Professional Documents
Culture Documents
FIBERGLASS Handbook of Composites - S. T. Peters PDF
FIBERGLASS Handbook of Composites - S. T. Peters PDF
COMPOSITES
SECOND EDITION
Edited by
S.T.Peters
Process Research, Mountain View, Calfornia, USA
A catalogue record for this book is available from the British Library
CONTRIBUTORS
S.T. Peters was previously a fellow engineer He is a private consultant with worldwide
with Westinghouse Electric Corporation, clients and has presented tutorials on compos-
Marine Division prior to devoting full time to ites to many audiences, including the US
composite and materials and processing con- Navy and NASA, several technical societies
sulting for his own company, Process and two universities. He is a licensed profes-
Research, in Mountain View, CA. He has writ- sional engineer in the state of California, a
ten many articles on composites and filament member of ASM, and the composites division
winding, a book on filament winding, edited of SME and has been elected a fellow of
one previous book and holds several patents SAMPE.
on winding techniques and composite joints.
ACKNOWLEDGEMENTS
As with any large undertaking there is a sup- approach to resolving problems. Thanks also
porting group of people without whose help go to Mr Frank Heil and Dr Alvin Nakagawa
the objective would not be met. I wish to of Westinghouse Electric, Marine Division
acknowledge my wife, Lynn, for her help in (now Norton Grumman) for their editorial
deciphering and rewriting some of the articles and review help. I also wish to thank Dr Linda
and for enduing my sometimes uncivil Clements for her advice and support.
CONTENTS
Contributors ix
Preface xv
Foreword xvii
Acknowledgements xviii
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
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
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;
FOREWORD
Composites have emerged as a valuable class and is one of the prime drivers for ‘concurrent
of engineering materials because they offer engineering’. The needs of concurrent engi-
many attributes not attainable with other neering require all contributors to a successful
materials. Light weight, coupled with high composite structure design to have some
stiffness, and selectable properties have fos- knowledge of composites. It is hoped that this
tered their use for many years in satellites, handbook will facilitate the acquisition of that
high performance aircraft and world class sail- knowledge.
boats as well as submarines. Now, these There is little change in scope or objectives
materials demonstrate their worth in the mun- from the first edition, but many changes in
dane, but equally as demanding, consumer, content. Organic matrix composites are still
infrastructure, and sporting goods arenas. highlighted and a limited treatment of metal
However, the transition to many of these con- matrix, carbon and ceramic matrix compos-
sumer and infrastructure-related arenas has ites, as well as treatment of the new polymers,
been slow, primarily due to the lack of under- including the thermoplastic materials have
standing, the lack of validated data, absence of been added.
design allowables, lack of clear guidelines, The treatment of processing methods has
limited hands-on experience, low confidence been expanded for reader convenience, dou-
and less than optimum supplier data sheets. It bling the previous number of chapters. The
is hoped that this book, crafted by well known structural efficiency of a composite structure is
contributors, pre-eminent in their field, mem- often determined by its joints, not by its basic
bers of international universities, industrial structure. Thus, an extensive treatment of
research organizations, and government labs composite surface treatment, mechanical fas-
will remedy some of these weak areas and that tening, and adhesive bonding, which continue
this edition will continue as the primary refer- to be important, sometimes vexing areas of
ence in the composites field and as basic a text concern in composite structure fabrication,
for educational uses as was the first edition. have been added.
The editor of the first edition, George The analysis section has been expanded
Lubin, was a valued mentor to many, includ- with chapters dealing with laminate design,
ing the present editor. This book carries on the composite structure design and a new, impor-
legacy he started: that of a compact but thor- tant subject, design allowables substantiation.
ough sourcebook, with validated, useful data There are new chapters on repair, safety and
to increase understanding, incorporating reuse of composites as well as chapters on the
application guidelines, fabrication methods applications of composites to medical, con-
and tradeoffs, basic polymer information and struction and sporting goods uses that reflect
design recommendations. The successful, current concerns and important new uses for
cost-effective fabrication of composite struc- composite materials.
tures requires utmost cooperation between the
S.T. Peters
various design and manufacturing specialties
INTRODUCTION, COMPOSITE BASICS AND
ROAD MAP*
S.T. Peters
This is an introduction to composites and will metallic, ceramic or carbon. When the fiber
encourage the reader to obtain more informa- and the matrix are joined to form a composite
tion. Only the basic concepts will be covered they retain their individual identities and both
here; reference will be made to the chapters in directly influence the composite’s final proper-
the book that expand or follow up and elabo- ties. The resulting composite will generally be
rate on these basics. The reader will see that composed of layers (laminae) of the fibers and
the subjects of this book cover the spectrum of matrix stacked to achieve the desired proper-
composites and range from the basic and sim- ties in one or more directions.
ple to the complex. Thus, there are The high strength or stiffness to weight
complicated equations because they are the ratios of advanced composites are well known,
tools that are used every day to describe real but there are other advantages also (Table 1.1).
structures; and there will also be the more gen- These advantages translate not only into air-
eral, less complicated approaches that are craft, but into everyday activities, such as
limited in analysis power. These chapters have longer drives with a graphite-shafted golf club
been developed by the most knowledgeable (because more of the mass is concentrated at
composite professionals in the world; a blend the clubhead) or less fatigue and pain because
of academicians and the engineers who fabri- a graphite composite tennis racquet has mher-
cate real composite structures. ent damping. Generally, the advantages accrue
Modern structural composites, frequently for any fiber/composite combination and dis-
referred to as ’Advanced Composites’, are a advantages are more obvious with some. These
blend of two or more components, one of advantages have now resulted in many more
which is made up of stiff, long fibers, and the reasons for composite use as shown in Table
other, a binder or ’matrix’ which holds the 1.2. Proper design and material selection can
fibers in place. The fibers are strong and stiff circumvent many of the disadvantages.
relative to the matrix and are generally
orthotropic (having different properties in two 1.1 MATERIAL SYSTEMS
different directions). The fiber, for advanced
structural composites, is long, with length to An advanced composite laminate can be tai-
diameter ratios of over 100. The fiber’s lored so that the directional dependence of
strength and stiffness are usually much strength and stiffness matches that of the load-
greater, perhaps several times more, than the ing environment. To do that, layers of
matrix material. The matrix material can by unidirectional material called laminae are ori-
polymeric (e.g. polyester resins, epoxies),
* This chapter has been adapted from S.T. Peters, in
Handbook of Plastics Elastomers and Composites, 3rd edn, (ed.
Handbook of Composites. Edited by S.T. Peters. Published C.A. Harper). McGraw-Hill, New York, 1996, and is used
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7 with permission of the McGraw-Hill companies.
2 Introduction, composite basics and road map
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
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 1.2 MATRIX SYSTEMS
in personal protective armor. In spite of the If parallel and continuous fibers are combined
drawbacks, production of both of these fibers with a suitable matrix and cured properly, uni-
is enjoying strong worldwide growth. directional composite properties such as those
Boron fibers (Chapter 8), the first advanced shown on Table 1.3 are the result.
composite fibers to be used on production The functions and requirements of the
aircraft, are produced as individual mono- matrix are to:
filaments upon a tungsten or carbon substrate
by pyrolytic reduction of boron trichloride 0 keep the fibers in place in the structure;
(BC1,) in a sealed glass chamber. The relatively 0 help to distribute or transfer loads;
large cross section fiber is used today primar- 0 protect the filaments, both in the structure
ily in metal matrix composites which are and before and during fabrication;
processed at temperatures which would attack 0 control the electrical and chemical proper-
carbon/graphite fibers. ties of the composite;
0 carry interlaminar shear.
Table 1.3 Properties of typical unidirectional graphite/epoxy composites (Fiber volume fraction, V , = 0.62)
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
Matrix systems 5
The needs, or desired properties of the composite. The common thermoset matrices
matrix, that depend on the purpose of the struc- for composites include the following:
ture are:
0 polyester and vinylesters (Chapter 2);
0 minimize moisture absorption; 0 epoxy (Chapter 3);
0 have low shrinkage; 0 bismaleimide (BMI) (Chapter 4);
0 Must wet and bond to fiber; 0 polyimide (Chapter 4);
0 low coefficient of thermal expansion; cyanate ester and phenolic triazine
0 must flow to penetrate the fiber bundles (Chapter 5).
completely and eliminate voids during the
Each of the resin systems has some drawbacks,
compacting/curing process;
which must be accounted for in design and
have reasonable strength, modulus and
manufacturing plans.
elongation (elongation should be greater
Polyester matrices have been in use for the
than fiber);
longest period, and are used in the widest
0 must be elastic to transfer load to fibers;
range and greatest number of structures. The
0 have strength at elevated temperature
usable polymers may contain up to 50% by
(depending on application);
weight of unsaturated monomers and solvents
0 have low temperature capability (depend-
such as styrene. Polyesters cure via a catalyst
ing on application);
(usually a peroxide) resulting in an exothermic
0 have excellent chemical resistance (depend-
reaction, which can be initiated at room tem-
ing on application);
perature.
0 be easily processable into the final compos-
The most widely used matrices for
ite shape;
advanced composites have been the epoxy
0 have dimensional stability (maintain its
resins. These resins cost more than polyesters
shape).
and do not have the high temperature capabil-
There are many matrix choices available; each ity of the bismaleimides or polyimides, but
type has impact o n the processing technique, because of the advantages shown in Table 1.4
physical and mechanical properties and envi- they are widely used.
ronmental resistance of the finished
Advantages Disadvantages
Adhesion to fibers and to resin Resins and curatives somewhat toxic in uncured form
No by-products formed during cure Absorb moisture
Low shrinkage during cure Heat distortion point lowered by moisture absorption
High or low strength and flexibility Change in dimensions and physical properties
due to moisture absorption
Solvent and chemical resistance Limited to about 200°C upper temperature use (dry)
Resistance to creep and fatigue Difficult to combine toughness and high
temperature resistance
Solid or liquid resins in uncured state High thermal coefficient of expansion
Wide range of curative options High degree of smoke liberation in a fire
Adjustable curing rate May be sensitive to ultraviolet light degradation
Good electrical properties Slow curing
6 Introduction, composite basics and road map
There are two resin systems in common use radiation under cryogenic conditions was a
for higher temperatures, bismaleimides and prime cause for their choice for use in the
polyimides. New designs for aircraft demand superconducting supercollider, subsequently
a 177°C (350°F) operating temperature not met canceled by the US Congress.
by the other common structural resin systems. Polyimides are the highest temperature
The primary bismaleimide in use is based on polymer in general advanced composite use
the reaction product from methylene dianiline with a long term upper temperature limit of
(MDA) and maleic anhydride: bis (4-maleimi- 232°C (450°F) or 316°C (600°F). Two general
dophenyl) methane (MDA BMI). types are: condensation polyimides, that
Two newer resin systems have been devel- release water during the curing reaction, and
oped and have found applications in widely addition type polyimides with somewhat eas-
diverse areas. The cyanate ester resins, mar- ier process requirements.
keted by Ciba-Geigy, have shown superior
dielectric properties and much lower moisture
1.3 FIBER MATRIX SYSTEMS
absorption than any other structural resin for
composites. The dielectric properties have The end user sees a composite structure.
enabled their use as adhesives in multilayer Someone else, probably a prepregger, com-
microwave printed circuit boards, and the low bined the fiber and the resin system and
moisture absorbance have caused them to be someone else caused the cure and compaction
the resin of universal choice for structurally- to result in a laminated structure. A schematic
stable spacecraft components. of the steps to arrive at a finished composite
The phenolic triazine (PT) resins also have from the initial fiber is shown in Fig. 1.1.
superior elevated temperature properties, In many cases, the end user of the structure
along with excellent properties at cryogenic has fabricated the composite from prepreg,
temperatures. Their resistance to proton which is a low-temperature-stable combination
ROVING WEAUE?
N?
COLLIMRTE
UNI TRPE
of the resin, its curing agents and the fiber. The The prepreg process for thermoset matrices
three types of continuous fibers, roving, tape can be accomplished by feeding the fiber con-
and woven fabric available as prepregs give tinuous tape, woven fabric or roving through a
the end user many options in terms of design resin-rich solvent solution and then removing
and manufacture of a composite structure. the solvent by hot tower drying. The excess
Although the use of dry fibers and impregna- resin is removed via a doctor blade or meter-
tion at the work (i.e. filament winding, ing rolls and then the product is staged to the
pultrusion or hand lay-up) is very advanta- cold-stable prepreg form, (B stage) (Fig. 1.2).
geous in terms of costs; there are many The newer hot melt procedure for prepregs
advantages to the use of prepregs as shown in is gradually replacing the solvent method
Table 1.5, particularly for the manufacture of because of environmental concerns. A film of
modem composites. resin that has been cast hot onto release paper
Table 1.5 Advantages of prepregs over wet impregnation
Release
Poly
Unwind
Prepreg
Wind
Fig. 1.2 Schematic of typical solvent prepregging process. (Adapted from Reference 2.)
8 Introduction, composite basics and road map
0 0
Pauer
Paper
T
Doctor
Plate 1
Impregnation
Zone Take-up
Creel Paper Prepreg
Windup
Chill
Plate 2 Plate
Fig. 1.3 Schematic of typical film impregnating process. (Adapted from Reference 2.)
1.4 PLY ORIENTATIONS, SYMMETRY AND lined to indicate that half of it lies on either
BALANCE side of the plane of symmetry (Fig. 1.4(f)).
1.4.1 PLY ORIENTATIONS
1.4.2 SYMMETRY
One of the advantages of using a modern com-
posite is the potential to orient the fibers to The geometric midplane is the reference sur-
respond the load requirements. This means face for determining if a laminate is
that the composite designer must show the symmetrical. In general, to reduce out-of-
material, the fiber orientations in each ply, and plane strains, coupled bending and stretching
how the plies are arranged (ply stackup). of the laminate and complexity of analysis,
A 'shorthand' code for ply fiber orientations symmetric laminates should be used.
has been adapted for use in layouts and studies. However, some composite structures (e.g. fila-
Each ply (lamina)is shown by a number rep- ment wound pressure vessels) can achieve
resenting the direction of the fibers in degrees, geometric symmetry so that symmetry
with respect to a reference ( x ) axis. 0" fibers of through a single laminate wall is not neces-
both tape and fabric are normally aligned with sary, if it constrains manufacture. To construct
the largest axial load (axis) (Fig. 1.4(a)). a midplane symmetric laminate, for each layer
Individual adjacent plies are separated by a above the midplane there must exist an identi-
slash in the code if their angles are different cal layer (same thickness, material properties,
(Fig. 1.4@)). and angular orientation) below the midplane
The plies are listed in sequence, from one (Fig. 1.4(e)).
laminate face to the other, starting with the ply
first on the tool and indicated by the code
1.4.3 BALANCE
arrow with brackets indicating the beginning
and end of the code. All laminates should be balanced to achieve in-
Adjacent plies of the same angle of orienta- plane orthotropic behavior. To achieve balance,
tion are shown by a numerical subscript (Fig. for every layer centered at some positive angle
1.4(c)). +e there must exist an identical layer oriented
When tape plies are oriented at angles equal at -8 with the same thickness and material
in magnitude but opposite in sign, (+) and (-) properties. If the laminate contains only 0"
are used. Each (+) or (-) sign represents one and/or 90" layers it satisfies the requirements
ply. A numerical subscript is used only when for balance. Laminates may be midplane s p -
there are repeating angles of the same sign. metic but not balanced and vice versa. Figure
Positive and negative angles should be consis- 1.4(e) is symmetric and balanced whereas Fig.
tent with the coordinate system chosen. An 1.4(g)is balanced but unsymmetric .
orientation shown as positive in one right
handed coordinate system may be negative in
1.5 QUASI-ISOTROPICLAMINATE
another. If the y and z axis directions are
reversed, the f 45 plies are reversed (Fig. 1.4(d)). The goal of composite design is to achieve the
Symmetric laminates with an even number lightest, most efficient structure by aligning
of plies are listed in sequence, stating at one most of the fibers in the direction of the load.
face and stopping at the midpoint. A subscript Many times there is a need, however, to pro-
'S' following the bracket indicates only one duce a composite which has some isotropic
half of the code is shown (Fig. 1.4(e)). properties, similar to metal, because of multi-
Symmetric laminates with an odd number ple or undefined load paths. A 'quasi-isotropic'
of plies are coded as a symmetric laminate laminate lay-up accomplishes this for the x and
except that the center ply, listed last, is over- 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 \ \
[0/903/0]
T
[0/90/*45]s
P I
Typical Callout
90"
+45"
-45"
-45"
+45"
Line of Symmetry
90"
V I
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"
j 0",90" I h)
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.
