixtures, clas-
sical lamination theory, and micromechanics.
These analysis techniques all account for the
fact that composites have material properties
that depend on the fiber directions of each ply.
The overall directional properties of the lami-
nate are calculated by adding the relative
effects of each ply. The analyses are more com-
plicated than with isotropic materials such as
steel and aluminum. However, the wide-
spread use of computers has made the task of
analyzing composites relatively simple.
Composites are in many cases much
stronger and stiffer than metals such as steel,
aluminum or titanium. When one takes into
account the much lower density of composites
as compared to metals, composites have an
even greater performance advantage over
metals. To compare material properties on an
equal weight basis (instead of an equal volume
basis), a property such as ultimate strength is
divided by the density of the particular mater-
ial. The resultant is termed specific strength.
The same can be applied to stiffness (modulus)
and is called specific modulus. Comparing
materials this way is very important when
designing weight critical parts.
Figures 49.3 and 49.4 show the strength,
modulus, and specific properties of represen-
tative composites and metals. The composite
data are for composites with all fibers oriented
in one direction (unidirectional ply data). The
test loads are applied to the specimens in the
same direction as the fibers. Also, all compos-
ite data presented here are for 60% fiber and
40% resin by volume samples. This ratio is
typical for advanced composite laminates. The
epoxy resin used to make the samples is not
indicated specifically because its effect on the

-MACHINE DRIVE
Fig. 49.2 Layout of a typical filament winding machine (Courtesyof Composites Machines Company.)
unidirectional ply properties is negligible
compared to the effect of the fibers.
In Fig. 49.3 it can be seen that composite
plies are up to twice the strength of high
strength steel and three to five times stronger
than titanium and aluminum. Comparing
specific strengths, composites are three to
eight times stronger than the metals. The stiff-
ness of the materials, shown in Fig. 49.4, range
from fiberglass composite at the low end to
high modulus carbon composite at the high
end with metals in between. Composites com-
pare more favorably to metals in specific
modulus. The specific modulus of the com-
posites shown are one to six times greater
than for metals.
Fatigue resistance is another important
material property to consider when designing
Manufacturing techniques 1047
orlzontal and VeWtical
a product. Fatigue describes the phenomenon
of reduced strength over time of load applica-
tion (static fatigue) or the number of times a
load is applied (cyclic fatigue). Aluminum and
fiberglass composites suffer from poor fatigue
performance whereas carbon compositesexcel.
Figure 49.5 displays the cyclic fatigue
strength of various metals and composites.
Specimens of each material were loaded
repeatedly in tension to various predeter-
mined loads and then the loads were removed,
until the specimens failed. A curve of cyclic
stress against number of cycles to failure can
be constructed for each material, from which
the 10 million cycle failure stress for each
material can be obtained. The 10 million cycle
life is considered by designers to approximate
an infinite life for most applications.
1048 Composites in the sporting goods industry

Specific Strength, E6 in.

Material 0 2 4 6 8
34 msi carbon

42 msi carbon

50 msi carbon

5-2 glass

E glass

Kevlar

Spectra 1000

Titanium

-
4340 Steel

Aluminum
0 100 200 300 400 500
Strength, ksi
Strength Specific Strength
Fig. 49.3 Strength of composites; comparison with metals at 60% fiber volume.
Specific Modulus, E6 in.
Material 800
34 msi carbon

42 msi carbon

50 msi carbon

S-2 glass

E glass

Kevlar

Spectra 1000

Titanium

4340 Steel

Aluminum
0 5 10 15 20 25 30 35
Modulus, Msi
-Modulus Specific Modulus
Fig. 49.4 Stiffness of composites; comparison with metals at 60% fiber volume.
 Sporting goods applications 1049

Tension - tension ratio at 10 E + 7 cycles

Material

-
34 msi carbon
42 msi carbon

-
50 msi carbon

-
S-2 glass

-
E glass
Kevlar
Titanium
4340 Steel
Aluminum
100 200 300 400 500 600
Alt. stress density, ksi/lb. per cu. in.

Fig. 49.5 Fatigue strength of composites; comparison with metals at 60% fiber volume.

The failure loads shown in Fig. 49.5 are because of the changes in 'feel' of the rod.
given as stress density which is the test stress Many golf shafts incorporate both
divided by the material density. For the mate- carbon/graphite and boron reinforcements to
rials tested, composites have two to six times change flex point, reduce shaft weight, increase
the specific fatigue resistance as metals. torque resistance and increase clubhead
It is important to mention that the previous speed5.
comparisons of metals and composites do not
tell the whole story. Often, the benefits of a
49.3 SPORTING GOODS APPLICATIONS
composite part compared to a metal one
would not be as great as indicated by the dif-
49.3.1 RACKETS
ferences in ply strength and stiffness. The
design allowable composite ply strength is There are approximately 22.5 million tennis
10-20% lower than the test specimen players and 7 million racquetball players in
strengths. Other factors including voids, long- the USA. These players purchased 2.45 mil-
term environmental effects, use temperature lion tennis rackets at a cost of $170 million and
and imperfect fiber alignment all reduce the 1 million racquetball rackets at a cost of $53.4
ultimate strength of composites. Finally, when million retail dollars in 1992. Approximately
all the reinforcing fibers are not in the direc- 73% of these rackets were composite4.
tion of the load, the fibers do not carry the load Most all of these rackets are produced in
as efficiently. However, when these factors are the Far East using a compression molding
adequately controlled, there are many applica- process with an internal bladder. This process
tions where composite structures greatly consists of hand lay-up of prepreg around a
outperform their metal counterparts. Sport straight metal mandrel and plastic bladder.
and recreation applications are one market After lay-up the prepreg/bladder is removed
area where composites have a decided advan- from the mandrel and placed in a compres-
tage over metals. sion mold. The mold is closed, the bladder is
There are other not easily quantifiable rea- pressurized, and the part is temperature
sons for choosing a particular composite or an cured. A significant portion of the labor in
individual lay-up. Fishmg rods generally do manufacturing a racket is in the surface fin-
not have hoop reinforcement or angle plies ishing, painting and labeling.
1050 Composites in the sporting goods industy

Other processes that have been used

include injection molding, braiding, and resin
transfer molding and combinations of these
processes. Filament winding is being consid-
ered because it can allow the use of wet
winding, which reduces the raw materials
costs and labor content in racket manufactur-
ing. This process uses wet resin and dry
fibers and provides product consistency
because the operation is machine controlled.
The preform can be wound on a straight man-
drel to allow standard filament winding
techniques to be used. After winding, the pre-
form can be removed from the mandrel and
placed in the mold. The key technology is to
place the wet fiber preform in the mandrel
without disturbing or kinking the fibers. The
process then continues as the typical
processes now being used. A typical product
of this method is shown in Fig. 49.6. Filament
winding can also be used to dry wind the
fiber to make a cheap oriented fiber preform.
Then using RTM, the resin can be injected
with the prospect of further reducing hand
surface finishing. An additional advantage to
filament winding is the design flexibility of
changing strength and stiffness around the Fig. 49.6 Prince graphite extender racket. (Courtesy
racket head, which is difficult to accomplish of Spyrotech.)
using lay-up techniques.
impact on the acceptance of carbon fiber com-
posites in the bicycle industry. In 1991 more
49.3.2 BICYCLE FRAMES AND COMPONENTS
than 50% of the carbon bicycles produced
Advanced composite bicycle frames first worldwide (>lo0 000) were manufactured in
appeared in the early 1970s. These frames Taiwan6.
were not successful due to poor design and Tube and lug designs dominated the mar-
manufacturing techniques and market resis- ket until 1993. The technique consists of
tance to the new materials. In the mid-l980s, bonding premade tubes into forged or cast
composites in bicycles had success in the mar- metal lugs. Trek developed a composite lug
ket place and today are the materials of choice that is offered in some of their frames. Kestrel
for new designs6. For the past few years introduced a molded monocoque frame in
approximately 12 million bicycles were sold 1987. Molded monocoques are manufactured
annually in the USA. Of these, approximately by lay-up of composite material into female
10% were considered high-end (sales price mold halves with the reinforcing metal pieces
over $750) products. as required. The female mold sections are
In 1989 and 1990 Greg LeMond won the brought together and internal bladders are
Tour de France Bicycle Race using a carbon inflated to provide compaction pressure dur-
fiber frame. His success has had a significant ing the curing operation.

Tube and lug frames are relatively simple to
manufacture. However, the frames can have
durability problems if the tubes and tube to
lug joint are not properly designed to prevent
significant stiffness mismatches. Galvanic cor-
rosion potential is a concern. Filament
winding offers an inexpensive method for
manufacturing frame tubes. Wet winding
techniques allow using the required materials
in the lowest cost form. Since the process is
machine controlled, labor requirements are
minimized. Currently the most widespread
manufacturing method is roll-wrapping. Roll-
wrapping requires cutting prepreg plies of
composite and hand wrapping them around a
metal mandrel prior to curing.
Frame tubes are not the only use of com-
posites in the bicycle industry. Handlebars are
filament wound, removed from the mandrel,
and then cured in a mold to provide the
proper shape and curvature. An internal blad-
der provides the compaction pressure. Seat
posts, swing arms, and handlebar extensions
can be made using this process. Titanium
tubes in some front wheel suspension systems
are reinforced with composite tubing. Wheels
and spokes are also being made of composite
materials using combinations of roll wrap-
ping, hand lay-up and resin transfer molding.
49.3.3 GOLF SHAFTS
In 1992 over 100 million composite golf shafts
were made world wide with a wholesale dol-
lar value of $900 million7.The majority of the
shafts were manufactured in the Far East and
sold for less than $10 each wholesale. At the
present time, virtually all composite golf
shafts are manufactured using the roll-wrap
process. This process relies on manual orien-
tation of the plies of material on the mandrel
and ply alignment can be inconsistent from
part to part. The alignment directly affects the
shaft performance; flex, and torque. The cut
plies also create a seam down the length of
the shaft which causes inconsistency in the
shaft performance. Attention to ply alignment
Sporting goods applications 1051
helps to reduce the seam effect on perfor-
mance consistency.
Grafalloy introduced a filament wound
shaft for the 1993 season. Filament wound
shafts provide superior performance at low
weight and cost compared to roll-wrapped
shafts available with comparable performance
specifications. Those familiar with the indus-
try believe filament winding will be the
process of choice in manufacturing golf shafts
in the next few years.
Player tests and mechanical golfer testing
have proven the performance improvements
of a filament wound shaft over roll-wrapped
shafts. Many original equipment manufactur-
ers are evaluating filament wound shafts for
their product lines. One factor where roll-
wrapped shafts can have an advantage over
filament wound shafts is in tip durability.
Filament winding can introduce more voids in
the composite laminate than roll-wrapping.
Special attention is needed by filament
winders to insure that their product has suffi-
cient tip strength.
ASTM is working to establish test methods
for golf shafts. Standard tests will allow for a
better comparison of products and give the
customer more confidence in the quality and
performance of the product being purchased.
49.3.4 FISHING POLES
In 1992, 16 million fishing poles were pur-
chased in the USA. Virtually all were produced
in the Far East using the roll-wrap process. It is
estimated that about 20% are high-end prod-
ucts and may be amenable to the
manufacturing costs of automated processes in
the USA. For filament winding, this market
segment is the least developed. Development
work is underway to produce a cost competi-
tive high-end fishing pole in the USA.
49.3.5 OTHER APPLICATIONS
Other applications for composites in the sport-
ing goods industry include softball bats, pool
1052 Composites in the sporting goods industry
cues, kite tubing, shoe inserts, ski poles and
model aircraft. The majority of these products
are currently being manufactured by either
roll-wrapping, hand lay-up, or pultrusion.
Improvements in material properties, reduc-
tion in material prices, and significant
improvement in component performance has
created a market for composites in the sport-
ing goods industry*. Unfortunately for USA
manufacturers, the majority of the sporting
goods products are fabricated overseas. This
business will only come back to the USA if
companies are cost competitive and/or offer a
product of higher value which is superior in
performance. One method to improve cost
competitiveness is through the use of automa-
tion. Filament winding, along with innovative
engineering, offers the possibility of bringing
composites to the forefront in the sporting
goods industry.
REFERENCES
1. Segal, C.L. Worldwide Markets For Advanced
Fibers, 23rd Intern. SAMPE Tech. Conf.,
Kiamesha Lake, NY, October 23,1991.
2. Anon. Westinghouse ESG News, Oct, 1994.
3. Kline & Company The Changing Advanced
Polymer Composites Market, 1993.
4. Feeney, B. Composites in Racquetball and Tennis
Rackets, SME Conf. Composites Manufacturing
and Tooling '94, Anaheim, California, January
17-20.
5 . Levin, S. The Use of Composite Materials in the
Bicycle Industry, SME-Effective Applications of
Composites in the Sporting Goods and
Recreational Industry Clinic, August, 1992.
6. Textron Specialty Materials, Boron Backgrounder.
7. McConnell, V. Composites in sports: goingfor the
gold, Adv. Comp., September/October 1992.
8. Mcconnell, V. Sports Applications - Composites
at Play, High Performance Comp., Jan/Feb 1994.
TYPICAL PROPERTIES FOR APPENDIX A
ADVANCED COMPOSITES
Kenneth R. Berg

A.l INTRODUCTION material and configuration is selected, a mini-

For a company or institution that is designing mum test program would then be initiated.
composite material structures, or embarking Having a set of typical composite materials
for the first time into the application of has advantages and disadvantages. For exam-
advanced composite materials for structural ple, if one were to design a structure utilizing
purposes, it is imperative that material prop- only typical material properties, without the
erties be available. Of course it would be knowledge of the scatter that may occur in
desirable to have a complete set of statistical those properties, structural failure may occur.
Design Allowables, such as the statistical 'A' Perhaps not immediately, nor on every struc-
values for properties, or even the 'B' values, ture produced, but on an unknown statistical
(see Chapter 33 for detailed definitions of basis, at some point in time. However, prior to
these values and Neal and Spiridgliozzi, 1987). a final design for a structure, the normal engi-
Since complete statistical Design Allowables neering procedure is to initiate the test
are not available, the next sought after mater- program. The purpose of the test program is
ial properties would be 'typical' properties. threefold: one, confirmation of the design;
two, determine the scatter that occurs due to
However 'typical' properties are not defined
variations in materials and the manufacturing
statistically and may be defined in many dif-
process; and three, over a period of time,
ferent ways. Therefore it is important to
either to confirm the material properties data-
discuss typical material properties and also
base being used, or to accumulate test data for
discuss the means to achieve a set of typical
a material properties database.
proper ties.
The purpose of having a complete set of
typical properties is to be able to design com- A.2 TYPICAL PROPERTIES - CONSTITUENTS
posite structures with a minimum of testing
confirmation. Having a complete set of typical A.2.1 FIBERS
properties will allow design optimization, pre-
liminary design, cost and weight optimization One of the problems of determining typical
and other trade-offs with a number of different properties is the variations that occur in the
materials and candidate laminates with differ- materials making up laminates. In the case of
ent fiber orientations. Once an optimum glass fiber, the types of glass fiber and number
of manufacturers is considerably less than
with carbon fiber.
Handbook of Composites.Edited by S.T. Peters. Published However, even with this limitation, there are
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 at least two major types of glass fiber, E-glass
1054 Typical properties for advanced composites

and S-2 glass. Withm each of these glasses are Table A.l Typical products from carbon fiber man-
variations in chemical composition, fiber diam- ufacturers (available in USA)
eter, fiber finish, fiber sizing, the number of
A M O C O (Thornel)” Toho Rayon (Besfight)
individual fibers in a tow, roving, yarn, etc.
Manufacturers have different names for the P-100 HTAWlOO
similar type of glass, for example the higher P-75 im600
strength, higher modulus glasses. These fiber T-300 HM35
T650/35
glasses are the older S-glass (no longer avail- T650/42
Toray (Torayca)
able commercially), s-2 glass and the R-glass T300
by a French manufacturer. Other countries fab- Toho (Celion)
t7005
ricate the same type of glass, but with only G30-500 T800H
minor differences in properties. G40-800 M40
For carbon fiber, not only are there the same G40-600 M46J
variations as mentioned above for glass, but in Grafil (Grafil)b AKZO (Fortafil)
-
addition, there are large variations in strength
34-700 F-5
and modulus and in manufacturers, see Tables 42-650 F-3
A.l and A.2. 42-750
Based on the large number of variations in
fibers, it would be virtually impossible to Hexcel (Magnamite)
obtain complete statistical material properties AS4
for each variation. Even to obtain typical prop- IM6
erties for each variation would not be IM7
IM8
practical.
To reduce this problem to a practical level, it a Typical product name
is necessary to analyze the usage of glass and Grafil is a subsidiary of Mitsubishi Rayon Co. Ltd and
carbon fibers (or other fibers). The usage of their fibers are called Grafil or Pyrofil.
advanced composite fibers by ‘pounds used
per dollar expended’, is estimated to be, in
order of highest usage: E-glass, high strength Table A.2 Torayca fiber types (Toray, 1991)
carbon (modulus of 227 GPa, (33 x lo6 psi))
Fiber type Number offilaments
and then S-2 glass. With this list, it is possible
to develop typical properties for composites T300 lK, 3K, 6K, 12K
fabricated from each of these fiber types. An T300J 3K, 6K, 12K
example of the determination of the strength T400H 3K, 6K
T700S 12K
and modulus of the typical high strength car- T800H 6K, 12K
bon fiber is shown in Fig. A.l. The ’typical’ TlOOOG 12K
property becomes: Tensile modulus of 227 GPa TlOOO 12K
(33 x lo6 psi), and tensile strength of 4000 MPa M35J 6K, 12K
(580 ksi). M40J 6K, 12K
M46J 6K, 12K
M50J 6K
A.2.2 RESIN SYSTEMS M55J 6K
M60J 3K, 6K
The matrix for fiber composites can be classi- M30 lK, 3K, 6K, 12K
fied into two categories, metallic and M30SC 18K
non-metallic. This discussion on typical prop- M40 lK, 3K, 6K, 12K
erties involves only non-metallic resin matrix M46 6K
systems. M50 lK, 3K
 Typical properties - constituents 1055

300
Typical Property
Typic.i Prop.rt1.r

Strength 4 GPa
Modulu6 22.0 GPO
Modulus 227 GPa n 20
0 a

g 100
Data horn various Rbsr manufacturers

5(I
0
0
0 1 2 3 4 5
5

0
' EpoxyIAmlne
Polymstw

100 ZOO 300

+ EPoxy/Anhydrld*
bpisal Property

400 500 800

Vlnyl*stwr

700 800 900 1,000

Strength GPa Strength MPa

Fig. A.l Typical strength and modulus for high Fig. A.2 Typical strength and modulus for E-glass
strength carbon fiber. (Courtesy of Eggs composite - flexural strength. (Courtesy of Riggs
Corporation.) Corporation.)

As was discussed for fibers, only the high
usage matrix systems in advanced composites
are considered as candidates for typical prop-
erties. In addition, for typical properties of
advanced composites for structural applica-
tions, only structural resin systems are
candidates. Structural resins are defined as
resins that have similar modulus and tensile
strength as standard epoxy systems. For exam-
ple, an applicable resin for structural
composites would have a modulus of approx-
imately 3.5GPa (0.5 x 106psi) and a tensile
strength of approximately 100 MPa (15 h i ) .
The more popular structural resins are
polyester, epoxy, vinyl ester and phenolic. For
typical composite properties, the use of any of
these resins will allow a single typical prop-
erty (Fig. A.2) (CertainTeed Corporation,
1989).
A comparison for composites with different
environmental considerations. Key among
these characteristics are: temperature, frac-
ture toughness, compression after impact,
crack propagation, humidity, stress concen-
trations, interlaminar shear, mechanical
fasteners in laminates, holes in laminates,
creep, damage tolerance and compatibility
with fiber finish. In determining typical prop-
erties, these characteristics are not included
but, as applicable, need to be considered for
the final design.
cp o o /
L

400
epoxy sizing from different manufacturers and -
0

a typical value is shown in Fig. A3.

Figure A.4 shows a number of different
t 300

resin systems and the typical values for * Cellon G30/6-F 1

strength and modulus (Lubin, 1987).This data Herculee AS-4mpe 0 X Hercules AS-4ffreated
is for primarily fiber controlled properties. 0

There are properties in which the resin is

the significant factor. These characteristics are Fig. A.3 Typical compression strength for carbon
associated with stress concentrations and fiber fabric composites. (Courtesy of Riggs
Corporation.)
1056 Typical properties for advanced composites

100
90
80
2 70
60
-2 50
40
B 30
20
10
-
0
0 100 200 300 400 500 600 700
Tensile Strength MPa

Fig. A.4 Typical strength and modulus for carbon fiber fabric composites. (Courtesy of Riggs Corporation.)

A.3 TYPICAL PROPERTIES - COMPOSITES ence the transverse strength and modulus of
the base unidirectional laminate (100% 0"
A.3.1 FIBER CONTROLLED TYPICAL plies). The different strength resins shown on
PROPERTIES Fig. A.5, are as follows:
Fiber-reinforced composite materials are pri-
marily used to take advantage of the high Transverse Transverse
modulus tensile strength
strength and stiffness of the fiber. Therefore in
(GPa) (MPaa)
most applications, the laminate orientation is
designed so that the strength and modulus are Lower strength resin 8.6 41.4
controlled by the fiber properties. For example, Typical strength resin 10.0 55.2
Higher strength resin 11.4 69.0
for a typical fiber orientation in a laminate of
0"/&"/90", the 0" plies control the failure of
the laminate whenever the percentage of 0"
Laminate 15% 0",15% f Oo, 70% 9 0
plies is greater than lo%, (with a I3 greater than 700
I
*loo). For I3 less than do", if the combined per-
centage of 0" and &"plies is greater than lo%,
then the laminate is also controlled by fiber
fracture. These limitations are approximate
and depend on the fiber strength and modulus,
but are valid for carbon, aramid fibers and
glass. For high I3 angles and for 90" laminates,
the tensile strength of the laminate is reduced
0 15 30 46
below the tensile strength of the resin due to
Angle 20'
stress concentrations between the fibers (Berg,
1967). Figure A.5 shows the tensile strength of Fig. A.5 Effect of resin properties on tensile
a carbon fiber laminate of 0"/+eo/9O0 plies, strength of high strength carbon composites.
with the strength of the resin varying to influ- (Courtesy of Riggs Corporation.)

As can be seen in Fig. A.5, the typical fiber
fracture composite properties (ultimate fail-
ure) are not affected by large variations in the
properties of the resin. However, for resin sen-
sitive properties, for example, the first ply
failure (limit) of the 90" plies, the resin prop-
erty is influential.
For the fiber fracture controlled composites,
which are the main interest in structures, typi-
cal composite material properties are valid
over a wide variation in resin characteristics.
A.3.2 MATRIX CONTROLLED TYPICAL
PROPERTIES
The main interest in structural components is
the high strength and modulus obtainable
from the fiber reinforcing of the matrix.
Therefore in the design of the laminate, for
most of the applications, the resulting failure
modes are fiber fracture critical. Unfortunately,
there are cases where the matrix is the critical
element in the failure mode for all laminate
orientations. This does not mean that the fiber
does not contribute to reinforcing the matrix in
both strength and modulus, but only that the
ultimate failure is the result of failure in the
matrix.
Among the cases where the matrix is the
critical failure mode are laminates that are
subjected to shear, the first ply failure (limit
load) of a laminate (Fig. A.5, first ply failure
curves and Berg, 1982) and most cases of the
transverse strength property of a laminate
with no 90" plies. Even for these cases, a typ-
ical property can be determined utilizing the
typical set of unidirectional properties repre-
sented by most of the epoxy systems in use
by the prepreg manufacturers as well as most
of the structural epoxies sold. A typical set of
unidirectional properties for high strength
carbon composites, for example would be:
Strength 0" 90"
Tension 2100 MPa 55 MPa
Compression 1380 MPa 190 MPa
In-plane shear 55 MPa
Modulus 138 GPa 9.7 GPa
Shear modulus 6 GPa
Selecting the use of typical properties
A.4 SELECTING THE USE OF TYPICAL
PROPERTIES
A.4.1 WHERE TYPICAL PROPERTIESARE
ACCEPTABLE
The acceptability of material properties in the
design of structures is based on a number of
factors. If a design is being produced for a cus-
tomer, the customer is often the final word on
the acceptability of the material properties uti-
lized. An alternate possibility is that the
customer is not interested in accepting or
rejecting the material properties used, but
would rather accept the product against a
specification. Final acceptance is a qualifica-
tion of the product through testing.
The third case is where a product is pro-
duced by the company itself and sold to the
consumer directly. Of course the consumer
(public) is not interested in accepting or rejec-
tion the material properties database. An
example of this is the automobile industry.
In the case of a company that subcontracts
the design and fabrication of composite struc-
tures, the company may either want to review
the subcontractor's material properties data-
base, or be able to review the design of the
subcontractor with the use of the company's
typical properties database.
In each of the above cases, a typical mater-
ial properties database can be used for cost
and weight trade-offs, selection of the best
materials, optimizations studies and prelimi-
nary design.
It is important to note that the final design
would always go through an extensive test
program to verify the material properties
selected, the final design, the manufacturing
process and to determine the variability of the
product.
Thus, a typical material properties database
is acceptable and useful to reduce the cost of
engineering design, reduce the cost of testing
and allow a more intelligent and less time con-
suming approach to the final design.
1058 Typical properties for advanced composites

A.4.2 WHERE TYPICAL PROPERTIES ARE NOT the composite transformations equations (Tsai,
ACCEPTABLE 1988). A typical property database for all ori-
entations and selected materials is available
In the above discussion, the customer require-
(Berg, 1993), but also a typical composite mate-
ments were mentioned as one of the criteria
rial database could be generated by a
for acceptance or rejection of a material prop-
company using composite engineering analy-
erties database. There are cases where the
sis as discussed above.
customer will insist upon enough testing to
Although this discussion of typical proper-
develop a statistical property database. For
ties has mentioned only static strength and
that requirement the typical material database
modulus, typical properties are also available
would not be acceptable. However in any sta-
for fatigue, CTE and for elevated temperatures
tistical database, the applicability is confined
(Berg, 1993). Fatigue typical properties include
to the specific fiber, matrix and fabrication
all fatigue stress ratios. Fatigue statistical
process. The statistical testing process is
properties, of course, would be prohibitively
expensive and time consuming. In most cases,
expensive.
the statistical database would be limited to the
If users of typical composite material prop-
laminate orientations tested, which would also
erties are aware of their limitations, typical
be very limited.
properties can be a very useful database for
For applications where sigruficant environ-
cost effective design and analysis.
mental conditions are present, the use of typical
material properties may not be applicable due
to large variations in the response of different
REFERENCES
resins to these environmental conditions. These
conditions were summarized above and Berg, K.R. 1967. The effect of fiber spacing on the
included impact, humidity other corrosive flu- strength of composites laminates, Paper pre-
ids, stress concentrations, temperature, etc. sented at AAIAIASME 8th Structures, Structural
Dynamics and Materials Conference, Palm
Springs, CA.
A.5 SUMMARY Berg, K.R. 1982. The effect of matrix strain limita-
The design of composite material structures tions on composite design allowables. Proc. 27th
Nat. S A M P E Symp., May, 1992, San Diego, CA.
requires a knowledge of the material proper-
Berg, K.R. 1993. Composite Material Properties Data
ties for all combinations of laminates. It is Books - Sample Data Sheets. RIGGS Corporation,
cost-prohibitive to test all combinations of Seattle, WA.
laminates, even to obtain typical properties. To CertainTeed Corporation. 1989.Sales Brochure, Test
obtain statistical design properties for a lim- Data, Wichita Falls, TX.
ited number of laminate configurations is also Hashin, Z. and Rotem. A. 1975. Failm modes of
expensive, but in some cases may be required angle ply laminates. I. CompositeMater., Volume 9.
by a contract. Typical composite material Lubin, G. (ed.) 1987. Handbook of Composites. New
York: Van Nostrand Reinhold.
properties can provide useful data and be cost Neal, D. and Spiridgliozzi, L. 1987. An efficient
effective for the design engineer. The data can method for determining the 'A' and 'B' design
be generated by utilizing typical unidirec- allowables. Army Materials and Mechanics
tional data for each class of materials, (as Research Center ,Watertown, MA.
discussed above for high strength carbon com- Toray Industries, Inc. 1991. Toruycu Sales Brochure,
posites). To generate all the laminate Typical Fiber Properties.
configuration, both limit (first ply failure) and Tsai, Stephen W. 1988. Composites Design. Dayton,
OH: Think Composites.
ultimate, requires a comprehensive computer Tsai, Stephen W. and Hahn. H. 1980. Introduction to
program, including a failure criteria (Tsai, Composite Materials. Westport, CT Technomic
1988; Hashin and Rotem, 1975) and utilizing Publication.
SPECIFICATIONS AND
STANDARDS FOR POLYMER
COMPOSITES
Frank T. Traceski
B.l USES OF SPECIFICATIONS AND
STANDARDS
Material specifications and engineering stan-
dards for advanced composite materials have
a very broad applicability across the entire
spectrum of defense and commercial applica-
tions. From basic research, through engineering
and manufacturing development, in produc-
tion, and for maintenance and field repair,
material and process specifications establish
requirements and procedures.
In research and development, testing stan-
dards are used for material characterization to
determine physical, chemical, mechanical, ther-
mal and electrical properties. In manufacturing
development, material specifications are used
to establish material quality and processability
requirements. In production, the material pro-
ducer uses test standards and material
specifications for statistical process control
(SPC)to ensure batch-to-batch consistency.
Material testing standards are used exten-
sively in design engineering to determine
material design allowables (i.e. strength and
stiffness limits beyond which catastrophic fail-
ure occurs) at various temperatures and
environments. Material testing to standards
enables one to quantify material performance
Handbook of Composites.Edited by S.T. Peters. Published
in 1998 by Chapman &Hall, London. ISBN 0 412 54020 7
APPENDIX B
limits. A list of typical composite material
qualification tests is provided in Table B.l.
These examples are representative of the mate-
rial properties which are determined in a
typical material qualification program in
accordance with various test standards.
A concurrent engineering approach to com-
posites engineering requires that material
selection (as part of the design process) be inte-
grally linked with engineering and
manufacturing process development. In com-
posite manufacturing development, material
process specifications are defined for a given
composite material and manufacturingprocess.
Once optimized, process specifications reduce
manufacturing risk and enhance producibility.
Another aspect of composites manufactur-
ing is the nondestructive testing and
inspection (NDTI) of composite structures to
verify structural integrity during production.
Ultrasonic inspection, infrared thermography,
and a host of other NDTI methods are
employed to locate voids, delaminations,
cracks, and other types of structural defects.
Standards are also employed here to define
NDTI procedures and acceptance criteria.
In summary, engineering test standards and
material and process specifications are
employed extensively in composites research,
development and production. Appendix B
identifies specific material specifications and
test standards for polymer composites and the
1060 Specifications and standards for polymer composites

Table B.1 Typical composite material qualificationtests

Physical Mechanical Chemical

Resin content Tensile strength and modulus Infrared spectroscopy (IR)
Resin areal weight Compression strength and Liquid chromatography (HPLC)
Resin flow modulus Hydraulic fluid/solvent
Glass transition temperature Short beam shear (SBS) resistance
(Tg) 245 In-plane shear Fuel (JP-4)resistance
Rheological dynamic Open-hole tension
spectroscopy (RDS) Open-hole compression Thermal
Gel time Compression after impact
Volatiles content (CAI) Thermogravimetricanalysis
Fiber density Flexural strength and modulus (TGA)
Fiber mass per unit length Fatigue strength Thermomechanical analysis
Fiber content Creep (W)
Prepreg tack Dynamic mechanical analysis Differential scanning
Laminate ply thickness (DMA) calorimetry (DSC)
Laminate void content Instrumented impact Thermal oxidative resistance
Laminate density (toughened resins) Thermal expansion (CTE)
Laminate fiber volume Fracture toughness (toughened Thermal cycling
Laminate flammability resins) Thermal conductivity
Solvent sensitivity compression
strength, SBS Electrical
Bolt bearing Dielectric constant
Dielectric strength
Dissipation factor
Volume resistivity
Dielectrometry
-
Some of these tests are specific to resin, fiber reinforcement, prepreg or laminate. There is no established universal set of
qualification test procedures which is widely adopted. See MIL-HDBK-17 for recommended guidelines.

organizations that develop them. It is limited
to consensus-type standards and does not
include private sector specifications which are
generally not available.
B.2 STANDARDS-DEVELOPING
ORGANIZATIONS
The two principal organizations which
develop test methods for composites in the
USA are the American Society for Testing and
Materials (ASTM) and the Suppliers of
Advanced Composite Materials Association
(SACMA). The Society of Automotive
Engineers (SAE) Polymeric Materials
Committee is the organization which pub-
lishes Aerospace Material Specifications
(AMS) for advanced polymer composites. The
Department of Defense (DoD) has also issued
several military specifications and standards
for polymer composite materials. Other pri-
vate sector organizations, such as the
Aerospace Industries Association (AIA) and
Composite Materials Characterization (CMC),
Inc., are involved in the standardization of
composite materials and tests in order to reap
long-term economic savings.
Japan, Germany, France and UK are also
major players in composites technology. The
European Association of Aerospace
Manufacturers (known as AECMA in Europe)
produces European Norm (EN) standards for
aerospace composites. Japanese Industrial
Standards (JIS) serve as a basis for standard-
ization of composites in Japan. Germany has
issued DIN standards for composite materials.
France has AFNOR standards and the UK has
British Standards.
 Standards used in USA 1061

Engineering standards for polymer com-
posites also promote international commerce.
In the global arena, the International
Standardization Organization (ISO) is the
body which develops international standards.
The ISO/TC 61 Subcommittee (SC) 13 on
Composites and Reinforcements Fibers is cur-
rently coordinating new standards for glass
and carbon fiber composites. USA participa-
tion with IS0 not only promotes international
commerce but also enhances USA global com-
petitiveness in the composites industry.
B.3 STANDARDS USED IN USA
B.3.1 ASTM STANDARDS
The ASTM Committee D30 on High-Modulus
Fibers and their Composites develops standard
test methods for advanced polymer compos-
ites. Table B.2 lists the principal ASTM
Table B.2 ASTM Standards for advanced polymer composites
standards for determining the physical and
mechanical properties of polymer composites.
ASTM standards are developed by a consensus
process and are widely used. The ASTM
Committee D20 on Plastics also has developed
standards which may be used for testing plastic
resins and reinforced plastics.
8.3.2 SACMAMETHODS
The SACMA has developed recommended test
methods for determining the physical, mechan-
ical, and chemical properties of composite
materials (Table B.3). Although SACMA is not a
standards-setting body, it works actively with
ASTM, SAE, ISO, DoD, AIA and others towards
standardization of composite test methods.
SACMA does not regard its SRMs to be ’stan-
dards’ in the truest sense because they have not
been developed by a consensus process which
is typical of standard-developing bodies.

ASTM C613 Resin Content of Carbon and Graphite Prepregs by Solvent Extraction
ASTM D695 Compressive Properties of Rigid Plastics
ASTM D790 Flexural Properties of Unreinforced and Reinforced Plastics
ASTM D2290 Plastics, Ring or Tubular, Apparent Tensile Strength of, By Split Disk Method
ASTM D2344 Apparent Interlaminar Shear Strength of Parallel Fiber Composites by Short-Beam Method
ASTM D2734 Void Content of Reinforced Plastics
ASTM D3039 Tensile Properties of Polymer Matrix Composite Materials
ASTM D3171 Fiber Content of Resin-Matrix Composites by Matrix Digestion
ASTM D3379 Tensile Strength and Young’s Modulus for High-Modulus Single-Filament Materials
ASTM D3410 Compressive Properties of Polymer Matrix Composite Materials with Unsupported Gage Section by Shear
Loading
ASTM D3479 Tension-Tension Fatigue of Oriented Fiber, Resin Matrix Composites
ASTM D3518 In-Plane Shear Response of Polymer Matrix Composite Materials by Tensile Test of a +/- 45 D e p e
Laminate
ASTM D3529 Resin Solids Content of Epoxy-Matrix Prepreg by Matrix Dissolution
ASTM D3530 Volatiles Content of Epoxy Matrix Prepreg
ASTM D3531 Resin Flow of Carbon Fiber-Epoxy Prepreg
ASTM D3532 Gel Time of Carbon Fiber-Epoxy Prepreg
ASTM D3544 Reporting Test Methods and Results on High Modulus Fibers
ASTM D3800 Density of High-Modulus Fibers
ASTM D3878 Standard Terminology of High-Modulus Reinforcing Fibers and their Composites
ASTM D4018 Properties of Continuous Filament Carbon and Graphite Tows
ASTM D4102 Thermal Oxidative Resistance of Carbon Fibers
ASTM D4255 In-plane Shear Properties of Composite Laminates
ASTM D5229 Moisture Absorption Properties and Equilibrium Conditioning of Polymer Matrix Composite Materials
ASTM D5300 Measurement of Resin Content and other Related Properties of Polymer Matrix Thermoset Prepreg by
Combined Mechanical and Ultrasonic Methods
ASTM D.5467 Compressive Properties of Unidirectional Polymer Matrix Composites Using a Sandwich Beam
ASTM D5528 Mode I Interlaminar Fracture Toughness of Unidirectional Fiber-Reinforced Polymer Matrix Composites
1062 Specifications and standards for polymer composites

Table B.3 SACMA Recommended methods (SRM)

SRM 1 Compressive Properties of Oriented Fiber-Resin Composites

SRM 2 Compression After Impact Properties of Oriented Fiber-Resin Composites
SRM 3 Open-Hole Compression Properties of Oriented Fiber-Resin Composites
SRM 4 Tensile Properties of Oriented Fiber-Resin Composites
SRM 5 Open-Hole Tensile Properties of Oriented Fiber-Resin Composites
SRM 6 Compressive Properties of Oriented Cross-Plied Fiber-Resin Composites
SRM 7 In-plane Shear Stress-Strain Properties of Oriented Fiber-Resin Composites
SRM 8 Short Beam Shear Strength of Oriented Fiber-Resin Composites
SRM 9 Tensile Properties of Oriented Cross-Plied Fiber-Resin Composites
SRM 10 Fiber Volume, Percent Resin Volume and Calculated Average Cured Ply Thickness of Plied Laminates
SRM 11 Environmental Conditioning of Composite Test Laminates
SRM 12 Lot Acceptance of Carbon Fibers
SRP 1 Printing and Applying Bar Code Labels
SRM 13 Determination of Mass Per Unit Length of Carbon Fibers
SRM 14 Determination of Sizing Content on Carbon Fibers
SRM 15 Determination of Density of Carbon Fibers
SRM 16 Tow Tensile Testing of Carbon Fibers
SRM 17 Determination of Twist in Carbon Fibers
SRM 18 Glass Transition Temperature Determination by DMA of Oriented Fiber-Resin Composites
SRM 19 Viscosity Characteristics of Matrix Resins
SRM 20 High Performance Liquid Chromatography of Thermoset Resins
SRM 21 Fluid Resistance Evaluation of Composite Materials
SRM 22 Determining the Resin Flow of Preimpregnated B-Staged Materials
SRM 23 Determination of Resin Content and Fiber Areal Weight of Thermoset Prepreg with Destructive Techniques
SRM 24 Determination of Resin Content, Fiber Areal Weight and Flow of Thermoset Prepreg by Combined
Mechanical and Ultrasonic Methods
SRM 25 Heat of Reaction, Onset Temperature and Peak Temperature for Composite System Resins Using Differential
Scanning Calorimetry (DSC)
SRM 26 Fiber/Matrix Adhesion of Carbon Fiber Reinforced Polymer Matrix Composites

However, SACMA recommended methods Table B.5 lists military specifications for various
fiber reinforcements and composite materials.
(SRMs) are being used as standards by various
-
organizations. The Military Handbook 17 effort is the most
widely r e c o h e d DoD standardization pro-
ject. The purpose of this handbook is to provide
B.3.3 AEROSPACE MATERIAL SPECIFICATIONS a SOUTCe of based
The Society of Automotive Engineers (SAE) is ical property data for current and emerging
the primary organization in the USA which composite materials. The MIL-HDBK-17 gov-
issues material specifications for polymer ernment/industry coordination group meets
composites. Table B.4 lists some typical twice annually to develop this handbook.
Aerospace Material Specificationsfor -polymer
-
composites. In general, the SAE has published
B,3.5 NASA STANDARDS
specifications for carbon, aramid, glass and
boron fiber composites. The National Aeronautics and Space
Administration (NASA) has developed five
B.3.4 MILITARY SPECIFICATIONS
standard tests and a material specification for
carbon (graphite) composites. Table B.6 lists
The Department of Defense (DoD) has issued the specific tests and the NASA/aircraft
several military specifications for polymer com- industry specification for toughened epoxy
posite materials used in aircraft applications. composite materials.
 Standards used in USA 1063

Table 84 Aerospace material specifications (AMS) for polymer composites

CarbonEpoxy Composites
AMS 3892B Fibers, Carbon Tow and Yam, for Structural Composites
AMs 3894E Carbon Fiber Tape and Sheet, Epoxy Resin Impregnated
AMS 3895B Broadgoods and Tape, Multi-Ply Carbon Fiber/Epoxy, Resin Impregnated, Uniform Fiber

Aramid/Epoxy Composites
AMS 39018 Organic Fiber (Para-Aramid),Yarn and Roving, High Modulus
AMS 3902C Cloth, Organic Fiber (Para-Aramid),High Modulus for Structural Composites
AMS 3903A Cloth, Organic Fiber (Para-Aramid),High Modulus, Epoxy Resin Impregnated

GlassEpoxy Composites
-
AMS 3821B Cloth, Type 'E' Glass, ' B Stage Epoxy-Resin-Impregnated,7781 Style Fabric, Flame
Resistant
AMS 3828C Glass Roving, Epoxy-Resin-Impregnated,Type 'E' Glass
AMs 3831A Cloth, Type 'E' Glass, ' B Stage Epoxy Resin Impregnated, 7781 Style Fabric, Flame
Resistant, Improved Strength
AMS 3832C Roving, Type '$2' Glass, Epoxy Resin Impregnated
AMs 3906B Glass Tape and Flat Sheet, Non-Woven Cloth, Epoxy Resin Impregnated, For Hand and
Machine Layup

Boron/Epoxy Composites
AMs 3865C Filaments, Boron, Tungsten Substrate, Continuous
AMs 3867I3 Boron Filament Tape, Epoxy-Resin-Impregnated

B.3.6 FAA ADVISORY CIRCULARS (AC) Division is the Materials and Structures
Committee (AIA/MSC) which is responsible
The Federal Aviation Administration (FAA)
for the coordination and review of proposed
has issued Advisory Circulars (AC) to assist
specification requirements for materials,
commercial aircraft manufacturers in demon-
processes and structures. To promote stan-
strating compliance with the requirements of
dardization AIA has initiated Project 340-1
the Federal Aviation Regulations in the design
Standardization of Advanced Composite
and manufacture of composite material struc-
Materials and has issued two National
tures. Table B.7 lists two Advisory Circulars
Aerospace Standards (NAS) for composites
issued by the FAA. As of this writing, AC
manufacturing which are listed in Table B.8.
145-6 is a draft document undergoing coordi-
nation. AC 145-6 addresses requirements for
composite repairs, including materials, 8.3.8 COMPOSITE MATERIALS
processes, and quality control tests. CHARACTERIZATION,INC. (CMC)
Composite Materials Characterization, Inc.
(CMC) is a joint enterprise funded by users of
B.3.7 AEROSPACE INDUSTRIES ASSOCIATION
advanced aerospace composite materials. CMC
(AIAI was formed as a result of an Aerospace
The Aerospace Industries Association (AIA) Industries Association (AM) initiative to pro-
plays a lead role in composites standardiza- mote industry research collaboration.CMC is a
tion. Within the AIA Engineering Standards Delaware corporation chartered in 1987 to
1064 Specifications and standards for polymer composites

Table 8.5 Military specifications and standards for polymer composite materials

MIL-Y-1140H Yam, Cord, Sleeving, Cloth, and Tape-Glass

MIL-C-8073D Core Material, Plastic Honeycomb, Laminated Glass Fabric Base, For Aircraft Structural and
Electronic Applications
MIL-S-9041B Sandwich Construction, Plastic Resin, Glass Fabric Base, Laminated Facings and Honeycomb
Core for Aircraft Structural and Electronic Applications
MIL-C-9084C Cloth, Glass, Finished, For Resin Laminates
MIL-P-94OOC Plastic Laminate and Sandwich Construction Parts and Assembly, Aircraft Structural, Process
Specification Requirements
MIL-P-17549D Plastic Laminates, Fibrous Glass Reinforced, Marine Structural
MIL-C-19663D Cloth, Woven Roving, For Plastic Laminates
MIL-T-29586 (AS) Thermosetting Polymer Composite, Unidirectional Carbon Fiber Reinforced Prepreg Tape
(Widths Up to 60 Inches), General SpecificationFor
MIL-M-43248C Mat, Reinforcing Glass Fiber
MIL-A-46103D Armor, Lightweight, Ceramic-Faced Composite
MIL-A-46165 (MR) Armor, Woven Glass Roving Fabrics
MIL-I-46166 (MR) Plastic Laminates, Glass Reinforced (For Use in Armor Composites)
MIL-P-46169A Plastic, Sheet Molding Compound, Polyester, Glass Fiber Reinforced (For General Purpose
Applications)
MIL-P-46187 Prepreg, Unidirectional Tape, Carbon (Graphite) Fiber Polyimide (PMR-15) Resin
Impregnated, 316 C (600 F)
MIL-P-46190 Prepreg, Woven Fabric, Carbon Fiber Bismaleimide (BMI) Resin Impregnated
MIL-PRF-46197A Laminate: High-Strength Glass, Fabric-Reinforced, Polyester Resin Preimpregnated
MIL-R-60346C Roving, Glass, Fibrous (For Prepreg Tape & Roving, Filament Winding & Pultrusion
Applications)
MIL-A-62473B Armor: Aluminum-Aramid, Laminate Composite
MIL-F-64156 Fabric, Carbon (Graphite) Fiber, Nickel-Coated
MIL-Y-83370A (AF) Yam, Roving, and Cloth, High Modulus, Organic Fiber
MIL-Y-83371 (AF) Yams, Graphite, High Modulus, Continuous Filament
MIL-G-83410 (AF) Graphite Fiber Resin Impregnated Tape and Sheet, For Hand Layup
MIL-R-8712OA (AF) Rods, Pultruded, Graphite Fiber Reinforced, Processing of
MIL-F-87121A (AF) Fabric, Graphite Fiber
MIL-Y-87125A(AF) Graphite, 1000/3000 Filaments
MIL-STD-368 HPLC of PMR-15 Polyimide Resin and Prepregs
MIL-STD-373 Transverse Tensile Properties of Unidirectional Fiber/Resin Composite Cylinders
MIL-STD-374 Transverse Compressive Properties of Unidirectional Fiber/Resin Composite Cylinders
MIL-STD-375 In-Plane Shear Properties of Unidirectional Fiber/Resin Composite Cylinders
*MIL-STD-2031(SH) Fire and Toxicity Test Methods and Qualification Procedure for Composite Material Systems
Used in Hull, Machinery, and Structural Applications Inside Naval Submarines
* Military Standard

Table B.6 NASA Standards for composites

NASA RP 1092: Standards Tests for Toughened Resin Composites, July 1983
NASA RP 1092 defines five standard tests (STs) for graphite/epoxy composite laminates:
ST-1: Compression after impact
ST-2: Edge delamination
ST-3: Open-hole tension
ST-4: Open-hole compression
ST-5: Hinged double cantilever beam
NASA RP 1142: NASA/ Aircraft Industry Standard Specification for Graphite Fiber Toughened
Thermoset Resin Composite Material, June 1985

Table B.7 FAA Advisory circulars for composites
AC 20-10A Composite Aircraft Structures
AC 21-26 Quality Control for the Manufacture of
Composite Structures
AC 145-6 Repair Stations for Composite and
Bonded Aircraft Structure
Table 8.8 National aerospace standards for
composites
NAS 990 Composite Filament Tape Laying
Machine - Numerically Controlled
NAS 999 Non-Destructive Inspection of
Advanced Composite Structures
conduct research and development on emerging
composite materials including characterization,
screening, fabrication, and inspection of materi-
als or structures made from the materials.
The primary focus of CMC is on screening
testing of emerging composite materials. The
CMC effort generates a standardized database
of consistent properties for advanced compos-
ite materials which can be shared between
member companies (Table B.9). CMC subcon-
tracts to third parties the material
procurement, test specimen fabrication, inspec-
tion, test, data analysis, and documentation of
results. All tests and data are conducted in
accordance with CMC-approved procedures to
produce a consistent and standardized data-
base necessary for comparative assessment of
material properties. Physical and mechanical
properties testing is performed, including lam-
ina and laminate evaluations under tensile,
Table B.9 CMC Member companies
Dow Chemical
General Electric
Northrop Grumman
Lockheed Martin
UTC /Sikorsky
Loral Vought
Rohr Industries
Non-US Standards in use 1065
compressive, and shear loadings at selective
hygrothermal test conditions. CMC also works
with other national organizations to promote
composites standardization.
B.4 NON-US STANDARDS IN USE
B.4.1 AECMA STANDARDS
The European Association of Aerospace
Manufacturers (known as AECMA in Europe)
is developing various standards for carbon
fiber composites for aerospace applications.
Table B.10 lists proposed European Norm (EN)
standards for determining the physical and
mechanical properties of carbon fibers and
their composites.
B.4.2 JAPANESE INDUSTRIAL STANDARDS (JIS)
Standardization efforts in Japan are managed
by the Standards Department under the
Ministry of International Trade and Industry
(MITI).The Japanese Standards Association is
in charge of publishing Japanese Industrial
Standards (JIS).Table B . l l lists Japanese stan-
dards for carbon fibers and their composites.
B.4.3 GERMAN (DIN) STANDARDS
German aerospace specifications for carbon,
aramid, and glass fiber polymer composites
are listed in Table B.12. The DIN specifications
and standards are published by the German
Institute for Standardization, which is the
’Deutsches Institut fur Normung’ (DIN) in
German.
B.4.4 INTERNATIONAL (ISO) STANDARDS
The International Organization for
Standardization (ISO) Technical Committee 61
on Plastics, Subcommittee 13 on Composites
and Reinforcement Fibers is the body which is
developing international standards for poly-
mer composites. The USA is represented at
international meetings through the American
1066 Specifications and standards for polymer composites

Table B.10 AECMA Standards for carbon fibers and their composites

AECMA prEN2557 Carbon Fibre Preimpregnates, Test Method for the Determination of Mass Per
Unit Area
AECMA prEN2558 Carbon Fibre Preimpregnates, Test Method for the Determination of the
Percentage of Volatile Matter
AECMA prEN2559 Carbon Fibre Preimpregnates, Test Method for the Determination of the Resin
and Fibre Content and the Mass of Fibre Per Unit Area
AECMA prEN2560 Carbon Fibre Preimpregnates, Test Method for the Determination of the Resin
Flow
AECMA prEN2561 Unidirectional Laminates Carbon-Thermosetting Resin Tensile Test Parallel to the
Fibre Direction
AECMA prEN2562 Unidirectional Laminates Carbon-Thermosetting Resin Flexural Test
AECMA prEN2563 Unidirectional Laminates Carbon-Thermosetting Resin Test Method,
Determination of Apparent Interlaminar Shear Strength
AECMA prEN2564 Carbon Fibre Laminates, Test Method for the Determination of the Fibre and
Resin Fractions and Porosity Content

Table B . l l Japanese standards for carbon fiber Table B.12 German specifications for polymer
composites composites

JIS R 7601 Testing Methods for Carbon Fibers
JIS R 7602 Testing Methods for Carbon Woven
Fabrics
JIS K 7071 Testing Methods for Prepreg,
Carbon Fiber and Epoxy Resins
JIS K 7073 Testing Method for Tensile
Properties of Carbon Fibre
Reinforced Plastics
JIS K 7074 Testing Methods for Flexural
Properties of Carbon Fibre
Reinforced Plastics
National Standards Institute (ANSI). Table
8.13 lists draft and published (ISO) standards
for composites.
DIN 29965 Aerospace; Carbon Fibres, High
Performance Carbon Fibre Filament
Yams, Technical Specification
DIN 29971 Aerospace; Unidirectional Carbon
Fibre-Epoxy Sheet and Tape Prepreg,
Technical Specification
DIN 65090 Aerospace; Textile Glass,
Preimpregnated Filament Glass Cloth
for E-Glass (Prepreg),Technical
Specification
DIN 65426 Aerospace; Aromatic Polyamide
Part 1: (Aramid) - Preimpregnated Woven
Fabric, High-Modulus Filament Yam
(Prepreg);Dimensions, Masses
DIN 65426 Aerospace; Aromatic Polyamide
Part 2 (Aramid)- Woven Filament Fabric
Prepreg from High-Modulus Filament
Yam and Epoxy Resin, Technical
Specification

B.5 PROPRIETARY SPECIFICATIONS

This appendix does not include the many
composite material and process specifications
which have been developed a n d are used by
individual private sector companies (i.e.
primes, fabricators and suppliers). Most, if not
all, of the companies which either produce or
use composites have some proprietary specifi-
cations for composite materials and processes.
It is known that proprietary specifications con-
stitute a substantial data base which cannot be
included herein. Please note that this appendix
addresses only polymer matrix composites.
Specifications and standards for other types of
composite materials (MMC, CMC, and C/C)
are still in early stages of development and
may be either subject to export control or
proprietary.
 Proprietary spec$cations 1067

Table 813 International (ISO) standards for polymer composites

CD 1268 Fiber Reinforced Plastics - Test Plates Manufacturing Methods -Part 1- General Conditions
CD 3341 Textile Glass - Yams - Determination of Breaking Force and Breaking Elongation
CD 3374 Textile Glass - Mats - Determination of Mass Per Unit Area
CD 4605 Reinforced Products - Woven Fabrics - Determination of Mass Per Unit Area
CD 14127 Composites - Determination of Resin, Fiber and Void Content for Composites Reinforced
with Carbon Fiber
CD 15024 Determination of Mode I Delamination Resistance of Unidirectional Fiber Reinforced
Polymer Laminate Using the Double Cantilever Beam Specimin
CD 15034 Plastics - Prepregs - Resin Flow
CD 15040 Plastics - Prepregs - Gel Time
CD 15310 Reinforced Plastics - Determination of In-Plane Shear Modulus by Plate Twist Method
DIS 3374 Reinforcement Products - Mats and Fabrics - Determination of Mass Per Unit Area
DIS 5025 Textile Glass - Woven Fabrics - Determination of Width and Length
DIS 14126 Fiber Reinforced Plastic Composites - Determination of Compressive Properties in the In-
Plane Direction
FDIS 1889 Reinforcement Yarns - Determination of Linear Density
FDIS 1890 Reinforcement Yarns - Determination of Twist
FDIS 3344 Reinforcement Product - Determination of Moisture Content
FDIS 12114 Fiber-reinforced Plastics - Thermosetting Moulding Compounds and Prepregs -
Determination of Cure Characteristics
FDIS 11667 Fiber-Reinforced Plastics - Moulding Compounds and Prepregs - Determination of Resin,
Reinforced Fiber and Mineral Filler Content - Dissolution Methods
FDIS 12115 Fiber-Reinforced Plastics - Thermosetting Moulding Compounds and Prepregs -
Determination of Flowability, Maturation and Shelf Life
IS0 2559 Textile Glass - Mats (made from Chopped or Continuous Strands) Basis for a Specification
IS0 3605 Textile Glass - Rovings - Determination of Compressive Properties of Rod Composites
IS0 8515 Textile Glass - Reinforced Plastics - Determination of Compressive Properties in the
Direction Parallel to the Plane of Lamination
IS0 10119 Carbon Fiber - Determination of Density
IS0 10120 Carbon Fiber - Determination of Linear Density

CD - Committee Draft
DIS - Draft International Standard
JDIS - Final Draft International Standard
1068 Specifications and standards f o r polymer composites

REFERENCES 11. Documentation from Mr. Cecil W. Scheider,

President of Composite Materials
1. National Advanced Composites Strategic Plan, Characterization, Inc., 28 October 1991.
National Center for Advanced Technologies, 12. ISO/TC61/SC13/WG14 Letter Correspondence
September 1991. from Mr. Junichi Matsui, Toray Industries
2. Traceski, Frank T., Specifcations and Standards for (Composite Materials Research Laboratories;
Plastics and Composites, ASM International Japan), 5 August 1992.
(Materials Park, Ohio), August 1990. 13. ISO/TC61/SC13 Report to ASTM D20.61, Gary
3. Test Standards and Engineering Databases for Williams, July 1997.
Advanced Composites, Draft Position Paper by
Aerospace Industries Association, January 1992.
4. Advanced Composites Standardization, “White ACKNOWLEDGEMENTS
Paper,” Prepared by the Committee for
Standardization of Advanced Composite The following individuals reviewed and com-
Materials, 4 November 1992. mented on this paper and are acknowledged
5. Annual Book of ASTM Standards, Vol. 15.03, for their constructive comments: Mr. Jerome
American Society for Testing and Materials Persh (retired), formerly Office of the Director
(Philadelphia, PA), 1991.
of Defense Research and Engineering; Dr.
6. S A C M A Recommended Methods, Suppliers of
Advanced Composite Materials Association, Gary L. Hagnauer, US Army Research
(Arlington, VA), 1997. Laboratory (ARL), Materials Directorate; Mr.
7. SAE A M S Index, Aerospace Material Specifications, Gary Hansen, formerly Hercules Advanced
Society of Automotive Engineers (Warrendale, Materials & Systems Company; * - Mr. Jerome R.
PA), July 1996. Jaeb, Chief Engineer, Structures Technology,
8.’ Department of Defense Index Of Specifications and Boeing Defense & Space Group; Mr. Samuel J.
Standards (DoDISS), 1January 1997.
Dastin (retired), formerly Director, Advanced
9. Military Handbook 17, Polymer Matrix
Composites, Draft Volumes 1, 2 & 3, US Materials, Grumman Aircraft Systems.
Department of Defense, 17 June 1991.
10. Communication with Mr. Joseph R. Soderquist,
Federal Aviation Administration (FAA),
4 September 1997.
INDEX