E x = 76 GPa
a x = 4.98peK
r a2 >ay
Table 1.6 shows mechanical values for sev- 1.7 COMPOSITE FABRICATION TECHNIQUES
eral composite laminates with the fiber of
The goals of the composite manufacturing
Table 1.3 and a typical resin system. The first
process are to:
and second entries are for simple 0/90 lami-
nates and show the effect of changing the 0 achieve a consistent product by controlling
position of the plies. The effect of increasing - fiber thickness;
the number of 0 plies is shown next and the - fiber volume;
The tool face is commonly the surface the introduction of elastomeric tooling
imparted to the outer surface of the composite wherein the thermal expansion of an elas-
and must be smooth, particularly for aerody- tomer provides some or all of the pressure
namic surfaces. The other surface frequently curing cure, or a rubber blanket is used as a
may be of lower finish quality and is imparted reusable vacuum bag. The volumetric expan-
by the disposable or reusable vacuum bag. This sion of an elastomer can be used to fill a cavity
surface can be improved by the use of a sup- between the uncured composite and an outer
plemental metal tool known as a caul plate. mold. The use of elastomeric tooling can pro-
(Press curing, resin transfer molding, injection vide the means for fabricating complex
molding and pultrusion require a fully closed box-like structures such as integrally stiffened
or two sided mold). Figure I. 6 shows the basic skins with a co-cured substructure in a single
components of the tooling for vacuum bag or curing operation.
autoclave processed components and Table 1.7 Tooling (Chapter 25) and the configuration
shows the function of each part of the system. of the reinforcement have a great influence on
Tooling options have been augmented by the curing process selected and vice-versa. The
2 3 4 5 6 7 8 9
12 13 14 9 10 11
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
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
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-
1.7.2 RESIN TRANSFER MOLDING
cent bands or in repeating bands that are
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-
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).
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.
Design of composites 19
1.9.1 LAMINATE DESIGN loads. This improves handling character-
RECOMMENDATIONS istics, and serves to prevent large matrix
1. Take advantage of the orthotropic nature of cracks from forming.
the fiber composite ply. Locally reinforce with fabric or mat in
0 To carry in-plane tensile or compressive
areas of concentrated loading. (This tech-
loads align the fibers in the directions of nique is used to locally reinforce pressure
these loads. vessel domes).
0 For in-plane shear loads, align most
0 Use fabric, particularly fiberglass or
fibers at -c 45" to these shear loads. Kevlar, as a surface ply to restrict surface
0 For combined normal and shear in-plane
(handling) damage.
loading provide multiple or intermediate Ensure that the laminate has sufficient
ply angles for a combined load capabil- fiber orientations to avoid dependence
ity. on the matrix for stability. A minimum
coverage of 6 to 10% of total thickness in
2. Intersperse the ply orientations. 0, ?45", 90" directions is recommended.
0 If a design requires a laminate with 16
plies at *45", 16 plies at 0", and 16 plies at 3. Select the lay-up to avoid mismatch of
90°, use the interspersed design (90,/ -c properties of the laminate with those of the
45,/0,),s rather than (90,/ .+ 45,/10,)s. adjoining structures - or provide a
Concentrating plies at nearly the same shear/separator ply.
angle (0" and 90" in the above example) Poisson's ratio: if the transverse strain of
provides the opportunity for large a laminate greatly differs from that of
matrix cracks to form. These produce adjoining structure, large interlaminar
lower laminate allowables, probably stresses are produced under load.
because large cracks are more injurious Coefficient of thermal expansion: tem-
to the fibers, and more readily form perature change can produce large
delaminations than the finer cracks interlaminar stresses if coefficient of ther-
occurring in interspersed laminates. mal expansion of the laminate differs
0 If a design requires all 0" plies, some 90"
greatly from that of adjoining structure.
0 The ply layer adjacent to most bonded
plies (and perhaps some off-angle plies )
should be interspersed in the laminate to joints should not be perpendicular to the
provide some biaxial strength and stabil- direction of loading. Thicken the com-
ity and to accommodate unplanned posite in the joint area, soften the
composite by adding fiberglass or angle
plies and select the highest strain-capa-
Composite bility adhesive.
Material
4. Use multiple ply angles.
Typical composite laminates are constructed
Environmental
Considerations from multiple unidirectional or fabric layers
which are positioned at angular orientations
in a specified stacking sequence. From many
Component 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
Fig. 1.9 Design considerations for composites. 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)
OVERVIEW OF COMPOSITE MATERIALS 1
Theodore J. Reinhart
\
'
MAT -===I:----- PULTRUSION COMPRESSION MOLDING
INJECTION MOLDING
THERMOPLASTIC
PARTICULATE *TRANSFER MOLDING
THERMOSTAMPING
call from the using communities for structural presently decreasing, and the commercial air-
materials that could reduce weight and reduce plane producers, specifically Boeing and
corrosion and fatigue problems in aircraft com- Aerospaciale, will continue to be a market for
ponents. Fiberglass reinforced resin base advanced composites. Large scale applications
composites have been used successfully in fila- in transportation, both air and ground, and in
ment wound rocket motor cases as well as in the civil engineering infrastructure arena are
various other aircraft and missile applications. and will continue to be an unrealized goal for
Fiberglass reinforced composites in general advanced composite materials at least in the
lacked the stiffness that is desired in h g h per- near term.
formance structural applications in aircraft, Fibers are inherently stronger than the bulk
missiles and spacecraft. The search for higher form of a material for a number of reasons.
modulus glass fibers met with only limited suc- Two major reasons are (i) the fiber’s small
cess, however the use of boron, carbon, diameter with the probability of fewer flaws
graphite and other compositions resulted in a and (ii) the opportunity to align or preferen-
technological breakthrough and provided a tially orient molecular or crystal structure. All
new class of structural materials called structural materials fail mechanically because
’Advanced Composites’. More recent develop- of the formation, propagation and growth of
ments have led to the commercialavailability of flaws. Since composite construction provides
a wide range of high strength, high stiffness very large numbers of load-carrying fibers,
fiber materials, both organic and inorganic in catastrophic failure requires the failure of
nature, for use in high performance composite many fibers. This situation then provides
applications. many early warning signs when significant
Advanced composite materials, while basi- damage is accumulating in a fiber-reinforced
cally more expensive as a raw material, more composite structure.
expensive and complicated to design with, Fibrous materials such S-glass, (Kevlar 49)
more difficult to characterize, more expensive aramid, Spectra, boron and the many types of
to manufacture and assemble and more diffi- carbon fibers produced commercially possess
cult to inspect when compared to conventional specific properties (strength/density) and
structural metallic materials, have found sig- (modulus/density) many times greater than
nificant commercial, recreational, and military structural alloys of aluminum, titanium or steel.
applications. However, when the fibers are combined with a
Inexpensive fiberglass reinforced plastic matrix into a near quasi-isotropic lay-up, a
composites, initially put to broad use in the highly useful engineering form of the material,
1950s, are found in a variety of industrial and the specific properties are greatly reduced but
consumer products from automotive and are still superior compared to conventional
truck applications, to corrosion resistant pip- homogeneous metallic materials. Figure 1.1
ing and construction, to large and small water plots the specific tensile strength versus the
craft. The service performance of these materi- specific tensile modulus for a number of unidi-
als in the above and many other applications rectional composites and compares them to
has been highly satisfactory. steel, aluminum and titanium materials. These
Advanced composites have found exten- are calculated values based upon literature
sive applications in many areas where cost is fiber values and 65 vol.% fiber content. It can
secondary to performance. Sporting and recre- readily be seen that these high performance
ational applications including golf club shafts, fiber materials form the basis for the advanced
fishing rods, and skis, have provided a signifi- composites technology. The wide variety of
cant market and will continue to do so for the materials that can be combined to form com-
foreseeable future. Military applications, while posites having highly acceptable levels of
24 Overview of composite materials
engineering properties can make the selection certain threshold stress levels. The phenome-
of specific materials a challenging task. non known as stress-rupture failure has been
This introduction will present the basic thoroughly investigated by researchers in the
materials, design factors, material forms and industry and government.
fabrication methods used in the manufacture The glass fiber that is the industry standard
and assembly of advanced composite compo- is E-glass, which is a calcium aluminoborosili-
nents. cate formulation having very good mechanical
and electrical characteristics at very reason-
able cost. Average mechanical property levels
1.2 GLASS FIBERS
for individual filaments are 3450 MPa (500 ksi)
The development of glass fibers on a commer- for tensile strength and 72.4 GPa (10.5 x lo6psi)
cial scale was the enabling technology that for Young’s modulus. Extensive research has
allowed the glass fiber-reinforced organic been conducted to develop glass fibers pos-
resin matrix composite industry to begin. The sessing higher strength and stiffness
initial understanding of organic matrix com- characteristics.
posites was based on glass fiber reinforcement. Glass formulations producing filaments of
Glass fiber composites of all descriptions increased strength and stiffness have been
have found extensive and successful applica- found to be toxic (beryllium glasses) or very
tions including low performance non-structural high melting and difficult to handle in com-
applications as well as high performance struc- mercial scale equipment. S-glass fibers contain
tural applications. The applications range from a higher percentage of alumina compared to
the building construction trades, to auto, truck E-glass. Filament strength, modulus and melt-
and rail transportation, seagoing applications ing point are higher than E-glass. Typical
including high performance racing craft and filament strength and stiffness are close to
commercial and military aerospace. Specific 4600 MPa (670 ksi) and 85.5 GPa (12.4 x lo6psi).
applications involve, decorative panels, appli- The technology developed using glass
ances, ship and boat hulls, light aircraft and fiber-reinforced resin matrix composites
glider construction, nearly all forms of recre- resulted in many high performance applica-
ational equipment, high pressure gas tions, and was the start of the effort to develop
containers and rocket motor casings. This wide stronger and stiffer fibers to meet high perfor-
spread use of glass fiber-reinforced organic mance structural needs in commercial and
composites and their continued future growth military aerospace applications. Figure 1.3
is due to many factors, including: cost, avail- shows the installation of a large commercial
ability, handling and processing ability, useful fiberglass composite pipe.
properties and characteristics and past good Closely related to the E- and S-glasses are the
experience in service. Many improvements to high silica and quartz fibers produced commer-
glass fiber composites have been made over the cially for highly specialized applications in
years including the development of hghly ben- rocket motors and electrical windows. High sil-
eficial silane coupling agents. These agents, ica fibers are produced by chemically leaching
which can be tailored for compatibility with the highly soluble components from E-glass
almost any resin matrix, provide a higher level fibers and then consolidating the fibers by a
of engineering properties and environmental heat treatment. These fibers contain upwards of
durability far exceeding earlier composites. 95% silica.
Glass fiber composites provide high levels of Quartz fibers are drawn from mineral
engineering properties, however the glass fiber quartz rods using oxy-hydrogen or laser heat-
surface is sensitive to moisture attack under ing sources. Commercially available fibers are
certain conditions of exposure and above 99.95% silica. Quartz fibers typically have
Carbon/graphitefibers 25
< -
4
similar mechanical properties as the E-glass organic precursor fibers such as rayon or poly-
materials but have a much higher melting point. acrylonitrile (PAN). The process, shown in
Fig. 1.4, involves highly controlled steps
including heat treatment and tension, to trans-
1.3 CARBON/GRAPHITE FIBERS form the organic precursor into a highly
The search for advanced fibers led to the ordered carbon or graphitic structure. Carbon
development of carbon and graphite fibers. and graphite fibers are also produced from
These fibers are currently the best known and pitch base precursor materials. Although the
most widely utilized in high performance potential for low cost exists, complex process-
resin base composites. Primarily developed ing steps involved in the pitch treatment have
for military aerospace applications, these prevented the production of really low cost
materials have found wide-spread commer- fibers. US manufactured pitch base carbon and
cial and industrial applications. This situation graphite fibers while having a very high mod-
has resulted in the availability of a wide vari- ulus, up to 830GPa (120 x 106psi), have
ety of fibers having various levels of
engineering properties at costs once thought
unachievable. These materials are now avail-
able on a world wide basis at competitive
prices and are now experiencing increasing
levels of interest for applications such as com-
mercial aerospace, ground transportation and
the infrastructure.
The production of carbon/graphite fibers is
well suited to large scale continuous operation
where economies of scale operate effectively
and the stability of operating conditions pro-
vides a narrow band of fiber mechanical
properties. Carbon fibers are produced com- Fig. 1.4 Conceptualized production process for car-
mercially by the thermal decomposition of bon fiber manufacture.
26 Overview of composite materials
demonstrated low tensile properties and thus applications in high performance structural
have not been seriously considered for high applications.
performance structural applications. The high tensile strength and low density of
Advances in PAN precursor carbon fiber aramid fibers allowed applications in filament
technology have resulted in cost reductions wound pressure vessels and rocket motor
and properties increases which have improved cases replacing S-glass. Combined with its
the status of these materials in high perfor- lower density and high levels of properties,
mance structural applications. PAN base very lightweight structures resulted. Aramid
carbon fibers are now commercially available fibers are highly damage- and cut-resistant
having modulus values of 280450 GPa and provide high levels of damage tolerance
(40-65 x lo6psi) and tensile strengths of to composite components. Other applications
4140-5170 MPa (600-750 h i ) and some versions involved aramid usage in lightly loaded sec-
up to 6890 MPa (1000 ksi) in tensile strength. ondary structures on commercial aircraft and
High fiber elongation has long been considered helicopters, reducing structural weight com-
a very desirable trait. Elongations of 2% and pared to glass composites. Issues in the use of
above are highly desirable and provide tough- these fibers have involved moisture absorp-
ness in the composite that low elongation tion by the fiber, relatively low adhesion to
fibers (<l.8%) cannot provide. Since high most resin matrix materials, low compression
strain fibers must be coupled with a tough properties and difficult machining compared
matrix resin the availability of these fibers has to other composites.
stimulated the introduction of new formula-
tions of high elongation resin matrix materials.
1.4.2 OTHER ORGANIC FIBERS
In many instances in aerospace applications,
compression is the design controlling factor. Continuing research into the various other
The new high strength, high modulus carbon rigid rod molecule fiber forming polymers
fibers have smaller diameters thus requiring including the spinning of polyethylene fibers
higher levels of support from the resin under by Allied Chemical Co. and others has
compression loading. Thus, the limiting factor resulted in high performance organic fibers
becomes resin shear modulus and the newer that are finding specialized and general com-
fibers have not resulted in increased levels of mercial applications. Spectra fiber, a high
compression strength in the composite. performance product spun from polyethylene
offers high abrasion resistance, high strength,
and high modulus at a very low density. This
1.4 ORGANIC FIBERS
material has found use in combat equipment
for both ground troops and aviators.
1.4.1 ARAMID
Recreational uses of this material include ship
Aramid is a generic term for the class of aro- sails and lines. Applications of Spectra are lim-
matic-polyamide fibers produced using ited to temperatures of about 120°C (250°F)
para-phenylene terephthalamide. These mate- due to its low crystallite melting point.
rials were introduced by E.I. DuPont de
Nemours & Co., Inc. in the 1960s. Competing
1.4.3 PBO AND PBT FIBERS
fibers are now produced in Europe and Asia.
Although organic polymer fibers can be pro- High modulus high strength organic fibers
duced that have fiber tensile strength and have been prepared by the Air Force Materials
modulus values approaching the mid-range Laboratory from the rigid rod molecules of
carbon fibers, low fiber compression capabili- poly (p-phenylene benzobisoxazole) (PBO)
ties have limited organic fiber composites and poly (p-phenylene benzobisthiazole)
Other inorganicfibers 27
(PBT). These rigid rod polymers yield high technology, carbon-epoxy composites still
modulus fibers due to their high degree of cannot compare in compression properties to
aromaticity, high planarity, and linearity in those of boron-epoxy.
the chain. These polymers in general are diffi- Boron-epoxy composites have been used in
cult to process into fiber due to their the sporting goods industry and boron fibers
infusability and insolubility in anything have been used in metal matrix composites
except the most powerful organic solvents (MMC) because of their excellent mechanical
such as methanesulfonic acid or concentrated properties, thermal stability, and reduced reac-
phosphoric acid. tivity with the matrix (compared to carbon
The h g h axial molecular orientation whch fibers). In order to prevent reaction between
leads to extreme anisotropy of mechanical the boron fiber and the molten metal matrix
properties is a distinctive feature of rigid rod during MMC production, boron fibers were,
molecule fibers. While tensile strength and until recently, available with silicon carbide or
modulus may in some instances be competitive boron carbide coatings that acted as diffusion
with carbon fibers the transverse properties of barriers. Boron fibers with these coatings are
the fiber are less than 20% of the axial proper- no longer commercially available because sili-
ties. In tension the axial characteristics con carbide fibers are now replacing boron in
dominate and excellent properties are achieved. metal matrix composites.
In compression and flexure the low transverse Boron fibers are produced as a rather large
properties result in low mechanical properties monofilament fiber or 'wire' (100-200 pm or
in composites of PBO and PBT fibers. 4-8 mils) by chemical vapor deposition (CVD)
High modulus organic fibers have not of boron onto a tungsten or pyrolyzed carbon
found serious applications in structural com- substrate. The resulting fibers have excellent
posites due to their poor compressive strength (3450 MPa or 500 ksi) and stiffness
performance and relatively high cost. (400GPa or 58 x 106psi)).However, because
both the precursor gases and the manufactur-
ing process are inherently expensive, boron
1.5 BORON FIBERS fibers cannot compete with carbon fibers on
Boron fiber in organic resin matrices was ini- the basis of cost.
tially developed by the Air Force Materials
Laboratory in the early 1960s and became the
1.6 OTHER INORGANIC FIBERS
first high performance reinforcement for use
in structural composite materials. Early appli- Continuous filament forms of other inorganic
cation of these fibers was found on the US Air fibers are also now commercially available.