Page numbers in bold type refer to figures; those in italics refer to tables

A-glass 134 bending failures 644 damage to 656

Abrading, surface preparation 669 bending stresses 644 ductile response 6516,652,657
Abrasion composite 630,660,662-3 ductility 627-8,629-30,655-6
mechanical 668 deformable 633,634 elastic-plastic response 649
particulate fillers 252 deformations 630 environmental conditions 630
resistance, PET 224,233 dissimilar 635,660 epoxies 275
Abrasive water jet, see AWJ ductility 630 failure in 628
Abrasives equal thickness 650 fillet forming 271
machining 606 failures 627-9,628,657 flow, sandwich 288
inslurry 607 fully tapered 646, 647 heavy liquids 275-6
types of 607 identical 639 high temperature 658
ABS layered 646 joints 610-63
compressive strength 258 loading stress 642 bonded doubler 628
density 258 modulus 643 bonding techniques 611
maximum service temperature moisture absorbancy 630 double-lap 628
258 rigid 632,633, 634 double-strap 628
shear modulus 259 stiffness 636 durability 631-2
shear strength 259 unbalance 629,648 inspection methods 627
tensile strength 258 stretching elongations 633 manufacturing deficiencies
thermal conductivity 259 tapering 627,629,64451,645, 611
Accelerators 59-61,60-2 647, 648, 649, 650, 653, 656, poor bonding 611
anhydride-cured system 72 658 scarf 628,629
Acceptance values 724 thermal expansion 630,661 single-strap 628
Accumulation, damage 797 thickness 627-9,628,628,65&7, single-lap 628
Acids, Lewis 60-1 658 stepped-lap 628,629
Acoustic transverse shear 630 stressesin 632
emission 849 weaker matrix 630 surface preparation 611
honeycomb assemblies 849 Adhesion tapered single-lap 628
fatigue testing 811 aramids 26 tapered-strap 628
pressure vessel 472,472 failure 674-5 unsupported single-lap 628
Acoustical properties, fiberglass 135 Adhesives 255,271,2744,517-18 light liquids 2754
Acousto-ultrasonics 849 adaptability 274 mechanical 518
Acrylic acid, and polypropylene 251 aerostructural 651,652 nylon 670
ACTS, reflectors 1017,1017 blisters 271 pastes 2754
Acute toxicity 8234,824 bond line control 274 peel
measuring 824 bonding 127,255,727 strengths 274-5
Adaptability, adhesives 274 aluminum alloy 683 stresses 628
Additives pressure 271 phenolics 255
low profile 382 brittle 651 blended 275
pultrusion 515-18 cell-edge 276 Plycosite 255
wetting agents 515-16 co-curing 868,870 putties 275-6
Adducts, thermoplastic polymers cohesive failure 674-5 Redux 255
526 core 271 repairs 869
Adherends cure temperature 661 reticulating films 276
axial stress 644 Cycleweld 255 scrim-supported 873
1070 Index

self-adhesive skins 276 Agglomerates 313,314 thermal cycling 818

shear stresses 632-7,633,634, Aging through-the-face, sheet
635,636 air 85, 90 evacuation 865
strain energy 629-30,653 aircraft 860 water evacuation 863
supported films 276 thermoplastics 127 water ingestion 859
syntactic foams 275-6 Air wet lay-up repairs 865-7
test methods 630 aging 85,90 Aircraft Energy Efficiency (ACEE)
thixotropic liquids 275-6 3F/36F polyimides 85 1035
toughness 274-5 AFR700B/S2 laminates 94,95 Alignment, graphitization 191
unsupported films 276 AvimidN 85 Aliphatic
urea-formaldehyde 255 Skybond 85 amine-cured ("ETA) 65
urethanes 275 release agents 516 amines, health effects 832,833
water absorption 668 Airbus A320, composite applications content 75
Adjusting, lamina properties 763 1036,1038 polyether triamine (APTA),
Advanced Communications Aircraft viscosity 54
Technology Satellite, see ACTS aging 860 system 70
Advanced composites aluminum core removal 862 Alkaline
applications 23 applications 1022-42 cleaning, metal surfaces 871
military 23 certification requirements 1022-3 degradation 1000
Advanced fibers, repairs 877 components 1029-30,1029 All purpose vehicles 908,908
Advantages current prices 1024,1026 Allco 59
AWJ 604 damaged protective coatings Alternative, tooling 449-50,449,450
correlators 834 859-60 Altex 309,309
hand lay-up 352 design 878 Alumina 249-50
injection pultrusion 497 process 10245,1026 composites 325
machining 596 requirements 713,1022-3 grit, light grit-blasting 675,676
laser 605 effect of contaminants 863 silicate
ultrasonic 608 environmental exposure 860-1 boria modified 309,320
preform 438 face sheet materials removal 864 . strength 309
pull winding 497 face sheets removal 862 Young's modulus 309
R T M 434-5 fixed wing, current prices 1024, trihydrate 245
tapering 646 1026 Aluminosilicate, staple 160
turning 597 fluid contamination 859 AlUminUm
twin-screw extruders 539 flushing contaminants 864 alloy
vertical pultrusion 495 honeycomb core removal 862 adhesive bonding 683
AECMA standards 1065,1066 impact damage 858-9 linear thermal expansion 705
Aerospace interim repairs 859 core removal 862
applications, materials selection leak paths 859-60 CTE 558,589
1009 maintainability 1024 density 170,558
design 709 maintenance 878 elastic modulus 170
goal 712,713 metal face sheets removal 862 fiberglass cloth repairs 877
equipment 1004-21 metal repairs 857 foil 820
Industries Association (AIA) minor damage 859 fracture elongation 170
1063 moisture barrier removal 863-4 oxide
industry non-metallic core removal 862 fibers 27
composite tools 593 open core evacuation 865 particulate fillers 250
facing material 255 production 840-1,841 rivets 668
prepregs 885 costs 1024 specific
material specifications 1062,2063 reinforced plastics 1023 modulus 1049
Aerostructural, adhesives 651,652 repairs 8574,857-80,1024 strength 1049
AFR7008, chemistry of 81 planning 861 surface preparation 871,876
AFR700B/S2 laminates skin damage removal 861,861 tensile strength 170
air aging 94,95 skin penetration 858,859 tension-tension ratio 1049
compression strength 93 speed tape repairs 859 thermal conductivity 558
flex strength 93,95 stabilizer America's Cup yachts 922
shear strength 93 design requirements 710 Amine curing 49-50,51
tensile strength 93 preliminary materials 711 epoxy resins, aliphatic 70
weight loss 94 structural applications 1027-8, Amines, aliphatic 53,54
AFRF 605,1024 1027,1028 Amino resins, health effects 834
 Index 1071

Aminolysis, degradation 888 biomedical, thermoplastics 127--8 uranium enrichment centrifuges

Amoco 58 boron 163, 265,166 953-4
anhydride curing agents 56 bridges 9324,933 valves 954
Analysis business equipment 934,934 wind turbine blades 954
composites 736-57 cable cars 934-5 Aramid 23,26,425
cost of 736 carbon fibers 196-7 adhesion 26
equilibrium equations 737 casting 38 composites 210,210
Ancadride MHHPA (Ciba-Geigy) 57 ceramic fibers 163,165, 166 compression 26
Anchorage 987 CMCs 935 costs 717
grounded 986 consumer products 946 density 26
prestressed concrete 9 8 5 6 cooling towers 936-7 fibers 202-22
Angle of impact, meteoroids 815 drive shafts 936-7 applications 216,217-20,
Angle ply 741 electrical 937,937 222-3
Anhydride electronics 937,937 athletic shoes 222
curing 50 firefighter breathing apparatus attributes 358
agents 56-9,56-9 937-8 availability 216,217
health effects 832, 833 flywheel mechanical battery by-products 222
high temperatures 50 systems 938,938 chemical properties 213-15,
Anhydride-cured system 72 fuel tanks 939-40 214
accelerator 72 glulam beams 940-1 choice of resin 222
cure cycle 72 grating 936 composites 207
curing agent 72 health 9434,944 compressive properties 221
heat distortion temperature 72 high silica 163, 165, 166 costs 223
maximum stress 72 high-pressure tubing 941 creep resistance 216,222
modulus of elasticity 72 high-speed train brakes 941 cutting 222
pot life 72 hydrogen fuel storage 941 definition 202
solvent absorption 72 industrial equipment 951 design of 216,221-2
tensile properties 72 ladders 936 electrical insulators 215
viscosity 72 laptop computers 942 electrical properties 215
Anis0tropic lighting poles 948-9, 948 environmental properties
bodies, thermoelastic behavior loom components 942 213-15,214
470-1 maglev train guideways 942-3 equilibrium moisture content
composites 797 marine 916-28 215,241
materials 687, 688 medical 9434,944 failure 210
material constants 688 metal surfaces 871 fatigue resistance 221,222
pitches, stabilization 178 MMCs 9 4 4 5 flame resistance 205,207
Anisotropicity, PAN 185 mobile storage 945 forms 216
Anisotropy molding compounds 945-6 handling 222
crystal 334,335 musical instruments 946 health effects 835
GFRP 1006 non-aerospace 935 length-to-diameter ratio 204
PET 224 O-rings 953 limitations 207
Annealing, and coating thickness oil and gas 946-7,947 machining 222
297 PBOfiber 238 manufacture 2 0 3 4
Anodizing 667 PET 230 mechanical properties 207-13,
aluminum alloys 668 pick-up trucks 936-7 208-9,209,210,211,212
low voltage 871 pipeline rehabilitation 947-8 melting 205
non-tank 871 piping 936 point 204
Antennas 932-3 PMR-15 96 microbuckling 207
Antimony oxide 244 ports and harbors 949 moisture absorption 221
highcost 244 power poles 948-9,948 opaque 221
synergism 244 quartz 163,165,166 optical properties 215
Antistatic agents, fiberglass 146-7 railways 950 physical properties 2057,206
Appliances, reuse 901 rolling stock 949-50 pricing 216
Applications 3,270,931-56 rolls and air shafts 950-1, 951 properties 20515
aircraft 11 safety 9434,944 reinforced plastic, see AFW
antennas 932-3 seals 953 safety 222
aramid fibers 216,217-20,222-3 SMEs 952 sandwich construction 222
AS4/PEKK 127-8 structural 709 self-screening 215
battery casings 941 tunnels 950 solvents 204
1072 Index

specific ligaments, PET 234 Kevlar 217-18

stiffness 207 AS-4 carbon fiber 123 PET 231
strengths 207 in-plane shear modulus 124 Spectra 231
strength 205 tensile modulus 123 SVM 220
to weight ratio 223 tensile strength 123 Technora 220
structure 20P5 A S 4 / PEEK(APC) Tekmilon 231
temperature resistance 205 observed life 806,807 Twaron 219-20
tensile predicted life 806, 807 Vectran 236
modulus 715,716 residual strength 806,807 Aviation, price of 1024
stiffness 209 strength 125 Avimid N, air aging 85
strength 209 AS-4/PEKK, applications 127-8 An7
thermal Asbestos, health hazards 252 advantages 604
properties 205-7,206 Assembly bowing, GFRP 1014,1014 disadvantages 604
resistance 205 ASTM drilling 604
thermoplastic matrices 222 methods, cured epoxy resin linear cutting 603,603
toughness 221 systems 72 machining 600,602
treatments 215-16 numbers 66’66 milling 604
twisted 215-16 standards 1061,1061 process 602
UV absorption 215,221 Atmospheric electricity 860 traverse rates 603
water absorption 215 Atomic oxygen 813-14,814 tumingwith 6 0 s
weave 222 destructiveness 813 without abrasives 600
weight 222 erosion 814 AXAF orbiting observatory 970
mechanical properties 718 fluence 813 Axial
moisture absorption 26 reaction efficiency 814 compressive properties, Spectra
paper honeycomb 269-70 Atomite 247,247 226,226
applications 270 ATOTech 61 loading 745-7
price 716 ATR72 orientation, PET 224
strength retention 230 CFRP wing box 1038 stress 613
strengths 718 composite applications 1038, adherends 644
tensile strength 26 1937 tensile properties, Spectra 226,
Aramid/epoxy, CTE 589 Autoclave 22,116,461 226
Aramid/fiberglass 359 consolidation 298,577 Axisymmetric deformation
Aramid/graphite 359 cure cycle 84 circular plates 752-3
hybrids 354 definition 577 cylindrical shells 7 5 3 4
Arc jet tests, carbon-carbon repairs 868 disks 752-3
composites 347 tooling 589-91,590 AZ epoxy N (AZS Corp) 63
Archimedean screw 538 Autoclave/oven, molding 361
Architecture, microstructural 795, Automated Real-time Inspection Bag molding 352-77,361,362,
796 System (ARIS) 842 366-72,368,369,370,371
Areas of transition 731-2,732 Automated Tool Manufacture for thermal cures 367
Armos Composite Structures 566 Bagging 577
availability 220 Automation, cost savings 16 Balance 9,lO-11
elongation at break 208 Automobiles, reuse 900-1 Balanced laminates 693
initial tensile modulus 208 Automotive Balls, tooling 565
sources of information 221 body applications 909-10,913 Barcol hardness
specific gravity 208 SMC 909 recycled PET 894
tensile strength 208 industry testing 38
Aromatic design requirements 713 Barium ferrite, fillers 527
amine-cured MPDA 65 recycling 901-2 Barium sulfate 249
amines, health effects 832,833 surface preparation 669 fillers 527
polyamide fiber, see aramid fibei‘S interiors 912, 913 Barrier
polyester fibers 235-7,235,235 market, GMT 127 creams 829-30,830
system 71 suspension 911 layers, silicon carbide 292
Aromatization, and carbonization Availability materials 863-4
183 aramid fibers 216,217 Bars
Articulation components 962-3 Armos 220 bending 785
Artificial Dyneema 231 testing 784
blood vessels 963 glass fibers 24 Bases, Lewis 60-1
joints 810 Hoechst Celanese 231 Basic structural units, see BSUs
 Index 1073
Basket weave 140,145 melting point 60 commercial 380
Bathtub manufacture, Japan 889 Besfight 2054 compression molding 492
Battery casings 941 properties of 2 70 definition 379
Beams 745-7,746,995-7,996 BF,MEA 59 fatigue properties 386,387
bending stiffness 997 Biaxial flexural modulus 386,386
curved 791 fabrics, non-woven 504 flexural strength 386,386
deflection 995,996 plain-weave 399 injection molded 380
displacements along 747 stretching 546 IZOD impact 386,386
modes of failure 997 Bicycles 1050 recycling 890-3
properties of 283 carbon fiber frame 1050 specific gravity expansion 386,
shear deformation 748-9’995 frame tubes 1051 386
strength analysis 308-9 handlebars 1051 tensile modulus 386,386
stresses in 747 tube and lug designs 1050-1 tensile strength 386,386
thin-walled 747-9,748 Binders thermal coefficient 386,386
types 283 fiberglass 147 BMI 30,99-114
sandwich 281 organic 314 CAI performance 105
Bearing solutions, availability 82 compressive modulus 211
failure 616,729 Bioabsorbable composites 961 dielectric properties 1 0 6 7
load 620-1,620 biocompatibility 962 edge delamination 111
contact region 620-1 Biological attack 810-11 F-22 fighter 113,113
edge distances 621 Biomaterials 957-64 film adhesives 114
joints 626 Bisaleimide resins 30 galvanic corrosion 108-9
strength 6265,625 seenlso BMIs homopolymers of 99
joints 618-19 Bisphenol A hydrolysis 212
tests 625 fumarates 36,39 matrices 106
stress 619,619 homopolymer property 102 mechanical strength 121
at fasteners 620 structure precursor 102 molding compounds 114
Beech Starship 472,627,1022,1039, supplier 102 monomers 100,103
1040 tradename 102 suppliers 112
Bell mouth 500-1 Bisphenol A-based, health effects thermal properties 106,209
Bend radius 308 832 toughening, diepoxides 105
Bending 785,791-2 Bisphenol E BMI-DAB 100-1
bars 785 homopolymer property 102 definition 105
deflections 637 structure precursor 102 BMI-MDA, definition 105
fasteners 626 supplier 102 Boat hulls 1045
single lap joint 641 trade name 102 Boeing 777
failures Bisphenol M composite structure 1035,1036
adherends 644 homopolymer property 102 Bolt
joints 617,617 structure precursor 102 hole 621
fasteners 625,625 supplier 102 tensions, torque levels 626
longitudinal 747 tradename 102 Bolted
nonlinear 747 Blast pressure 6754,676, 677 joints 728,728,729,1015
rings 785,792 Bleed-out 367 edge distance 617,617
skin fracture 751 Bleeder 577 Bolting and riveting 517
stiffness 745 permeability 581 Bond
strength 791 ply, molding 584-6,585 defects 630-1
Kulon 305 Blistering failures 627-9, 628
testing 446 CFRP 918 layer 656-8,657
VMN-4 305 isophthalic polyesters 918 line control, adhesives 274
stresses marine applications 918,918 stresses 640
adherends 644 orthophthalic polyesters 918 lateral deflections 640
formulas 284 permeation barrier 918 thickness 631
three-point 785,791 Blisters, adhesives 271 to adherend, thickness 641
andtwisting 3 Blow van der Waals 224,226
whole rings 785 molding 529,532,549 Bonded
3,3’,4,4‘-Benzophenone- accumulator 549 doubler, adhesive joints 628
tetracarboxylic dianhydride polymer properties 550 joints 728, 728,1015
(BTDA), melting point 59,76 Blown core, NDE 854 cracking 659,659
Benzyldimethylamine (BDMA), BMC 379-80,491-2 creep failure 658
1074 Index

design 728 interlacing patterns 415,415 Butt tensile test 638,638

durability 658-9 Maypole machines 413,414 Butyl glycidyl ether (BGE), viscosity
environmental extremes 658 multidirectional 473 61
viscoelasticity 631 prepreg 418 By-products
step lap joints 627 processing technology 413-15 aramid fibers 222
Bonding rackets 1050 volatile 48,78
adhesives 127,255 sporting goods 1045-6 Bypass load 616,619,620
agent 190-1 structural geometry 415-16 definition 620
fiber and matrix 801-2 tape 418 joints 626
fusion 127 track and column 414,414,416 pure 620,621
hydrogen PPTA 204 tubular 413 ratio 620
inspection 668 Break-out 597
interfacial 149 Breakage 302,319 C-glass 134
andjoints 374 Breaking strength C-scan
metals 668 fiberglass 13940,141-4 pulse-echo testing 842,842
pressure 872-4 Kevlar 214 ultrasonic through-transmission
adhesives 271 Technora 224 testing 841, 841
skin/core 927-18 Breather 288 Cable cars 934-5
techniques, adhesive joints 611 Bremsstrahlung radiation 816 Cables 927
Bondline Bridges 9334,933 Calcium
adhesive voids, NDE 854 deck 986,986 aluminoborosilicate 24
thickness control 872-3 enclosures 992-3,994 carbonate 246-7,247
Bone cement 962 rehabilitation 988 abundance 243
Boron 23 Brittle fillers 527
applications 163, 165,166 adhesives 651 low shrinkage 243
continuous fibers 163 composites 797 Mohs hardness scale 243
fibers 27 fiber breakage 291 particulate fillers 243,247
reinforced plastics (BFRP) materials, ultrasonic machining stiffness 243
1023 605 Calcium-sodium metaphosphate 957
forms 161-3 solids 188-9 Calendering 532
manufacture 156-7 Broken fibers 803 Carbide, coating 296
properties 161 buildup 803 Carbon
trifluoride (BF,) 59 Bromine, halogens 43 black 245
trifluoride-monoethylene amine BSUs 169 content 306
(BF,MEA), melting point Buckling 547, 747,750-2, 752 fiber 254,234,33543,336,337
61 asymmetric 755 see also CF
Boron-aluminum, MMC 299 column-type 755 aluminum interaction 297
Boron-epoxy columns 997 applications 196-7
CTE 589 cylindrical shells 755-7 in carbon, matrix 337
stabilizer covers 1030-1 flange 998 compatibility of 295,296
Bosses 392,392 local 997-8 competitive prices 25
mold making 390 pressure 756 composites 190-1
Boundary conditions 588,750 sandwich 282 IS0 standards 1067
laminates 689 Buffalo Color 58 typical compression
Bowing, GFRP 1013 Building strength 1055
Braiding 18,33,164,402,402, construction, recycling 901-2 cost of 196,917
413-18,413,414,415,417,436, systems 989,991 CVD 335
437 Buildup, broken fibers 803 discontinuous 337-8
2-D 413 Bulk molding compound, see BMC elastic modulus 169
definition 415 Bumpers 815 electrical
2-step 416 Bundle theory 189-90 conductivity 169
3-D 413 Buoys and floats 927-8 properties 1845,185,186
geometric parameters 416 Bushings filament directionality 335
angle, and fiber volume fraction fiberglass 138 from PAN 171,335,336
417 platinum 133 from pitch 171
cross section 417,417 tooling 562 health effects 835
definition 413 Business equipment heat treatment 335
dry tows 418 applications 934,934 high modulus 335
horizontal 413,413 shielding 936 h g h strength 335

honeycomb 270-1
laminate, tensile strength
1056
MPa 425
nanoporous 183
noncircular 336
PAN-based 169
attributes 358
pitch-based 25,353
attributes 358
production 25
pyrolysis 335
reinforced
composites 358-9
plastics, see CFRP
reuse 884
rovings 502
selection 90
shape 335,336,337
shear strength 295
tensile
modulus 335
strength 169
thermal
conductivity 169
decomposition 25,25
properties 184-5,185,186
torsional strength 295
volume fraction 335
Young’s modulus 295
fiber-epoxy, drilling 599
fillers 527
specific modulus 1049
specific strength 1049
tension-tension ratio 1049
typeT300 503
Carbon-aluminum
infiltration 303
layer reinforced 304
magnesium evaporation 303-4
MMC, tensile strength 300
plate reinforced 304
producing 303
rolling 303
soldering 303
Carbon-carbon, rocket nozzles 712
Carbon-carbon composites 333-50
advanced 344
applications 341,349-50
arc jet tests 347
coating 343-4
cure cycle 342
density 333
high temperatures 340,344
impact damage 334
lay-up 342
linear thermal expansion 333
manufacturing 341-4
mechanical properties 344-5,345
melting point 333
modulus of elasticity 333
multiformity 333,333
oxidation resistance 333
pistons 349
powders 343
pyrolysis 341,342
reproducible strength levels 333
stiffness 333
strength efficiency 344
tensile strength 333
TEOS 349
thermal
conductivity 333,349
expansion 333,349-50
gradients 333
oxidation 345,347-8
thermophysical properties 348-9,
349
Carbon-carbon part
2-D 340
in oxidizing atmosphere 340
Carbon-epoxy 1031
composites 27
laminates 669
prepreg 558
Carbon-fiberglass 359
Carbon-graphite, quasi-isotropic
laminates 13, 23
Carbon-matrix composites 333
Carbonic, properties of 270
Carbonization
and aromatization 183
chemical changes 181-3
and effluent loss 183
emissions during 181-2
microstructural changes 183-4,
184
stabilized PAN 181
Carbonized organic composites
33941,340
curing temperatures 33940
impregnation 340
pyrolysis 340
starting material 339
Carbonyls, thermal decomposition
2934,294
Carcinogenicity 824
Cards combs 495
Carpet plots 718-20,719
construction 719
laminate selection 720
lay-up sequence 719
shear modulus 720,721
strength values 719
tensile
modulus 719
strength 720, 720
Cartilage 958
Index 1075
Carving bits, honeycomb 289
Cast
aluminum, tooling 442
boron, aluminum cable 299
ceramic, CTE 589
lamina, composites 299
Casting, applications 38
Catalysts 49,832
homopolymerization 49
metal coordination 104
Catalytic curing 50-1, 51
Caul plates 14,288-9
design 591
tooling design 590
Cavity pressure 443
CDS 798,798
CE 99-114,104
adhesives 114
composition 208
compression 122
dielectric properties 106-7
edge delamination 221
galvanic corrosion 108-9
hot-wet performance 108
hydrolysis 112,112
of cyanurate linkages 107
mechanical strength 211
moisture absorption 107
monomers 105
prepreg reinforced 113
property of casting 108
reinforcement 111
suppliers 112
tensile strength 108
thermal properties 106,209
Young’s modulus 208
Celion 1054
compressive strength 87
flexural strength 87
fracture toughness 87
shear strength 87
interlaminar 91
tensile
modulus 87
strength 87
weight loss 91,93
Cell
configurations, honeycomb 262
size, honeycomb 263
Cell-edge, adhesives 276
Celluloid acetate
compressive strength 258
density 258
maximum service temperature
258
shear modulus 259
shear strength 259
tensile strength 258
thermal conductivity 259
1076 Index

Cellulosic, fillers 527 PET 221 applications 1035-9,1036,1037,

Central cylinder, satellites 375-6 polyamide 6,6 221 1038,1039
Centred injection, ports 451,451 polyamide 12 122 material weights 1027
Centreless polybutylene-terephthalate 121 Civil engineering, pultrusion 519-20
grinder 429 polyesters 122 Clamping 501-2
sander 429 polyolefin 122 levels 625
Ceramics 307-29 polypropylene 121 pressure 625
applications 328-9,328 Charge joints 618
brittle 361 pattern 384-5 loss of 626
continuous unidirectional 317-18 preparation 384-5 Clay
cutting tool inserts 328,328 Chassis application 910-11, 923 grades of 244
densities 307 Chemical particle sizes 244
density 312 composition, fiberglass 147-8 particulate fillers 244
electrical conductivity 307 contamination 860 Clearances, fasteners 624, 626
fibers 27 degradation 299,888-9 Cleavage 50
applications 163,165,166 name 221 asymmetric 50
continuous 163 oxidation, direct wet 191 thermolytic 81
forms 161-3 precipitation 292-3 Climb, milling 596
health effects 835 properties, aramid fibers 213-15, Close packing 403,403
manufacture 156-7 214 Closure, of mold 442
properties 161 resistance 38 CMCs 935
fracture toughness 312 and crystallinity 120 ultrasonic machining 605
hardness 307 feldspar 243-4 CNC, lathes 597
matrices, designing 317-23,318, fiberglass 134 CO,, gas laser 605
319,320,321 Kevlar 214 Co-poly-p-phenylene/3,4'-
matrix nepheline 243-4 oxydiphenylene
composites, see CMCs PBI 237 terephthalamide 203,203,205
lamina, fiber fracture 799 PET 224,230 Coarse fillers
materials 311-12 Technora 214 silica 516
melting thermoplastics 126 talc 516
point 322 stability 214 Coating
temperatures 307,311 vapor deposition, see CVD aluminum foil 820
modulus of rupture 312 vapor infiltration, see CVI by precipitation 293,294
Poisson's ratio 312 Chemically resistant, gloves 829 carbide 296
powder processing 312-14,313, Chimneys 983 carbon fibers 2924,294,295
314 rehabilitation 988 chemical precipitation 292-3
reinforcing 307-11,308,308,309, Chlorendic 39 electroless deposition 292-3
310,311 anhydride (CA), melting point in gas phase 294-8
strengthening 3224,323 58 in-mold 385
thermal conductivity 307 resins 36,36,43 medical applications 957
thermal expansion 312 Chlorinated solvents, health effects metal, heating temperature 294
tolerance to flaws 307 836 nickel 292
unreinforced 328-9 Choice of resin, aramid fibers 222 nickel vapor-deposited 819-20
Young's modulus 307,312 Chopped strand, mat 155,917 nitride 296
Certification requirements Chopped-fiber, reinforced polyurethane 813
aircraft 1022-3 composites 355 protective 819-20,819
military aircraft 1023 Chopper gun 353 silicon carbide 294
CF/PEEK 115 Chord, winding 462 thickness 293,294,297
CF/PPS 115 Chromic acid anodized, aluminum andannealing 297
CF/PSU 115 foil 820 and deposition time 294
CFFW 1023-4 Chronic toxicity 824 Kulon 306
blistering 918 testing 824 VMN-4 306
cathodic 918 CIC 381 two-layer 300
prepregs 1-23 modified 381 Cockroft-Walton accelerator 848,848
Chain folding, PET 224 Circuit boards, fiberglass 136 COD 124
Channeling 443 Circular plates, axisymmetric Coefficient of thermal expansion
Char yield, NR-150 82 deformation 752-3 see also CTE
Characteristic damage state, see CDS Circumferential, reinforcement 461 aluminum 558
Characteristic temperatures Civil aircraft carbon-epoxy prepreg 558
 Index 1077