Force F-15 and the US Navy F-14 fighter air- Silicon carbide (Sic) fiber is produced from
craft. Boron composites in honeycomb CVD of Sic by a method similar to that used in
structure were utilized in the empennage boron fiber production. Sic fibers are also pro-
structure of these aircraft. Subsequent studies duced from an organic borosilane precursor
have found that carbon-epoxy composites that is spun and pyrolyzed to produce silicon
could be utilized in these aircraft to reduce carbide. Aluminum oxide fibers are produced
costs of the composite structure. Considering in both the mono and polycrystalline forms.
the enormous changeover costs involved in Advanced forms of ceramic fibers are now
such a project and the limited production under intensive development for use in metal
quantities of these aircraft remaining to be matrix composites for high temperature tur-
produced it has been determined that return bine engine applications.
on investment costs would not be achieved. In
spite of the advances made in carbon fiber
28 Overview of composite materials
offer better mechanical properties. Even though No degradation of the composite materials
the elongation to failure of most cured epoxies has been observed even after over 20 years of
is relatively low, epoxies provide an attractive service exposure. The moisture absorption of
combination of handling characteristics, pro- epoxy resins causes a decrease in the glass tran-
cessing flexibility, composite mechanical sition temperature (Tg) of the material and
properties, ease of manufacture, and acceptable limits (for conservative engineering practice)
cost. Recent developments include modified epoxy resins to use at temperatures not exceed-
epoxy resin formulations that have improved ing the wet T of the cured material. While this
elongation capabilities. In addition, a substan- use limitatio$is conservative, its imposition has
tial data base exists for epoxy resins since both generally avoided unwanted service experience
the US Air Force and the US Navy have been problems. Figure 1.7 shows the range of com-
flying aircraft with epoxy matrix structural posite applications on the C-5 cargo aircraft.
components since 1972, and the in-service expe-
rience with these components has been very
1.9 CYANATE RESINS
satisfactory. Figures. 1.5 and 1.6 show epoxy
composite applications on the AV-8B horizontal The more recent commercial availability of
stabilizer and forward fuselage. cyanate resins from a number of commercial
A L u no I r
rF- r i (c -71
e-\ TE STRUCTUR€
Fig. 1.5 Application of epoxy composites to the horizontal stabilizer of the AV-8B aircraft.
30 Overview of composite materials
Fig. 1.6 Application of epoxy composites to the forward fuselage of the AV-8B aircraft.
sources has provided a matrix material gener- epoxies in maximum hot/wet use tempera-
ally tougher and far more moisture resistant ture, extending the safe in-service temperature
compared to epoxies. Thus they possess better to 205-220°C (400430°F) or higher. They are
electrical characteristicsand are not subjected to available from a number of suppliers.
the so called hot/wet Tg service temperature The BMI materials have been selected for
reduction. The lack of a data base and manufac- structural applications on the US Air Force
turing experience base tend to inhibit the F-22 fighter in combination with carbon fiber
introduction of the cyanate materials into new reinforcements.
systems.
1.11 OTHER THERMOSETTING RESINS
1.10 BISMALEIMIDE RESINS
Polyimide resins including the PMR
BMIs have a very competitive set of features (Polymerization of Monomeric Reactants) and
including; toughness, moisture resistance, acetylene terminated versions are available
ease of handling and manufacture and good and possess service temperature capabilities,
engineering properties. They are superior to in air, close to 260°C (500°F). Applications in
Thermoplastic resins 31
Nonstructural parts,
liners, troop seats A
7 Carbon/Epoxy
Carbon/Kevlar/Epoxy
v m GFRP/Nornexcore
m Kevlar/foarn core
Kevlar/Nomex
0 CarbonlNornex
Fig. 1.7 Composite applications on the C-5 cargo aircraft; total weight of composites: 7167 kg (15 787 lb);
weight saving: 1997 kg (4398 lb).
military turbine engine casings (liners) and sulfide (PPS),polyether ketone ketone (PEKK)
electronics form the major present day appli- and several others. Most thermoplastic matri-
cations for these materials. Lack of toughness ces do not absorb any significant amount of
and difficulty in handling and in manufacture water, but organic solvent resistance is an area
characterize this family of heat resistant of concern for the noncrystalline thermoplas-
organic matrix materials. tics. Because thermoplastic matrices have an
unlimited shelf life before molding (unlike
thermosetting matrices), and because they can
1.12 THERMOPLASTIC RESINS
potentially be remolded by the application of
The families of amorphous and semicrys- heat and pressure, thermoplastic matrix com-
talline thermoplastic materials have been posites also offer the possibility of lower-cost
thoroughly evaluated for use as matrix resins. fabrication. However, cross-linking or thermal
Thermoplastic matrix materials are generally degradation with repeated temperature
tougher than most thermoset resins and offer cycling is a concern with most of the systems.
the potential of improved hot/wet resistance. The fabrication procedures necessary for the
Because of their high strains to failure, they low-cost manufacture of thermoplastic matrix
also are the only matrices currently available composites have been extensively studied,
that allow thermoforming and other forms of including effort to determine and understand
rapid manufacture to be utilized. the mechanical properties obtained from the
The thermoplastic resin materials include various techniques currently available for fab-
polyether ether ketone (PEEK),polyphenylene ricating thermoplastic matrix composites.
32 Overview of composite materials
Thermoplastic composites are deemed to be craft (Fig. 1.8) that successfully circumnavi-
a mature technology and will compete with gated the earth non-stop.
other composites on a properties and cost
basis. 1.14 MATERIAL FORMS
materials can be produced and stored for process. High prepreg lay-down rates and
future use, normally under refrigeration for fairly low scrap rates are possible. However,
thermosetting matrices, and then used in most of the existing automatic lay-up
processes ranging from hand lay-up to highly processes are quite limited in their ability to
automated filament winding or machine tape produce satisfactory components having com-
laying. Processes such as pultrusion and plex curvatures. This is more an artifact of the
braiding can also use prepreg forms instead of tape raw material than it is an equipment lim-
in-line resin impregnation. While the latter itation.
may be lower in initial cost, it may be prohibi- To select the best composite fabrication
tive for some resin systems (such as process, the designer generally chooses the
thermoplastics), and parameters such as process that will provide an acceptable quality
fiber/resin ratio may not be as easily con- component for the lowest cost. In evaluating
trolled as is the case with a prepreg. cost and quality, however, tooling cost, pro-
duction rate, materials cost, desired part finish
and many other factors must be considered.
1.15 MANUFACTURING/FABRICATION
Only after all the relevant factors have been
The most common composite lay-up processes weighed can the fabrication method (or the
include: hand lay-up, fiber placement and material) be selected.
machine tape lay-up. In lay-up, material that is This overview chapter was intended as a
usually in prepreg form is cut and laid up, primer to introduce the reader to composite
layer by layer, to produce a laminate of the technology. Fiber and matrix materials, design
desired thickness, number of plies, and ply concerns, material forms and fabrication
orientations. In filament winding, a fiber bun- processes have been described briefly. For
dle or ribbon is impregnated with resin and more specific and detailed data and guidelines
wound upon a mandrel to produce a simple on these topics, the reader should consult the
shape, such as a tube or pressure vessel, or a technical sections in this volume. However,
more complex shape, such as a wind turbine this introduction should have clarified that
or helicopter rotor blade. composites offer tremendous opportunities -
Hand lay-up processes are usually accom- as well as impressive challenges - for the
panied by a compaction step for each one or designer and manufacturer of high perfor-
more plies that are applied. Lay-up of thermo- mance components.
plastic matrix material is always accompanied
by heat and pressure.
FURTHER READING
For most components produced for aero-
space applications, except filament wound 1. Weeton, J.W. and Peters, D.M., eds, Engineers’
components, the autoclave is the curing tool of Guide to Composite Materials, American Society
choice. The autoclave cure process is chosen for Materials, 1987.
2. SPI Composites Institute, lntroduction to
for many reasons, these include: reproducible, Composites, SPI, Washington, 1992.
high quality, low void content, parts at reason- 3. Beukers, A. and de Jon, Th., Materials Delft
able production rates and costs. There are also University Press, Delft, Netherlands, 1992.
a number of other fabrication processes that 4. Corish, P.J., ed, Concise Encyclopedia of Polymer
are used including pultrusion, resin transfer Processing and Applications, Pergamon Press,
molding and press curing. These processes Oxford, 1992.
have found application in the fabrication of 5 . Schwartz, M., ed Composite Materials Handbook
2nd edn, McGraw-Hill, New York, 1992.
various components for aerospace usage.
Very sophisticated, numerically controlled
equipment is presently available for the lay-up
POLYESTER AND VINYL ESTER RESINS 2
Frank A. Cassis and Robert C. Talbot
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
0
reacted with maleic anhydride and diluted
with styrene monomer to produce a cost effec-
tive terephthalic polyester.
c=o
‘OH Bisphenol A fumarate resins
Terephthalic
acid These resins are unsaturated rigid polyesters
made by reacting bisphenol A with propylene
Fig. 2.4 oxide to produce the glycol shown in Fig. 2.5.
This propoxylated bisphenol A is then
Therephthalic resins
reacted with fumaric acid to form an unsatu-
Unsaturated polyesters can be produced from rated polyester. The bisphenol structure
terephthalic acid with the expectation that the illustrated above imparts a high degree of
resin property improvement obtained in going hardness, rigidity and thermal stability to this
from phthalic anhydride to isophthalic acid particular resin.
will be matched in going from isophthalic to
terephthalic acid. This, however, is not the case
and terephthalic resins appear to offer only a Chlorendic resins
slight advantage in heat distortion tempera- These unique polyester resins are based on
ture over their isophthalic counterparts. Other HET acid (hexachlorocyclopentadiene) or the
important resin properties such as modulus, anhydride shown in Fig. 2.6.
hardness and overall chemical resistance favor When reacted with an unsaturated acid and
the is0 resins. a stable glycol such as neopentyl, an extremely
Because of its lower solubility and poorer rigid unsaturated polyester results with out-
reactivity, therephthalic acid requires the use standing thermal stability and resistance to
of esterification catalysts or pressure process- oxidizing environments. The inherent chlorine
ing to produce a resin economically. Without in the resin chain imparts some fire retardancy
these, processing time for a terephthalic poly- as well.
H H
..
I - CH2 - O
HO - C o l @ I - OH
0 - CH2 - C
CQ
;?!
CI CI-c-CI -c=o
I I
CH3 CH3
'Literature values.
1
_ _ _ _ _ _ ~
Hexenel .-
Hexene-1
___-_-.___~_-- 0.1 ~-
.
~
- -.
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 ~~
In addition to tailoring the resin for specific cations which do not involve reinforcing mate-
applications by varying the building blocks, rials. These so-called casting applications
the properties of unsaturated polyesters can include buttons, bowling balls, putties, cul-
often be altered significantly by selection of tured marble, gel coats and decorative
the esterification process. This is particularly products. The marble industry and the more
true with isophthalic/terephthalic polyesters recently developed polymer concrete industry
which are slower reacting than phthalic anhy- represent outstanding applications for highly
dride. By using a two stage or modified two filled unsaturated polyesters which offer very
stage reaction with these aromatic diacids, the economical materials to the building and con-
molecular structure of the resultant polyester struction industry. Fiberglass reinforced
can be changed to markedly improve heat dis- polyesters (FRP) are used in the manufacturing
tortion temperature, hydrolytic stability and of boats, automobile and truck parts, building
chemical resistance2.In the two stage process panels, corrosion resistant equipment such as
the aromatic acid and glycol are fully or par- pipes, tanks, ducts, scrubbers, etc., appliances
tially reacted before the faster reacting and business equipment, electrical equipment,
unsaturated acid is added to the cook. This construction products such as grating and rail-
processing method, compared to charging all ing, sporting equipment and consumer
ingredients at once (one stage method), also products that are almost endless. According to
leads to a more random distribution of the the Composites Institute of the Society of
unsaturation in the polymer chain which Plastics Industry (SPI), automotive, construc-
changes the character of the final cross linked tion, marine and corrosion resistant
network in the cured resin. equipment are the four largest FRP markets, in
Cure plays one of the most important roles that order, in the United States which pro-
in the chemical resistance developed by unsat- duces 2.5 billion pounds of FRP annually.
urated polyester resins. Theoretically, the Mechanical properties are most often the
curing reaction should go to completion at critical factor in the selection of a polyester resin
room temperature with all the double bonds for a specific application. Testing of mechanical
converted to single bonds in the three-dimen- properties for both resin castings and fiberglass
sional network. However, complete cross remforced composites is carried out using stan-
linking is rarely achieved at ambient tempera- dardized ASTM (American Society for Testing
tures. This then will result in reduced chemical and Materials) tests for all plastics.
resistance and, quite often, poorer than
ASTM D-638 Standard Test Method for
expected mechanical properties. In addition,
Tensile Properties of Plastics
unreacted diluent (styrene ) can remain in the
ASTM D-790 Standard Test Method for
not-so-well cured polymer leading to major
Flexural Properties of Plastics
problems when the polyester is used for food
ASTM D-695 Standard Test Method for
grade applications. Accordingly, maximum
Compressive Properties of
chemical resistance and certain other property
Rigid Plastics
improvements can most often be achieved by
ASTM D-256 Standard Test Method for
utilizing elevated temperatures for ‘post cure’
Impact Strength (IZOD) of
of the polyester resin finished product.
Plastics
Unsaturated polyester resins are used in the
ASTM D-648 Standard Test Method for Heat
manufacture of a broad range of plastic prod-
Distortion Temperature of
ucts. A high percentage of these products
Plastics
utilize reinforcing materials, particularly fiber-
ASTM D-2583 Standard Test Method for
glass. It is estimated that less than 20% of the
Barcol Hardness of Plastics
polyester resins produced are utilized in appli-
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
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 Table 2.2 summarizes the resin casting
excellent balance of properties in corrosion properties of the various resins used in corro-
applications, these unsaturated polyesters and sion resistant applications today.
vinyl esters now dominate the corrosion mar- The outstanding balance of properties pro-
ket. The bonus provided by vinyl esters is of vided by vinyl ester resins is obvious and
course higher heat resistance and extended life bodes well for continued strong growth in US
at higher operating temperatures, but at sig- corrosion markets. Other significant markets
nificant additional cost compared with the for vinyl esters includes pultruded construc-
iso/ terepolyesters. tion and electrical components, automotive
The next major market area for vinyl esters structural applications, polymer concrete ves-
utilizes the high tensile elongation characteris- sels for mining and chemical operations,
tics of these resins to produce linings and grating, high performance marine applications
coating with outstanding adhesion to other and sporting goods.
types of plastics and conventional materials
such as steel and concrete. For example, vinyl
2.4 FLAME RETARDANT VERSIONS
esters are an excellent barrier coat for fiberglass
boats and acrylic spas. Vinyl ester corrosion The need for flame retardant polymers is
coatings are used everywhere today for steel essential in many plastics applications today.
tank linings and industrial flooring. In dual The combustibility of plastics has drawn so
laminate structures, a vinyl ester is often the much attention to the safety aspects of these
back up for exotic thermoplastics or the supe- materials in construction applications, that
rior corrosion barrier for lower cost polyesters designers and specifiers have been pressured
in many FRP tank and pipe applications. by fire officials to provide fiberglass-rein-
The growth of vinyl esters has also been forced construction materials that exhibit low
boosted by their excellent handling character- flame/low smoke characteristics. Since all
istics and ease of cure. For example, vinyl plastics are based on organic constituents, they
esters are much preferred by FRP fabricators are inherently flammable and once ignited will
in filament winding operations because of burn until they are completely consumed.
excellent glass wet out and in fabrication of There are, however several methods available
large structures because the resins are forgiv- for making thermosetting resin flame retar-
ing and provide predictable curing over a dant and these provide the capability to
wide range of temperatures. The latter situa- supply fire retardant FRP and corrosion resis-
tion has resulted in a virtual exclusive use for tant/fire retardant FRP for the numerous
vinyl esters in field fabrication of large FRP applications that have a need for some degree
structures. of fire retardancy.
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 and distance of the flame front advancing
versions, the addition of a halogen to the resin down the test tunnel during a ten-minute
formulation has very little, if any, effect on the duration test and compared to those values
chemical or mechanical properties of a FRP established for asbestos-cement board (at
laminate, whereas the use of additives such as 0-FS) and red oak material (at 100 FS). This
aluminum hydrates, clays, carbonates or test method establishes the rating at 0-25FS as
fumed silica will have a direct and adverse Class I, 25-75FS as Class I1 and 76-plus FS as
effect on the chemical resistance of FRP lami- Class 111. During the test procedure, the
nates. In critical corrosion applications such smoke emission is measured and can range
filler additions could result in early failure of from 450 to 1000 or more for unfilled lami-
FRP laminates. nates. When additives such as ATH are used,
smoke emissions of less than 450 can be
achieved.