glass-epoxy 558 fiber dominated 795 hot-wet 108

high carbon cast steel 558 flywheels 474-5 measuringin 195
Invar 558 glass-reinforced 716, 717 molding 22,43,374,384,529,
laminates 322 graphite-remforced 716,717 532,545
mahogany 558 health and safety 880 composite parts 549
monolithic graphite 558 history 3 5 M fiber orientation 548
steel 558 hybrids 353 GMT 117
whiskers 308 inhomogeneous 797 one-dimensional flow 583-4,
Cohesive fracture 674,675 inspection 880 584
Collision avoidance 484,485 layer, permeability 581 polyimides 545
Color, stability 43 Materials Characterization, Inc PTFE 545
Columns 997-9,999 (CMC) 1065,1965 and pultmsion 490
buckling 997,999 panels 909 rackets 1049
crushing 997 preventive maintenance 880 thermoplastics 116,544-9
failure mechanisms 997 processes two-dimensional flow 584
properties 998,999 health hazards 831 UHMWPE 545
slenderness 997 safety hazards 831 molds 394,395,395
testing 999 processing 879 properties 360
Commercial preforms 397 strength
resins 101,102,103 times 353 AFR700B/S2 laminates 93
stabilization 178 protective coatings 879 marine laminates 920
Comminuted polvmers, fillers 527 pultruded, outdoor use 504 normalization 721
Compacted plies, Springer’s model quality controls 880 strength after impact 125, see also
588 reasons for using 3 impact energy
Compaction 470 repair methods 880 and tension 786-9
pressure 457 repairs, aircraft 857-8 TEOS 346
Compliance 195 sealants 879 testing 781
Compliant ring method 788-9 sealing 302 buckling 787
Components standard tests 880 flat specimens 787
of composites 879 talc 246 rings 782,788-9
design 709 testing 194-6 transverse cracking 787
sizing 712 thermal properties 661 unidirectional composites 787
Composites 166 Ti-A1-C 303 Compressive
adherends 630,660 tools 56675 fiber stress, and fiber volume
A1-B-C 304 aerospace industry 593 fraction 581
analysis 736-57 ease of preparation 592 modulus
anisotropic 797 low density 592 BMI 212
aramid prepreg 566,567-71 PMR-15 laminates 88
fibers 207 thermal expansion 592 properties
reinforced 716, 717 thermal stability 592 aramid fibers 221
beam wet lay-up 566 testing 38
cost 723 toxicological properties 831-7 strength
design example 722-3,722, tubes ABS 258
723 curing 428-9 Celion 87
design values 723 fishing rods 427 cellulois acetate 258
bolting and riveting 516-17 unidirectional 191 epoxies 258
brittle 797 whisker-alumina 320-1 fiberglass epoxies 153
cast lamina 299 Composition honeycomb 2665,266-7
components of 879 CE 108 Kulon 305
coupling agents 250 continuous ceramic fibers 309 laminate 616
damage fiberglass 138-9 Nomex 272,273
assessment 880 fibers 258 PBO fiber 238
sources 838 whiskers 158 phenolics 258
definition 378 Compound structures 456 plied-yam 151
density thermoplastics 534 Compression PMR-15 82,88
environmental effects 879-80 aerospace applications 26 polyurethane 258
fabrication 879 after impact (CAI) 105 polyvinyl chloride 258
failure 193 aramids 26 recycled phenolic 894
analysis 880 CE 111 S-glass epoxies 152
1078 Index

single-yarn 151 areas 184 splices 276,278,278

skinned molded foam 258 inverse method 611 Comers
thermoplastics 124 region, bearing load 620-1 flexure, TEOS 346
thermosets 124 Continuity condition, resin flow injection, ports 451,451
VMN-4 305 582-3 preform 438
yam distribution 154 Continuous Corporate Average Fuel Economy
stress, surface 321 casting 298-9 (CAFE) 907
Compton scattering 845 ceramic fibers 163,309 Correction method, tooling 590-1
Computed tomography 846-7,848 dry jet wet spinning 204 Corrective Optics Space Telescope
advantages 846-7 fiber-reinforcement 22 Axial Replacement, see
density map 846-7 fibers 156,338,338 COSTAR
Computer codes, joints 624,630 alumina-based 156-7 Correlation, ultrasonic 8434,844
Computer numerical controlled, see density 162 Correlators
CNC description 162 advantages 834
Concrete diameter 162 block diagram 844
dilation 988 elastic modulus 162 PTFE 834
forms 925 filament Corrosion
linear thermal expansion 705 directionality 338 barrier 47
polymer 984,984 winding 338 galvanic 108-9
post-tensioning 986,987 layer interlocking 338 resistance 38,42,303
prestressed 985-6 manufacturers 162 construction 982,983
rehabilitation 988 multilayer locking 338 high-temperature 322
reinforcing 999-1000 reinforced composites 355 reinforced composites 387
Condensed core, NDE 854 specific strength 162 Corrugated configuration, reinforced
Conductivity, and modulus of thermal expansion coefficient composites 389
elasticity 186 162 Corrugation process, honeycomb
Consolidation 314,576-94 trade names 162 257
autoclave 298,577 filament, fiber architecture 401-2 Cortical bones 958
definition 576 glass, rovings 492 COSTAR 1018-19,1019
equation 582 impregnated compound, see CIC costs
one-dimensional 584 reinforcement 502 aramid 717
equipment selection 577 strand mat 436,503 carbon fiber 917
fiber deformation 576 whisker 156 E-glass 717
history 578-86 Contour, variation 372-3 glass fibers 24
mechanisms involved in 576 Contoured tape, lay-up 16 graphite 717
models 57846,581-6 Control surfaces, marine meta-aramids 205
pressure 577 applications 924 metals 717
resinflow 576 Coolants, drilling 600 particulate fillers 242
techniques 576 Cooling towers 936-7,993-4,995 PBOfiber 238
temperature 577 Coordinating partial plies, tooling S2-glass 917
thick composites 585 design 590 count
thin composites 585 Copolymerization 34 fiberglass 1 4 1 4
time 585 Core plied-yam 151
window 588 corrosion single-yam 251
tooling materials 577 adhesives 271 Countersinking, and drilling 598-9
Constituent NDE 854 Countersunk
materials 22 edge treatment 277 fasteners 624,624,625,625
properties 766-7 fatigue, NDE 854 head 729
Constitutive equations 739,741 materials 256-7 Coupling
stiffness coefficients 7 4 3 4 movement, adhesives 271 agents 671
Construction node disbonds, NDE 854 chemical functionability 147
applications 982-1001 plug repair 866 commercial 148
materials selection 982 selection, sandwich 284 composites 250
carpet plots 719 shaping 289,289 effect on mechanical
methods 1014-15 shear stress, formulas 284 properties 149
mold 447 sue, sandwich 288 fiberglass 146-7
pultrusion 519-20 splitting, adhesives 271 polypropylene and acrylic
Consumer products 946 Cores acid 251
Contact density 276 resin interaction 149
 Index 1079
silanes 147,250-1 795 and resin viscosity 354,355
titanates 251 Crooked chain, meta-aramids 205 RTM 433
viscosity 250 Cross section selecting 585,586
zirconates 251 constant 489 times, tools 559
with diepoxides 105 shape of 461 degree of 587,587
eliminating 193-4 Cross sections, strength 613 monitoring 67-9,67,68,69
and stiffness 702-3 Crosslinking 31,48,100 in situ 69
Coupon tests 195,687,688 matrix 460 infrared spectroscopy 68
Coupons reversible 887-8 off-line 67-9
configuration 721 rotational molding 552 part slippage 432
standard 721 Crowfoot satin, weave 145,145 rate 509-10,509,510
Crack Crushed core epoxy resins 509
bridging 320,3234,323 NDE 854 polyesters 509
deflection 320,323-4,323 sandwich 282 shrinkage 48
formation 469 Crystal, anisotropy 334 temperature 105
growth, fatigue 811 Crystalline adhesives 661
initiation 124,632 polymers 118,120 Cured epoxy resin systems, ASTM
opening displacement, see COD silica 250 methods 72
propagation 124 Crystallinity Curing 13,16,37,385
Cracking advantages of 126 agents 49,513,813,832
bonded joints 659,659 and chemical resistance 120 amine 5 3 4 , 5 6 6
matrices 319 PET 224 anhydride 56-9,56-9
Crashworthiness 3 Crystallite melting point, Spectra 26 anhydride-cured system 72
Cratering 814 Crystallization kinetics epoxy resins 509
Crazing 343 injection molding 540 amine 49-50,51
Creel rotational molding 552 anhydride 50
bookshelf 492 CTE 698-9,704 autoclave 33
horizontal feed 494 aluminum 589 composite tubes 428-9
loaded multiple spindle 494 aramid-epoxy 589 cyclotrimerization 99-101
mat/fabric 494 boron-epoxy 589 dicyanates 100
package positions 493 cast ceramic 589 low temperature 567
pultrusion 492-5 compatibility 557 non-autoclave 589
Creep electroformed nickel 558 ovens 22,428-9
effects 126 fiberglass-epoxy 589 press 22
environmental 1000 graphite-epoxy 589 reaction 49
failure high-temperature cast epoxy 589 RTM 4456,445
bonded joints 658 iron (electroformed) 589 shrinkage 41
hot-wet conditions 659 M401/F854 704 temperatures, carbonized organic
fatigue 631 nickel (electroformed) 589 composites 33940
homopolymers 212 shrink factors 557-8 thermal 499
low temperatures 800 silicone rubber 589 time 385
para-aramids 212 tool steel 589 Curved
resistance tooling 556-7,557-8 beams 791
aramid fibers 216,222 urethane board stock 558 pultrusion 489-90
PET 227 Cupping 541,541 cut-off
Spectra 227,228-9,230,232 polyoxymethylene 541 high pressure water jet 502
rupture 797,800,806 Cure saw 502,502
time-dependent 800,800 catalysts 104 station 502
viscoelastic 797 control 5869,586,587,588 wastage 502
Cresyl glycidyl ether (CGE), objective 588 Cut-outs, in cylinders, GFW 1013
viscosity 62 cycle cutting
Crimp 416 anhydride-cured 72 aramid fibers 222
Critical aromatic system 71 Kevlar 600
bend radius, continuous ceramic autoclave 83-4 plies, surface preparation 870
fibers 309 stepped 355 speed 5967,598,605
energy, failure criteria 795 carbon-carbon composites tools 329,329
load, orthotropic plates 751 342 CVD 27,157,294,296,311,338-9,
processing temperature 326 elements 67 339
shear resistance, failure criteria no-bleed 673 carbon fibers 335
1080 lndex

drawbacks 317 Debulking 567,569,592 textile preforming 397

isothermal 338-9,339 periodic 574 thermosetting reaction 49
silicon carbide 157 Deburring 565 tows 476
temperatures 316 Decking 925 toxic 822
thermal gradient technique 339, Decomposition temperature viscosity 527
339 Kevlar 206 weaving 404
CVI 316,316,401 Nomex 206 Deflection
forced flow-thermal gradient PBOfiber 238 effect 640
processing 317,317 Technora 206 equations 750
isothermal processing 317 Teijinconex 206 fasteners 624,626
Cyanate Twaron 206 formulas 284-5
ester, see CE Decontamination, PMC 863 lateral 644
resins 29-30 Deep delamination, NDE 854 sandwich 284
Cyanates 358 Deep submergence devices 474,475 Deformable, adherends 633,634
Cyanurate trimer 99,100 Defective fibers 303 Deformation 398
CYCAP 93 Defects, inspection methods 733-4, adherends 630
chemistry of 81 734 degree of 448
Cycle times, RTM 433 Defibrillation 215 laminates 691
Cycles to failure, Kevlar 213 Definitions point 302
Cycleweld 255 aramid fibers 202 Degradation 215,796
Cyclic loading, microcracking 801 autoclave 577 aminolysis 889
Cycloaliphatic amines, health effects BMC 379 chemical 88&9
832,832,833 BMI-DAB 105 factor 697
Cylinders BMI-MDA 105 fiber length 536
filament winding 467 braiding 413 glycolysis 889
Cylindrical shells 466,752-3,753 bypass load 620 hydrolysis 889
axisymmetric deformation 7 5 3 4 composites 378 methanolysis 889
buckling 755-7 consolidation 576 NDE 838
pressure 756 damage tolerance 794,794 PET 889
nonsymmetric deformation denier 241 products obtained 889
754-5 detailed design 710 strength 796
shear deformation 756 durability 794,794 Degreasing, metal surfaces 871
stiffnesses 756 electroforming 591 DEH 20 (Dow) 54
Czochralski method 160 epoxide 48 DEH 24 (Dow) 54
equilibrium moisture content 241 DEH 26 (Dow) 54
D-glass 134 extrusion 534 de Havilland Mosquito 686, 686
Dagger drill 599400,599 fiber 242 Delamination 548,5974,598,599,
Damage placement 476 615,798-9,799,801
accumulation 797 hazard 823 atedge 798
assessment heat capacity 532-3 helical winding 789
composites 880 hygrothermal 694 Delta Clipper experimental launch
wet lay-up repairs 866 knitting 408 vehicle 974-5,974
drivers 801-3 lamina 687 Demolding 443,4467
inspection, NDE 854 material properties 709 precautions 446
low velocity impact 839-40 matrix 378 DEN 431 (Dow) 52
modes 797-800,798,799,800 particulate fillers 242 DEN 438 (Dow) 52
protective coatings, aircraft preliminary design 710 DEN 439 (Dow) 52
859-60 prepreg 425 Denier, definition 241
resistance 801-3 pultrusion 488 Denitrogenation 183
tolerance 107, 222, 794, 794-808 pyrolysis 888 Densification 314
definition 794,794 reinforcements 378 shuttle parts 343
Darcy’s law 447,581 rheology 527 Density
resin flow 578 risk 823 ABS 258
DCB, tests 124 specific heat 532-3 aluminum 270,558
DCPD 37,37,39 specific modulus 715 aromatic system 71
low cost 37 steering 482 carbon (Type T300) 503
maleate half ester 37 strength retention 241 carbon-carbon composites 333
Debonding, moisture 811 tenacity 241 carbon/epoxy prepreg 558
Debris impacts 814-15,814,815 Tex 136,241 cellulois acetate 258
 lndex 1081
ceramic composites 322 continuous fiber 162 Dicyandiamide (DICY), melting
ceramics 307 staple 162 point 56
continuous ceramic fibers 309 whiskers 162 Dicyclopentadiene, see DCPD
continuous fiber 162 Design 32 Dicyclopentadienyl bisphenol
E-glass 503 aerospace 709 homopolymer property 102
electroformed nickel 558 allowables 709, 758-77 structure precursor 102
epoxies 258,511 nomenclature 759,759 supplier 102
glass/epoxy 558 processing variables 762-3 trade name 102
high carbon cast steel 558 testing 758 Dielectric
Invar 558 checklist 712,714 constant 95
Kevlar 206,503 components 709 E-glass fibers 231
Kulon 305,306 of composites 18-20,19 PET 224
mahogany 558 considerations 994-1001 Spectra 231
meteoroids 815 data, using 724-7 thermoplastics 107
and modulus 23 detailed 710 thermosetting 107
monolithic graphite 558 laminates 686708,697-706 properties 106-7
Nomex 206 low strain 838 strength, Skybond 95
NR-150 82 methodology Dielectrometry 68,69
PAN-based fibers 170 knitting 410-13 bulk 68,69
phenolics 258 nonwoven textiles 419 Diels-Alder 101
pitch-based fibers 170 preliminary 710 reverse 80
PMR-15 82 process 710 Dies 497
polyester 511 requirements chrome plated 501
polyurethane 258 aircraft 713,1022-3 forming 497
polyvinyl chloride 258 stabilizer 710 heating and curing 498-501
recycled NBC 897 automotive industry 723 inspecting 501
recycled phenolic 894 helicopters 713 internal profile 499-500
regrindRIM 895 industrial pressure vessels manufacturing 500
resin, aliphatic system 70 713 multi-cavity 491,500
S-glass 503 marine submersibles 713 positioning 498
SiC/Al,O, 315 recreational 713 purging 514
skinned molded foam 258 rocket motors 713 steel 500
Spectra 503 sailboats 713 temperature
staple 162 satellites 713 control 511-13,512,513
steel 170,558 team 709,712,714,715 profile 511, 513
and strength 23 materials supplier 715 stability 514
Technora 206 values 720-2 Diethyl ester diacid derivative 80-1
Teijinconex 206 verification 733-4733 Diethylaminepropylamine (DEAPA),
titanium 170 Designations, continuous ceramic viscosity 54
Twaron 206 fibers 309 Diethylenetriamine (DETA),
urethane board stock 558 Despooling 479 viscosity 54
vinylester 511 Detailed design 710, 723-34 Different thicknesses, sandwich
VMN-4 305,306 definition 710 structures 744
whiskers 162,308 Determinable values 779 Diffusion welding, solid stage
Dental applications, hydroxyapatite Diacids, and glycols 34-5 production 291
(HA) 958 Diameter Diglycidyl ether of 1,4-butanediol
Dentin 958 continuous fibers 162 (BDE), viscosity 62
Deoxidizing, metal surfaces 871 ceramic 309 Diglycidyl ether of bisphenol A
Deposition low 160 (DGEBA)
electrolytic method 293 staple 262 crystallization 51
time, and coating thickness 294 whiskers 262,308 viscosity 51
DER 330 (Dow) 52 3,Y-Diaminodiphenylsulfone, Diglycidyl ether of bisphenol F
DER 331 (Dow) 52 melting point 55 (DGEBF) 52
DER 332 (Dow) 51 4,4'-Diaminodiphenylsdfone (DDS), crystallization 52
DER 661 (Dow) 51 meltingpoint 55 Diglycidyl ether of neopentyl glycol,
DER 732 (DOW) 63 Diaphragm forming 117 viscosity 63
DER 736 (DOW) 63 thermoplastics 116 Diglycidyl ether of polypropylene
Derivatives, phenolic 382 Dibromoneopentyl glycol 43 glycol 63
Description Dicyanates, curing 100 Diluents 61-3,62-3
1082 Index

reactive 66,66 cantilever beam Duramite 247,247

Dimensional see also DCB Dust particles, milling 597
stability, reinforced composites specimens 124 Dy 023 (Ciba-Geigy) 62
387 head, pull winding 496-7 Dy 027 (Ciba-Geigy) 61
tolerances 560-1 lap DY 062 (Ciba-Geigy) 60
drawings 731 adhesive joints 628 DY 064 (Ciba-Geigy) 60
Dimensions, joints 612,649 balanced 655 Dyeing, PET 233
DIMOX 315-16,315,316 joints Dyes 516
Dimpling, sandwich 282,284 stress distribution 654 Dynamic mechanical analysis
Direct wet, chemical oxidation 191 thermal stress 662 (DMA) 816
Direction dependence 698 shear, joints 624,625 Dynamic mechanical thermal
Directional metal oxidation, see strap analysis, see DMTA
DIMOX adhesive joints 628 Dyneema 223
Directionally reinforced molding joints, tapering 646,647, 648 availability 231
compound, see XMC Doublers 279-80,280 elongation at break 225
Disadvantages Draft 389,390 fibertype 225
AWJ 604 zero 389 pricing 232
hand lay-up 352 Drapability, preform 438 specific gravity 225
injection pultrusion 497 Draping simulation 448,448 tensile modulus 225
laser machining 605 Drawings 730-3 tensile strength 225
preform 438 construction 730-3
RTM 434-5 dimensions 731 E-glass 24,134,425
turning 597 tolerances 731 composite tanks 985
twin-screw extruders 539 material description 731,731 compression properties 360
ultrasonic machining 608 thickness 731 constituent properties 766
Disbonds Drill costs 717
inspection 839 cutting parameters 600 density 503
NDE 854 dagger 599400,599 dielectric constant 231
surfaces 677 fixtures, fabrication 573 elastic properties 764-7
Discontinuous fully fluted 600 elongation at break 503
fiber 156 geometry 599-600 fiber modulus 360
representative volume 804 performance 599 Kevlar, fiber modulus 360
whisker 156 templates 5 7 3 4 polyester rods 985
Discrete, fiber architecture 401,401 twist 600 references 774-7
Disks, axisymmetric deformation Drilling 597400,598,599 reinforced concrete 984
752-3 carbon fiber-epoxy 599 reinforcement 383
Displacements, measuring 779 coolants 600 specific
Disposal and countersinking 598-9 gravity 383
see also recycling, reuse damage 729 modulus 1049
nonrecyclables 899-900 glass fiber-epoxy 599 strength 1049
and reuse 883-904 machining 602 strength properties 764-7
Dissimilar adherends 635 secondary 598 tensile
Dissipation factor 95 Drive shafts 911,93&7 failure 383
fiberglass 135 Dry spots, eliminating 453,453 modulus 360,383,503,716
thermoplastics 107 Dry tows, braiding 418 properties 360
thermosetting 107 Drying, of composite 811 strength 24,383,503
Distortion temperature, testing 38 Dual-shell reflector, Kevlar 1004, tension-tension ratio 1049
Diving equipment 926-7,926,927 1004 thermal expansion 383
Dixie Chemical 57 Ductile response 655 typical properties 1055
DMP 30 (Rohm & Haas) 60 adhesives 65145,652,657 uniaxial strength 194
DMTA 120,120 Ductility, adhesives 62743,629-30, Young’s modulus 24
Dodecenyl succinic anhydride 655-6 Ears 371
(DDSA), melting point 57 DuPont FP fiber 309 Earthquakes 197
Domes, contours 467 elastic modulus 309 Ease of preparation, composite tools
Domier 328 Durability 794-808 592
composite applications 1037, bonded joints 658-9 ECN 1273 (Ciba-Geigy) 52
1039 definition 794,794 ECN 1280 (Ciba-Geigy) 52
rear fuselage and fin 1039 PET 233 ECN 1299 (Ciba-Geigy) 52
Double predicting 796 Economics, land transportation
 Index 1083

9056,906 conductivity Teijinconex 209

Eddy current testing 849-50 carbon black 245 Tekmilon 225
Edge carbon fibers 169 Twaron 208
definition, preform 438 ceramics 307 Vectran 235
delamination 111 equipment, pultrusion 519 vinylester 511
distances insulators, aramid fibers 215 VMN-4 306
bearing load 621 properties EM1
bolted joints 617,617 aramid fibers 215 testing 982
effects 780,789 carbon fibers 184-5,185,186 buildings 989,991,991
turning, reinforced composites fiberglass 135 EMI-24 (Air Products) 60
390 resistance, reinforced composites End effects 780
Edge-defined film-fed growth, see 387 End grain balsa 917
EFG resistivity, and microtexture 189 End-capping 81
Effect of contaminants, aircraft 863 Electrically conductive, particulate Energy
Effluent loss, and carbonization 183 fillers 250 equation 586-7
EFG 160 Electroformed nickel fracture surface 320
Egg crate structure 569,570,572 CTE 558 release rates 632
Eight-hamess satin, weave 145,145, density 558 Engineering
436,436 mandrel 591 constants
Einstein coefficient 531-2 thermal conductivity 558 IM6/epoxy 699,700,701
fillers 533 tooling 591-2,592 laminates 693
Ejection, part 385 Electroforming 591-2 parameters, preforms 421
Elastic definition 591 properties 22
constants Electroless deposition, coating 292-3 Environmental
graphite/epoxies 4 Electromagnetic interference, see EM1 aspects, recycling 902-3
Kevlar 210 Electron diffraction 186 conditions, adhesives 630
preform 449 Electronics, applications 937,937 effects 810-20,1000-1
displacement 195 Electroplating 820 composites 879-80
modulus Element tapering 624 creep 1000
aluminum 170 Eliminating history 810
carbon fibers 169 dry spots 453,453 relaxation 1000
continuous fiber 162 microcracking 1012 exposure 860-1
duPont FP fiber 309 Elongation 26 extremes, bonded joints 658
Kevlar 205 epoxy resins 29 properties, aramid fibers 213-15,
Kulon 305 NR-150 82 214
PAN-based fibers 170 nylon 6/6 PCI-glass 899 resistance 3,49, 65, 564
pitch-based fibers 170 PMR-15 82 Epi-Rez 5014 (Hi-Tek Polymers) 62
staple 162 PP and granulated SMC 897 Epon 826 (Shell) 51
steel 170 recycled NBC 897 Epon 1001 (Shell) 51
titanium 170 recycled PP 895,896 Epotuf 37-053 (Reichold) 62
W - 4 305 regrindRIM 895 Epotuf 37-057 (Reichold) 61
whiskers 162 Skybond 86 Epoxides 51-3,51-3
properties Elongation at break curing agent ratio 64
E-glass 764-7 Armos 208 definition 48
graphite epoxies 768-71 carbon (Type T300) 503 molecules 49
Kevlar 764-7 Dyneema 225 Epoxies
laminate 764-7 E-glass 503 adhesives 275
S2-glass 764-7 epoxy 511 compressive strength 258
Spectra 764-7 Hoechst Celanese 225 density 258,505
response 319,655 Kevlar 205,208,503 elongation at break 505
stress-strain, microcracking 798 Kulon 306 flexural modulus 505
symmetry, axis of 779 Nomex 209 flexural strength 505
zone length 658 particulate fillers 252-3 heat distortion 505
Elastomer, tooling 14 PBO 235 laminates, tooling 562
Elbows 464 polyester 511 maximum service temperature
Electric discharge machining (EDM) Sglass 503 258
605 Spectra 225,503 nitrile rubber modified 275
Electrical SVM 208 pultrusion 511
applications 937,937 Technora 209 reinforced 196,442
1084 Index

resins 2&9,29,30,382,504,832 routes 826 lap joints 643

bismaleimides 6 to moisture, PET 227 criteria 193, 795,802-3,802
curerate 509 Extended critical energy 795
curing agents 509 chain critical shear resistance 795
cyanate ester 6 PET fibers 202,223-34 laminates 695-7
elongation 29 manufacture 223-4 envelopes 696
flexibility 63 exposure, mechanical properties load, joints 615
formulation 63-4,64 215 mechanisms, columns 997
gel times 510,510 Extruder die modes 621,622,797400,798,
glass content 510 extrusion 535,535 799,800,804
modifiers 105 shape 535 properties 194-5
moisture absorption 29 Extruders stresses, joints 626
phenolic triazine (PT) 6 single screw 536 Fairings 1024
polyimides 6 twin-screw 536 marine applications 9234, 923,
pull loads 510 Extrusion 529 924
rigidity 63 cf. pultrusion 488-9 Fasteners
selection of 5 definition 534 bending 625,625,729
viscosity vs. time 510,510 extruder die 535,535 deflections 626
shear modulus 259 melt pumping 5365,535 clearances 624,626
shear strength 259 melting 534 countersunk 624,624,625,625
tensile modulus 505 orientation 538 deflections 623,624,625,626
tensile strength 258,505 plasticating 534,535 design issues 729
thermal conductivity 259 solid stage production 291 diameter 6234,625
Equations solids conveying 534,535 increasing 614
of continuity 582 thermoplastics 526,534-8 effects 612,624-6,624,625
lamina material 760 Eye protection 830 joint around 612,612
of motion 738-9,740-1 loads 622
inertia terms 739 3F dianhydride 77 mechanical 517
strain-displacment 739 3F/36F polyimides, chemistry of 77 multi-rowed 620
Equilibrium FAA advisory circulars 1063, 2065 multiple arrays 612
crack spacing 798 Fabric formation 402 parameters 517
moisture content, definition 241 Fabrication 31,33 protruding head 624,624
Equipment composites 879 selection 729, 729
selection, consolidation 577 drill fixtures 573 tension head 625
wet lay-up repairs 867 first article 372 Fatigue 811
ERL 4206 (Union Carbide) 63 lowcost 33 crack growth 811
Erosion 813 marine applications 919-20 low temperature 811
atomic oxygen 814 methods 762 para-aramids 213
Ester formation 34 quality 33 properties 386,387
Esterification 35,38 techniques 13-18,14,25,16 resistance
Etching 667 Fabrics, orientation 504 aramid fibers 221,222
Ether linkages, Technora 210 Face PET 230
2-Ethyl-4-methylimidazole (EMI), dimpling, formulas 285 Technora 213
melting point 60 sheet thermoplastics 115
Europe, recycling 884 materials removal 864 Feedrates 598
European retrievable carrier 971 repair 866-7 Feldspar 243-4
Evacuation, PMC 863 wrinkling chemical resistance 243-4
Evaluation, strength 737 formulas 285 particulate fillers 243-4
Exothermic reactions 827-8 sandwich 282,284 refractive index 2434
Exotherms 68 Facing Female tooling, large power yachts
Expansion process, honeycomb 257 failure, sandwich 282 921
Expendable materials 35940 material 25.56 Femoral components 960-1
Exposed surface, voids 432 Failure 193 design 960
Exposure adherends 627-9,628,657 development 961
alkaline 46 analysis, composites 880 FEP 362
assessment 826 aramid fibers 210 mold releases 362
limits 824-5, 826 bond 627-9,628 Fiber
terminology 826 characteristics alignment 494
preventing 827 joints 659,660 aluminum based 159
 Index 1085
architecture 398 separation 615 rebars 999
continuous filament 401-2 shape, carbon fiber 335,336,337 reinforced plastics 23
discrete 401,401 strength, degradation 806 reinforced polyesters, see FRP
infiltration 401 tensioning 457 reinforcing 38
integrated 401,401 to resin ratio 509 rovings 136,1467,353
interlooped 402 trade names 258,225 specific gravity 135
laminar 401,401 type 225 spire 991
linear 401,401 volume 721 staple fibers 131
planar interlaced 402 fraction 21,404,412,416,578 strand 131
areal weight 425 3-D fabric 416 suppliers 236
breakage, NDE 838 and braiding angle 417 surface resistivity 135
breakout 599 carbon fiber 335 tapes 146
breaks, NDE 854 and compressive fiber, Teglass 134
bundles 403 stress 581 tensile strength 134
coating 166,802 Gutowski's model 588 thermal properties 135
composition 158 high 585-6 thickness 1 4 1 4
continuous 156 and permeability 399400, three-dimensional fabrics 146
definition 242 400 volume resistivity 235
deformation 580-1 processing window 412, warp yam 2424
consolidation 576 412 water resistance 136
curve 580-1,581 waviness 780 weave 1 4 1 4
diameter 156 Fiberfrax 160 weight 2414
structural hierarchy 778 Fiberglass yam 138
direction, tensile strength 804 acoustical properties 235 designation 13940
discontinuous 156 aircraft industry 136 yield 139-40
distribution 154, 154 antistatic agents 1 4 6 7 Fiberglass-epoxy, CTE 589
preform 438 binders 147 Fiberite 99
dominated, composites 795 breaking strength 239-40,141-4 Fibrous
flow 527-31 bushing 138 dust 835
cf. particulate flow 530 chemical composition 147-8 reinforcement types 795,796
fracture 799,799 chemical resistance 134 Filament
fragments, inhaling 835 circuit boards 136 angle of 456
length, degradation 536 composition 133-4,234,13&9 cross-section, PET 225
low risk 835 continuous 131 diameter 139,148-9
manufacturers 158 strands 147 Kevlar 206
manufacturing processes 258 count 1 4 2 4 Kulon 306
modulus 360 coupling agent 146-7 Nomex 206
orientation 527-31 dissipation factor 135 PET 225
compression molding 548 electrical properties 135,136 Technora 206
injection molding 543,543 epoxies 153 Teijinconex 206
preforms 421 fabric count 140 Twaron 206
packing fraction 412 fibers W N - 4 306
placement 17,47687,477 attributes 358 directionality, carbon fibers 335
definition 476 hollow 134 equilibrium, equation 459
head 476 milled 146 equilibrium 459-61
inspection 4867,487 filament designations 133 lay-up 457
machines 478,482 filament diameter 133 shape 206
materials 478-9 filling yam 1 4 1 4 strength, S-glass 24
steering 482 fire resistance 134 on surface 459-61
surface geometry 484-6 fluted core fabrics 146 tension 457
tooling 479-80 heat resistance 134 winding 17,17,66,116,117,
properties 400,400 laminates 356 456-75,762
pull-out 320,3234,323 lubricants 14G7 applications 471-5
rayon-based 173 manufacturing 132 continuous fiber 338
reinforced polymers, see FRP mat 137-8 cylinders 467
reinforcement 22,23,216,435-6 mechanical properties 135 low costs 463
for reinforcing 166 optical properties 235 machine 463,464
and resin 425 platforms 989 marine applications 920
rovings 492,503 proof testing 849 pressure vessels 471
1086 Index