2.4.2 TESTING AND CLASSIFICATION
Corrosion resistant FRP ducting exhibiting
Most halogenated resin systems require a syn- low flame/low smoke characteristics is
ergist such as antimony usually 3-5'/0 Sb,O, by required for waste water/odor control and
weight of resin in order to achieve a class I semiconductor applications. This can be
flame spread rating. Other proprietary syner- achieved with brominated vinyl esters or
gists can be substituted, especially in brominated isopolyesters as the base for the
translucent laminates as used for siding and FRP duct which is then coated with an intu-
roofing materials. Antimony oxide enhances mescent paint to reduce smoke emissions.
the flame spread rating by forming a char on Such systems are currently qualified by the
the burning surface of a laminate and effec- International Conference of Building Officials
tively subdues the rate of flame progression by (ICBO) with tunnel test ratings of <25FS and
snuffing the flame out when the source of igni- <50 smoke development.
tion is removed or extinguished. Such flame Unfortunately, many specifying engineer-
resistant FRP laminates will burn when sub- ing companies will request and specify
jected to a high temperature flame source, but values that are not readily achievable for
the rate of burning is substantially less than for most flame retardant resin systems. Ideally, a
non-flame retardant systems. The use of Sb,O, Class I system with 25FS (max) to 450 (max)
will turn laminate opaque, which restricts smoke is acceptable for corrosion service,
visual inspections of a laminate in production. when the use of additives cannot be toler-
It is not a good idea to allow the addition of ated. A FSC of <25FS is usually acceptable for
Sb,O, in the corrosion resistant barrier. Alone, most applications. However, some specifiers
Sb,O, will not improve a non-halogenated will claim that 15-20FS is better than 20-25FS,
resin; its use becomes an unnecessary expen- when under actual burning conditions there
sive filler with no flame retardant properties. is a negligible difference in the combustibility
The most commonly used test method for of FRP laminates. When selecting a flame
evaluating flammability is ASTM Method E-84 retardant resin, it is important to qualify a
(the tunnel test) also known as NFPA 255. This system to meet the properties required. Flame
test method measures the comparative burn- retardant resins are available in a wide vari-
ing characteristics of a material by evaluating ety of formulations, including lower cost
the flame front propagation over the surface of general purpose to premium grade types
the test material, which is exposed to con- with better high temperature properties.
trolled temperatures in a forced air chamber or Class I flame spread thermosetting resin
tunnel. A flame spread (FS) classification (FSC) systems can also be achieved without the need
is obtained which measures the ignition time 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 process. Simply, ’you can select the best resin
application. A good rule to follow here is that and fiberglass in the world and if you don’t
no single FRP resin can handle every kind of envi- put them together correctly - failure will prob-
ronmental problem, so resin selection is of the ably result’. Material selection added to design
utmost important. It should also be under- and production requirements leads to a deter-
stood that knowledge of the molecular mination of the fabrication process. Many
structure of these higher performance resins methods of fabrication are used to manufac-
does not eliminate the need for actual testing ture products for the numerous FRP markets.
to determine resin suitability in a given appli- These methods vary from hand lay-up/spray-
cation. For example, certain vinyl esters are up, filament winding and resin transfer
reasonably resistant to alkaline exposure while molding which utilize low temperature curing
other types are poor. The corrosion fabricators’ to various high temperature molding com-
guide for the suitability of a thermosetting pound (SMC), pultrusion, and continuous
resin in a corrosive environment is ASTM C- panel. The designer must analyze the end use
581. The procedure involves complete property requirements such as color, surface
exposure of a FRP test laminate for one year, characteristics, strength and chemical resistance
with intermittent strength testing, to establish requirements and then add-in cost factors,
a curve which depicts loss of flexural strength part volume, part size and finishing to finalize
versus time. It is absolutely essential that the the selection of process. For example, trans-
resin selected for that environment form a portation body panels would be a high
plateau during the one year test period. volume application requiring outstanding sur-
Obviously, it is also important that this plateau face finish and excellent strength properties.
be achieved at a satisfactory retained flexural All of these can be satisfied with a isopolyester
strength. Table 2.3 summarizes a comparison sheet molding compound that is compression
of FRP properties of various thermosetting molded under heat and pressure. This process
resin types versus carbon and stainless steel. can be automated and delivers the highest vol-
ume and highest part uniformity of any
thermoset molding method. Lower part finish-
2.5.2 EFFECT OF PROCESS AND END USE
ing cost is achievable because subsequent
REQUIREMENT
trimming machining is minimized.
There is an old saying in the FRP business that Corrosion resistant equipment would be
heightens awareness of the fabrication fabricated, on the other hand, by either filament
use the term epoxy resin when referring to the When the amine nitrogen contains two hydro-
uncured or cured formulated system. gens, each reacts with a different epoxide ring.
This scheme is shown in Fig. 3.1, where the
developing network is evident. This scheme
3.2.2 THE THERMOSETTING (CURING)
applies to both aliphatic and aromatic amine
REACTION
curing agents. The reaction between epoxide
The thermosetting reaction is the joining of and amine produces a C-N bond, whose envi-
many small molecules by chemical reaction to ronmental resistance is good, but whose
produce an extended network structure. stability to elevated temperature is highly
Although this process is a polymerization, it is dependent on the adjacent molecular structure.
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
- OH
I
CH-CH,
\ /
cH2-m-
OH
I
/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.
/O\ /O\
CH2- CH- CH2- 0 0 - CH2 -CH- CH2
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
Diethylenetriamine (DETA)
Triethylenetriamine(TETA)
Diethylaminepropylamine (DEAPA)
CH3- CH2,
- (CHZ)3- NH2
CH3- CH2
65 50 Available from Union Carbide.
(5000)
Tetraethylenepentamine(TEPA)
4,4'-Methylenedianiline (MDA)
rn-Phenylenediamine (MPDA)
NH2
I
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.
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
40% MPDA-60%MDA
Dicyandiamide (DICY)
28 Melting point 207-209°C Slow reacting. Used for prepregs. Available from
(405408°F) Cytec Ind.
Table 3.3 Structures and characteristics of commonly used anhydride curing agents
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.
270 Liquid at 25°C (77°F) Available from Dixie Chemical and from
(0.200 Pa s) 200 cP Humphrey Chemical.
58 Epoxy resins
,o
\\
0
\\
0
/p
l0
100 120 (248) Available from Buffalo Color.
Constituents used in formulated systems 59
Methyltetrahydrophthalicanhydride
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.
Table 3.4 Structures and characteristics of commonly used catalysts and accelerators
Benzyldimethylarnine (BDMA)
2,4,6-Tris(dimethylaminomethyl)phenol
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 3.5 Structures and characteristics of commonly used, commerciallyavailable epoxide reactive dilutents
/O\
CH3-(CH2)3 -0 - CH2- CH-CH2
/O\
CH3-((CH2)7 - 0 - CH2- CH- CH2
CH3
/O\
0 - CH2 - CH- CH2
I -
/O\
0 - CH2 -CH-CH2
CH3
13CL145 0.005-0.015 Example: AZ epoxy N (AZS Corp.);not a pure
(5-15) compound.
/O\
A CH - C H ~
O ’ W
76 0.20 Example ERL 4206 (Union Carbide).
(20)
system if low viscosity for processing and a in all but a few cases; the anhydride-cured sys-
room temperature cure are needed1’,12. tem is degraded in strong base due to basic
Constituents with aromatic ring structures hydrolysis of its ester linkages and both the
react sluggishly or not at all at room tempera- anhydride-cured and the homopolymerized sys-
ture13J4.Thus aromatic-amine cured systems tems are vulnerable to swelling by the strong
require elevated temperature cures. solvent, trichloroethylene.
As cited earlier in the discussion on cure
reactions, the relative amount of curing agent
3.5 PROCESSING CONSIDERATIONS IN
to epoxide is important in achieving a well-
EPOXY RESIN COMPOSITES
developed network. The formulations
presented in Table 3.6 are approximately what The goals of the processing procedures used to
would be used for some specific epoxide-curing make a good quality fiber composite are to
agent formulations. The reader should verify ensure that the resin forms a void-free contin-
the correctness of the formulations by comput- uous phase, surrounds each filament, is evenly
ing the appropriate weight ratios from the distributed, is present in the desired amount
molecular structures given in Tables 3.1, 3.2 relative to the fiber and is fully cured. The ease
and 3.3. with which these goals can be achieved is
highly dependent on the rheological proper-
Table 3.6 Formulations for selected epoxy resin ties of the resin as it progresses through its
systems cure and on the engineer’s ability to evaluate
rheology and degree of cure throughout the
Constituents Epoxide Curing agent processing cycle.
PbV Pbw‘ In the early years of epoxy resin technol-
Diglycidyl ether of ogy, processing procedures were developed
bisphenol A triethylene by a trial and error approach. This is still a
tetramine 100 14 viable approach, especially for engineers
Diglycidyl ether of skilled in the art of thermoset composite pro-
bisphenol A rneta- cessing. However, in recent years,
phenylene diamine 100 16 rheologica116-18 and chemorheologica119~20
models that relate viscosity, rigidity and
Diglycidyl ether of
bisphenol A degree of cure to time and temperature have
hexahydrophthalic been developed. These models predict rheo-
anhydride 100 90 logical changes during cure and can serve as
Parts by weight an aid to processing and cure cycle develop-
ment.
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), Homopolymerized (BF,MEA),
Aromatic amine-cured (MPDA), @ Anhydride-cured (PA), mrm
reduced to achieve the desired flow require- the simplest approach, can result in bubble or
ments. The two major approaches to reducing void formation within the composite if the
viscosity are thinning the mixture with low solvent cannot escape completely. This could
viscosity organic solvents and adding low vis- be a problem for component fabrication by
cosity reactive diluents, such as those wet filament winding, where layers contain-
presented in Table 3.5. ing the freshly mixed epoxy resin system are
Thinning with organic solvents, although placed sequentially on top of one another.
66 Epoxy resins
Filament winding processors do not use sol- By contrast, reactive diluents, being them-
vents to reduce viscosity, rather selecting selves epoxides, chemically react to become a
lower viscosity resins, reactive diluents, or permanent part of the crosslinked network.
diluting with heat. On the other hand, the use Figure 3.5 shows the relation between L'1SCOS-
'
of small amounts of solvent to reduce resin ity and the amount of diluent added to a
viscosity during fabrication of prepreg viscous epoxide. Ideally, the engineer wants to
(pre-impregnated fiber) presents no prob- use just enough diluent to lower viscosity as
lems, since prepreg is made in the form of needed without dramatically altering the
single, thin-layer sheet, tape or tow from properties of the final cured network.
which solvent can vaporize easily and the The length of time that an epoxy resin for-
prepreg is heat treated to eliminate solvent mulation remains fluid is important.
and to advance cure. 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
3.5.2 MONITORING OF CURE ods where samples were taken and tested at
Once the cure is underway in an epoxy resin intervals in the cure cycle. The time needed to
system, all of the properties of the system develop one data point depended on the par-
change rapidly until the final crosslinked net- ticular laboratory method. Off-line testing has
work is reached. Not only is flow decreasing been made more convenient with the develop-
and rigidity increasing, but all other properties ment of continuous monitoring techniques
(electrical, chemical, optical, etc.) are chang- (i.e. data points in real time) used on small
ing. When the curing epoxy resin system is dedicated specimens of resin or prepreg.
subjected to temperature and pressure Recently, real time, in situ methods where cure
changes, the resin response will be characteris- can be monitored in the composite structural
tic of its degree of cure at that moment. Cure component itself have been developed.
cycle events, such as temperature and pressure
changes, need to be carefully timed with this Traditional off-line methods
in mind.
The degree of cure can be defined in terms Intermittent off-line methods include chemical
of any one of a large number of chemical or titration of the unreacted epoxide groups pre-
physical (including mechanical) properties that sentz4jz5, specific gravity to measure
change continuously during the curing reac- densificationzh and differential scanning
tion and reach a constant value at end of the calorimetry to measure the residual cure
cure. Evaluation of the degree of cure is usually e~otherm*"~ Figure
~ ~ ~ ~3.6
* .shows a plot of spe-
based on one of these properties and full cure cific gravity data obtained on specimens cured
is then defined as the point at which this for increasing lengths of time at a single tem-
selected property reaches a constant value. perature. Figure 3.7 shows differential
Originally, the only available methods for scanning calorimeter scans for two epoxy resin
evaluating cure were off-line laboratory meth- specimens of the same formulation, but with
different degrees of cure.
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.
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 The off-line methods, real time or not, are
s p e c t r o s ~ o p y ~ ,parallel
~ ~ , ~ ~ , plate-type bulk useful for developing a cure schedule for a
diele~trornetry~’,~~ and dynamic mechanical new epoxy resin formulation, for optimizing
s p e ~ t r o m e t r y ~Figure
~ ” ~ . 3.8 shows the results processing variables and for quality control of
of infrared monitoring for five different neat incoming resins or prepregs. They have also
resin specimens, each cured at a different tem- been used successfully for the development of
perature and Fig. 3.9 shows data obtained by mathematical models of cure kinetics.
bulk dielectrometry. 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
--------
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.
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
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
- 4
20
- 2
0
0 2 4 6 a io-
Strain YO
epoxy resin formulations are often available procedures exist, e.g. as from the American
from resin suppliers. Data for new or unusual Society for Testing and Materials, they should
formulations must be generated by the user. be followed. Where they do not exist, litera-
Whether the data are generated by the resin ture references are helpful. Table 3.11 lists
supplier or the user, it is important that stan- some commonly tested properties and the
dard test procedures be followed. This will standard methods (American Society for
ensure that the resin systems can be compared Testing and Materials) describing the tests.
on an equal basis. Where standardized test
72 Epoxy resins
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
References 73
31. Yalof, S. and Wrasidlo, W. 'Crosschecking 40. Day, D.R., Lewis, T.J., Lee, H.L. and Senturia,
between dielectric measurements, DTA, and S.D. 'The role of boundary layer capacitance at
other methods of thermal analysis in research blocking electrodes in the interpretation of
and production,' J. Appl. Polym. Sci., 1972, 16, dielectric cure data in adhesives,' J. Adhesion,
2159-21 73. 1985,18,73-90.
32. Delmonte, J. 'Electric properties of epoxy resins 41. Micromet Instruments, Inc., Cambridge,
during polymerization,' J. Appl, Polym. Sci. 1959, Massachusetts, Technical literature, 1991.
2, 108-113. 42. Ciriscioli, P.R. and Springer, G.S. 'Dielectric cure
33. Lewis, A. 'Dynamic mechanical behavior dur- monitoring - a critical review,' S A M P E J., 1989,
ing the thermosetting curing process,' SPE 25, 3542.
Trans., 1963, 3,201-212. 43. Sung, C.S.P., Pyun, E. and Sun, H.L.
34. Kreahling, R.P. and Kline, D.E. 'Thermal con- 'Characterization of epoxy cure by UV-visible
ductivity, specific heat, and dynamic and fluorescence spectroscopy: azochromic
mechanical behavior of diglycidyl ether of labeling approach,' Macromolecules, 1986, 19,
bisphenol A cured with m-phenylene diamine,' 2922-2932.
J. Appl. Polym. Sci., 1969, 13,2411-2425. 44. Sung, C.S.P. and Mathisen, R. 'Cure characteri-
35. Arridge, R. and Speake, J. 'Mechanical relax- zation of an epoxy network by fluorescence
ation studies of the cure of epoxy resins: 1. behavior of trans-diaminostilbene,' Polymer,
Measurement of cure,' Polymer, 1972, 13, 1987,28,941-945.
443449. 45. Compton, D.A., Hill, S.L., Wright, N.A. et al. 'In
36. Kline, D.E. 'Dynamic mechanical properties of situ FTIR analysis of a composite curing reac-
epoxy resins during polymerization,' J. Appl. tion using a Mid-Infrared Transmitting Optical
Polym. Sci., 1960,4, 123. Fiber,' Appl. Spectros. 1988,6,972-979.
37. Babayevsky, P. and Gillham, J. 'Epoxy ther- 46. Young, P.R., Druy, M.A., Stevenson, W.A. and
mosetting systems: dynamic mechanical Compton, D.A. 'In situ composite monitoring
analysis of the reactions of aromatic diamines using infrared-transmitting optical fibers,'
with the diglycidyl ether of bispenol A,' J. Appl. S A M P E J., 1989,25,11-16.
Polym. Sci., 1973,17, 2067-2088. 47. Myrick, M.L., Angel, S.M., Lyon, R.E. and Vess,
38. Enns, J.B. and Gillham, J.K. 'The time-tempera- T.M. 'Epoxy cure monitoring using fiber-optic
ture transformation (TTT) cure diagram: Raman spectroscopy,' S A M P E J., 1992, 28,
modeling the cure behavior of thermosets,' J. 3742.
Appl. Polym. Sci., 1983,28,2567-2591. 48. Mijovic, J., Kenny, J.M., Nicolais, L. and
39. Senturia, S.D. and Sheppard, N.F. 'Dielectric Pejanovic, S. 'Present and future trends in in-
analysis of thermoset cure,' Adv. Polym. Sci., situ monitoring of processing of advanced
1986, 80, 1 4 7 . composites,' SAMPE J., 1992, 28, 3946.
HIGH TEMPERATURE RESINS 4
Hugh H.Gibbs
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
Condensation polyimide chemistry 77
1 m-phenylene diamine
Skybond700
4,4'-methylene dianiline +
Skybond703
moiety leading to branching and intractability reactive and present in stoicluometric propor-
of the matrix resin. This is probably one of the tions, extremely high molecular weight
reasons why it is difficult to fabricate low void polyimide is ultimately produced. Also, since
composites using this type of chemistry. the bridging hexafluoroisopropylidene group
is inert under normal cure conditions, the poly-
imide produced is essentially linear and & that
4.2.3 CHEMISTRY OF NR-150
sense thermoplastic.
The formation of DuPont's monomeric binder
solution NR-150 (used to make Avimid@N
4.2.4 CHEMISTRY OF 3F/36F POLYIMIDES
prepreg) is illustrated in Fig. 4.3. The
2,2-bis(3',4'-dicarboxyphenyl) hexafluoro- One of the keys to success in producing an
propane (6F tetraacid) is dissolved in a suitable essentially linear condensation polyimide is to
solvent (e.g. ethanol, diglyme or NMP) along have a chemically inert flexibilizing linkage in
with a 95/5 mixture of p-phenylenedi- the dianhydride moiety. As indicated in
amine/rn-phenylenediamineto form a low Section 4.2.3 one of the ways of doing t h s is to
viscosity, stable monomeric solution' suitable employ a hexafluoroisopropylidene bridging
for prepregging. During the cure both solvent group. Since the phenyl group is also very
and 2 moles of by-product water per repeat inert another approach is to replace one of the
unit are eliminated to initially form the tran- CF, groups with a phenyl group3. This results
sient intermediate polyamide acid. According in the so-called 3F dianhydride. When the 3F
to the studies of Sonnett et aL2, although a low monomer is used along with PPD the poly-
concentration of amide acid persists for a rela- imide produced is called 3F-PPD polyimide.
tively long time period during the early stages If, on the other hand, a mixture of the 3F and
of cure, most is rapidly converted to the imide 6F monomers are employed along with the
form by the thermally induced elimination of same diamine the copolyimide is designated
water (2 moles per repeat unit). Since the 36F-PPD.
tetraacid and diamines are very pure, highly
78 High temperature resins
H O -O
C
II
0
- !/D
CF3
~ F D /~ - - OOH H +
C
0
00 NHZ
NH2
/ +
NH2
/ NH,
r 1
L NR-150 Polyimide
4.3 ADDITION POLYIMIDE CHEMISTRY difficult for these volatiles to escape. Therefore,
ideally one would want to eliminate all of the
4.3.1 OVERALL CHEMISTRY OF ADDITION volatiles prior to pressurization. In order to
POLYIMIDE PRECURSOR SOLUTIONS accomplish this in a conventional condensation
One of the important concerns in the cure of polyimide it is necessary to have a high enough
conventional condensation polyimides is the monomer imbalance so that the polymer mole-
proper management of the evolution of volatile cular weight and melt viscosity will be low
by-products. During the early stages prior to enough to allow for complete consolidation.
pressurization the composite is generally some- The problem is that this molecular weight is
what porous and volatiles can readily diffuse generally so low that the matrix resin properties
out. However, once pressure has been applied are adversely affected. Properties such as
and a low void state is achieved the diffusivity strength, toughness and T, will be much lower
dramatically decreases making it much more than desired.
Addition polyimide chemisty 79
CrosslinkedPMR-15
Fig. 4.4 PMR-15 polymerization chemistry.
80 High temperature resins
L
V-CAP imide prepolymer
$$
CH, -CH,
L
AFR700B imide prepolymer
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
Processing characteristics 83
polyimides except for neat resin densities (1.35 because such data was either considered pro-
and 1 . 4 2 g ~ m -for
~ the 3F and 36F resins prietary or classified as secret by the
respectively) and Tg of 365-370°C (689-698°F) Government Laboratories. In other cases,
for both systems in the as-molded state and where some processing information was avail-
405-410°C (761-770°F) for the post-cured able in the open literature, very little was
state3.TRW-R-8XX has been reported25to yield usually said about the quality of the part pro-
polyimides having T g in the 400-426°C duced by a given cycle so it is difficult to
(750-800°F) range and composite weight loss compare the processibility of one resin system
characteristics at 371°C (700°F) up to 10 times with another since the quality of the laminates
better than PMR-15. All of the resin systems produced is generally unknown. To make mat-
described in this chapter appear to possess ters worse there are also the issues of the
good strength and stiffness. Thus, provided processing characteristics of thick compared
that complete cure is achieved during process- with thin sections and how processing can be
ing and low void composites are produced handled, if at all, when both thin and thick sec-
possessing good fiber/matrix adhesion, high tions are present simultaneously in a given
levels of composite mechanical properties part. It is, therefore, of paramount importance
should be obtained with good retention (at for workers in this field to have as clear an
least 50%) of these properties to just below understanding as possible of the chemistry
their Tg. 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
4.7 PROCESSING CHARACTERISTICS
cycles presented below will give the reader an
approximate idea of the kinds of conditions
4.7.1 GENERAL COMMENTS
that have been employed to produce a part.
One of the features that can clearly differenti-
ate one resin system from another is the ease
4.7.2 SKYBOND PROCESSING CONDITIONS
with which a fully cured low void composite
can be produced having a specified fiber vol- The following autoclave cure cycle has been
ume. Also, although all polyimides can have recommended by MonsantoZ6for 12 ply
their Tgincreased from post-cure, some sys- (3.2 mm, 0.125 in thick) 181 style E-glass (soft
tems respond much more readily than others. A-1100 finish) fabric/Skybond 700 laminates:
In all cases there is a problem of properly man-
0 apply full vacuum;
aging the release of a significant amount of
0 heat to 177°C (350°F) at 1.7-2.8"C/min
volatiles (normally 10-15% of the weight of
(3-5°F /min);
the prepreg). The ways in which this can be
0 hold 5 min at 177°C (350°F);
accomplished can vary significantly from one
0 apply 0.69 MPa (100 psi);
resin to another depending on the chemistry
0 hold 30 min;
involved. Factors such as the techniques
0 cool under pressure and vacuum.
employed during lay-up of the vacuum bag
assembly, pressure, heat-up rate, maximum In order to maximize high temperature prop-
cure temperature, vacuum application and erties it is recommended that a post-cure
intermediate holds all must be carefully con- should be carried out up to and including the
trolled and optimized for each system. expected use-temperature. For laminates of
Unfortunately the story on the processing of the type described above a post-cure is sug-
the various systems covered in this chapter is gested in which the part is heated to 200°C
very incomplete. In a majority of cases infor- (392"F), 225°C (437"F), 250°C (482"F), 300°C
mation on processing was simply not available (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- noted that pressurization does not occur
ature. It is recommended that if thicker until a temperature of about 238°C (460°F)
laminates are involved the post-cure cycle is reached. At that temperature essentially
should be extended. all of the solvent and imidization volatiles
For the same type of laminate based on have been eliminated. Normally PMR-15
Skybond 703 a similar autoclave cure cycle can laminates are subjected to an oven post-cure:
be employed. The only significant differences 0 heat from room temperature to 204°C
are a slower heat-up rate (l.l-1.7"C/min, (400°F) at 5.6"C/min (10"F/min);
2-3"F/min) with the pressure being applied at 0 heat from 204°C to 288°C (400°Fto 550°F) at
121°C (250°F)on the way to the final cure tem- 1.1"C/min (2"F/min);
perature of 177°C (350°F).Also a similar post- 0 dwell at 288°C (550°F)for 1 h;
cure cycle is suggested in order to achieve 0 heat from 288°C to 316°C (550°F to 600°F) at
maximum heat resistance. 1.1"C/ min (2"F/min);
While there is very little definitive informa- 0 dwell at 316°C (600°F)for 10-16 h;
tion on the void content of Skybond based 0 cool to room temperature at 2.8"C/min
laminates it is believed that they are generally (5"F/min) maximum.
in the 5-20% range. A most important feature
of this particular polyimide system is that the
4.7.4 PMR-I1 AND V-CAP PROCESSING
maximum autoclave processing temperature
CONDITIONS
is only 177°C (350°F). No other resin system
described in this chapter can make that claim. 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-
4.7.3 PMR-15 PROCESSING CONDITIONS mum processing temperature has been
increased from 316°C to 371°C (600°F to
The following represents a typical autoclave
700°F). The following typical autoclave cure
cure cyclez8cited for PMR-15:
and post-cure cycles for graphite reinforced
apply 7-21 kPa (1-3 psi) vacuum; PMR-I1 composites has been rep~rted'~?
raise autoclave temperature to 227°C
0 apply full vacuum at room temperature;
(440°F)at 0.83-1.l0C/min (1.5-2.O0F/min);
0 heat to 149°C (300°F) at 3.9"C/min
at 163-177°C (325-350°F) apply full vacuum;
(7.O"F/ min);
dwell at 227°C (440°F) for 1 4 h depending
0 hold for 30min at 149"C, then apply
on part thickness (up to 2.8 mm, 0.11 in =
172 kPa (25 psi);
1 h, 2.8-6.4mm, 0.11-0.25 in = 2 h,
0 heat to 288°C (550°F) at 3.9"C/min
6.4-12.8 mm (0.25-0.50 in) = 3 h);
(7.O0F/min) with the pressure being
raise temperature to 238°C (460°F) at
increased to 344 kPa (50 psi) at 177°C
1.1"C/ min (2.0°F/ min);
(350°F) and then to 1.38MPa (200psi) at
hold at 238°C (460°F) while 1.38MPa
232°C (450°F);
(200 psi) autoclave pressure is applied.
0 heat from 232°C to 371°C (450°F to 700°F) at
Do not hold longer than 15 minutes while 2.8"C/min (5"F/min);
pressure is being- applied
__ 0 cool under full pressure and vacuum to
232°C (450°F)slowly;
raise temperature to 316°C (600°F) at
cool from 232°C to temperature
2.2-3.3"C / min (46°F/min);
rapidly.
dwell at 316°C (600°F) for 3 h;
cool to room temperature. Vent autoclave As with PMR-15, a post-cure is normally car-
pressure below 204°C (400°F) It should be 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
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
Fig. 4.7 Effect of accelerated thermal cycling on the compressive strength of PMR-l5/graphite fabric lam-
inate~.~~
I I I I I I I
I
12 A PMR-15
0 PMR-11-30
10
0 PMR-i1-5(i
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 '
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
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
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- performance in comparison with PMR-11.
forced with other fibers such as Thornel 40R, These same researchers have also shown that
Thornel 650-42, Celion G40-700 and Celion V-CAP/graphite compositespossess improved
G40-800. It is of interest to note that according thermal-oxidative stability compared with
to the data in Fig. 4.1132there was not a one-to- PMR-11-50. However, with the advent of
one correlation with the basic carbon fiber AFR700B where significant improvements in
stability. While Celion G40-600 had one of the thermal-oxidative stability have been realized
lowest weight losses in 371°C (700°F) air aging by simply capping one end only with the low
the Thornel 650-35 had one of the highest. cost nadic anhydride, it is not clear whether
either the V-CAP or CYCAP polyimides with
their more expensive end-capping agents will
4.8.6 V-CAP AND CYCAP
be successful in the market place.
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
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
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
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 reported to be 3.2 and 3.7 respectively.Also, in
One of the useful properties of aromatic poly- the same types of laminates the dissipation
imides is their good all around electrical factors have been measured to be 0.001 for
properties. Low dielectric constants and dissi- Avimid N and 0.015 for the Skybond. The par-
pation factors have been measured in quartz tial fluorocarbon character of the 6F monomer
is undoubtedly the reason behind the
fabric reinforced Avimid N and Skybond
improved properties of Avimid N compared
based composite^^^. For instance, the room
with Skybond. Some other miscellaneous elec-
temperature dielectric constants for Avimid N
trical properties26 of E-glass reinforced
and Skybond Astroquartz laminates have been
Skybond based composites are tabulated in
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.
End-use applications 97
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
@-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
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
-
5.4.1 MEETING RHEOLOGICAL
HoMoPoLY- REQUIREMENTS
MERIZATION
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.
Fig. 5.3 Sequence Of reactions between Phe- Figure 5.4 illustrates the limiting direct rela-
nols and BMI monomers involves grafting via the tionship in families of thermosetting resins
'ene' reaction and fused ring formation via
Diels-Alder. Crosslinking with di(po1y) functional between fluid monomer (150 mPa s viscosity)
components involves completion of these reactions temperature and Tg On curing. High
and/or maleic double bond homopolymerization. temperature polyimides locate Off-sCalein the
102 Speciality matrix resins
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
* 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
Matrimidm5292A
o,o'-DiallylBisphenol A
Ciba Reactive toughener
12 000-20 000 mPa s at 25°C
Matrimid 5292B
Bisallyl polyphenoxide
Inspec Reactive toughener
Compimide TM 121 120-250 mPa s at 71°C
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
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.
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.
Composition (PBW)
- -
AroCy B-30 100 -
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 -
Composition (PBW)
AroCy B-30 100 - - -
AroCy M-20 - 100 - -
AroCy L-10 - - 100 -
Matrimid 5292A - - - 100
Matrimid 5292B - - - 85
Nonylphenol 2 2 2 -
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- strength and generates destructive heat, limit-
posites are use of titanium rather than ing power and range. CE composites curing at
aluminum rivets, placement of a fiberglass 121°C (250°F), e.g. Bryte Technologies'
reinforced insulating ply and/or modification EX-1515, are thermally compatible with high
of CE resin with 55-70% epoxy resin. modulus polyethylene reinforcement. Such
composites are characterized by D, values as
low as 2.6 and D, values as low as 0.004 when
5.6.3 MICROWAVE TRANSPARENT
measured at 10 GHz.
COMPOSITES
Composite design for radomes, antennas and
5.7 SUPPLIERS OF PREPREG AND OTHER
advanced stealth structures should utilize low
FORMULATED PRODUCTS
dielectric loss materials (Speak, 1991; Shimp,
1994b; Stonier, 1991a,b). Figure 5.14 summa- Table 5.8 lists suppliers of BMI and/or CE
rizes microwave interactions with a radome prepreg, adhesive, syntactic foam, RTM/fila-
wall. Reflection weakens returning signals and ment winding systems and chopped fiber
overheats emitter sources; refraction distorts reinforced molding compounds formable by
signal quality; absorption decreases signal 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
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) - -
% WEIGHT GAIN
121
91 AROCY B
Bryte Technologies CE CE CE CE -
Cytec BMI, CE BMI, CE BMI, CE BMI -
Hexcel BMI, CE BMI - - -
+1.0
AROCYBIEKXY
w H.5
P3 -I
AROCYM
I
t
0 10 20 30 40 50 60 Y
DAYS IMMERSION IN 20% NaOH AT 50°C TRANSMISSION
Fig. 5.14 Interactions of microwaves with a radome
Fig. 5.13 Cured CE and BMI resins hydrolyze (etch) wall.
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) were used to construct EFA (Eurofighter) pro-
increase resistance to alkaline environments gener- totypes and are used in construction of the
ated in galvanic cells. Dassault Rafale. Both materials are candidates
for HSCT (High speed civil transport) use.
Principal applications for CE composites
5.8 APPLICATIONS
(McConnell, 1992) include radomes for mili-
Toughened BMI/carbon fiber composites have tary aircraft, fighter aircraft retrofitted with
been specified as the principal composite mate- improved tracking systems, skins over phase
rial for F-22 fighter primary and secondary array radar, weather tracking aircraft radar
structures (Fig. 5.15).BMI service temperatures and missile nose cones. CE prepreg reinforced
are sufficiently high for cowlings, nacelles and with high modulus pitch-based carbon fibers
thrust reversers of jet engines. CE composites 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 Rottloff, G. et al. 1977. US Patent 4 028 393.
resistance and resistance to lo9rads of ionizing Shimp, D.A. 1988. US Patent 4 785 075.
radiation (Willis, 1991). Applications in space Shimp, D.A., S.J. Ising and J.R. Christenson. 1989.
Cyanate esters: a new family of high tempera-
include communication satellites, solar arrays, ture thermosetting resins. SPE/Case Western
parabolic antennas, optical benches and preci- Conf. on High Temperature Polymers and Their
sion segmented reflectors. Uses, 1, 127-140.
BMI film adhesives are employed in jet Shimp, D.A. and J.E. Wenhvorth. 1992. Cyanate
engine or high speed aircraft sandwich panels ester-cured epoxy resin structural composites.
where hot-wet service up to 190°C is required. Int. SAMPE Symp., 37,293-305.
CE film and paste adhesives are used together Shimp, D.A and M. Southcott. 1993. Controlling
moisture effects during the curing of high T
with syntactic foams in the construction of cyanate ester/aramid composites. lnt. S A M P f
radomes. BMI molding compounds reinforced Symp., 38,370-379.
with up to 65 wt.% of chopped reinforcements Shimp, D.A. 1994a. Technologically driven applica-
are used to mold ducts, drive sprockets for tions. In Chemistry and Technology of Cyanate
heated rolls in copy machines, helicopter gear Ester Resins (I. Hamerton Ed.) Chap 10. Blackie,
boxes and missile strongback mounting sup- Glasgow, pp. 282-327.
ports. Shimp, D. and B. Chin. 1994b. Electrical properties
and their significance for applications. In
Chemistry and Technology of Cyanate Ester Resins
REFERENCES (I. Hamerton Ed.) Chap 8. Blackie, Glasgow, pp.
230-257.
Bargain, M. et al. 1971. US Patent 3 562 223. Speak, S.C., H. Sitt and R.H. Fuse. 1991. Novel
Boyd, J.D. and D.A. Shimp. 1987. US Patent cyanate ester based products for high perfor-
4 644 039. mance radome applications. Int. S A M P E Symp.,
Boyd, J.D. and Hon-Son R. 1990. US Patent 36,336-347.