rackets 1050 impact strength 249 plied-yam 151

spherical shapes 466-7 mica 249 polyester 511
sporting goods 1046,1047 silver 249,250 recycled PET 894
wet 762-3 Flame recycled phenolic 894
Filed inspections, neutron polishing 157 recycled SMC 890,892,893
radiography 848 spread 44 S-glass epoxies 152
Fill, yams 407,407 Flammability, evaluating 44 short fiber mat 401
Fillers 382, 516 Flank wear 599 single-yam 151
barium ferrite 527 Flat SMC 386,386
barium sulfate 527 cylinders, filament winding 467 unidirectional tape 401
calcium carbonate 527 specimens vinylester 511
carbon 527 compression testing 787 woven laminates 401
cellulosic 527 testing 781,786-7 yam distribution 154
clay 516 tension 786-7 ZMC 386,386
coarse, disadvantages 516 tape, lay-up 16 stress
comminuted polymers 527 Flat-layer, microstructures 177 PP and granulated SMC 897
effect on processing 552 Flaws, planar 840 recycled PP 895,896
Einstein coefficients 533 Flex modulus Flexure
fine 516 NR-150 82 TEOS 346
functional 382 PMR-15 laminates 88 testing 195
glass 527 Skybond 86 Float 150
ground limestone 382 Flex strength Floc 216
ground petroleum coke 527 AFR700B/S2 laminates 93,95 Flocking lay-up, short fibers 337,338
inorganic phosphate-based 957 Celion 87 Flow
medical applications 957 NR-150 82 measurements 357
metallic oxides 527 PMR-15 laminates 88 andrigidity 67
mica 527 Skybond 86 Fluid contamination, aircraft 859
molybdenum disulfide 527 Flexibility 161 Fluids
non-functional 382 Flexible aircraft 812
pultrusion 516 backbone polyester resin 381 automotive 812
shape of 531 mold wall 444 methylene chloride 812
silica products 527 Flexural Newtonian 527,528
silicon carbide 527 modulus Fluorine, toxicity 362
specific heat 533 BMC 386,386 Fluoroethylene propylene, see FEP
Fillet forming, adhesives 271 epoxy 511 Flushing contaminants 864
Filling 301,301,302 LPMC 386,386 Fluted core fabrics, fiberglass 146
mold 442 nylon 6/6 PCI-glass 899 Flywheel mechanical battery systems
single-yam 151 polyester 511 938,938
yam 140 polyetherimide 545, 546 Flywheels 474-5
fiberglass 1 4 1 4 polysulfone 546 Foam
Film impregnation 8 PP and granulated SMC 897 adhesive voids, NDE 854
Film-stacking 117-18, 718 recycled NBC 897 core materials 256-7
Filter cloths, PET 233 recycled PET 894 cores for fiberglass 256
Finish 215 recycled PP 895,896 injection 256
S-glass epoxies 152 recycled SMC 890,892,893 insulation 256
Fire regrindRIM 895 in place system 257
prevention 367 SMC 386,386 polystyrene 256-7
resistance, fiberglass 134 vinylester 517 PVC 257
retardance 36,42-5 ZMC 386,386 radar transparency 256
halogen inclusion 43 properties shear strength 257
retardants, particulate fillers 249 Spectra 226,226 Folding 547
Firefighter breathing apparatus testing 38 low-cost 117
937-8 strength thermoplastics 216
Fishing poles 427, 1045, 1051 BMC 386,386 Forced flow-thermal gradient
FIT-technology 117 epoxy 511 processing, CVI 317,317
Flags fibreglass epoxies 153 Foreign materials
bias 425,426 LPMC 386,386 NDE 854
longitudinal 425 marine laminates 920 X-ray imaging 844
Flakes 248 nylon 6/6 PCI-glass 899 Formability
 Index 1087
jamming angles 399 fire retardant 42 cut-outs in cylinders 1013
preforming 398-9 flame resistant 44 development 1016
weft knitted fabrics 399 low bending stiffness 960 diffusivity 1008
woven glass fabrics 399 orthopedic applications 959 economics 1020
yarn slippage 399 permeability 959 hygroscopic nature 2006
Forming dies 497 pins 959 impact damage 1006
fabrication 497 properties of 46 joints 1012,1012
materials used for 497 pultrusion 47 material cost 2006
Forms strength of 45 microcracking 2006
aramid fibers 216 thermal performance 45 moisture effects 1007-10
boron 161-3 total hip arthroplasty 959 new materials 1019-20
ceramic fibers 161-3 Fuel tanks 93940 peel strength 2006
high silica 161-3 Fully fluted drill 600 predictions 1019
quartz 161-3 Functional fillers 382 properties 1005
Vectran 236 Fungal growth 810-11 undesirable 1006
Formulas Fusion 157 springback 1013
bending stress 284 bonding 127 temperature extremes 1004-21
core shear stress 284 PEEK 127 warping 1013,1013
deflection 284-5 Future directions, transportation 915 woven broadgoods 1024
face dimpling 285 Gibbsite 245
face wrinkling 285 Galvanic, corrosion 108-9 Glass
moment of inertia 285 Gap 487 bottle industry 97
safety factor 285 Gas laser content
Formulation applications 605 epoxy resins 510
diglycidyl ether of bisphenol A CO, 605 nylon 6/6 PCI 899
hexahydrophthalic Gas-sparging 174-5 pP/PCI 898
anhydride 64 Gate 541,542 fabrics, knitted 917
diglycidyl ether of bisphenol A fiber orientation 543 fiber-epoxy, drilling 599
triethylene diamine 64 Gating 450-1 fibers 24-5,25
diglycidyl ether of bisphenol A Gel alkaline environment 1000
triethylene tetramine 64 coat 567 applications 24
Fortafil 2054 spinning 223-4 availability 24
properties of 170 time 37, 66, 357, 446 cost 24
Fountain flow, injection molding 542 aromatic system 72 handling 24
Fractionizing plant 887 zone 505 health effects 835
Fracture 597 Gelation history 131
effects, isolating 799 pressure during 508 processing 24
elongation 170 resins 499 reinforced plastics (GFRP)
fixation devices 961-2 Gelstar Thermal Analyzer 515 1024
mechanics, joints 631-2 General reuse 884
path 324,324 aviation, applications 103940 S-glass 24
strength 325 equations 73845 silane coupling 24
toughness Geodesic toxicity 24
alumina composites 325 curvature 459 fillers 527
Celion 87 deviation, angle of 460 history 131
ceramic composites 322 line 457 length, recycled PP 895,896
high silica 156 Geometry mat thermoplastics, see GMT
moisture 811 joints 638-51 reinforced plastic, see GRP
NR-150 82 single lap joint 641 rovings 502
PMR-15 82 Germany to resin, ratio 150-4, 253
Silar 325 recycling 902 transition temperature
Tateho 325 standards 1065,2066 see also Tg
thermoplastics 222,224 GFRP 1004-21 aromatic system 71
Free radical generators 104 aerospace applications 2007 moisture 811
FRP 38,41 anisotropic behavior 1012-14 RTM 440
composites, pultrusion 517 anisotropy 1006 Glass/epoxy
corrosion resistant 44 applications 1026 coefficient of thermal expansion
corrosive attack 45 assembly bowing 1013,1014, 558
durability 959 1014 density 558
1088 Index

thermal conductivity 558 thermal data 828 fibrous dust 832

Gloves 828-9,828 weathering 813 HDPE
resistant 829 Graphite/polysulfone, weathering glass-fiber reinforced 549
types 829 813 graphite filled 549
Glued laminated timber 991 Graphite/wood, hybrids 354 mica flake reinforced 549
beams 940-1 Graphitization 169,183 HDT 126, 226
Glycidyl alignment 191 recycled PET 894
amines, health effects 832 large regions 170 Health
compounds 831-2,832 Grating 936 applications 943-4,944
ethers, health effects 832 Green form 314 effects
Glycol Green strength 446 aliphatic amines 832,833
and diacids 34-5 Grill opening panels, SMC 907 amino resins 834
propylene 35 Grinding 600 anhydride curing agents 832,
selection 39 accuracies 600 833
Glycolysis, degradation 888 cryogenic 886 aramid fibers 835
GMT 115 polymer matrix composites 600 aromatic amines 832,833
automotive market 127 silicon carbide wheels 600 bisphenol A-based 832
compression molding 117 surface speeds 600 carbon fibers 835
extrusion compounded 118 Grit blasting, surface preparation ceramic fibers 835
semi-finished 118,228 870-1 chlorinated solvents 836
Goland-Reissner 641 Ground limestone 382 cycloaliphatics 832, 832,833
Golf shafts 429,463,465,698,1051 Ground petroleum coke, fillers 527 glass fibers 835
filament wound 1051 Growth factors 558 glycidyl amines 832
test methods 1051 GRP 839 glycidyl ethers 832
Grafil 2054 Grumman F-14 1030 graphite fibers 835
Granulation Grumman X-29 aircraft 698,698 imides 834
knife 886 Guide pins 442 ketones 836
recycling 886-7 compression molds 395 phenolics 834
Graphite 245,334,334 Gutowski’s model 578,580,581,582, polyamides 832,833
3-D lattice 334 583,585 polyaminoamides 832,833
composites, machining 599 fiber volume fraction 588 polyurethanes 834
compression properties 360 numerical schemes 586 thermoplastic resins 834
costs 717 GY 281 (Ciba-Geigy) 52 hazards
epoxies GY 6010 (Ciba-Geigy) 52 asbestos 252
elastic properties 768-72 Gypsum 564 beryllium oxide 252
references 774-7 composite processes 831
strength properties 768-72 Half-discs, testing 782 particulate fillers 252
fibers 25-6 Halogens 44 and safety, composites 880
competitive prices 25 bromine 43 Heat
health effects 835 Hammer handles, pultrusion 491 application
modulus 360 Hand lay-up 352-77,762 heating blankets 874
price 716 advantages 352 repairs 874-7
production 25 applications, aerospace 375 risks of 875,877
reinforced plastics, see GFRP disadvantages 352 capacity
reinforcement 353 large power yachts 921 definition 532-3
specific gravity 383 marine applications 376,919-20 thermoplastics 5 3 2 4
tensile precautions 363 cleaned, reinforcements 898-9
failure 383 Handling deflection temperatures, see HDT
modulus 360,383,715,716 aramid fibers 222 distortion 41
properties 360 glass fibers 24 epoxy 522
strength 383 PET 233 polyester 512
thermal expansion 383 Hardeners 49,832 vinylester 522
turbostratic layers 184 Hardness distortion temperature 38
Graphite/epoxies 4 ceramics 307 aliphatic 70
CTE 589 regrind RIM 895 anhydride-cured 72
elastic constants 4 tooling materials 577 aromatic 71
physical properties 4 Harrier VTOL 1031-2 lamps, wet lay-up repairs 865,
strains 4 Hazard 823 866
strength properties 4 definition 823 resistance, fiberglass 134

treatment, carbon fibers 335
Heated curing dies 500-1
design 500
Heating
blankets
repairs 869
wet lay-up repairs 865
radio frequency 499
rate 181,499
single zone 511, 513
Heavy liquids, adhesives 2 7 M
Heel blocks, compression molds 394
Helical winding 460
delamination 789
reinforcement 461
Helicopters
applications 1040
current prices 1026
design requirements 713
rotor blades 1024
Heloxy WC-63 (Wilmington
Chemical) 62
Hercules
3501-6 epoxy resin 579,579
IM7 fiber, thickness 478
HETacid 36
Hexachlorocyclopentadiene, see HET
Hexafluorobisphenol A
homopolymer property 102
structure precursor 102
supplier 102
trade name 102
Hexafluoroisopropylidene,bridging
77
Hexahydrophthalic anhydride
(HHPA), melting point 57
High
carbon cast steel
CTE 558
density 558
thermal conductivity 558
local stresses 729
modulus, carbon fibers 335
pressure water jet, cut-off 502
silica
applications 163,165,166
continuous fibers 163
forms 161-3
fracture toughness 156
manufacture 156-7
properties 161
strength
carbon fibers 335
molding compound, see HMC
PET 233
reinforced composites 387
temperature
adhesives 658
applications 818
Index 1089
carbon-carbon composites 269
344 plate shear modulus 266-7,
cast epoxy, CTE 589 269
resins 818 plate shear strength 266-7,
sandwich 288 269
High-pressure tubing 941 Kevlar 271,272,273
High-speed train brakes 941 paper 271
Higher temperatures, and tensile metal, roll-forming 289
strength 182 non-metallic, thermal resistance
History 260
consolidation 578-86 panels, repairs 871-7
pultrusion 488 paper 263,268
recycling 883-4 plate shear modulus 264-5,
HMC 381 266-7
Hoechst Celanese plate shear strength 264-5,266-7
availability 231 specimen geometry 263
elongation at break 225 stainless steel based 257
fibertype 225 test method 263, 263
pricing 232 thickness 263
specific gravity 225 titanium based 257
tensile modulus 225 Hoop
tensile strength 225 stresses 621
Hole fittings, tooling 562 winding, reinforcement 461
Hollow fiber, fiberglass 134 wound, rings 789
Holography 851-3,852 Horizontal
laser interferometric 852 drawing 299
phase locked loop 852 tape wrapper 428,428
Homopolymerization 40,50-1, 51, Hot
511 air blowers, wet lay-up repairs
catalysts 49,59, 60-1 865
Homopolymerized BF,MEA 65 extrusion
Homopolymers, creep 212 compression 298
Honeycomb 257,260-71 MMC 291
aluminum 268 oil jackets 499
alloy pressing 314
compressive strength spots, particulate fillers 242
264-5 Hot-wet service 99
plate shear modulus HRDI optical bench 1017,1018
264-5 HS carbon composites
plate shear strength 264-5 shear modulus 1057
alloys 268 tension 1057
thermal resistance 260 HT 972 (Ciba-Geigy) 55
aramid paper 260,269-70 HT 976 (Ciba-Geigy) 55
assemblies, acoustic emission 849 HT 9720 (Ciba-Geigy) 55
carbon fiber 270-1 Hubble Space Telescope 967,969
carving bits 289 Humidity 3
cell configurations 262 Humphrey Chemical 57
cell shape 261-3,262 H Y 906 (Ciba-Giegy) 57
cell size 263 Hybridization, PET 233
compressive strength 264-5, Hybrids 795
266-7 aramid/graphite 354
core shear strength 261 composites, reuse 883
corrugation process 257 graphite/wood 354
defects, X-ray imaging 845 materials 359
density 261,261,262 Spectra/graphite 354
expansion process 257 Hydraulic
glass-reinforced 268 ejection, part removal 446
applications 268 system, testing 782
compressive strength 266-7, test technique 782, 788
1090 Index

Hydrocarbons 37 strength Nomex 209

Hydrocodes 815 aliphatic system 70 SVM 208
Hydrogen flakes 249 Technora 209
fuel storage 941 testing 38 Teijinconex 209
reduction 161 TEOS 346 Twaron 208
Hydrogenation 179 Imperfections 780 Initiators, and inhibitors 382
Hydrolic stability 38 Implants, biologic response 960 Injection
Hydrolysis Impregnation cycle 442
BMI 112 carbonized organic composites gate 452
CE 112 340 molded 380
degradation 888 powder 118 molding 22,529,532
resistance 41 prepolymer 118 cavity filling 542
Hydrophobic, PET 230 Impregnators, marine applications clamp 5 3 9 4 , 5 4 0
Hydrous aluminosilicate 244 919-20 crystallization kinetics 540
Hydroxyapatite (HA) 958 In-mold coating (IMC) 385 fiber orientation 543,543
dental applications 958 In-plane shear fountain flow 542
glass-reinforced 958 Kevlar 212 particulate fillers 242
Hygroscopic nature, GFRP 1006 methods, testing 783 plasticating 538, 538
Hygrothermal modulus, AS-4 carbon fiber 124 polymer 540
definition 694 Incineration 888 pumping section 538
effects 6 9 4 5 nonrecyclables 899-900 rackets 1050
load 695 Inclination angle, yams 407 resins 122
properties 96 Inclusion of particulates, polymers screws 539
Kevlar 222 528 thermoplastics 226,526
Hypersonic vehicles, materials for Inconel 329 ports 442-3
973 Industrial centred 451,451
equipment 951 corner 451,451
ICBM equipment 375 hygiene 825-30,827,828,829 pressure 444
Identical adherends 639 order of priorities 828 RTM 433
IM6/eqoxy pressure vessels, design pultrusion 497, 498
englneering constants 699,700, requirements 713 sensor controlled 452-3
701 Industry, pulp and paper 45 Inplane shear 374
longitudinal Inert,PET 230 Inspection
CTE 699 Inertia 3 bonding 668
extension 702 Infiltration composites 880
strain 702 carbon/aluminum 303 criteria 487, 838
tensile modulus 699 fiber architecture 401 disbonds 839
Poisson's ratio 699 improving 300 fiber placement 486-7,487
shear modulus 699 isothermal gradient 338 first article 486
stiffness coefficients 702, 703 of preforms 299 in-service 839
strength ratio 701 pressure gradient 338 methods
transverse pressure pulsation 338 adhesive joints 627
CTE 699 spontaneous 300 defects 7334,734
extension 701 technology 300 and nondestructive testing 1059
modulus 699 under pressure 299-300 on-aircraft 849
strain 703 vacuum 299-300 paint surfaces 839
volume fraction 699 Inflatable bladders 874 part 733
IM-7/PEEK, strength 125 Infrared thermography 850-1, 850, post cure 572-3
Imidazoles 104 851, 1059 speeds 842
Imides, health effects 834 aerospace 851 subsurface damage 839
Impact marine applications 851 times 839
damage Inhalation, measure by 824 ultrasonic 1059
aircraft 858-9 Inhibitors, and initiators 382 visual 839,839-40
carbon-carbon composites Inhomogeneities, NDE 838 Insulation
334 Inhomogeneous, composites 797 foam 256
GFRP 1006 Initial rise 646, 647 resistance, Skybond 95
tap testing 858 Initial tensile modulus Integrated, fiber architecture 401,
energy, thermoplastics 225 Armos 208 401
resistance, moisture 811 Kevlar 208 Inter-yam slip 448
 Index 1091

Interaction, constituents 801-2 NBC 897 single lap 626, 627, 729
Intercontinental ballistic missile PET 894 single shear 624
program 353 phenolic 894 bending moments 624,625
Interface, fiberlmatrix 123 PP 895,896 step lap 645-6, 645,649, 650, 651,
Interlacing patterns, braiding 415, SMC 892,893 652,659
415 SMC 386,386 strength
Interlaminar LPMC 386,386 experimental 616
fracture 682 recycled, SMC 890 predicting 615
shear 790-2 ZMC 386,386 tests 626
TEOS 346 stress analysis 611
shear strength Jamming 412,417 structural performance 613
Celion 91 angles 399 test methods 626
PMR-15 laminates 88 two fastener 623
Japan untapered 624
stresses 738 bathtub manufacture 889
eliminating 801 recycling 887,888,903
tension, TEOS 346 Japanese Industrial Standards 1065, Kaolin
Internal 1066 calcined, hardness 244
bone fixation 957 Jeffamine T 403 (Texaco)54 particulate fillers 244
friction background 296,296 Joining 727-30,728,729 Kapton 820
mold release 383 selection process 727,728 Kardos’ model 578,583
International Organization for thermoplastics 127 Kerf
Standardization 1066,1067 thermosets 127 cutting 604,606
Interphase, toughening 802 Joints width 606,695
Invar adhesive 517-18,61043,62743 Kerimid 99
CTE 558 bearing load 626 Ketones, health effects 836
density 558 bearing strengths 618-19 Kevlar 108,472,598,761,1024
linear thermal expansion 705 bending failures 617,617 availability 217-28
thermal conductivity 558 bolted 611, 617, 617,1015 breaking strength 214
Inverse method, contact 611 bonded 658-9,1015 charring 815
Ionic spraying 300 step lap 627 chemical
Ionizing radiation 816 and bonding 374 resistance 214
Iosipescu shear test 790 bypass load 626 stability 214
Iron (electroformed), CTE 589 clamping pressure 618 colored 216
IS0 standards, carbon fiber computer codes 624,627,630 constituent properties 766-7
composites 1067 design 728 cutting 600
Isophthalics 39 dimensions 612,649 cycles to failure 213
polyester disassembly 611,728 decomposition temperature 206
blistering 918 double shear 624 density 206,503
marine applications 916 failure 615,618,618,626,659,660 dual-shell reflector 1004,1004
resins 504 fracture mechanics 631-2 E-glass 360
resins 35,36 geometry 613-17,613,628,629, elastic
Isothermal 638-51 constants 210
processing, CVI 317 GFRP 1012,1012 modulus 205
thermal gradient, infiltration 338 load magnitude 728 properties 764-7
Isotropic materials 618-19,618,619 elongation at break 205,208,503
casting, short fibers 337,338 mechanical response 630 filament
layers, different moduli of mechanically fastened 61043 diameter 206
elasticity 744 advantages 517 shape 206
materials 687 cf. adhesive 610-11 hypothermal properties 212
metallic tape, winding 468 metallic 613 in-plane shear 212
nonwoven fabric 164 multi-fastener 612, 613,619-24, initial tensile modulus 208
plates 614 620,621,622,623 linear thermal expansion
Italian, talc 248-9, 248 multi-row 616 coefficient 206
Izod open hole coupon strength 626 longitudinal compression 212
impact predicting peak stresses 613 longitudinal tension 212
BMC 386,386 pure bearing load 626 machining 600
nylon 6/6 PCI-glass 899 scarf 611,623 marine applications 917
PP and granulated SMC 897 selecting design 627 melting 815
recycled single fastener 612, 612,613 temperature 206
1092 Index

milling 600 Kulon 300 fiberglass 356

modulus and temperature 210, bending strength 305 IM6/epoxy 699,700,701
211 carbon content 306 kinematics 690-1
moisture content 206 coating thickness 306 linear bending 749-50
properties 205 compressive strength 305 load carrying capability 696
references 774-7 density 305,306 loads on 689,693
refractive index 215 elastic modulus 305 macromechanics of 193-4
reinforcement 383 elongation at break 306 mechanical properties 717
sources of information 221 filament diameter 306 nonsymmetric 752
specific longitudinal CTE 306 off-axis stiffness 689-90
gravity 208,383 specific modulus 305 with plies 697
heat 206 strand properties 306 ply angle 689,689
modulus 1049 tensile modulus 306 ply stacking sequence 692
strength 1049 tensile strength 305, 306 quasi-isotropic 9-11,697
strength retention 205,215 reinforced 321-3,321,619
stress rupture 212-13,213 Labour requirements, pultrusion 489 resulting strain state 6 9 3 4
tensile Ladder polymer 178-9,178 selection, carpet plots 720
failure 383 Ladders skin 694
modulus 383,503 applications 936 stacking sequence 616,630
strength 208,383,503 pultruded 518 stiffness matrix 693
and temperature 210, 211 Lamina 687-9,688 strength 695,696, 764-7
tension-tension ratio 1049 allowables 759-62 ratio 696
thermal definition 687 stress
coefficient 383 macromechanics 192-3 patterns 322
conductivity 206 material resultants 691-3
transverse equations 760 symmetric 194,692,749
compression 212 properties 760 thermal stresses 322,589
tension 212 properties void free 588
trimming 600 adjusting 763 Land transportation 905-15
turning 600 estimating 761-2 economics 905-6,906
twist 215-16 references 772-3, 774-7 history 9068,907
ultimates 210 three-dimensional 761 market growth 905-6,906
weight loss 205 two-dimensional 760-1 Landfill, nonrecyclables 899-900
Kevlar/epoxy thickness, structural hierarchy Lap joints 638-44
thermal data 828 778 abrasive cleaning 872
weathering 813 Laminar failure characteristics 643
Kine1 99 discontinuities 843 peel stresses 637-8,637,638
Kinematics, laminates 690-1 fiber architecture 401,401 single 640,641
Kinking 302 Laminated symmetric 639
Kneaded molding compound 381 plate theory 689,690-2 Laptop computers 942
Knitted structures 585 Large Area Composite Inspection
glass fabrics 917 Laminates System (LACIS) 842,842
reinforcements 916-17 advantages of 322 Large diameter, PAN 180,181
Knitting 402,402,408-13,409,410, allowables 762 Large power yachts
411,412 analysis of 11 blister protection 921
3-D fabrics 409 balanced 194,693 displacement hulls 922
definition 408 bending 730 female tooling 921
design methodology 410-13 boundary conditions 689 hand lay-up 921
machines 409 carbon-epoxy 669 marine applications 921-2
multiaxial warp knit, see MWK coefficient of thermal expansion variable mold 921
stitch formation 409 322 Laser
unit cell geometry 411 compressive strength 616 beam 601
warp 408,409 cross-ply 322 heated floating zone, see LHFZ
weft 408,409 deformation 691 machining 605
Kortex 108,271 design 68&708 shearography 853,853
Kozeny constant 579 elastic properties 322, 764-7 immunity to vibration 853
Kozeny-Carman equation 400,422, engineering constants 693 Lateral
422,579 failure criteria 695-7 cohesion 184
Kraft paper 268 failure in tension 696 compression tests 449
 Index 1093

deflections 642 laminates 749-50 loading 213

bond stresses 640 cutting, machining 602 microcracking 801
Lathes, CNC 597 elastic response to failure 615 use temperature 206
Lattice fiber architecture 401,401 Longitudinal
fringe imaging 186 thermal expansion bending 747
structures 743, 744 aliphatic system 70 compression, Kevlar 222
Lay-up 15,16 aluminum alloy 705 CTE
carbon-carbon composites 342 aromatic system 71 IM6/epoxy 699
contoured tape 16 concrete 705 Kulon 306
comer techniques 373 Invar 705 M401/F854 699
filament 457 steel 705 PBOfiber 238
flat tape 16 titanium alloy 705 extension, IM6/epoxy 701
manual 16 thermal expansion coefficient ply waviness 432
molds 5 6 6 7 carbon-carbon composites strain, IM6/epoxy 701
operation 576 333 tensile modulus 699
sequence, carpet plots 719 Kevlar 206 tension
wet 353,355 Nomex 206 Kevlar 212
Layer reinforced, carbon/aluminum Technora 206 test 688
304 Teijinconex 206 Loom components 942
Layered, adherends 646 Twaron 206 Lot-to-lot variation
Layers yams, insertion 410,410 tensile modulus 725
coordinates 740,746 Linkages, flexible 75 tensile strength 725
orthotropic 742 Liquid Low
LDEF 970-2,970,971,972 injection molding simulation, see bending stiffness, FRP 960
composite specimen testbed LIMS cost parts, RTM 433
970-1 processing 314-16 density
orientation in orbit 971 stage, MMC 291 composite tools 592
Lead powders 249 waste 889 polyethylene, viscosity 528
Leaf springs 910,910 as fuel 889 K-glass 134
Liteflex 910 Lithium alumino silicate (LAS) 318 pressure
Leak paths, aircraft 85940 LMOs 179,182 grit blasting 631
Leakage 456 size of 179-80 molding compound, see
Legal aspects, recycling 902-3 Loading LPMC
Length conditions 736 temperature, fatigue 811
to diameter ratio, aramid fibers history, remaining strength 804 toxicity, thermoplastics 115
204 levels, particulates 528 viscosity, ZMC 380
whiskers 308 methods 779 void, composites 79
LEO 813-17 selecting 787 voltage anodizing, metal surfaces
Lewis sections, test specimen 786 871
acids 50-1,60-1 slow cyclic 627 Low-earth-orbit, see LEO
bases 50-1,60-1 stress, adherends 642 LPMC 381
LHFZ, directional solidification 160 Loads flexural modulus 386,386
Life expectancy, tools 559 bypass vs. bearing 620,620 flexural strength 386,386
Light carrying capability, laminates 697 formulation 384
aircraft 1024 direction of 779 IZOD 386,386
grit-blasting 668,670,671 distribution 621 shelf life 381
alumina grit 675,676 enhancement 655 specific gravity expansion 386,
machine 677,677 fastener, variable 622 386
liquids, adhesives 2754 hygrothermal 695 tensile modulus 386,386
weight, reinforced composites measuring 779 tensile strength 386,386
387 path eccentricity 637,637 thermal coefficient 386,386
Lighting poles 948-9,948 single lap joint 637,637 Lubricants, fiberglass 146-7
Lightweight fillers, particulate 249 transfer 610
Limitations, aramid fibers 207 Local molecular order, see LMOs M60J tape
LIMS 447,453 Localised, microbuckling 800 mechanical properties 718
Lindau 59 Logging 3 strengths 718
Line source 453 Long Duration Exposure Facility, see M401/F854
Linear LDEF CTE 704
bending 745-7 Long-term longitudinal 699
1094 Index