4 923 928. Stenzenberger, H.D. 1990.Chemistry and properties
Boyd, J.D. 1991a. US Patent 5 037 689. of addition polyimides. In Polyimides (D.
Boyd, J. et al. 1991b. Galvanic corrosion effects on Wilson, P.M. Hergenrother and H.D.
carbon fiber composites. Int. S A M P E Symp., Stenzenberger, Eds) Chap 4. Blackie, Glasgow.
36,1217-1231. Stenzenberger, H.D. et al. 1991. BMI/bis(allylphe-
Boyd, J.D. and L.N. Repecka. 1993a. US Patent noxy phthalimide)-copolymers: improved
5 189 116. thermal oxidative stability. Int. S A M P E Symp.,
Boyd, J.D. and G.E.C. Chang. 1993b. Bismaleimide 36 pp. 1232-1243.
composites for advanced high temperature Stonier, R.A. 1991a. Stealth aircraft and technology
applications. Int. S A M P E Symp., 38,357-369. from World War I1 to the Gulf, Part I. SAMPE
King, J.J., Chaudhari M. and Zahir. S. 1984. Nat. Journal, 27(4), 9-16.
SAMPE Conf., 29 392. Stonier, R.A. 1991b. Stealth aircraft and technology
Lee, F.W. and K.S. Baron. 1991. US Patent 5 045 609. from World War I1 to the Gulf, Part 11. S A M P E
McConnell, V.P. 1992. Tough promises from cyanate Journal, 27(5), 9-18.
esters. Adv. Comp., May/June pp. 28-37. Willis, P.B. and D.R. Coulter. 1991. Applications of
Olesen, K. 1991. Degradation of graphite/polymer cyanate resins to spacecraft composites. Paper
composites in the presence of a corroding metal. read at 8th Int. Con$ Composite Materials,
Read at the High Temple Workshop, 11, Reno, ECCM/VIII, Honolulu, 15-19 July 1991.
Nevada, 4 Feb 1991. Zahir, Sheik A-C. and A. Renner. 1978. US Patent
4 100 140.
THERMOPLASTIC RESINS 4
Lars A.Berglund
processing but low stiffness and strength. On Compression molding of glass mat thermo-
the other hand, materials with high fiber con- plastics (GMT) is a wide-spread process of
tent have high stiffness and strength but great sigruficance in the automotive industry
require slow processing and are difficult to (Berglund and Ericson, 1994).Resin injection of
shape into geometrically complicated struc- polymerizing prepolymer molecules of low
tures. For high fiber content materials, the high viscosity is in principle the same process as for
viscosity of a molten thermoplastic usually thermosets although the chemical reactions
requires some kind of prepreg fabrication step lead to increased molecular weight rather than
before final processing. The prepregs may need to cross-linking. Such a process does not pro-
to be combined into the consolidated, semi-fin- vide the advantages of infinite storage life
ished sheets before the final processing step. materials with low toxicity. Diaphragm form-
Regular autoclave processing can be used ing is a processing route where the problem of
for thermoplastic composites. For most high- low extensibility of prepreg-based materials is
performance thermoplastics, however, addressed (Mallon, O’Bradaigh and Pipes,
temperatures have to be higher than the typi- 1989).
cal 177°C used for epoxy-based composites.
Often, the composite manufacturer must pur-
6.3 MATERIAL FORMS
chase a new autoclave if this is the preferred
processing route. Autoclave processing of Thermoplastic composites are usually sup-
thermoplastics has been modeled (Lee and plied as semi-finished materials, with the
Springer, 1987). Consolidation of the prepreg exception of resin injection materials. In Table
layers is an important issue. At a given tem- 6.2, material forms for thermoplastic compos-
perature, sufficient time must be available for ites are presented. Prepregs of high fiber
the polymer molecules to diffuse from one volume fractions (V, = 0.6) may be prepared
prepreg layer into the other and form strong by solvent-, melt-, prepolymer- or powder-
physical entanglements (Howes, Loos and impregnation of the reinforcing fibers.
Hinkley, 1989). In addition, the air initially Solvent-impregnation is limited to amorphous
present in the material must be displaced. resins with high solubility. Melt-impregnation
For thermoplastic composites, filament is a technique successfully developed by IC1
winding has demonstrated good economic (Cogswell, Hezzell and Williams, 1981) pro-
potential (Egerton and Gruber, 1988). The ducing high-quality prepreg. The resulting
major problem is in the welding of filaments or prepreg is considered too stiff, for some pro-
the tape onto the underlying composite layers. cessing situations with little drapability in
Heat has been applied by means of a gas flame, comparison with CF/EP (epoxy) prepreg. This
IR, laser beam or simply from a hot metal sur- problem is addressed in prepolymer- and
face. Pultrusion of thermoplastic composites powder-impregnated prepreg. One example is
offers potential for faster processing than with the FIT-technology where small tubes contain-
thermoset composites (Astrom, Larsson and ing reinforcing fibers and polymer powder are
Pipes, 1991), due to the absence of exothermal used (Thiede-Smet, 1989). In addition, com-
heat generation from chemical reactions. mingled weaves (prepregs) are available. The
Profiles may also be produced by roll-forming resin is present in the form of fibers which are
techniques similar to those used in metal- melted during processing to form a matrix.
working. The shape of existing profiles can be Composites produced from commingled
changed. The low-cost folding technique (GE material forms may have a fairly inhomoge-
Plastics, 1990) has been used commercially by neous distribution of fibers (Olson, 1990).
Fokker and TenCate in Holland for quite large Film-stacking is a simple method often
components of fairly simple geometry. used for preparation of laboratory samples
118 Thermoplastic resins
(Hartness, 1982) although the technique has On the other hand, the material cost and
also been used commercially. In the category energy consumption is reduced, greater free-
of materials with low fiber volume fraction dom in materials selection is obtained and
(V,=: 0.2), semi-finished sheets of GMT-materi- recycling is facilitated. Suppliers of thermo-
als are available. They usually have random, plastic composites are listed in Table 6.3.
chopped or continuous fiber mat reinforce-
ments. Unidirectional prepreg may be used in
6.4 THERMOPLASTIC RESINS
order to selectively provide additional stiff-
ness, strength a n d creep resistance. A n Thermoplastics have either amorphous or
interesting step forward is provided by extru- semi-crystalline structure (Sperling, 1992). The
sion compounded GMT (Composite Products large, chain-like polymer molecules do not
Inc, 1994; Hoechst AG, 1994). No semi-finished show long-range order in amorphous thermo-
sheets are used, instead a special extruder is plastics, which may be viewed as polymer
used to produce a hot, soft 'cake' constituted glasses and, in the absence of color pigments,
of chopped fibers and the polymer matrix, are usually transparent. Thermosets are also
often PP. The cake is placed in a press and amorphous. In contrast, crystalline polymers
molded. The investment in technology is have regions of molecular order. In melt-
higher than for conventional GMT molding. processed crystalline polymers, a spherical
Thermoplastic resins 119
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
I I I
I
I
I
I I
Fig. 6.1 Shear modulus (G') compared with temperature for PET of different degrees of crystallinity.
Thermoplastic resins 121
Table 6.4 Characteristic temperatures for thermoplastic resins with T,< 90°C
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.
Many mechanical properties of composites based on LaRC-TPI, J-2, PAS-2 and K-111 show
are dominated by the influence of fiber mod- transverse strengths in the range 3 2 4 1 MPa.
ulus, fiber strength and fiber volume fraction. Otherwise, typical transverse strengths for
This is usually true for longitudinal tensile thermoplastic composites are in the range
modulus and strength as well as flexural 60-90 MPa. Toughened epoxy composites also
modulus and strength. For thermoplastic show fairly high transverse tensile strengths,
composites based on AS-4 carbon fiber, typi- typically around 75 MPa.
cal tensile data are: longitudinal tensile The use of transverse tension data in failure
modulus E,= 130 GPa, longitudinal tensile criteria will lead to conservative estimates.
strength (5, = 1950 MPa. In the present con- Data are higher for transverse plies in multidi-
text, we are more interested in properties rectional laminates (Berglund, Varna and
dominated by the matrix and the fiber/matrix Yuan, 1991). The modulus data for carbon
interface. One such property is the transverse fiber composites in Table 6.7 appear insensi-
tensile strength of unidirectional laminates. tive to small differences in matrix modulus.
When a multidirectional laminate is loaded in Variations in fiber volume fraction and trans-
in-plane tension, the first major damage verse fiber modulus between the materials
mechanism is likely to be matrix cracking in mask any such effect. The detrimental effect of
the plies with transverse orientation to the glass fiber as opposed to carbon fiber is appar-
maximum load direction. This reduces lami- ent from the GF/PA6,6 and CF/PA6,6 data.
nate stiffness and initiates other damage GF/PP shows very poor performance, proba-
mechanisms such as delamination. In Table bly due to poor fiber/matrix interfacial
6.7, transverse strength and modulus are pre- adhesion (note the low V, ). Interfacial weak-
sented for different thermoplastic composites. ness is also likely to explain the low strength
Fiber volume fractions are high, V ,= 0.5-0.6, for Kevlar / PEKK. For thermoplastic compos-
For composites based on brittle epoxies, typi- ites based on AS-4 carbon fiber, Table 6.7 can
cal transverse strength is 40 MPa. Composites be used to estimate typical data: transverse
tensile modulus E, = 8.6 GPa, transverse ten- on neat resins, energy is absorbed by yielding
sile strength (T, = 75 MPa. and other types of damage when the volume
High interlaminar toughness is desirable of material is relatively large. In a composite,
since this suppresses the tendency for delam- the presence of fibers tends to limit this mate-
ination crack formation during loading. rial volume. For shear strength, no
Interlaminar fracture toughness is determined comparable data for different thermoplastic
on double cantilever beam specimens (DCB), composites appear to be available in the liter-
usually unidirectional materials are used ature. The interlaminar fracture toughness in
(Whitney, Browning and Hoogsteden, 1982). mode I1 shear loading, Glrc,is higher for ther-
In Table 6.8 such data are presented. moplastic than for comparable thermoset
CF/PEEK shows the highest fracture tough- composites (Cantwell and Davies, 1993). This
ness. All thermoplastic composites show also indicates a higher shear strength for the
higher toughness than the thermoset compos- thermoplastic composites. A typical value for
ites. There is a difference between crack the in-plane shear modulus of thermoplastic
initiation and crack propagation data (Davies, composites based on AS-4 carbon fiber is
Benzeggagh and de Charentenay, 1987). The 4.8 GPa which is similar to toughened CF/EP
data presented here are crack propagation systems but slightly lower than for brittle
data; crack initiation data are in general much matrix CF/EP composites.
lower. For tough matrices one may question Compressive strength is lower for thermo-
the applicability of the data to design prob- plastic than for thermoset composites
lems. In DCB experiments, the crack opening (Table 6.9). Most of the thermoplastic compos-
displacement (COD) is very high, whereas the ites are in the range 900-1100MPa whereas
COD at small central cracks in stiff laminates typical thermoset composite data are
is much smaller. Local stress fields and dam- 1700 MPa. Fiber misalignment, shear stiffness
age mechanisms may therefore be different and strength have been shown to affect com-
and affect the measured fracture toughness. pression strength based on plastic kink band
At present, delamination fracture toughness formation (Budiansky, 1983). Compression
from DCB tests are therefore preferentially modulus data in Table 6.9 are similar, in sup-
used to compare material. It has been pointed port of similar fiber volume fractions for the
out that composite data are significantly materials compared. The composite based on
lower than resin data (Hunston, 1984).In tests PA6,6 has the lowest strength; PA6,6 also has
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 6.11 Glass and heat deflection temperatures Table 6.12 Glass melting and heat deflection tem-
for amorphous thermoplastics peratures for semi-crystalline thermoplastics
Increased market need for polymer compos- is that molecular mobility in the polymer is
ites with good performance at elevated increased dramatically as the temperature
temperature has generated interest in thermo- approaches T .
plastic composites. Materials with continuous In Table 8.12, similar data to those in
use temperatures above 150°C are of particular Table 6.11 are presented for semi-crystalline
interest since they perform better than epoxies. thermoplastics. HDT is usually somewhat
One question is how maximum use tempera- higher than Tg. However, for some semi-
ture relates to Tg. In Table 6.11, Tg and the heat crystalline polymers, HDT is below T (as for
deflection temperature (HDT) for amorphous amorphous polymers). Creep effects 'will be
thermoplastics are presented. HDT is deter- very strong close to and above Tg.For this rea-
mined by subjecting the material to static load son the maximum temperature for continuous
(typically 1.8 MPa) and slowly increasing the service under significant load is unlikely to
temperature. HDT is determined as the tem- exceed a temperature of 20°C below T' for
perature at which a critical deflection of the semi-crystalline thermoplastics. The primary
sample is obtained. Table 6.11 shows HDT to advantage of crystallinity is therefore chemical
be 620°C below the T of amorphous poly- resistance. This is apparent from Table 6.13,
6
mers. In comparison with room temperature where chemical resistance for different ther-
strength, the strength of the composite is sig- moplastics is indicated in a qualitative way.
nificantly reduced above the HDT. The reason Semi-crystalline thermoplastics have much
better chemical resistance than the amorphous induction welding. There are difficulties in con-
polymers. A notable exception is the high trolling the processes and very few methods
water absorption in PA6,6 caused by offer the promise of portable equipment.
hydrophilic groups in its chemical structure. Various bonding technologies for PEEK com-
The solvent resistance of a large selection of posites have been compared (Silverman and
different thermoplastic composites has been Criese, 1989).The study favored a technique for
reported (Johnston, Towel1 and Hergenrother, fusion bonding with a polyetherimide film.
1991). For most thermoplastics, e.g. PEEK, This approach can also be used in repair of
moisture expansion coefficients of the carbon damaged structures, since the temperature
fiber composite may be taken as 0. Thermal needed is below the T, of PEEK.
expansion coefficientshave been characterized
(Barnes et al., 1990) and are similar to epoxy
6.6 APPLICATIONS
composites. For AS-4/PEEK, the composite
density is 1600 kg m-3. Thermoplastic composites can be used in sim-
For polymers with high Tg, exposure to ele- ilar applications to thermoset composites. The
vated temperature may lead to increased following examples will demonstrate some of
density not connected with crystallinity but the reasons for choosing a thermoplastic com-
with the amorphous state. The phenomenon is posite material. In Europe, the automotive
termed physical aging and leads to a more market for GMT composites is significant.
brittle behavior of the polymer (Kemmish and Rapid processing by compression molding,
Hay, 1985). Further work is needed to eluci- cycle times of typically 30s even for large
date the importance of physical aging to structures, results in cheaper components. In
composite fracture behavior under practical addition, more functions can be integrated
service conditions. For composites processed into each component compared with sheet
at high temperatures, residual stresses will metal structures. Bumper beams dominate the
also affect fracture behavior. The magnitude of automotive market in the US whereas, in
the residual stresses and, consequently, detri- Europe, a wider variety of applications are in
mental effects will increase with increasing commercial production. Typical components
cooling rate (Manson and Seferis, 1992). are subjected to minor loads or impact and
Thermoplastic composites can be joined by surface appearance is not important. Battery
the same methods as thermoset composites. trays, beams supporting the hood, seat sup-
Bolted joint performance has been compared ports, oil trays, engine shields and even the
for thermoset and thermoplastic composites complete front end have been produced for
(Walsh, Vedula and Koczak, 1989) with results Volvo, Volkswagen and others.
in favor of thermoplastic composites. With the In the aerospace market, DuPont has sup-
semi-crystalline thermoplastics, adhesive plied thermoplastic polyimide composites to
bonding requires careful surface preparation the prototype programs for the F-22 fighter
(Kinloch and Taig, 1987).This is because of the aircraft. In the supersonic civil aircraft pro-
good chemical resistance and limited solubil- gram, the same thermoplastic polyimide is
ity of these polymers. However, with careful considered for wing skins. The main reason
surface preparation, as good adhesive bonds for this particular thermoplastic composite is a
are obtained as with thermoset composites. continuous high maximum temperature.
The thermoplastic nature of the matrix offers AS-4/PEKK (unidirectional discontinuous
another possibility: fusion bonding. Different fibers) was used by Bell Helicopter Textron in
methods have been compared (Davies and a V-22 tiltrotor thermoplastic wing rib for bet-
Cantwell, 1993), including hot gas, IR, laser, ter open hole compression behavior than
ultrasonic, vibration, electrical resistance and thermoset composites for high proportions of
128 Thermoplastic resins
I.:'i
Intralaminar Toughness on Transverse Cracking
Strain in Cross-Ply Laminates. Adv. Comp.
Mater. 1:225-34.
Bucknall, C.B. and A.H. Gilbert. 1989. Toughening
of a Tetrafunctional Epoxy Resins Using
! Polyetherimide. Polymer. 30: 213-18.
Budiansky, B. 1983. Micromechanics.Computers and
Structures. 16 6-10.
1
Cantwell, W.J. and Davies P. 1993. Short-Term
Properties of Carbon Fibre PEEK Composites.
In Advanced Thermoplastic Composites, ed.
Kausch, H-H. pp. 173-191. Munich: Hanser.
Carlsson, L.A., ed. 1991. Thermoplastic Composite
Materials. Composite Materials Series, Vol 7.