transverse 699 graphite 464 920-1

longitudinal tensile modulus 699 instrumented 468 oil platforms 9245,925
Poisson's ratio 699 low cost materials 464 phthalic anhydride 916
shear modulus 699 metallurgy 429 piping systems 926
transverse modulus 699 pressure on 468 pressure hulls 922
volume fraction 699 puller 428 propulsion shafting 925
m-phenylenediamine (MPD) 55,76 removable 464-5 reinforcements 916-17
McDonnell Douglas removal 466,467 resins 916
Bea AV-8B, material usage 1032 selection 465 transfer molding 919-20
C-17A, composite applications spider/plaster 466 shipboard armor 925
1033 surface 591 small boats 921
F/A-lSE/F, material usage 1031 table rolling 429 sonar domes 922
MD-11, composite structure 1036, tensometric 468 Spectra 917
1037 water-soluble sand 465-6 vacuum bag processing
Machinery, marine applications Manufacturers 919-20
925-8 continuous fibers 162 vinyl esters 916
Machines ceramic 309 bacteria 919
caterpillar type 502 fibers 158 construction 994
dual mandrel stations 477,478 PAN-based tow 198 fouling 81G11
fiber placement 478 pitch-based tow 199 laminates 920
light grit-blasting 677,677 staple 162 submersibles, design
tools 363-5 whiskers 158,162 requirements 713
Machining 363-5,364,596408 Manufacturing 6 Market growth, land transportation
abrasives 606 aramid fibers 2034 9054,906
advantages 596 boron 156-7 Mass transit applications 914
aramid fibers 222 ceramic fibers 156-7 Master models 563-6,592
characteristics 596 deficiencies, adhesive joints 611 fabricating materials 563
closed loop 3645,364 extended chain PET fibers 223-4 storing 563
drilling 602 fibreglass 132 Mat 164
electric discharge 605 high silica 156-7 chopped strand 138,155
graphite composites 599 options 22 continuous strand 138
Kevlar 600 quartz 156-7 fiberglass 137-8
h e a r cutting 602 SMC 381 surface 138
milling 602 Marine Matched die, molding 361
PET 233 applications 916-28 Materials
requirements 602 adhesives, paste 918 anisotropic 687,688
turning 602 America's Cup yachts 922 cost, GFRP 1006
ultrasonic 605-8 blistering 918,918 definition 731
Macromechanics, of laminae 1 9 2 4 buoys and floats 927-8 density, X-ray backscattering 846
Maglev 979 cables 927 description 731,732
train guideways 943 concrete forms 925 difficult to roll 430-2
Magnamite 1054 control surfaces 924 fabrication 786
Magnesium oxide, particulate fillers CORS 917-18 isotropic 687
250 decking 925 monolithic 460
Magnetic transparency 983 diving equipment 926-7,926, preliminary design 715-22
Mahogany 927 procurement costs 722
CTE! 558 environmental effects 918-19 properties 736
density 558 fabrication 919-20 definition 709
thermal conductivity 558 fairings 9234, 923, 924 T50 graphite 724, 724
Maleic anhydride 35 filament winding 920 T50/F584 epoxy 726,726
isomerization 35 future developments 928 property, equations 760
melting point 58 hand lay-up 919-20 quality 780
Mandrels 429,459,4646,465 impregnators 919-20 quasi-isotropic 687
basic requirements 465 isophthalic polyester 916 selection 45,712
collapsible 466 Kevlar 917 applications
cone-shaped 482,483 large power yachts 921-2 aerospace 1009
dissolvable materials 465 machinery 925-8 construction 982
electroformed nickel 591 microbial degradation 919 tools 559
fusible materials 465 mine counter measure vessels specification 722
 Index 1095
table rolling 429-30 resistant, gloves 829 density 815
weights 1027 Mechanics 18,18 impacts
wet lay-up repairs 867 Median lethal dose 824 angle of 815
for winding 458-9 Medical applications 9434,944, space 81615,814,815
Matrix 28 95744 Whipple-type shield 814-15,
adhesion 215 coatings 957 814
cracking 319,798 fillers 957 size of 815
rateof 806 polylactids 957 velocity 815
cracks polyorthoesters 957 Methacrylic acid 40
NDE 854 strength retention 957 Methanolysis, degradation 888
X-ray imaging 844 Melt Methylene chloride 812
crosslinking 460 extrusion, PET 224 4,4'-methylenedianiline (MDA) 55,
definition 378 flow index, see MFI 76
formulation 101-5 impregnation 117,118 Methyltetrahydrophthalic
materials 356-8 infiltration 315 anhydride, melting point 59
ceramic composites 311-12 pumping, extrusion 5365,535 MFI 529
polyester 28 spun, Vectran 235 Mica 2 4 5 4
systems 4 6 stretching 529-30 fillers 527
moisture absorption 5 Melting Microbial degradation, marine
thermosetting 28 aramid fibers 205 applications 919
transfer molding 315 extrusion 534 Microbuckling 799-800,800
vinyl ester resins 28 point aramid fibers 207
Maximum carbon-carbon composites localised 800
bond 333 Microcracking 323-4,323,797-8,
peel stress 642,642-3,644 ceramic composites 322 798,801,1011-12,1012
shear stress 642-3,644 4,4'-diaminodiphenylsulfone cyclic loading 801
service temperature 258 (DDS) 55 elastic stress-strain 798
stress PET 225 eliminating 1012
anhydride-cured system 72 recycled NBC 897 GFRP 1006
aromatic system 71 S-glass 24 long term loading 801
Maypole machines, braiding 413, temperature minimizing 1012
414 see also T,,, stiffness changes 796
Measuring ceramics 307,311 Micromechanics 191-2,796-7
displacements 779 Kevlar 206 Microspheres 246,248
loads 779 Nomex 206 hollow 246
strains 779 Technora 206 particulate fillers 246
Mechanical Teijinconex 206 types of 246
fastening 727 Twaron 206 Microstructures 803
joints, design process 729 Vectran 235 flat-layer 177
pressure 874 Mesophase onion-skin 177
properties injection 176 radial 177
aramid 207-13,208-9,209, pitch, precursors 335,336 random 177
220,211,212,718 Meta-aramids Microtexture
carbon-carbon composites cost of 205 and electrical resistivity 189
344-5,345 crooked chain 205 and tensile strength 188
extended exposure 215 manufacture 203-4 and Young's modulus 189
fiberglass 235 Metal Microwaves
laminates 717 matrix composites, see MMC radome wall 113
M60J tape 718 molten 812 testing 853
PlOO tape 718 repairs, aircraft 857 transparency 109
T300 fabric 718 surfaces 871 Migration 577
and weave pattern 252 Metallic Military
strength 112 devices, total hip arthroplasty aircraft
tests 778-92 960 certification requirements
Mechanically joints 613 1023
fastened oxides, fillers 527 components 1030-5
joints 610-63 Metallurgy, mandrels 429 applications 914-15
disadvantages 517 Metals, costs 717 specifications 1062, 1064
repairs 877 Meteoroids 81615 Milling 596-7
1096 Index

AWJ 604 CE 107 cavity design 442

ball or hammer 886 epoxy resins 29 closing 385,442
climb 596 PET 224 speed 385
disadvantages 597 PMR-15 82 construction 447
dust particles 597 resins 440 design 362
Kevlar 600 tooling 561 dual steel 361
machining 602 barrier removal, aircraft 8 6 3 4 elements of 541
with polycrystalline diamond contamination, X-ray imaging filling 385,442, 4 4 6 5
596 858 pressure during 452,452
recycling 886-7 content 206 simulation 450-1
square pockets 604 debonding 811 graphite-epoxy 590
Mine counter measure vessels 920-1 desorption 817 maintenance 361
Minimizing, microcracking 1012 detectors 858 making 390,390
Minor damage diffusion, GFRP 1007-8 materials 441-2
aircraft 859 effects 96 metal 441
dent fillers 859 fracture toughness 811 polymeric composite 441
Minor impact resistance, reinforced glass transition temperature 811 preparation 442
composites 387,388 impact resistance 811 release 361,362,428,429-30,514
Mix viscosity, resin 441 prebond 670 problems and solutions 568
MMC 27,291-306,944-5 regain, PBO fiber 238 secondary 430
alumina/carbon 291 resistance, PBO fiber 238 RTMdesign 441
applications 1005 transverse strength 811 sealing 443
boron/aluminum 299 vs. time, P75S/cyanate 1010 shrinkage
by hot extrusion 291 Moisturizers 829-30,830 nylon 6/6 PCI-glass 899
carbon reinforced 291 Molded surfaces 392 recycled NBC 897
continuous casting 298-9 Mo1ded -in steel 442
cross sections 298, 298 color, reinforced composites 388 selection 393
liquid stage 291 threads 392 stops, compression molds 395
production 291 Molding stresses 392-3
recyclability 944 autoclave 367 temperature control 541
solid stage production 291 autoclave/oven 361 Molecular
solution sedimentation 291 bag 36672,368,369,370,371 arrangement 133
Mobile storage 945 bleeder ply 5846,585 characteristics, rotational
Modulus blow 529-30,529,532 molding 552
adherends 643 compounds orientation 27
anddensity 23 applications 945-6 weight, thermoplastics 116
of elasticity BMI 114 Molybdenum disulfide, fillers 527
aliphatic system 70 compression 127,365, 384,545 Moment of inertia, formulas 285
anhydride-cured system 72 enclosed 366 Monobands, sealed 304
aromatic system 72 matched die 361 Monofilaments 164,307
carbon-carbon composites matched metal compression reinforcements 311, 322
333 378-88 Monolithic
and conductivity 186 negative draft 366 graphite 559,561,562-3
fiberglass epoxies 253 oven/press cure 366 coefficient of thermal
plied-yam 251 preparations 361-2 expansion 558
S-glass epoxies 252 pressure 385,545 density 558
single-yarn 252 bag 367 low CTE 567
yarn distribution 254 resin transfer 374,492 thermal conductivity 558
quasi-isotropic 12 seealso RTM material 460
of rupture, ceramics 322 sheet 374 Monolithicity
S-glass 24 thermal expansion 365-6,365, loss of 469
transverse 12 366,593 thick-walled structures 456
Mohs ratings 251-2 vacuum 385 Monomers
Moisture 811-12 bag 361,366,577 BMI 100
absorbancy waste 374 ratios 79
adherends 630 Moldless construction 257 reactive 34, 37
RTM 440 Molds 441 Montana talc 248-9, 248
absorption 695,811 aluminum 361 Morphology, resins 505
aramids 26,221 backingup 422 MPDA/MDA, viscosity 56
 Index 1097
Mullite 313,314,318 Neat polymers, shrinkage 541 Nonlinear, bending 747
heat treatment 310 Nepheline 2434 Nonrecyclables
Multi-fastener joints 619-24, 620, chemical resistance 2 4 3 4 disposal of 899-900
621,622,623 oil absorption 244 incineration 899-900
Multi-rowed, fasteners 620 particulate fillers 2434 landfill 899-900
Multifilament, continuous 28 refractive index 243-4 Nonwoven
Multilayer locking, continuous fiber syenite 244 fabrics 402,402
338 Neutral hydrolysis 887 textiles 418-20
Multiple Neutron radiography 847-9,848 3-D technology 418
gates 444 field inspections 848 design methodology 419
ply angles 19-20 military aircraft 849 orthogonal 3-D 418,419,420
stage drawing, PET 224 New York, talc 248-9, 248 processing 418
Multiwarp, weaving 406 Nextel 309,309,310,316,403 structural geometry 419
Musical instruments 946 312 Normalization 721
Mutagenicity 824 fiber 159 compression strength 721
MWK Nibbling 602 Notation, stacking sequence 619
3-D 409,410 Nicalon 310-11, 311,316, 318 Notched fatigue behavior 802
LIBA system 411 Nickel 249 Novolac resin
MY 0510 (Ciba-Geigy) 53 coating 292 homopolymer property 102
MY 720 (Ciba-Geigy) 53 electroformed, CTE 589 structure precursor 102
Mylar powder 250 supplier 102
film sheet 574 vapor-deposited coating 819 tradename 102
template 487 Nitride, coating 296 Novoltex 418,418
Nitrogen release, and tensile NR-150
N, N, N , N'- tetraglycidyl strength 182 char yield 82
methylenedianiline 53 Nomex 2034,269 chemistry of 77,78
N/Cratio 182 compressive strength 272,273 density 82
Nadic methyl anhydride (NMA) 57 cores 270 elongation 82
Nanoporous, carbon fiber 183 decomposition temperature 206 flex modulus 82
NASA standards 1063,1064 density 206 flex strength 82
NASP 972,972,974 elongation at break 209 fracture toughness 82
National Aerospace Plane, see NASP filament 206 neatcured 82
Natural composites initial tensile modulus 209 Rockwell hardness 82
cartilage 958 linear thermal expansion tensile strength 82
cortical bones 958 coefficient 206 Tg 82
dentin 958 long-term use temperature 206 thermal expansion 82
wood 958 melting temperature 206 Nuclear magnetic resonance (NMR)
Nd-YAG moisture content 206 982
applications 605 plate shear Nylon 6/6 PCI-glass
solid state laser 605 modulus 272,273 elongation 899
NDE 733,838-55 strength 272,273 flexural modulus 899
blown core 854 specific gravity 209 flexural strength 899
bondline adhesive voids 854 specific heat 206 glass content 899
condensed core 854 tensile strength 209 izod impact 899
core 854 thermal conductivity 206 mold shrinkage 899
damage inspection 854 Nominal thickness, reinforced tensile strength 899
deep delamination 854 composites 390,391 Nylon
degradation 838 Non-aerospace, applications 935 modulus and temperature 210,
disbonds 854 Non-functional, fillers 382 211
fiber breaks 838,854 Non-metallic core removal 862 peel plies 673
foam adhesive voids 854 Non-symmetric imprint 682
foreign material 838, 854 bending, testing 783 tensile strength and temperature
inhomogeneities 838 deformation, cylindrical shells 210,211
matrix cracks 854 754-5 weld line strength 544
porosity 854 laminates 752
records 733 Noncomposites 166 O-rings 443,953
shallow delamination 854 Nondestructive nitrile rubber 443
test methods 733-4734 evaluation, see NDE Observed life, AS-4/PEEK(APC)
water intrusion 854 testing, and inspection 1059 806,807
1098 Index

Octyl, decyl glycidyl ether blend, 4,4'-oxydialinine (ODA) 75,76 shape, and tooling 589-94
viscosity 62 slippage, during cure 432
Off-axis tension, testing 782 P75S/cyanate, moisture vs. time Particle
Oil 1010 accelerators 976-9,977,978
absorption PlOO tape size
nepheline 243 mechanical properties 728 clay 244
number, particulate fillers 251 strengths 728 distribution, rotational
containment, Spectra 2 3 3 4 p-t-butyl phenyl glycidyl ether, molding 552
and gas viscosity 62 Particulate fillers
applications 946-7,947 PA6,6, water absorption 127 abrasion 252
industry, pultrusion 521 Packages alumina trihydrate 245
platforms 9245,925 style of 493-4,493 aluminum oxide 250
One-dimensional weight 494 antimony oxide 244-5
consolidation equation 584 wound 493 calcium carbonate 243,247
flow, compression molding Packing carbon black 245
583-4,584 fraction 531-2 clay 244
stress analysis 627 interfiber 403 common 243-6
One-sided, pulse-echo testing 842 powder processing 313 cost 242
Onion-skin, microstructures 177 pressure 539 definition 242
Opaque, aramid fibers 221 Paint surfaces, inspection 839 electrically conductive 250
Open core evacuation, aircraft 865 PAN 25,169,171-3,172 elongation at failure 252-3
Open hole coupon strength, joints anisotropicity 185 enduses 253
626 cyclization 172 feldspar 243-4
Open packing 403,403 cyclized 179,181 fire retardants 249
Open unloaded holes 614 dryspinning 175 flakes 248
Openings 373,373 large diameter 180,181 orientation 252
Operational requirements 737 modified polymers 175 graphite 245
Optical properties molecule structure 172 hardness 251
aramid fibers 215 spinning 175 health hazards 252
fiberglass 235 stabilization 172,177-80,178,179 high
Organic solvents, thinning 65 stabilized, thermal degradation density 249
Orientation angle, yams 412 181 hardness 249-50
Orifice plates 495 wet spinning 175 thermal conductivity 250
Orthogonal nonwoven fabrics 163, PAN-based fibers hot spots 242
164 density 270 injection molding 242
Orthopedic applications 95943 elastic modulus 270 kaolin 244
FRP 959 fracture elongation 270 lightweight fillers 249
hydroxyapatite (HA) 958 oxidation 818 low density 243
PMMA 962 tensile strength 169, 270 low friction 250
Orthophthalics 35,39 PAN-based tow magnesium oxide 250
polyester, blistering 918 manufacturers 298 mica 245-6
Orthotropic trade names 298 microspheres 246
layers 742 Para-aramids natural 246
nonzero stiffness 742,743 available 203 nepheline 243-4
thermal coefficients 742 creep 212 oil absorption number 251
plates, critical load 751 fatigue 213 organic 243
Outgassing stress rupture 212 packing 252
measuring 817 Para-phenylene terephthalamide 26 production 2464,247
and vacuum 817 see also aramids shrinkage 242,252
Oven/press cure, molding 366 Parallel axis theorem 694 silica 244
Ovens, with thermocouples 429 Part specific 243
Overheat, environmental exposure consolidation 386 surface
860-1 ejection 385 properties 250-1
Overshoots 531 geometry 526,530 treatments 250
Oxidation inspection 733 synthetic 246
PAN-based fibers 818 methods used 733-4 talc 246
resistance 818 removal 446 thermal conductivity 242
carbon-carbon composites hydraulic ejection 446 toxicity 252
333 system 541 types of 242-3
 Index 1099

use of 242 Penetration 814 scrap 36

Particulates 307 Percolation 547 seawater resistance 233
flow, cf. fiber flow 530 matrix 548 shear modulus 120,120
inhaling 827 Perlite 249 sources of information 232
irregular shaped 249 low cost 249 specific
loading levels 528 Permeability 399400,1000 gravity 224
radiation 816 axial 579 modulus 224
Parts, RTM process 762 bleeder 581 strength 224
Pastes, adhesives 275-6 composite layer 581 stiffness-to-weight ratio 223
Patterns 362-3 and fiber volume fraction strength retention 227
control 463-4 399400,400 strength-to-weight ratio 223
PBI 237,237 preforms 438,439,449,578-9 structure 224,224
chemical resistance 237 Permeation barrier 918 surface treatments 231-2
chemical warfare applications Permissible exposure limits, see PEL sutures 234
237 Peroxides 382 use temperature 225
solvent resistance 237 Personal protective equipment 828 uv
structural formula 237 PET 35,120 resistance 224,230,233
PBIA 203,203,205 ability to float 225 stability 233
PBLA-based fibers, SVM 210 abrasion resistance 224,226,233 Phase locked loop, holography 852
PBO 26-7 anisotropy 224 Phenolics 504-5
elongation at break 235 applications 230,233-4 adhesives 255
fiber 236,237-8,237 artificial ligaments 234 compressive strength 258
specific gravity 235 availability 231 density 258
structural formula 237 axial orientation 224 health effects 834
tensile modulus 235 chain folding 224 maximum service temperature
tensile strength 235 characteristic temperatures 122 258
PDI fibers, sources of information chemical resistance 224,230 polypropylene, density 258
236 cleaning 230 pulling 5 0 4 5
Pedestrian bridges 991-2,992,993 creep resistance 227 pultrusion grades 505
PEEK 31,120 crystallinity 223,224 resins 268,504
glass transition temperature 812 degradation 889 resistance to fire 505
Peel design 232-3 shear modulus 259
plies 668, 669 dielectric constant 224 shear strength 259
bonded joints 669 durability 233 SMC 382
dry 672 dyeing 233 spa11 liners 914
evaluation 670 energy to break 227 tensile strength 258
imprint 678 exposure to moisture 227 thermal conductivity 259
nylon 682 fatigue resistance 230 Phenoxides
sanding 680 fibers, extended chain 202 allyl functional 101
nylon 673 filament 225 propenyl functional 101
polyester 681,681 filter cloths 233 Phenyl glycidyl ether (PGE),
preimpregnated 672 forms 232 viscosity 62
removing 683 gel-spun 225-6 Phosphoric acid anodized,
silicon transfer 670 handling 233 aluminum foil 820
surface preparation 683,870 high strength 233 Phthalic anhydride 35
strengths hybridization 233 chemical resistance 35
adhesives 274-5 hydrophobic 230 marine applications 916
GFRP 1006 inert 230 melting point 57
stress 629,631,637-8,637,638, machining 233 thermal stability 35
647,655,662 melt extrusion 224 Physical properties
adhesives 628 melting point 225 aramid fibers 2057,206
eliminating 644-5 moisture absorption 224 graphite/epoxies 4
lap joints 6374,637,638 multiple stage drawing 224 Pick-up trucks 936-7
linear variation 643 non-conductive 231 Pigments 516
maximum bond 642 non-woven 234 inorganic 516
reducing 644-5 processing temperatures 233 titanium oxide 516
tapering 646 recycling 883 zinc sulfide 516
PEKK 31 for reinforcing 234 Pins,FRP 959
PEL 825,826 resin penetration 233 Pipelines 466
1100 Index

rehabilitation 948 Nomex 272,273 PMR-I1

Piping 936 shear strength cf. PMR-25 90, 93
systems 926 honeycomb 2665,266-7 chemistry of 80-2,80
Pitch 1757,176 Nomex 272,273 processing conditions 84-5
fibers 169,352 stiffness 622 PMR-11-50
graphitized 183 thickness 790 flex strength 92
flow through spinneret 177 structural hierarchy 778 PMR-11-30 90
forming coke 173 Platelets 307 reinforced 90
mesophase 176 Platens, heated 499 Poisson’s ratio 19,698
precursors 173 Platforms 989 ceramic composites 312
carbon yield 197 fiberglass 989 IM6/epoxy 699
treatments 173-5,174 well bay 989,990 M401/F854 699
pretreatments 173,197 Pleating 547 Polar backscatter, ultrasonic 843
softening 197 Plied-yarn Polar winding 461-2,462
spinning conditions 1757,176 compressive strength 252 Poly (p-phenylene benzobisoxazole)
stabilization 177 count 252 see PBO
stirring 277 flexural strength 252 Poly (p-phenylene benzobisthiazole)
Pitch-based fibers 170 modulus of elasticity 252 see PBT
density 270 tensile strength 152 Poly-2,2’-rn-phenylene-5,5’-
elastic modulus 2 70 warp 252 benzimidazole, see PBI
fracture elongation 270 weave 252 Poly-rn-phenylene isophthalamids
tensile strength 2 70 Plugs 362-3 203,203
Pitch-based tow Ply Poly-p-phenylene terephthalamide,
manufacturers 199 alignment 689 see PPTA
trade names 199 angle 699-700 Poly-p-phenylene-benimidazole-
Placement, on mold 384-5 boundaries 481-2,481 terephthalamide, see PBIA
Plain locating, templates 574-5 Polyacrylonitrile, see PAN
strain 801 orientation 9,lO-11,374 Polyaluminoxane 159
weave 140,145,405,406 interspersing 19 Polyamide 6,6, characteristic
biaxial 399 properties 8,737 temperatures 221
fiber volume fraction 408,408 reinforcement 730,730 Polyamide 12, characteristic
triaxial 399 sequence, table 732 temperatures 222
Planar flaws 840 shape 482-2,481,482 Polyamide-imides
Plane generating 481 chemical name 222
source 453 stacking sequence 692 processing temperature 222
stress, stiffness 689 strength 745 structure 222
Plasma assisted CVD (PACVD) 316 Plycosite 255 suppliers 222
Plasma spraying 300 PMC T 222
Plaster masters 5644, 564 decontamination 863 l-: 122
follow board method 565,565 evacuation 863 trade name 221
NC machining 566 PMDA/ODA polyimide 76 Polyamides
sweep method 565-6 PMMA characteristic temperatures 222
template method 564-5 fatigue resistance 959 health effects 832, 833
Plasters, breakout/washout 465 orthopedic applications 962 Polyaminoamides, health effects
Plastic faced plaster 567,573 PMR-15 80 832,833
preparing 573 air aging 89 Polyarylene ether
Plastic zones 654 chemistry 79-80,79 chemical name 222
Plasticating 538 compressive strength 82 processing temperature 222
extrusion 534,535 density 82 structure 222
injection molding 538, 538 elongation 82 supplier 222
Plasticization 107 fracture toughness 82 T 122
moisture 112 laminates 88,89 r”, 221
Plastics, recycling 883 moisture absorption 82 trade name 121
Plate neatcured 82 Polybutylene-terephthalate,
elements 621 processing 84 characteristic temperatures
reinforced, carbon/aluminum tensile modulus 82 122
304 tensile strength 82 Polycarbonate, weld line strength
shear modulus T, 82 544
honeycomb 2665,266-7 thermal expansion 82 Polycrystalline diamond, milling
 Index 1101
596 Polymers shear strength 259
Polyester 28,34-9 composites 378 thermal conductivity 259
characteristic temperatures 722 properties 3854,386 viscosity 530, 531
chemical name 222 resin 382 weld line strength 544
curerate 509 compound grades 525 Polysulfone
density 505 crystalline 118, 120 see also PSU
elongation at break 505 economics 525 chemical name 222
flexural modulus 505 extrudate swell, injection flexural modulus 546
flexural strength 505 molding 540 processing temperature 222
glass fiber reinforced 28 fire retardant 42-5 structure 222
heat distortion 505 frictional coefficients, injection supplier 727
linear 34,34 molding 540 T , 122
modulus and temperature 210, inclusion of particulates 528 Tm 222
211 major processes 526 trade name 722
peel plies 681,681 matched metal dies 546 weld line strength 544
polyarylate 235 matrix composites Polytetrafluoroethylene, see PTFE
processing temperature 222 seePMC Polyurethane
reinforced 4.42 grinding 600 coatings 813
resins, shut down 515 matrix lamina, fiber fracture 799 compressive strength 258
shrinkage 507 melt compressibility, injection density 258
structure 222 molding 540 health effects 834
supplier 121 melt fracture potential, injection maximum service temperature
tensile modulus 505 molding 540 258
tensile strength 505 polymerization shear modulus 259
and temperature 210,211 condensation 7 5 4 shear strength 259
T, 721 shrinkage at 515 tensile strength 258
T, 721 pressure dependent shrinkage, thermal conductivity 259
trade name 222 injection molding 540 Polyvinyl chloride
unsaturated 35 processes 529,532 compressive strength 258
Polyether ether ketone, see PEEK unit costs532 density 258
Polyether ketone ketone, see PEKK processing 525 maximum service temperature
Polyetherimide, flexural modulus properties, blow molding 550 258
545,546 rheological concerns 525 shear modulus 259
Polyethylene selection 525 shear strength 259
recycling 883 semi-crystalline 534 tensile strength 258
terephthalate, see PET processing temperature 120 thermal conductivity 259
Polyglycidyl ether of o-cresol- shear sensitivity, injection Pontoon pier 995
formaldehyde Novolac molding 540 Poor bonding, adhesive joints 611
melting point 52 thermal properties, injection Porosity 90,300,630-1
viscosity 52 molding 540 bond layer 656
Polyglycidyl ether of phenol- thermoplastic, adducts in 526 NDE 854
formaldehyde Novolac thermoset 34 preform 439
viscosity 52 viscosity, injection molding 540 X-ray imaging 84.4
Polyimide Polymethylmethacrylate, see PMMA Ports and harbors 949
addition chemistry 78-81 Polyolefin 549 Post-curing 84-5, 385,446-7,589
aromatic 75 characteristic temperatures 222 Post-fabrication 732-3
binder solutions 76 Polyorthoesters 957 Post-processing 446-7
chemical name 127 Polyoxymethylene Post-tensioning 986,987
compression molding 545 cupping 541 anchors 987
condensation 78 shrinkage 541 Pot life 66, 510, 510
epoxy resins 6 warping 541 anhydride-cured system 72
precursor solutions, see binder Polyphenylene sulfide, see PPS NMA 66
solutions Polypropylene resins 440,513
processing temperature 227 see also PP Potassium
structure 227 and acrylic acid 251 aluminosilicate 2454
supplier 721 characteristic temperatures 721 metaphosphate 957
T 727 mica-reinforced 253 Powder
T: 222 phenolics 258 alloys 300
tradename 222 shear modulus 259 consolidation of 343
1102 Index

impregnation 228 disadvantages 438 tooling 562

processing drapability 438 unidirectional 118
ceramic composites 312-14, edge definition 438 waste 885
313,314 elastic constant 449 hazardous 885
packing 313 engineering parameters 422 wet 355
sintering 343 fabricated 438 Pressing
Powdered amorphous fiber distribution 438 temperature, SiC/Al,O, 325
thermoplastics (TPs) 105 fiber orientation 422 time, SiC/A403 325
Power heating 458 Pressure
poles 948-9,948 infiltration 299 compliant ring, testing 782
shears 426 permeability 438,439,449,578-9, consolidation 577
trowels 461 578 damage 874,875,876
Powertrain applications 911-12,911, porosity 439 gradient, infiltration 338
923 prefabricated 438 hulls, marine applications 922
PP and granulated SMC processing parameters 421 pulsation, infiltration 338
elongation 897 R T M 436-9,437,438 vessel, acoustic 472,472
flexural modulus 897 textile 401-2 vessels 471
flexural stress 897 thickness 438-9,438 X-ray backscattering 846
izod impact 897 uncured 456 PRESTEK 992
tensile modulus 897 winding 458 Prestressed concrete 985-6
tensile stress 897 Preforming 397422,448 anchorage 985-6
PP / PCI-glass 3-D 398 bridge deck 986,986
glass content 898 formability 398-9 bridges 987
strain at break 898 Preliminary steel tendons 985
tensile modulus 898 design 710-11,715-23 Preventive maintenance, composites
tensile strength 898 definition 710 880
yield stress at break 898 materials 715-22 Pricing
PPD 81 support data 711 aramid 216,716
PPS 31 materials, aircraft stabilizer 722 Dyneema 232
weld line strength 544 Preload relaxation 729 graphite fiber 716
PITA 203,205 Prepegging 6-7,7,32-3 Hoechst Celanese 232
chemical stability 213 advantages of 7 Spectra 232
hydrogen bonding 204 hot melt 7 Primary Adhesively Bonded
structural formula 203 roving 7 Structures Technology
Prebaking 871 thermoset matrices 7 (PABST) 6674,669
Precarbonization 180 Prepolymers 105 Principle strengths 803
Preceramic polymer chemistry 157 Prepregs Processing 64-9
Precured patching 867-8 aerospace industry 885 composites 879
limitations 867-8 availability 82 glass fibers 24
Precursors 335 braiding 418 parameters, preforms 422
fiber, pyrolysis 157 co-curing 868,870 polymers 525
materials 173 combining 117 speeds
mesophase pitch 335,336 composite tools 566,567-71 cf. pull loads 506,506
PAN 335,336 consolidation 117 pultrusion 514
pitch 173 definition 425 technology, braiding 413-15
polymeric 157 dry 425,430 temperature
rayon 335 facing material 255 PET 233
treatments, pitch 173-5,174 lay-up 576 polyamide-imides 221
Predicted life, AS-4/PEEK(APC) low tack 425 polyarylene ether 222
806,807 over metal substrates 870 polyester 222
Predicting ply kits 374 polyimides 222
durability 796 repairs 868-70, 869 polysulfones 122
joint strength 615 resins 352 thermoplastics 115,52552
peak stresses, joints 613 matrix 577 time, terephthalic resins 36
Preform reuse 884-5 window 176
advantages 438 shredding 885 Procurement costs, materials 722
ceramic 314 suppliers 109 Producing, carbon/aluminum 303
corners 438 tapes 430 Production
designing 438 thermoplastics 357 costs, aircraft 1024
 Index 1103