Fig. 6.3 Thermoplastic composite applications New York: Elsevier.
made by winding: pressure vessel, tubes, sealing Chang, I.Y. 1992. Thermoplastic Matrix Composites
and support rings. (Courtesy: Hoechst AG) Development Update. 37th Int SAMPE Symp.
References 129
Roving Strands. Polymer Eng. Sci. 31: 1316-29. Composite Materials. J. Reinforced Plas. and
Walsh, R, Vedula M. and Koczak M.J. 1989. Comp. 1:297-313.
Comparative Assessment of Bolted Joints in a Williams, D.F. and McNamara A. 1987. Potential of
Graphite Reinforced Thermoset vs Polyetheretherketone (PEEK) and Carbon-
Thermoplastic. S A M P E Quarterly 20: 15-19. Fibre-Reinforced PEEK in Medical
Whitney, J.M., Browning C.E. and Hoogsteden W. Applications. J. Muteu. Sci. Lett. 6 : 188-90.
1982. A Double Cantilever Beam Test for
Characterizing Mode I Delamination of
FIBERGLASS REINFORCEMENT* 7
Dennis J. Vaughan
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
,COAL, F,LMRSPAR ,
LIMESTONE SILICA SAND BORIC ACID
FORYUUTION
U I
I I I
W
DECORATIVE AND
INDUSTRIAL YARN
-1
INSPECTION
AND
r
WEIGHING
TWISTING
J
STRAND W
CHOPPING
7-77-
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
a viscosity in the molten glass that will allow improve dielectric loss properties in electri-
easy drawing. cal applications (similar in performance to
A number of glass compositions are avail- D-glass).
able depending on the properties desired from 0 Hollow fiber: A special glass whose fibers
the resulting fibers (Table 7.2). are tube-like or hollow; the material has
specific applications in reinforced aircraft
A-glass: A high alkali or soda glass is made
parts where weight could be significant.
into fibers for use in applications where
0 Te glass: A Japanese manufactured S-glass,
good chemical resistance is needed.
for higher strength structural application.
E-glass: A low alkali glass, based on alu-
minum borosilicate. This glass possesses
7.4 FIBERGLASS PROPERTIES
excellent electrical insulation properties
and is the premium fiber used in the major- The composition of the original glass melt
ity of textile fiberglass production. probably plays the biggest role in determining
C-glass: A material based on soda borosili- the properties of the fiberglass. The continuing
cate that produces a fiber that offers widespread use of fiberglass in numerous and
excellent chemical resistance. diverse applications can be directly related to
S-2 glass: This glass is made up of magne- its inherent unique properties (Table 7.3). The
sium, aluminum silicate and offers higher suppliers of these materials in the USA are
physical
-~ strength.
- Fibers produced from shown in Table 7.4.
this glass have an approximate per- 0 High tensile strength: Fiberglass has an
cent strength improvement Over exceptionally high tensile strength corn-
those of E-glass composition. pared with other textile fibers. Its strength
D-glass: This fiber made from a low dielec- to weight ratio exceeds steel wire in
tric composition has dielectric loss applications.
properties 'Onstant Of 3.8 at
0 Heat and fire resistance: Because fiberglass
mc s-l) superior to that of E-glass (6.O at is inorganic it does not burn or support
1mc s-l). combustion.
R-glass: A 'Pecial glass that 0 Chemical resistance: Fiberglass has excel-
produces fiber that is alkali resistant and is lent resistance to most chemicals and is
used in reinforcing concrete. impervious to fungal, bacterial or insect
Low K: An experimental fiber produced to
attack.
Table 7.2 Fiberglass compositions (wt.%)
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 0 Thermal properties: Due to its low coeffi-
not absorb water, it neither swells, stretches cient of thermal linear expansion and high
nor disintegrates. Fiberglass does not readily coefficient of thermal conductivity, fiber-
rot and continues to maintain its mechanical glass exhibits excellent performance in
strength in humid environments. thermal environments.
136 Fiberglass reinforcement
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
Chopped strand mat is a non-woven mater- the spirals conform in shape to the central
ial which the fiberglass strands are chopped position of the letter ’S’. Alternatively, a yarn
into 2-5 cm (1-2 in) lengths and evenly distrib- is said to have a ’Z’ twist if the spiral con-
uted at random onto a horizontal plane, bound forms in shape to the central position of the
together with some type of chemical size. The letter ‘Z’.
mats so produced weigh from 2.6-12g/m2 Strands that have a simple twist (greater
(0.7-3.0 oz/ft2)and are available in a variety of than one turn per inch) will kink, corkscrew
widths, 60-230 cm (24-90 in) with 9.6 cm (38 and unravel, because their twist is in only one
in) width being the most typical. direction. The plying operation will normally
Continuous strand mat is made of eliminate this problem by countering the twist
unchopped continuous strands of fiberglass in a twisted ’singles’ yarn with an opposite
deposited and interlocked in spiral fashion. twist in the plied yarn. For instance, a ’singles’
This mat is open and flexible, but due to its yarns which have a ’Z’ twist are plied with an
mechanical interlocking does not require ’S’ twist that will result in a balanced yarn. The
much application of size to achieve adequate twisting and plying operations allow the
handling strength. yarn‘s strength, diameter and flexibility to be
Surface mat, or veil as it is sometimes varied, which in turn allows scope in produc-
called, is a very thin mat of single continuous ing a wide range of suitable woven fabrics.
filaments used frequently as a decorative sur-
face reinforcing layer in hand lay-up or press
7.5.5 TEXTURED YARN
molding processes in order to minimize sur-
face defects and to prevent ’weep’ in ’Singles’ or plied yarn can be textured by using
pressurized wound tanks. a jet of air directed onto the yarn’s surface
which results in random but controlled break-
age of surface filaments, producing a general
7.5.4 TEXTILE FIBERGLASS YARN increased loft to the fiber surface. The term
A yarn can be described as an assembly of used to describe such a process is texturizing
fibers or strands which can be woven into or bulking and the degree to which it occurs
some form of textile material. can be controlled by regulating the air pres-
The continuous individual strand as it sure and yarn feed rate. The texturing process
emerges from the bushing opening represents opens the fiber bundles resulting in some
the simplest form of textile fiberglass yarn and mechanical damage to the surface filaments.
is designated ’singles’ yarn. However, to The increased surface area allows higher resin
ensure the correct and efficient utilization of absorption during impregnation and produces
this yarn in a weaving operation, additional low glass-to-resin ratios, resulting in more eco-
strand integrity has to be added by twisting nomical laminates.
the yarn slightly (less than one turn per inch).
A number of woven fabrics, however, require
7.5.6 YARN NOMENCLATURE
heavier yarns than can be drawn from the
bushing. These heavier yarns can be achieved Because of the wide variety of fiberglass yarns
by combining single strands using a twisting produced, it is necessary to have a precise sys-
and plying operation. This simply involves tem for yarn identification. The standard
twisting one or more single strands together or fiberglass yarn nomenclature is based on both
subsequently plying together two or more of alphabetical and numerical designations.
the twisted strands. The first alphabetical letter identifies the
A yarn can be defined as having an ‘S’ glass composition (E-glass), the second letter
twist if when it is held in a vertical position, 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 7.7 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
.-
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
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
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 over seven and under one filling yam in an
more warp yarns over and under two or irregular pattern. The resulting fabric is
more filling yarns in a regular pattern. This very pliable and readily conforms to com-
produces either a straight or a broken diag- pound contours. Because this weave
onal line in the fabric, which produces pattern allows comparatively high fabric
greater drapeability and stability. counts, it contributes maximum strength to
(d) Crowfoot satin weave: This weave pattern composites reinforced by it.
has one warp yarn interlocking over three (f) Unidirectional fabrics: Fabrics produced
and under one filling yarn in an irregular with heavy warp yarns and light filling
pattern. The fabric that results is extremely yarns, in either crowfoot or long shaft satin
pliable and lends itself to conforming to weaves. The filling yarns can also be com-
complex contours. posed of yarns other than glass. These
(e) Eight-harness satin weave: A fabric con- fabrics offer high strength reinforcements
structed with one warp yarn interlocking in the heavy yarn direction.
146 Fiberglass reinforcement
(g) Non-woven: Unidirectional fabrics that can ments together, lubricate the roving for contact
be produced by sticking the 'warp' and 'fill- with various processing equipment, and to
ing' yarns together chemically. Although permit the glass filaments to be thoroughly
this chemical bonding contributes to the wetted when combined with other materials.
fabric's stability, these fabrics have a firm Fiberglass roving sizes consist of polyvinyl
hand and do not drape over complex con- acetate, polyvinyl alcohol, or PVA/starch as a
tours. film former with the addition of such chemi-
cals as chrome complexes, organosilane
antistatic agents and lubricants that impart the
7.5.8 OTHER WOVEN FORMS
desired strand characteristics.The film former
Fiberglass yarns can also be woven into tapes, aids in adhering the filaments together and
contoured fabrics, fluted core fabrics and three giving strand integrity that will reduce fila-
dimensional fabrics. ment abrasion during fiber drawing, strand
Tapes are usually narrow fabrics [less than conversion and the end use of the rovings by
30 cm (12 in) wide], with a secured selvedge to the fabricator.
prevent unravelling. Contoured fabrics are An organosilane or coupling agent is
woven into a specific geometrical shape. added, that can react with hydroxyl groups on
Fluted core fabrics are two parallel layers of the glass fiber surface and also possesses one
fabric tied together by stringers of woven fab- or more reactive groups to react with other
rics so that the cross-section is triangular or materials, specifically those present in thermo-
rectangular. Three dimensional fabrics are plastic and thermosetting resins. The silane
really planar or fabrics woven with yarns in produces a form of chemical bridge between
three distinct directions within the fabric plane. the glass surface and the resin matrix.
That is, yams are interwoven in: (i) the machine The inclusion of antistatic agents and lubri-
direction, (ii) +45" from the machine direction, cants improves the softness and choppability
or (iii) -45" from the machine direction. of the roving. The selection of a roving size is
based on its resin compatibility, processing
and the expected end use performance.
7.5.9 MILLED FIBERS
The largest percentage of rovings are used in
Continuous fiberglass strands can be hammer processes that require relatively short fiber
milled into very short fiber lengths [approx. lengths (1-5 cm, 0.5-2.0 in). This type is used in
2-6 mm ( H 6 - X in) long]. The actual fiber processes such as spray-up, preform molding,
lengths are determined by the diameter of the bulk molding compounds and continuous
screen openings through which the fibers pass lamination.
during milling. These milled fibers are usually Rovings suitable for chopping are available
used as inert fillers for thermoplastic and ther- in varying degrees of softness; the softer rov-
moset resin systems. ings are generally more difficult to chop, but
they are recommended for use in applications
that require intricate shapes, sharp comers
7.6 SURFACE TREATMENTS
and difficult radii. Conversely, the harder
types of rovings are generally recommended
7.6.1 ROVINGS
for use where the choppability is of prime
In order for fiberglass rovings to be compatible importance and they are used in simple parts
with processing methods and materials, a with minimum contours and radii.
chemical size is applied during the basic fiber Single strand rovings that are commonly
forming operation. The formulation of this size used in filament winding and pultrusion
is designed to hold the individual glass fila- should have good strand integrity, controlled
Design considerations 147
level of broken filaments, good wettability and nated Y) and hydrolyzable groups (designated
uniform processability under controlled ten- X) in materials with a generic structure X,SiRY.
sion. The hydrolyzable groups are intermediaries in
S-glass based rovings have been used in the formation of silanol groups that bond to
applications where the composite needs the glass surface, whereas the organofunc-
increased physical properties ( e g filament tional groups are designed for reactivity or
wound pressure vessels). compatibility with the polymer to be used by
the composite manufacturer. (Table 7.8)
The chemical functionability of the cou-
7.6.2 FIBERGLASS TEXTILE YARNS
pling agent can determine the resistance to
The continuous fiberglass strands that will be varied environments, chemical, physical and
used in weaving are treated at the bushing thermal (Table 7.9). There are many functions
with a starch-oil binder; the general formula that may be attributed to coupling agents at
for such a binder can be a partially or fully the glass-resin interface. They may provide
dextrinized starch or amylose hydrogenated lubrication to protect against abrasion during
vegetable oil, a cationic wetting agent, emulsi- fabrication. The coupling agent mechanism
fying agent and water. These sizes or binders can protect against stress corrosion as a result
are intended to protect the fibers from damage of water incursion and can help improve the
during their formation and subsequent opera- mechanical and electrical properties of rein-
tions of twisting, plying and weaving. forced composites.
Fabrics directly from the loom still have the It is only recently that the engineering and
original binders that were applied at the yarn design criteria in the combination of such dif-
bushing; the warp yarns have also been treated ferent materials as thermosetting and
with a polyvinyl alcohol solution to help pro- thermoplastic polymers with reinforcing of
tect them during weaving. These binders and glass were properly understood. There are a
sizes are not compatible with the resins used number of basic considerations that are com-
by the composite manufacturers and must be mon to the use of fiberglass as a reinforcing
removed prior to impregnation with other media in the production of composites. The
polymers. This is usually accomplished by type form, weave pattern, weight, permeabil-
treating the fabric to carefully controlled ity and alignment of the fibers have direct
time-temperature cycles, which results in com- bearing on the mechanical properties of the
plete removal of all organic material. However, composite. Also in some instances the chemi-
after this heat treatment no suitable interface cal, thermal and electrical properties may also
exists between the fiberglass surface and the be influenced by the judicious choice of rein-
resin matrices that will eventually be used. An forcing material (Table 7.10).
improved interface with resulting good adhe-
sion even in adverse environment conditions
7.7.1 GLASS COMPOSITION
can be achieved by the application of a cou-
pling agent to the glass fiber surface. The chemical composition of the glass can
The most commonly used coupling agents have a direct bearing on the fiber properties
in current use are those termed silanes. The which can indirectly affect composite perfor-
coupling agent mechanism of these mance.
organofunctional silanes depends on a link It has been noted that 'E' glass composition
between the organofunctional group (desig- fibers can contribute 210 000-225 000 psi to the
148 Fiberglass reinforcement
/”\
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
Table 7.9 Effect of coupling agents on the mechanical strength properties of laminates
Filament diameter does not appear to play The effect of variation in the available sur-
an important role in the determination of the face area for stress transfer is affected by the
mechanical properties of such plied yarn fab- coupling agent-resin interaction. Larger sur-
rics as Style 1581 woven with ECG 150 1/2 face areas with poor coupling agents reduces
(EC 9 33 1 x 2 yarn and style) and Style 1281 specific shear loading on the interface and so
woven with ECB 150 1/2 (EC 3.8 33 1 x 2 produces high laminate flexural strengths. But
yarn). However, in comparison with commer- with improved interfacial bonding the surface
cially available singles yarn Style 7781 woven areas effect disappears because other failure
with ECDE 75 1 / 0 (EC 6.66 1 x 0) yarn, sin- modes appear first. Singles yarns produce
gles yarn Style B 7781 woven with finer higher composite strengths due to the smaller
filaments [ECB 75 1/0 (EC3 8.66 1 x 0 yarn)] angle between fiber axis and load axis in the
gives laminates with higher flexural lower twist yarns. This produces less tensile
strengths, flexural modulus and tensile loading across the interface; the magnitude of
strengths. Conversely a singles yarn G 7681 this effect will vary with the resin coupling
woven with coarser filaments [ECG 75 1/0 agent efficiency and the function of the twist of
(EC9 66 1 x 0 yarn)] gives composites with the yarn or the angle of the spiral of the fila-
improved compressive strengths. ments.
150 Fiberglass reinforcement
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
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
~ _ _ _ _
Table 7.12 Mechanical properties of S-glass fabrics-epoxy composites as a function of plied compared
with unplied yarn
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- pattern, weave density and yarn diameters. The
ent. Also, the stress transfer across the material optimum strengths of laminates are obtained
boundaries is greatly affected by the degree of with the lowest practical resin content.
adhesion at the reinforcement-resin interface. With coarse plain weave fabrics using hand
A more subtle effect is the possibility that lay-up, laminates can be produced with resin
wall effects at the surface may alter the matrix contents of 36-38%; with other weaves using
orientation and mechanical properties. less twist in the yarn and optimum yarn spac-
It must also be assumed that there will be ing, excellent physical properties can be
sufficient resin present to fill all of the spaces achieved in the 25% resin content range. Plain
between the fibers. Internal voids have been weave fabrics with higher twist yarn will
shown to produce considerable stress concen- require higher resin contents than low twist
trations resulting in premature mechanical singles fabrics of equivalent weave.
failure of the laminate. Woven fiberglass fabrics In filament winding applications parallel
by virtue of the weave interlocking reduce the strands of fiberglass are wound around a cylin-
effective glass-to-resin ratio below those of fila- drical mandrel, the resulting cross-section of
ment wound structures. The optimum glass to round filaments provides a close packing,
resin ratio then becomes dependent on weave 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 right angles to the other half), the resulting
glass fiber content of 70-75% product final mechanical strengths at either angle is less than
composites with high physical strengths. But, if that of the parallel alignment. As the distribu-
there is any variation from the parallel align- tion of strands varies between 0" to 90"
ment of the glass fibers, this will reduce the alignment to a +45" to a 45", this further
degree of packing and inevitably the optimum reduces mechanical strength in the primary
glass-to-resin ratio. The weaving of glass fab- direction, but shows an increase in the +45"and
rics will of course reduce the effective 4 5 " directions. Of course the yarn distribution
glass-to-resin ratios because of the weave inter- can be varied from 0" and 90" directions as part
locking. The correlation between glass-to-resin of the fabric design. A so called %balanced' fab-
ratios and composite strength is well known, ric, that is one with equal yarn distribution in
the composite's strength increases as resin con- the warp and filling directions, will have com-
tents are reduced (see Table 7.14 and Fig. 7.4). parable composite properties in both directions.