MMC 291 additives 515-18 definition 888

particulate fillers 2464,247 advantages 489 precursor fiber 157,159
Profile extrusion 532 applications 518-21 recycling 896-8
Programmed winding 469-70 basic process 489 tooling 341
Propeller shafts 911 cf. extrusion 488-9 yieldsfrom 895
Properties cf. pull forming 490,491 Pyromellitic dianhydride (PMDA)
aramid fibers 205-15 civil engineering 519-20 75,76
boron 161 and compression molding 490
casting, CE 108 construction 519-20 Quadratic failure 695-7
ceramic fibers 161 continuous production 489 criteria 707-8
elastic 194-5 creel 492-5 Qualification tests 1060
highsilica 161 w e d 489-90 Quality controls, composites 880
Kevlar 205 definition 488 Quartz
lamina material 760 dies 497 applications 163,165,166
polymer composites 385-6,386 electrical equipment 518-19 drawing 157
quartz 161 epoxy 511 fibers 24-5
Technora 205 fibers used 503 fused 163
thermoplastics 115 fillers 516 forms 161-3
Twaron 205 FRF 47,517 fusedrods 157
using recyclate 892 hammer handles 491 manufacture 156-7
Vectran 235-6 history 488 properties 161
Proprietary specifications 1066-7 injection 497,498 Quasi-isotropic
Propulsion labour requirements 489 laminates 9-11,697
shafting 925 machine 488 materials 687
systems 1041,1041 oil and gas industry 521 modulus 12
Prostheses 963 pigments 516 Quaternary ammonium salts 382
Protective coatings 292 processing speeds 514
composites 879 products 489
R-glss 134
Protruding head, fasteners 624,624 pull-winding 496-7 Racetracking 443
Pseudoisotropic laminates, CMEs resins 504 pattern 461-2
1011 impregnation 495
winder 462
PTFE 362 shapes 989 Racing yachts 353-4
see also Teflon shut down 515 Rackets 1049-50,1050
compression molding 545 sloughing 514 braiding 1050
velocity cf. temperature 843-4, sporting goods 1045-6 compression molding 1049
844 start-up 514-15 filament winding 1050
Pull surface finish 514 injection molding 1050
forming 490-2,490 thermoplastics 116 resin transfer molding 1050
automation 492 three zone model 505,505 Radar
cf. pultrusion 490,491 transportation 520-1 signals, transmission 472
curved 490,491,491 tubular structures 496-7 transparency, foam 256
straight 490,491-2 vertical 495-6 Radial
loads 512 wastage 489 microstructures
cf. processing speed 506,506 and winding 496-7 folded 177
epoxyresins 510 windmills 521 withwedge 177
winding 489,490,496-7 Pure bearing load, joints 626 Radiation 3,816
Pullers Purging 515 Bremsstrahlung 816
continuous belt 501 Putties, adhesives 275-6 ionizing 816
intermittent 501 PVC particulate 816
Pulling 501-2,501 foam 257 solar 816
continuous 501 crosslinked 917 thermal 816
Pulp molding, short fibers 337,338 linear 917 ultraviolet 817,817
Pulse-echo testing Pyrex 318 Radio frequency
advantages 842-3 Pyrolysis 159,182,888 see also RF
c-scan 842,842 carbon fibers 335 heating 499
one-sided 842 carbon-carbon composites 341, Radius of curvature 459
ultrasonic 842-3,842 342 sheets 186,187
Pultrusion 17-18,33,117,488-521, carbonized organic composites Radius of twist 459
529,532 340
1104 Index

Radomes 1024 polyurethane composites 893 recycling 388

composites, quartz reinforced pyrolysis 896-8 ribs 389,391,391
110 reinforced composites 388 shell and plate construction
Rail shear, testing 783 SMC 890-3 389,389
Railroad Sweden 887 size and shape 388
applications 912-14 thermoplastics 893-5 spray-up 355
rolling stock 949-50 Redux 255 structural requirements 388
Railways 950 bonding 667,669 surface quality 387
Random, microstructures 177 Re-entry temperatures, spacecraft concrete 983-8
Rapid cure, resins 440 816 beams 1000
Rate of relaxation, water absorption References cracking 1000
811 E-glass 774-7 E-glass 984
Ratio, glass-to-resin 1504,153 graphite epoxies 774-7 steel reinforced 983
Raw materials, falling cost 838 Kevlar 774-7 epoxies 442
Rayon 25 lamina property 772-3,774-7 polyester 442
RD-1 (Ciba-Geigy) 61 S2-glass 774-7 reaction injection molding, see
RD-2 (Ciba-Geigy) 62 Spectra 774-7 RRIM
Reaction efficiency, atomic oxygen Reflectors 1015 Reinforcement
814 ACTS 1017 CE 111
Reactive rubber, tougheners 106 Refractive index circumferential 461
Reactivity, resins 440 feldspar 243-4 composites
Reaming 598 Kevlar 215 continuous unidirectional
Rebars 984-5,984 nepheline 243-4 318-20,318,319
fiberglass 999 Regrind RIM discontinuous 320-1,320
placement 985 density 895 configurations 461-4
pultruded 999 elongation 895 continuous 308-11,309,310,502,
Recreation, design requirements 713 flexural modulus 895 762
Rectangular plates 749-53,749,751 hardness 895 definition 378
in-pane loading 750-1,751 tensile modulus 895 E-glass 383,916
Recyclability,MMCs 944 tensile strength 895 geometry 797
Recycled Rehabilitation glass fibers 378,383
materials 889-99 bridges 988 graphite 353
NBC 897 building construction 988 heat cleaned 898-9
PET 894 chimneys 988 helical winding 461
phenolic 894 concrete 988 hoop winding 461
PP 895,896 steel 988 Kevlar 383
SMC 890,892,893 wood 988 knitted 916-17
Recycling Reinforced local 730,730
see also reuse, disposal composites 712,713 marine applications 916-17
automotive industry 901-2 applications 38- materials 832, 835, 835
BMC 890-3 carbon fiber 358-9 RTM 435
building construction 901-2 chopped-fiber 355 monofilament 311,311
electrical parts 902 continuous-fiber 355 multi-directional 718
environmental aspects 902-3 continuously 358 plies 730,730
Europe 884 corrosion resistance 387 polar winding 461-2,462
Germany 887,902 corrugated configuration 389 S2-glass 383
glass-filled PP 893 dimensional stability 387 spatial 471
granulation 886-7 edge stiffening 390,391 specific heat 533
heat cleaning 889 edgetuming 390 thermoplastic polymers 526
history 883-4 electrical resistance 387 three-dimensional 456,801
Japan 887,888,903 high strength 387 two-dimensional 456
legal aspects 902-3 inserts 392 types
mechanical 886-7 light weight 387 fibrous 795,796
milling 886-7 minor impact resistance 387, unidirectional 438
organizations 903 388 volume 510-11,510
PET 883 molded-in color 388 woven 361,916-17
phenolic composites 893 nominal thickness 390,391 Reinforcing
plastics 883 non-structural requirements bars, see also rebars
polyethylene 883 388 ceramics 307-11,308,308,309,
 Index 1105
310,311 marine laminates 920 viscosity 64,440,578,579,579
load carrying capabilities 307 minimizing 673 and cure cycle 354,355
Relaxation, environmental effects epoxies 382,504 volume fraction 478
1000 and fibers 425 weather resistant 813
Release agents 362 flow 578-80 Young’s modulus 440
Releases 429-30 consolidation 576 Resistance
fluorocarbon 361,362 continuity condition 582-3 chemical 39
molds 361,362 Darcy’s law 578 to fire,phenolics 505
silicon 49-30 gelation 499 water 39
Remaining high performance 122 Resonance, ultrasonic 843
life 804-7,804,805,806,807 high temperature 818 Respirators, filter 830
strength 797,804-7,804,805,806, impregnation 495 Respiratory protection 830
807 ingredients 513 Restoration of coatings 867
estimating 797 injection 117 Resulting strain state, laminates
loading history 805 molding 122 693-4
normalized 805,805 system 433,434,440-1 Reticulating films, adhesives 276
predictions 806 thermoplastics 226 Reusable bags, silicone rubber 371,
Removal of peel ply 631 isophthalicpolyester 504 371
Repairs matrix 504 Reuse
adhesives 869 prepreg 577 see also recycling, disposal
advanced fibers 877 mixing 513-14 appliances 901
aircraft 857-80 temperature 441 automobiles 900-1
autoclave 868 viscosity 441 carbon fiber 884
heat application 874-7 moisture absorption 440 cutting 885
heating blankets 869 morphology 505 and disposal 883-904
honeycomb panels 871-7 penetration, PET 233 glass fiber 884
joint preparation 871 phenolic 504 hybrid composites 883
mechanically fastened 877 polymerization 499 prepregs 884-5
metal bondments 871-7 pot life 440, 496,513 sheet molding compound 883
methods 880 pultrusion 504 shredding 885
non-autoclave 868-9 rapidcure 440 technologies 885-9
prepreg 868-70,869 reactivity 440 RF preheating 513,513,515
resins 869 recycling 515 Rheology 527-31
skill requirements 878 removing excess 576,673 definition 527
standardization 878 repairs 869 Ribs
surface preparation 870-1 replenishing 513 designing 391
technical training 878 safety 831-2 geometry 391
vacuum pressure 869 selection 45,440,504 moldmaking 390
Repeatability 8 solvent based 431 parameters 743
turning 603 Tgpoint 440 reinforced composites 391,391
Representative volume 796,804,804 thermoplastic Rigid
discontinuous 804 matrix 496 adherends 633,633,634
Reproducibility 3 mechanical properties 122 fiber 802
Reproductive toxicity 824 toughness 440 tool, thickness 450,450
Residual transfer Rigidity, and flow 67
strength, AS-4/PEEK(APC) 806, molding 17,374,492 Ring specimens
807 see also RTh4 bending 785
stresses, control of 470,472 marine applications testing 782,784
Resins 382 919-20 Rings
bathlife 496 rackets 1050 compression testing 782,788-9
bleed sequence 367 transverse hoopwound 789
catalyzed 507 modulus 1056 thick-walled 789
changing 497 tensile strength 1056 thin-walled 789
chemistry 99-1,382 uncatalyzed 506 Risk 823
comparing 505-7,505,506 unsaturated polyesters 382 definition 823
consumption 513 used Rivets, aluminum 668
content 425 RTM 440 RK, properties of 270
byvolume 503 selecting 440 Rocket
fibreglass epoxies 153 vinyl esters 382,504 motor
1106 Index

cases 23,465 heating/cooling 441 resins 831-2

X-ray backscattering 846 injection pressure 433 Saffil 159
design requirements 713 low cost parts 433 grades of 159-60
nozzles, carbon-carbon 712 moistw absorbance 440 Sailboats,design requirements 713
Rockwell hardness, NR-150 82 mold sealing 441 Same materials, sandwich structures
Rods, testing 784 optimum viscosity 440 744
Roll reinforcement materials 435 S A N ,weld line strength 544
forming 117,289 resin 440 Sand bags 874
wrap process, sporting goods T6 446 Sanding 672,672,678-80,679,683
1045 sporhng goods 1046 peel-ply imprint 680
Roller press 426,427 tensile elongation 440 scuff 679
Rollers 461,495 tensile modulus 440 Sandwich
Rolling vacuum assisted 433,453 adhesive flow 288
carbon/aluminum 303 viscosity 440 beamtype 281
compaction 477 Rubbery sheet deformation 526 buckling 282
rate of 302 Rule of mixtures 150,318,588,697 construction 694
solid phase 302 Runner system 444 aramidfibers 221
solid stage production 291 conversion to 255
table 427,427 S2-glass 134 core
in vacuum 300-6,301,302,305 compression properties 360 crushing 282
temperature conditions 300 constituent properties 766 selection 276,278,279,284
Rolls and air shafts 950-1,951 cost of 917 sue 288
Rotational molding 529,532,550, elastic properties 764-7 deflection 284
551 references 774-7 limitations 281,284
crosslinking 551 specific gravity 383 design 281,284
crystallization kinetics 551 strength properties 764-7 compressive modulus 281
molecular characteristics 552 tensile failure 383 core 281
particle size distribution 552 tensile modulus 383 facings 281
polymer properties 552 tensile strength 383 notation 280-1
thermal properties 551 thermal expansion 383 designing 276-80,277,278,279
zero-shear viscosity 551 S twist, yam 138 dimpling 282,284
Router speeds 289 Sglass 23,24,425 fabrication 276
Routing 602 based, rovings 147 face wrinkling 282,284
Rovings 163,164 density 503 facing failure 282
carbon fiber 502 elongation at break 503 high temperatures 288
for chopping 146 epoxies 252 manufacturing 287-9,289,290
continuous glass 492 fibers, stress rupture 212-13,213 modes of failure 282,282
fiber 492 filament strength 24 shear crimping 282
fiberglass 136 meltingpoint 24 skin materials 284
glass 502 modulus 24 structures 467-8
harder 146 tensile modulus 503 design 467-8
nonwoven 164 tensile strength 503 different thicknesses 744
Sglass based 147 SS2-glass elements of 254,254
single strand 136,146 reinforcement 383 same materials 744
woven 136-7,137,164,917 specific modulus 1049 space vehicles 254
reinforced 237 specific strength 1049 thickness 284
yields 136 tensile modulus 360 transverse shear failure 282
RRIM 907 tension-tension ratio 1049 wall 742,743
RTM 433-54'762 SS2-glass, fiber modulus 360 transverse shear deformation
advanced technology 447 Striazine ring 99,100 743
advantages 434-5 SAAB JAS39 Gripen, composite Satellites
cavity design 441 applications 1034 central cylinder 375-6
compounds, rheology 101 SACMA standards 1061-2,1062 design requirements 713
curecycle 433 Safety Satin weave 405,406
curing 445-6,445 applications 943-4,944 Saturated acids 37
cycletimes 433 aramid fibers 222 Sawing 601
disadvantages 434-5 epoxy resins 831-2,832 Scarf
gate and vent 441 factor, formulas 285 adhesive joints 628,629
glass transition temperature 440 hazards, composite processes 831 joints 611,623,645
 Index 1107
shear stress 649 rail test 789 particulate fillers 242,252
distributions 6474,648, strength polyester 507
649 ABS 259 polyoxymethylene 541
Scarfing 6234 AFR700B/S2 laminates 93 rate 509
Scientific applications 96740 carbon fibers 295 recycled SMC 892,893
Screws, injection molding 538 Celion 87 volumetric 507
SCRIMP 919 cellulois acetate 259 Shut down, pultrusion 515
Scuff sanding 679 epoxies 259 Sialon 329
Sealants, composites 879 interlamina 196 SiC/AJO,
Sealing 577 phenolics 259 density 315
composites 302 polypropylene 259 pressing
Seals 953 polyurethane 259 temperature 315
Seawater resistance, PET 233 polyvinyl chloride 259 time 315
Secondary, drilling 598 skinned molded foams 259 SiC/SiC composites 401,401
Section stress 636,636 Signal-to-noise ratio, ultrasonic 834
failure curves 615-16,615 5-step 649,650 Silanes 250-1
load, last fastener 620 10-step 649,651 coupling agent 147
stress 615 adhesive 632-7,633,634,635, organofunctional 147
Secured Modular Automotive Rail 636 Silar
Transport (SMART) 914 distribution 636 fracture
Selection process, joining 727,728 scarf joints 6474,648,649 strength 325
Self-adhesiveskins 276 maximum bond 642 toughness 325
Self-screening, aramid fibers 215 peak-to-average 648 work of 325
Semifabricatedcomposite, winding scarf joints 649 Young’s modulus 325
468 TEOS 346 Silica
Sensitization 824 test 688 crystalline 249
cross 824,825 in-plane 196 fillers 527
equations 825 Shearing, weave 439 flocculated varieties 244
Sensors Shearout failures 618,619 fumed 247-8
pressure 499-500 Sheet fused 244
temperature 499-500 extrusion 532 natural 244
Separation 597 molding 374 particulate fillers 244
Shallow delamination,NDE 854 molding compound surfaces 244
Shear 394,395 seealso SMC thixotropic effect 244
coupling, coefficient 193 reuse 883 Silicates, fillers 527
crimping, sandwich 282 radius of curvature 186,187 Silicon
deformation 448 Shelf life, before molding 31 carbide 27,319
cylindrical shells 756 Shell and plate construction, coating 294
edges 394 reinforced composites 389, CVD 157
failure 195 389 fillers 527
in-plane 783,789-90 Shells, netted-ribbed 473 wheels, grinding 600
interlaminar 790-2 Shims 570,572 nitride, whiskers 161
knifeedge 394 Shipboard armor 925 releases 429-30
lag analysis 633-9 Shipments 955 Silicone rubber 365,366
modulus Short CTE 589
ABS 259 beam shear properties, Spectra reusable bags 371,371
cellulois acetate 259 226,226 Silver flake 250
epoxies 259 fiber mat, flexural strength 401 Simple twist 138
IM6/epoxy 699 fibers 337,338 Single
M401/F854 699 term exposure limit, see STEL head, p d winding 496-7
PET 120 Shredding lap
phenolics 259 mobile 887 joints 626,627,628,729
polypropylene 259 prepregs 885 bending deflections 641
polyurethane 259 Shrink factors 557-8 load path eccentricity 637,
polyvinyl chloride 259 Shrinkage 5,179,506,507-9,507, 637
skinned molded foams 259 508 shear, joints 624
properties fillers 508 strand, rovings 146
aliphatic system 70 following gelation 508 strap, adhesive joints 628
aromatic system 71 neat polymers 541 Yam
1108 Index
compressive strength 151 grill opening panels 907 Vectran 236
count 151 IZOD impact 386,386 Sources of pressure 460
filling 151 lower density 381 Space 813-17
flexural strength 151 manufacturing 381 atomic oxygen 813-14
modulus of elasticity 151 molding 384 composite systems 814
tensile strength 251 phenolics 382 debris impacts 81415,814,815
warp 151 recycling 890-3 meteoroid impacts 81415,814,
weave 151 regrinding 890,891 815
Size, meteoroids 815 specific gravity expansion 386, shuttle 344,345,347,472
Siziig 802 386 tooling development 1015-16
agent 495 tensile modulus 386,386 Spacecraft 968-72,969,970,971
fiber reinforcement 435 tensile strength 386,386 heat sources 816
Skill requirements, repairs 878 thermal expansion 386,386 LDEF 970-2,970,971,972
Skin SMEs 952 re-entry temperatures 816
core, bonding 917-18 Snowflake P.E. 247,247 thermal cycling 818
creams 829-30,830 Sodium-calcium-aluminum- truss structure 968-70
grafts 963 polyphosphate 957 Spa11 liners, phenolic 914
materials, sandwich 284 Soft gauge, machine tools 364 Spallation 814
penetration Soft tissues, composites for 963-4 Sparging 1745
aircraft 858,859 Sol-gel technology 156-7 gas 174-5
foil tape repairs 858 Solar Spatial reinforcement 471
protection 828-30 absorptance 816 Spatially sewn structures 456
Skinned molded foam array Special tests 792
compressive strength 258 backing 820 Specific gravity
density 258 panels 353 Armos 208
maximum service temperature radiation 816 Dyneema 225
258 Soldering, carbon/aluminum 303 E-glass 383
shear modulus 259 Solid expansion 386,386
shear strength 259 conveying, extrusion 534,535 fiberglass 235
tensile strength 258 phase, rolling 302 graphite 383
thermal conductivity 259 rubber, tooling 670 Hoechst Celanese 225
Skybond 76-7,77 stage production 291 Kevlar 208,383
dielectric strength 95 state laser, Nd-YAG 605 Nomex 209
electrical properties 95 Solution sedimentation,MMC 291 PBO 235
elongation 86 Solvents 812,8357,836 PET 224
flex modulus 86 absorption, anhydride-cured recycled SMC 890,892,893
flexstrength 86 system 72 S2-glass 383
insulation resistance 95 aramidfibers 204 Spectra 225
processing conditions 84 impregnation 117,118 SVM 208
surface resistivity 95 polar 175 Technora 209
tensile strength 86 removal 159,175 Teijinconex 209
volume resistivity 95 resistance Tekmilon 225
weight loss 86 PBI 237 Twaron 208
Skylab oxygen tank 471,471 thermoplastics 115,127 Vectran 235
slip forming 547,547 toxicity 361,362 Specific heat
Slot camera, X-ray backscattering trichloroethylene 64 aromatic system 71
846,846 Sonar domes, marine applications definition 532-3
Sloughing 508,510 922 fillers 533
SlUrry-Spinning 159 Sonotrode Kevlar 206
Small boats 921 material 607,608 Nomex 206
SMC 380-1,890-3,892,893,895-6, non-rotating steel 608 reinforcements 533
897 Sources of information Teijinconex 206
automobile industry 381 Armos 221 Twaron 206
currentuse 381 Kevlar 221 Specific modulus 715,716
early applications 380 PBOfibers 236 aluminum 1049
fatigueproperties 386,387 PDIfibers 236 carbon 1049
flexural modulus 386,386 SVM 221 definition 715
flexural strength 386,386 Techora 221 E-glass 1049
formulation 384 Twaron 221 Kevlar 1049
 Index 1109

Kulon 305 Spectra Shield 234 laminate 616,630

PET 224 Spectroscopy notation 619
S2-glass 1049 fluorescence 69 Stackup, laminate pre-bleed 569
Spectra 1049 infrared 69 Stainless steel, thermal data 818
steel 1049 Raman 69 Stamping 545
titanium 1049 Speed sensitivity 463 Standard tests, composites 880
VMN-4 305 Speed tape repairs, aircraft 859 Standards, organizations 1060-1
Specific stiffness, aramid fibers 207 Spherical shapes, filament winding Staple 15940,216
Specific strength 466-7 alumina 159
aluminum 1049 Spherulites 120 alumina-silica 160
aramid fibers 207 Spin process, Technora 213 density 162
carbon 1049 Spinning 1 7 5 7 description 162
continuous fiber 162 conditions, pitch 175-7,176 diameter 162
E-glass 1049 PAN 175 elastic modulus 162
Kevlar 1049 temperatures 175 green 159
metals, vs. composites 1047,1048 Spirit of Australia 354,376-7, 376, manufacturers 162
PET 224 377 specific strength 162
S2-glass 1049 carbon/epoxy mast 377 thermal expansion coefficient 162
Spectra 1049 Split rings, testing 784 trade names 162
staple 162 Sporting goods 1044-52 unfired 159
steel 1049 braiding 1045-6 Static mixers 441
titanium 1049 filament winding 1046,1047 Steel
whiskers 162 manufacturing techniques CTE 558
Specifications 10459 density 170,558
materials 722 pultrusion 10454 dies 42&7,429,430
and standards 1059-67 roll wrap process 1045 thermal expansion 507
Specimen geometry, honeycomb 263 RTM 1046 elastic modulus 170
Specimen width 780 Sports cars 910 fracture elongation 170
Spectra 23,26,223,228,229,761 Spray lay-up, short fibers 337,338 linear thermal expansion 705
attributes 358 Spray metal, tooling 442 rehabilitation 988
availability 231 Spray-up 436,437 selection, mold 393
axial compressive properties 226, Spraying specific modulus 1049
226 ionic 300 specific strength 1049
axial tensile properties 226,226 plasma 300 tendons, prestressed concrete 985
carbon 359 Springback 557 tensile strength 170
constituent properties 767 GFRP 1013 tension-tension ratio 1049
creep resistance 227,22&9,230, Springer’s model 578,581,582,585 thermal conductivity 558
233 compacted plies 588 Steering 482,483
crystallite melting point 26 numerical schemes 586 definition 482
density 503 Sprue and runner 541,542 radii 482
dielectric constant 231 Square packing 403,403 Stefan-Boltzmann law 850
elastic properties 7 6 4 7 Squeeze flow 548 STEL 826
elongation at break 225,503 SRIM 433 Step lap
fiber type 225 machine 434 joints 628,629,6454,645,649,
flexural properties 226,226 Stability 650,651,652,659
graphite, hybrids 354 color 43 design 652
marine applications 917 PBOfiber 238 Stiffness
for oil containment 233-4 and temperature 49 adherends 636
pricing 232 thermal-oxidative 75,92 carbon-carbon composites 333
references 7 7 4 7 Stabilization changes
short beam shear properties 226, anisotropic pitches 178 microcracking 796
226 commercial 178 with time 800
specific oxygen addition 173 coefficients
gravity 225 PAN 172,177-80,178,179 constitutiveequations 743-4
modulus 1049 rate of 180 determining 737
strength 1049 Stabilizers IM6/epoxy 702,703
strength retention 230 covers, boron-epoxy 1030-1 and coupling 700
tensile modulus 225,503 uv 43 cylindrical shells 756
tensile strength 225,503 Stacking sequence matrix, laminates 693
1110 Index

plane stress 689 T50 graphite 724,724 polyamide-imides 721

to weight ratio, PET 223 weight ratio 21 polyarylene ether 121
tooling materials 577 aramid fibers 223 polyester 121
unbalance, adherends 629 PET 223 polyimides 121
weightratio 21 stress polysulfones 121
Stitched fabric 436,436 analysis prepreg 109
Stitching 801 joints 611 thermoplastics 119
Storage 357-8 one-dimensional 627 Supported films, adhesives 276
freezer 425 concentration 610,613,614,788 Surface
Strains distribution, double lap joint 654 area 607-8
at break, PP/PCI-glass 898 interlaminar 738 compressive stress 321
displacment, equations 739 patterns, laminates 322 crusting 339
energy, adhesives 653 residual 466 of curvature 479
graphite/epoxies 4 resultants, laminates 691-3 damage 322
measuring 779 defect healing 295
to failure 319 failure 24 disbonded 677
Strand mat Kevlar 212-13,213 energies 316,316
continuous 503 para-aramids 212 finish
fiber structure 503 Sglass fibers 212-13,213 pultrusion 515
Strand properties straincurve 319 tools 597
Kulon 306 thermally induced 640 flaws 840
VMN-4 306 thermoelastic 466 geometry
Strands 164 transfer 149 concave surface 484
Strap joints, tapering 645 Stretching elongations 633 fiber placement 484-6
Strength Strip heaters 499 radii of curvature 484,486
alumina silicate 309 Structural types of 484
aramid 718 applications 709 ply,veil 503
bending 791 aircraft 1027-8,1027,1028 polish, compression molds 395
anddensity 23 formula,PW 237 preparation 630-1,667-84
efficiency, carbon-carbon geometry abrading 669
composites 344 braiding 415-16 adhesive joints 611
envelopes 802,802 nonwoven textiles 419 aerospace industry 669
evaluation 737 hierarchy 778 aluminum 871,876
M60J tape 718 reaction injection molding see automotive industry 669
PlOO tape 718 SRlM cuttingplies 870
properties testing 792 grit blasting 870-1
E-glass 764-7 structure history of 667-71
graphite/epoxies 4,768-71 aramid fibers 204-5 non-autoclave 871-2
laminate 764-7 PET 224,224 peel plies 683,870
predicting 318,318,319 polyamide-imides 121 removal 631
S2glass 764-7 polyarylene ether 121 repairs 870-1
T50/F584 epoxy 726,726 polyester 121 testing 669
ratio polyimides 121 properties, particulate fillers
Ih46/epoxy 701 polysulfones 121 250-1
laminates 696 Styrene quality, reinforced composites
retention 213 addition 34 387
aramids 230 polyester 382 resistivity
definition 241 Submarines 473 fiberglass 135
Kevlar 205,215 Substrates 157 Skybond 95
medical applications 957 heating 293 roughness, tooling materials 577
Spectra 230 Subsurface damage, inspection 839 slick 682
Technora 205 Succinic anhydride (SA), melting speeds,grinding 600
structural 795 point 58 treatment 190-1
T300fabric 718 Superconducting waviness 603
tests, joints 626 magnetic energy storage systems, weave, yams 407,407
three-dimensional 489 see SMEs Sutures, PET234
tooling materials 577 SuperCollider magnets 978,978 SVM
values Supennite 247,247 availability 220
carpet plots 719 Suppliers elongation at break 208
 Index 1111
initial tensile modulus 208 adherends 653 long-term use temperature 206
PBIA-based fibers 210 adhesive joints 628 melting temperature 206
sources of information 221 Tapering moisture content 206
specific gravity 208 adherends 627,629,644-51,645, specific gravity 209
tensile strength 208 647,648,649,650,656,658 specific heat 206
Sweden, recycling 887 advantages 646,647 tensile strength 209
Sweep method, plaster masters peel stresses 646 thermal conductivity 206
565-6 strap joints 645,647,648 Tekmilon 223,228
Swelling stresses, water absorption double 646,647,648 availability 231
811 Tappers, mechanical 840 elongation at break 225
Symmetric, laminates 692,749 Tateho fibertype 225
Symmetry 9,10-11 fracture strength 325 specific gravity 225
Synergism 43 fracture toughness 325 tensile modulus 225
Syntactic foams, adhesives 275-6 work of fracture 325 tensile strength 225
Synthetic marble 253 Young’s modulus 325 Telescopes 1014-15
Teglass 134 Temperature 817-19
T50 graphite Technical training, repairs 878 consolidation 577
material properties 724, 724 Technology control, dies 511-13,512, 513
strength values 724,724 reuse 885-9 cryogenic 817
T50/F584 epoxy winding 458-66 modulus 212
material properties 726,726 Technora 204 decomposition 76
strength properties 726,726 availability 220 elevated 817
T300 fabric breaking strength 214 extremes, GFRP 1004-21
mechanical properties 728 chemical resistance 224 glass transition 75
strengths 718 chemical stability 214 gradients 470-1
Table rolling 425-32 decomposition temperature 206 profile, dies 511,512
equipment, suppliers 431 density 206 resistance, aramid fibers 205
mandrels 429 elongation at break 209 spinning 175
materials 429-30 ether linkages 210 stability 49
Tabs 787 fatigue resistance 213 dies 514
Tack 3567,479 filament diameter 206 and viscosity 1724,174
controls 356-7 filament shape 206 Template method, plaster masters
desired 479 formsof 216 564-5
excessive 357 initial tensile modulus 209 Templates
heavy on prepregs 357 linear thermal expansion ply locating 574-5
requirements 357 coefficient 206 trim and router 574
Tactical aircraft, material weights long-term use temperature 206 Tenacity, definition 241
1027 melting temperature 206 Tennis rackets 463
Talc 246 modulus and temperature 210, Tensile
composites 246 211 elongation 41,42
impact strength 246 moisture content 206 recycled PET 894
Italian 248-9,248 properties 205 RTM 440
low cost 246 sources of information 222 failure 383
Montana 248-9,248 specific gravity 209 forces, transmission 787
New York 248-9,248 spin process 213 load, fibreglass epoxies 253
polypropylene filled 246 strength retention 205 modulus
Tank solution processing 871 tensile strength 209 aramid fiber 715,716
Tap test 840 and temperature 210,211 A S 4 carbon fiber 123
laminar type flaws 840 thermal conductivity 206 BMC 386,386
Tape 164 Teflon 250,360,834 carbon fibers 335
braiding 418 Teijinconex 205 carbon (Type T300) 503
collimated 359 decompositiontemperature 206 carpet plots 719
fiberglass 146 density 206 Celion 87
non-woven 359 elongation at break 209 continuous ceramic fibers 309
placement 456 filament diameter 206 Dyneema 225
reinforcement 25 filament shape 206 E-glass 360,383,503,715,7l6
slit 478 initial tensile modulus 209 epoxy 522
unidirectional 298,359 linear thermal expansion graphite 360,383,715, !7l6
Tapered coefficient 206 Hoechst Celanese 225
1112 lndex

Kevlar 383,503 Kevlar 208,383,503 carbon-carbon composites 349

Kulon 306 Kulon 305,306 compression 346
lot-to-lot variation 725 lot-to-lot variation 725 flexure 346
LPMC 386,386 LPMC 386,386 comer 346
marine laminates 920 marine laminates 920 impact 346
PBO 235,238 and microtexture 188 impregnation 341,3434,344
PMR-15 82 and modulus 21,21 interlaminar shear 346
laminates 88 and nitrogen release 182 interlaminar tension 346
polyester 522 Nomex 209 process 341
PP and granulated SMC 897 NR-150 82 shear 346
PP/PCI-glass 898 nylon 6/6 PCI-glass 899 tension 346
recycled NBC 897 PAN-based fibers 169,270 thermal expansion 346
recycled PP 895,896 PBO 235,238 Terephthalic acid 35
recycled SMC 890,892,893 phenolics 258 Terephthalics 36,39
r e g r i n d m 895 pitch-based fibers 270 processing time 36
RTM 440 plied-yam 252 reactivity 36
S2-glass 360,383,503 PMR-15 82,88 solubility 36
SMC 386,386 polyester 511 Tertiary amines 104
Spectra 225,503 polyurethane 258 Test
and strength 21,21 polyvinyl chloride 258 direction, yam distribution 154
Tekmilon 225 PP/PCI-glass 898 methods 721
thermoplastic resins 222 recycled PET 894 adhesives 630
Vectran 235 recycled SMC 890,892,893 joints 626
vinylester 522 regrind RIM 895 specimen
VMN-4 306 S2-glass 383 dimensions 786-7
ZMC 386,386 Sglass 503 loading sections 786
properties epoxies 252 transition sections 786
aliphatic system 70 single-yam 251 Testing
anhydride-cured system 72 skinned molded foam 258 barcol hardness 38
E-glass 360 Skybond 86 bars 784
graphite 360 SMC 386,386 compression 38,782
testing 38 Spectra 225,503 distortion temperature 38
stiffness, aramid fibers 209 steel 270 eddy current 849-50
strength SVM 208 flat specimens 786-7
ABS 258 Technora 209 flexural properties 38
AFR700B/S2 laminates 93 Teijinconex 209 half-discs 782
aluminum 270 Tekmilon 225 history 779
aramid fibers 209 thermoplastic resins 222 hydraulic system 782
Armos 208 titanium 270 impact strength 38
AS-4 carbon fiber 123 Twaron 208 in-plane shear methods 783
BMC 386,386 Vectran 235 incoming materials 20
carbon fibers 169 vinylester 522 microwave 853
carbon (Type T300) 503 VMN-4 305,306 non-symmetric bending 783
carbon-carbon composites yam distribution 254 off-axis tension 781
333 ZMC 386,386 pressure compliant ring 782
carbon/ aluminum MMC 300 stress rail shear 783
carpet plots 720,720 PP and granulated SMC 897 requirements 779-80
CE 208 recycled NBC 897 ring specimens 782,784
Celion 87 recycled PP 895,896 rods 784
cellulois acetate 258 Tension selecting techniques 779
continuous ceramic fibers 309 and compression 786-9 special tests 792
Dyneema 225 failure in 787 specimens 780,786
E-glass 24,383,503 head, fasteners 625 splitrings 784
epoxies 258,512 tension ratio 1049 structural 792
fiberglass 134 TEOS 346 tensile properties 38
epoxies 253 testing 781,782, 788 tension 782
graphite 383 rings 782,788 torsion of square plate 783
and higher temperatures 182 Tensioning 469 tubes 784
Hoechst Celanese 225 TEOS 340 ultrasonic through-transmission
 Index 1113
8404,841 polypropylene 259 stress 659,660,661-2
Tetraethylenepentamine (TEPA), polyurethane 259 laminates 322
viscosity 54 polyvinyl chloride 259 Thermally
Tetraethylorthosilicate, see TEOS skinned molded foams 259 induced stresses 640
Tetramethylbisphenol F steel 558 resistant gloves 829
homopolymer property 102 Technora 206 Thermoelastic behavior, anisotropic
structure precursor 102 Teijinconex 206 bodies 470-1
supplier 102 thermoplastics 531-2 Thermoforming 436,437,526,
tradename 102 Twaron 206 529-30,529,532,5459
Tex, definition 136,241 urethane board stock 558 polymer properties 545
Textile control tape 819 Thermoplastics 356
fibers 307 cycling 89,89,816,817 aerospace 115
prefonning aircraft 818 aging 127
definition 397 spacecraft 818 amorphous, HDT 126
linear 398 data 818 automotive market 115
planar 398 decomposition, carbonyls 293-4 chemical resistance 126
three-dimensional 398 degradation 31 composite density 534
preforms 401-2 diffusivity, thermoplastics 534 composites
role of 398-401 expansion 3,5,19 extrusion 526
selecting 401 adherends 630,661 injection molding 526
T, 120 carbon-carbon composites processing 525-52
NR-150 82 333 compression molding 116,544-9
PMR-15 82 ceramic composites 312 compressive properties 124,125
polyarylene ether 121 coefficient diaphragm forming 116
polyester 121 continuous fiber 162 dielectric constant 107
polyimides 121 staple 162 dissipation factor 107
polysulfones 121 whiskers 162 extrusion 534-8
resins 440 composite tools 592 fatigue resistance 115
Thermal correction, tooling design 590 fiber content 117
accelerators 509 E-glass 383 folding 116
coefficient graphite 383 fracture toughness 124
BMC 386,386 molding 593 heat capacity 5 3 2 4
Kevlar 383 NR-150 82 high price of 1024
LPMC 386,386 PMR-15 82 impact energy 125
ZMC 386,386 S2-glass 383 injection molding 116
coefficients,orthotropic layers SMC 386,386 joining 127
742 steel dies 507 low toxicity 115
conductivity TEOS 346 manufacturing 116-17
ABS 259 thermoplastics 127 matrices, aramid fibers 221
aliphatic system 70 tooling materials 577 melt, high viscosity 116
aluminum 558 extremes 816-17 molecular weight 116
aromatic system 71 gradients, carbon-carbon polymers
carbon fibers 169 composites 333 adducts 526
carbon-carbon composites inertia technology 444 fillers for 527
333,349 mismatch 638,661,662 reinforcements 526
carbon/epoxy prepreg 558 oxidation 79 prepregs 357
cellulois acetate 259 carbon-carbon composites processing 115
ceramics 307 345,347-8 properties 115
electroformed nickel 558 properties pultrusion 116
epoxies 259 aramid fibers 2057,206 reinforcing 528
glass/epoxy 558 BMI 106,209 remelting 115
high carbon cast steel 558 carbon fibers 1845,185,186 resins 31-2
Invar 558 CE 106,109 fracture toughness 122
Kevlar 206 composites 661 health effects 834
mahogany 558 fiberglass 135 injection 116
monolithic graphite 558 rotational molding 551 tensile modulus 222
Nomex 206 radiation 816 tensile strength 122
particulate fillers 242 resistance, aramid fibers 205 solvent resistance 115,127
phenolics 259 stability, composite tools 592 structure 118
1114 Index

suppliers 119 Three zone model, pultrusion 505, use of caul plates 590
thermal 505 development, space 1015-16
conductivity 531-2 Three-dimensional elastomer 14
diffusivity 534 fiberglass 146 elastomeric 5934,593
expansion 127 lamina properties 761 electroformed nickel 591-2,592
thermofonnbg 544-9 reinforcement 456,801 employee induced damage 563
tougheners 106 Threshold limit values, see TLV epoxy laminates 562
trade names 124,125 Through-the-facesheet evacuation, fiber placement 479-80
transverse modulus 123 aircraft 865 fiber separation 562
transverse strength 123 Time weighted average, see TWA fixed-volume method 593,593
unidirectional Time window, consolidation 588 graphite-epoxy 592-3,593
compression strength 125 Titanates, coupling agents 251 hole fittings 562
tradenames 125 Titanium leakage 562
winding 458 alloy, linear thermal expansion master models 563-6
Thermosets 705 materials 589
amorphous 118 carbide 319 bleeder 577
compressive strength 124 density 170 consolidation 577
joining 127 diboride 319 hardness 577
polymers 34 elastic modulus 170 metals 577
Thermosetting 37,356 fracture elongation 170 properties of 558
binders 458 specific modulus 1049 stiffness 577
dielectric constant 107 specific strength 1049 strength 577
dissipation factor 107 tensile strength 170 surface roughness 577
reaction, definition 49 tension-tension ratio 1049 thermal behavior 589
resins 518 TLV 825,826 thermal expansion 577
Thermostamping 22 Tm moisture absorption 561
Thick composites, consolidation 585 polyamide-imides 121 and part shape 589-94
Thick molding compound, see TMC polyarylene ether 121 prepreg 562
Thick-walled structures 456,468-71 polyester 121 resin system 562
loaded in torsion 473-4 polysulfones 121 rubber 366
monolithicity 456 Th4C 380 sealers 561
residual stresses 469 Tolerance selecting materials 557
torsion strength 473 stackup 561 sheet wax 574
Thickeners 383 to flaws, ceramics 307 solidrubber 670
Thickness Tonox 60-40 (Uniroyal Inc) 56 spray metal 442
adherends 627-9,628,628,658 Tool urethane based 567
bond 631 geometry 439 variable volume method 593,594
layer 628,656 life 599 wet lay-up repairs 867
toadherend 641 factors 5967 Tools
drawings 731 pins 574 composite 361
fiberglass 141-4,153 separating from master 570 curecycletimes 559
Hercules IM7 fiber 478 stee1,CTE 589 depth of cut 597
honeycomb 263 surface design 556-63
preform 438-9,438 area 480 durability 558
sandwich 284 strength 480 fabrication, cost 558,559-60
section 512 usage 559 life expectancy 558,559,561
variation 372-3 wear 599 machinability 558
Thin composites, consolidation 585 Tooling 14,361-6,392-5,429-30, materials available 560
Thin-walled 447,47940,480,556-75 materials selection 559
beams 747-9,748 alternative 449-50,449,450 methods of fabrication 560
shear stress resultants 748, balls 565 mounted 480
748 bushings 562 multi-cavity 500
uses 747 castaluminum 442 resistance to failure 561-3
shells 456 correction method 590-1 selection 598
structures 466-8 CTE! 5567,5574 surface finish 597
Thinning, organic solvents 65 design 590 usage rates 558
Thixotropic liquids, adhesives 275-6 coordinating partial plies 590 wear ratio 597
Thomel 1054 thermal expansion correction Torayca 1054
properties of 170 590 fiber types 1054
 Index 1115

properties of 170 whiskers 158,162 density 206

Torque levels 625 Transfer molding 22 elongation at break 208
bolt tensions 626 Transformation relations 707 filament diameter 206
Torsion 784,790 Transition, areas of 731-2,732 filament shape 206
square plate, testing 783 Transportation 905-15 forms of 216
strength, thick-walled structures future directions 915 initial tensile modulus 208
473 land 90515 linear thermal expansion
Total hip arthroplasty 960-1 pultrusion 520-1 coefficient 206
femoral components 960-1 Transverse long-term use temperature 206
FRI' 959 compression, Kevlar 212 melting temperature 206
metallic devices 960 CTE 699 moisture content 206
Total overlap length 658 extension, Ih46/epoxy 701 properties 205
Tougheners modulus 12 sources of information 221
reactive rubber 106 Ih46/epoxy 699 specific gravity 208
thermoplastic 106 M401/F854 699 specific heat 206
Toughening 104-5 resins 1056 tensile strength 208
interphase 802,802 thermoplastics 123 thermal conductivity 206
Toughness 801 shear Twill, weave 145,145,405,406
adhesives 2765,274 adherends 630 Twin-screw extruders 535-6
aramid fibers 221 failure, sandwich 282 advantages 539
interlaminar 124,124 strain, IM6/epoxy 701 classification 537
measuring 274,274 strength disadvantages 539
resins 440 moisture 811 Twist
Tows 164 thermoplastics 223 drill 600
bridging of 487 tensile strength, resins 1056 Kevlar 215-16
buckled 480 tension Two-dimensional
carbon fiber 292,293 Kevlar 212 flow, compression molding 584
cutting 483 test 688 lamina properties 760-1
definition 476 Treatments, Vectran 236 reinforcement 456
dropping and adding 4834 Triaxial, plain-weave 399 Typical
end locations 481 Triethylenetriamine (TETA), compression strength, carbon
folded 487 viscosity 54 fiber composites 1055
selecting 478 Triglycidyl p-aminophenol 53 properties 1053-8
thickness 478 Trimellitic anhydride (TMA), E-glass 1055
twisted 487 melting point 58 selecting 1057-8
wandering 487 Trimming 446 Tyranno 316
width Kevlar 600
histogram 479,479 2,4,6-Tris( dimethylaminomethy1)- UHMWPE 959,962
of material 479 phenyl 60 compression molding 545
Toxic 8 2 2 4 Trucks 912 reinforcement 963
definition 822 Truss structure, spacecraft 968-70 Ultimates, Kevlar 210
Toxicity TRW-R-8XX 94 Ultrahigh molecular weight
acute and chronic 823-4 chemistryof 81 polyethylene, see UHMWPE
fluorine 362 Tubes, testing 784 Ultrasonic
particulate fillers 252 Tubular structures 425-32 correlation 8434,844
reproductive 824 pultrusion 496-7 cutting 601
solvents 361,362 Tunnels 950 machining(USM) 6058
Trade names Turning 597,598,601 advantages 608
continuous fiber 162 advantages 597 applications 607-8
fibers 158 withAWJ 603-4 brittle materials 605
PAN-based tow 198 disadvantages 597 ceramic matrix composites
pitch-based tow 199 Kevlar 600 605
polyamide-imides 121 machining 602 disadvantages 608
polyarylene ether 121 repeatability 603 rates 608
polyester 121 surface finish 603-4 polar backscatter 843
polyimides 121 TWA 826 pulse-echo testing 842-3,842
polysulfones 121 Twaron resonance 843
staple 262 availability 219-20 signal 840
thermoplastics 124,225 decomposition temperature 206 tonoiseratio 834
1116 Index
through-transmission testing
840-2,841
automation 840
C - S C 841,841
~~
vibrations 607
Ultraviolet Coronagraph
Spectrometer, see UVCS
Ultraviolet resistance, PET 224
UMC 381
Uniaxial loading, allowable 802
Unidirectional
composites 107-8
compression testing 787
fabrics, weave 145,145
laminates 4,8
molding compound, see UMC
ply 741
tape, flexural strength 401
Uniformity 301,301,302
Unit costs, polymer processes 532
Unsaturated polyesters, resins 382
Unsaturation 39
Unsupported
films, adhesives 276
single lap, adhesive joints 628
Untapered, joints 624
Uranium enrichment centrifuges
953-4
Urea-formaldehyde, adhesives 255
Urethane board stock
ceofficient of thermal expansion
558
density 558
thermal conductivity 558
US Air Force Materials Laboratory
22-3
US Federal Aviation Regulations
(FAR) 1022
Use temperature, PET 225
uv
absorption, aramid fibers 221
radiation, carbon black 245
resistance, PET 230,233
stability
PBOfiber 238
PET 233
UVCS 1017-18,1018
V-cap 93
chemistryof 81
processing conditions 84-5
Vacuum
assisted resin injection, see VARI
assisted resin transfer molding,
see VARTM
bag 14,14
autoclave tooling 589
molding 361,577
nylon 577
pressure 918 pultrusion 495-6
processing 919-20 advantages 495
silicone rubber 577 tape wrapper 427,428
bagging 569,593,872-3 Viiyl cyclohexene dioxide, viscosity
applications, aerospace 375 63
with autoclave 593 Vinyl esters
bridging 369-71,369 applications 41-2
eliminating 369,370,371 corrosion resistance 41,42,42
edge bleeder 368 density 505
expendable 367-71 elongation at break 505
bags 371 flexural modulus 505
precautions 363 flexural strength 505
reusable 371-2 general purpose 40
thermoset composites 371 heat distortion 505
vertical bleeder 368 heat resistant 40-1
drying 818 marine applications 916
infiltration 299-300 properties 41-2
pressure resins 28,382,504
cures 870 structure 40
repairs 869 tensile modulus 505
Valves 954 tensile strength 505
Vapor Viscoelasticity 122
barriers 817 Viscosity 37
processing 316-17,316 aliphatic system 70
VAN 910 anhydride-cured system 72
VARTM 919 aromatic system 71
advantages 919 coupling agents 250
Vectran 234-7,234,235 definition 527
aerospace applications 236 elongational 529-30
applications 236-7 low density polyethylene 528
availability 236 polypropylene 530,531
cost of 234-5 predicting 528-9
dielectric constant 236 resins 440,578
elongation at break 235 RTM 440
forms 236 shear rate-dependent 528
melt spun 235 and temperature 173-4,174
melting temperature 235 vs. time, epoxy resins 509,510
properties 235-6 Visual inspection 839-40
protective garments 236 VLS 160
resin 235 timeneeded 160
safety materials 236 vMN-4
sources of information 236 bending strength 305
specific gravity 235 carbon content 306
tensile modulus 235 coating thickness 306
tensile strength 235 compressive strength 305
treatments 236 density 305,306
Veils 436,438 elastic modulus 305
surface ply 503 elongation at break 306
surfacing, application 436 filament diameter 306
Velocity, meteoroids 815 specific modulus 305
Velsicol 58 strand properties 306
Venetian blinding 482 tensile modulus 306
Vent design 442-3 tensile strength 305,306
Ventilation 830 Voids 430,548,588,630-1
volatiles 683 capture 450-1
Venting 450-1 content
ports 443 checks 430
Verification, design 733-4, 733 marine laminates 920
Vertical exposed surface 432
 Index 1117
stability map 588, 588 Weather resistant, resins 813 core plug 866
Volatiles Weathering 813 damage assessment 866
content 356 climate 813 elevated temperatures 868
elimination 78,79 graphite/epoxy 813 equipment 867
ventilation 683 graphite/polysulfone 813 face sheet 866-7
Volkersen Kevlar/epoxy 813 heat lamps 865,866
model 662-3 Weave heating blankets 865
solution 635 aramid fibers 222 hot air blowers 865
Volume basket 140,145 materials 867
expansion, water absorption 811 crowfoot satin 145,145 precured patching 867-8
fraction eight-hamess satin 145,145 procedures 866-7
fiber reinforcement 435 fiberglass 2414 repair environment 867
IM6/epoxy 699 non-woven 145,146 restoration of coatings 867
M401/F854 699 patterns 140,145,150 tooling 867
resistivity and mechanical properties tworesins 571
fiberglass 235 2 52 Wet mat molding 43
Skybond 95 plain 140,145 Wetout 443
Volumetric shrinkage biaxial 407 Wettability, fiber reinforcement 435
aliphatic system 70 plied-yam 252 Wetting agents, additives 516
aromatic system 72 shearing 439 Wetting speed 495
Von Mises criterion 708 single-yam 252 Whipple-type shield 814-15,814
Vortex, tennis rackets 1046 twill 145,145 Whiskers 160-1,308,308,308,314
Voyager aircraft 32, 32 unidirectional fabrics 145,145 alumina 161
Weavers 407,407 coating 166
Walleffects 153 Weaves commercially available 308
Warp 541 hybridized 128 composition 258
knitting 408,409 reinforcing 118 continuous 156,160
plied-yam 252 Weaving 18,402,402,4044,405, CTE 308
single-yam 252 406,407,801 density 262,308
yam 140 biaxial 406 description 262
fiberglass 141-4 plain weave 405 diameter 262,308
Warpage 374,467,557 satinweave 405 discontinuous 156,160-1
Warping twill weave 405 elastic modulus 162
GFRP 1013,1013 definition 404 length 308
polyoxymethylene 541 design methodology 407-8 manufacturers 258,262
Wash resistance, fiber reinforcement multiwarp 406 manufacturing processes 258
435 loom 405 for reinforcing 166
Wastage three-dimensional 405,405 Sic 308
cut-off 502 triaxial 405, 405,406 elastic modulus 327
pultrusion 489 two-hamess loom 405 fracture strength 325,326,
Water Web, yams 407,407 326,327
absorption 110,811 Weft, knitting 408,409 fracture toughness 325,326,
aliphatic system 70 Weibull distribution 189 326,327
aramid fibers 215 Weight silicon nitride 161
aromatic system 72 aramid fibers 223 specific strength 262
rate of relaxation 811 fiberglass 142-4 thermal expansion coefficient 262
recycled NBC 897 fraction 1027-8 trade names 258,262
recycled PET 894 loss vapor-liquid-solid process 160-1,
recycled SMC 890 AFR700B/S2 laminates 94 326
swelling stresses 811 PBOfiber 238 Young’s modulus 308
volume expansion 811 Skybond 86 Whole rings, bending 785
evacuation, aircraft 863 savings 1028,1028 Width of material 479
immersion 110 Weld Wind
ingestion, aircraft 859 lines 542,544 eye 461
intrusion, NDE 854 strength 544 tunnel blades 975-6,976
jet 602 Wet lay-up 355,571-3 turbine blades 954
resistance 3 composite tools 566 Winders
soluble sand mandrels 465-6 repairs lathe type 461
Weak bonds 671-5’671 aircraft 865-7 race-track 462
1118 Index

stationary whirling arm type 461 Silar 325 slippage 399

Winding Tateho 325 surface weave 407,407
angle 496-7 Work-around technique 1006,1012 textured 138
with braiding 473 Workmanship 715 twisted, geometry 404
chord 462 Woven warp 140
direction 496-7 fabric 359 web 407,407
dry 458 laminates 818 Z twist 138
extra pressure 470,470 flexural strength 401 Yield
geometry 459 reinforcements 91&17 fiberglass 139-40
helicalangle 460 Wrapping tapes 429 stress at break, PP/PCI-glass 898
history of 458 Wrinkles 487 Young’s modulus
inaccuracies 463 alumina composites 325
isotropic metallic tape 468 aluminasilicate 309
X-ray
layer-by-layer curing 470 carbon fibers 295
backscattering 8454,846,547
materials for 458-9 CE 108
imaging 844-9
non-geodesic 457 ceramic composites 312
cost advantages 845
pattern 459 ceramics 307
foreign materials 844
closure 459 E-glass 24
honeycomb defects 845
control 4 6 3 4 and microtexture 189
matrixcracks 844
pitch of 496-7 resins 440
moisture contamination 858
planar-polar 462 Silar 325
non-film 845
preform 458 Tateho 325
porosity 844
process 456,457 whiskers 308
XMC 381
programmed 469-70
pull 489,490 Z molding compound, see ZhtC
and pultrusion 496-7 Yams Z twist, yam 138
semifabricated composite 468 classification 402 Zero-shear viscosity, rotational
speeds 463 content, distribution 154 molding 552
stages 469 crimp 416 Zirconates, coupling agents 251
technology 458-66 cross sections 411 ZMC 380
theory of 468-9 designation, fiberglass 23940 flexural modulus 386,386
thermoplastics 458 distribution 154 flexural strength 386,386
of a torus 462 filament 164 formulation 384
wet 458 fill 407,407 injection machine 380
Windmills 521 filling 140 IZOD 386,386
Wood 256,838,958 geometry 4034,403 low viscosity 380
durability 256 identification 138-9 specific gravity expansion 386,
end-grain balsa 256 inclination angle 407 386
low Cost of 256 jamming 412 tensile modulus 386,386
rehabilitation 988 longitudinal 415 tensile strength 386,386
Work of fracture orientation angle 412 thermal coefficient 386,386
alumina composites 325 Stwist 138 Zonyl 251