When fiberglass yarn is woven with yarn
primarily in the warp direction with only the
7.7.5 FIBER DISTRIBUTION
minimum amount of filling yarn (enough to
Reinforced composites that have the glass give the fabric stability), the result is a unidi-
strands aligned parallel to each other have rectional fabric. Composites reinforced with
their maximum strength and stiffness in the this type of fabric have the maximum mechan-
direction of the alignment. This type of paral- ical strength in the direction of the greatest
lel alignment is conducive to certain filament concentration of yarn5.
winding and pultrusion operations. The differences between the mechanical
When the reinforcement is aligned at right properties, bidirectional and unidirectional
angles to itself (half of the strands are laid at reinforced composites, can be seen in Table 7.15.
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
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
a, 8
e
e
m irl
N
m
2 5
%
3
2-
I
0
a ti
Y
. 3
F;
3 2
s:
3
%
W W
0 0
8
a,
2 =
.3
m
Fi
Y
. 3 mI
e .I
8
0 8 .3
e
3
.3
m
d
T I
.2 2
C E;
'23
a!3
2 8
.e
3
0 3
m 5 d
0
3
3
X
2
W W
Y
8
2z x
z" rf!
F4
h
3
v1
m
5a
.e
b
m
Y
g
U
$ bD
$
U
.$ 30
s3 e
6
a"
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
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,
Forms 161
diameter Sic fiber (KO, 1989). Fine diameter and two diagonal directions. Figure 8.1 shows
(less than 20 pm) continuous ceramic fiber is the 3D and 5D fabrics. See Ngai (1990) for dia-
more flexible, can be formed into nontwisted grams of 4D, 7D and 11D fabrics.
strands (sometimes called nontwisted yarn) Continuous boron fibers are supplied in the
and braided or woven into two- or three- form of borodepoxy prepreg tape and
dimensional shapes. The quartz fibers, being boron/aluminum preform sheets. The
the most flexible, can be twisted into filament boron/aluminum preform sheets are made by
yarn and braided or woven into two- or three- resin bonding the boron fibers to the side of
dimensional shapes. aluminum foil. The fibers can be aligned in
Figure 8.1 shows some of the many forms any direction. These preform sheets are used
that fibers can take. Each strand of the fine in solid state (low temperature, high pressure)
diameter ceramic fibers can contain anywhere diffusion bonding processes (TextronSpecialty
from 250 to 1000 filaments per strand, depend- Materials, 1993a).
ing on the product. The strands may be Continuous Sic fibers with a core are
bundled to form roving. Fused quartz formed into plasma-sprayed aluminum or
untwisted strands are formed into roving that titanium preform sheets for hot molding (a
contains either 2880 or 4800 filaments per rov- low pressure, hot pressing process) and into
ing. As mentioned earlier, fused quartz fibers ’woven fabric’ for investment casting or diffu-
may be twisted into yarn at 4 turns per inch, sion bonding. In diffusion bonding, the fabric
with 120, 240, 480, 960, or 1920 filaments per is placed between two metal foils prior to con-
yarn and in a variety of yarn constructions. solidation. The ’woven fabric’ is similar to
Fine diameter ceramic and fused quartz fibers nonwoven roving because the fibers are
can be formed into many multidimensional aligned in one direction and held together by a
structures, such as orthogonal nonwoven fab- cross-weave of metallic ribbons (Textron
rics (Fiber Materials, Inc., 1993; KO, 1989). Specialty Materials, 199313; Mittnick 1990).
Orthogonal nonwoven fabrics are so-called Continuous high silica fibers are processed
because there is no interlacing of fibers. Other into a variety of forms such as cloth, tape,
names for these fabrics are xyz fabrics, multi- sleeving, yarn, cordage, rope, nonwoven mat,
directional preforms and 3D, 4D, 5D, 7D or blanket, felt, rigid tile and sewing thread.
11D woven blocks. The 5D, 7D and 11D blocks Alumina-silica staple fibers are made into
have strands going in the three orthogonal paper, rigid board and cylinders, other rigid
directions and in diagonal directions. The 4D three-dimensional shapes and into most of the
blocks have strands going in two orthogonal high silica fiber forms. Alumina staple fibers
are processed into paper, mat, felt, blanket,
rigid board and cylinders and other rigid
Footnotes for Table 8.2 three-dimensional shapes.
aAll values, except those for silicon carbide whiskers, are
from the manufacturers’ product literature.
Test methods may varv between manufacturers.
i ,
8.8 APPLICATIONS
All values are averages, are for reference only and are
not to be taken as a specification. Table 8.3 provides a sampling of the many
Most fibers are under continual development. Contact applications for boron, high silica, fused
the manufacturers for the most up to date property values.
DNA = Data Not Available.
quartz and ceramic fibers. For other applica-
The silicon carbide whisker values are from Petrovic and tions, see Bracke, Schurmans and Verhoest
Hurley (1990). (1984), Mortensen and Koczak (1993),
This value in metric units was converted from a value
that was given in English units.
Schwartz (1992) and the other chapters within
Most of the tradenames are registered trademarks. Each this handbook.
trademark belongs to the manufacturer listed to its left
164 Boron, high silica, quartz and ceramicfibers
0
U
0
mI
U
0
0-
I N
$3
mz
2
m
z
0
B
4 812 271. Mar. 14, 1989. Assigned to Mitsui Price, G.B. and Kielmeyer, W.H. 1980. Method for
Mining Co Ltd. Making I-ligh Purity, Devitrification Resistant,
LaBelie, Jr., H.E.1980. EFG, The Invention and Amorphous Silica Fibers. US Patent 4 200 485.
Application to Sapphire Growth. J . Crysf. Apr. 29, 1980. Assigned to John-Manville Gorp.
Growth 50 (1980): 8-1 7. Richerson, D.W. 1992. Modern Ceruniic Engineering,
L,asday, S.B. 1993. Ceramic/Ceramic Composite 2nd edn. New York: Marcel Dekker, Inc.
Components Advance Furnace Systems and Schwartz, M.M. 1992. Composite Materials I$andbook,
Processes. lndiistriai Heating LX (4): 26-9. 2nd edn. ed. M.M. Schwartz. New York:
LeGrow, G.E., et al. 1987. Ceramics from McGr a w-Hill , Inc .
tlydridopolysilazane. A m Ceram. Soc. B d l . 66 Shalek, P.D. 1987. Process for Growing Silicon
(2): 363-67. Carbide Whiskers by Undercooling. US Patent
Milewski, J.V., et al. 1985. Growth of Beta-silicon 4 702 901. Oct. 27, 1987. Assigned to The United
Whiskers by the VLS Process. 1. Mater. Sci. 20 States of America.
(1985): 1160 66. Shalek, P.D., Katz, J.D., Hurley, G.F. 1988.
Milewski, J.V. 1991. Whiskers. In Concise Prealloyed Catalyst for Growing Silicon
Encyciopediu oj Advanced Cmutric hlatwials, ed. Carbide Whiskers. US Patent 4 789 537. Dec. 6,
R.J. Brook, pp. 516-19. Oxford: Pergamon Press. 1988. Assigned to The United States of America.
Mittnick, M A . 1990. Continuous S i c Fiber Schramm, Dale E. 1988. Process for Producing
Reinforced Metals. SME Metal Matrix Clinic, Silicon Carbide Whiskers. US Patent 4 789 536.
13-14 R-ovember 1990, at Anaheim, Ca. Dec. 6, 1988: Assigned to J.M. Huber Corp.
Mohn, W.R. and Vukobratovich, D. 1988. Engineered Sowman, H.G. 1988. Alumina-Boria-Silica Ceramic
Metal Matrix Composites for Precision Optical Fibers from the Sol-Gel Process. In Soi-Cel
Systems. SAMPE J . 24 (1):26--35. Technology for 7 h i n Films. Fibers. Prefornzs.
Mortensen A. and Koczak, M.J. 1993. The Status of Electronics. und Specialty Shapes, ed. Lisa C .
Metal-Matrix Composite Research and Klein, pp. 162-83. New Jersey: Noyes
Development in Japan. ]OM 45 (3): 10-18. Publications.
Motojimi, S., et nl. 1989. Preparation of Whiskers 'Takeda, M. rt al. 1992. Thermal Stability of the Low
and Spring-like Fibres of Si,N, By Impurity- Oxygen Silicon Carbide Fiber Derived From
Activated Chemical Vapor Deposition. J. Cryst. Polycarbosilane. Ceram. Eng. Sci. Proc. 13 (7--8):
Growth 96: 383-89. 209-1 7.
hhik, S.K., et a / . 1991. Ceramic Matrix Composites Tanaka, M., Kawabe, T. and Kobune, M. 1986.
and its Application in Gas Turbine Engines. Method of Manufacturing Crystalline Silicon
Presented at the International Gas Turbine and Carbide Employing Acid Pretreated Rice
Aeroengine Congress and Exposition, 3-6 June Husks. US Patent 4 591 492. May 27, 1986.
1991, in Orlando, F1. Assigned to Tateho Kagaku Kogyo Kabushiki.
Narasimhan, K. and Bhat, D.G. 1992. Process for Tech Trends 1990. Ceramic Matrix Composites:
Producing Single Crystal Titanium Carbide Technology and fndustriul Applications. Paris:
Whiskers. US Patent 5094711. Mar. 10, 1992. lnnovation 128.
Assigned to GTE Valenite Corporation. 'Textron Specialty Materials 1993a. Boron
Ngai, T. 1990. Carbon-Carbon Composites. In Aluminum Preform Sheets. Textron Specialty
lnternational Encyclopedia of Composites, ed. Materials. Lowell, MA, USA.
Stuart M. Lee, pp. 158-87. New York: VCH Textron Specialty Materials 1993b. Continuous
Ptiblishers. Silicon Carbide Metal Matrix Composites.
Pearson, A. and Easley, M.A. 1992. Process For Textron Specialty Materials. Lowell, MA, USA.
Production of Small Diameter 'Titanium Carbide Tricoles, G.P. 1988. Radome Electromagnetic
Whiskers. US Patent 5 160 574. Nov. 3, 1992. Design. In Antenna Handbook, ed. Y.T. Lo and
Assigned to Aluminum Company of America. S.W. Lee, pp. 31-1 to 31-31. New York: Van
Petrovic, J.J. and Hurley, G.F. 1990. Nostrand Reinhold.
Vapor-Liquid-Solid (VLS) S i c Whiskers: Tsirlin, A.M. 1985. Boron Filaments. In Strong Fibres,
Synthesis and Mechanical Properties. In Fiber ed. W. Watt and B.V. Perov, pp.155-99. Vol.1 of
Reinforced Ceramic Conzposites, ed. K.S. Handbook of Composites, Series ed. A. Kelly and
Mazdiyasni, pp. 93-121. New Jersey: Noyes Yu. N. Rabotnov. Amsterdam: Elsevier Science
Publications. Publishers R.V.
168 Boron, high silica, quartz and ceramicfibers
Wagner, R.S. 1970. VLS Mechanism of Crystal Xiao, H., Ai, X and Yang, H.S. 1993. Effect of
Growth. In Whisker Technology. ed. Albert P. whisker orientation on toughening behavior
Levitt, pp. 47-119. New York John Wiley & and cutting performance of SiCW-A1203 com-
Sons. posite. Mat. Sci. Technol. Vol. 9:21-25.
Wawner, F.E. 1988. Boron and Silicon Yajima, S. 1985. Silicon Carbide Fibers. In Strong
Carbide/Carbon Fibers. In Fibre Reinforcements Fibres, ed. W. Watt and B.V. Perov, pp. 201-37.
for Composite Materials, ed. A.R. Bunsell, pp. Vol.1 of Handbook of Composites, Series ed. A.
371425. Vol. 2 of Composite Materials Series, Kelly and Yu. N. Rabotnov. Amsterdam:
Series ed. R.B. Pipes. Amsterdam: Elsevier Elsevier Science Publishers B.V.
Science Publishers B.V. Yamamoto, A. 1985. Process for Preparing Silicon
Weddell, J.K. 1990. Continuous Ceramic Fibers. 1. Carbide Whiskers. US Patent 4 500 504. Feb. 19,
Text. Inst. 81 (4): 333-59. 1985. Assigned to Tokai Carbon Co Ltd.
Withers, J.C., Loutfy R.O. and Lee, C.T. 1988. Yamamura,T., et al. 1988. Development of a New
Process to Produce Titanium Diboride Whiskers Continuous Si-Ti-C-0 Fibre Using an
as Reinforcement for Metal and Ceramic Organometallic Polymer Precursor. 1.Mater. Sci.
Composites. NSF Grant ISI-8760300. National 23: 2589-94.
Science Foundation, Washington D.C. October
1988.
CARBON FIBERS 9
Khalid Lafdi and Maurice A. Wright
thermal conductivity parallel to the fiber axes. properties (o/p, E/p) tend to remain relatively
Unfortunately, large graphitized regions tend to constant; structures designed to resist a given
produce high local stress concentrations, espe- set of loads tend to weigh the same irrespective
cially if they are misaligned (Reynolds and of whether they are made from aluminum, tita-
Sharp, 1974; Reynolds and Moreton, 1980). nium or steel. These mechanical property/
'rhus, pitch-based fibers tend to exhbit high density relationships are not followed by car-
modulus and high electrical and thermal con- bon fibers; so, compared with metals, similar
ductivities, but low strength. PAN-based fibers structures made from carbon fiber reinforced
tend to be of intermediate modulus and rela- composites will be lighter.
tively high strength. The most successful use of carbon fiber rein-
The mechanical properties of structural met- forced materials has been for military
als generally vary in direct proportion to purposes, especially aeronautical structures
density. Thus, as shown in Table 9.1, the specific (Schwartz, 1984; Hadcock, 1982). Composite
use in civilian aviation has been more limited, a precursor material is prepared, spun into a
largely because of cost. However, in 1985 the fibrous shape, stabilized to change it from a
European Airbus consortia used carbon/epoxy thermoplastic to a thermoset, then heated until
vertical stabilizers on their A310 and, since all unwanted elements are expelled. Depending
1993, delivered their A340 and A330 models on the final heat treatment temperature, a fiber
equipped with composite tail sections, floor is produced that is primarily carbon. A strik-
panels, landing gear doors and carbon-carbon ingly similar production technique is used to
brakes. The new Boeing 777 and the projected produce either type of fiber; however, the initial
McDonnell-Douglas MD-12 contains similar pretreatment and the chemical reactions that
composite structures (High-Performance occur within either PAN or pitch during stabi-
Composites, 1994). lization and carbonization are markedly
different. These differences are discussed in the
following sections since they determine the
9.2 OVERVIEW
ultimate properties and the cost of the carbon
Ln this chapter we have chosen to combine, fibers that are produced.
rather than separate, the discussion of the
preparation of carbon fibers from PAN or from
9.2.1 POLYACRYLONITRILE
pitch. This style of presentation is attempted
since the methods used to fabricate carbon The chemical composition of PAN-based pre-
fibers from either of these precursor materials cursors tends to be proprietary; however, in
seem to be almost identical, as shown in general it consists of small diameter linear
Fig. 9.1; for example, both methods involve the molecules that are made up from nitrogen,
preparation, spinning and subsequent thermal hydrogen and carbon (Fig. 9.2). Spinning
degradation of organic precursors. Essentially, 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
fiber axis, but they continue to be randomly of carbon fibers from PAN is relatively minor;
oriented transverse to that direction. Thus, a more important is the chemical makeup of the
fiber with a twisted fibrillar structure is pro- PAN and the presence of small amounts of
duced. This fiber is supplied by the textile other constituents that influence the complex
industry to the carbon fiber fabricator who sta- chemical reactions that occur during stabiliza-
bilizes it under tension before converting it tion and carbonization. Stabilization involves
into a carbon fiber using a controlled heat cyclization of the oriented molecules and
treatment process. Apart from the obvious results in the release of most of the hydrogen
generation of the fibrous shape, the impor- and part of the nitrogen as NH, and other
tance of the spinning process to the fabrication 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).
Pitch precursor treatments 173
retained nitrogen is very important to both the Mochida et al., 1988; Lewis and Nazem, 1987a).
crosslinking process and to the development Today, fibers are produced commercially from
of optimum properties during carbonization. rayon, PAN and the various pitches. However,
the process to produce fibers from rayon is
very expensive because it involves stretching
9.2.2 PITCH
at very high temperatures and the yield of car-
A pitch precursor taken from a petroleum or bon after carbonization is small. Rayon-based
coal tar feedstock initially contains individual fibers are therefore fabricated in such small
molecules that exhibit appreciably different amounts that they are really of no commercial
molecular weights. These untreated precur- importance. Additional information can be
sors have been used to produce fibers; obtained from: Yanagida et al., 1991; Bacon,
however, they are isotropic and exhibit rela- 1973; US Patent 3107152, 1963; Yoneshoga
tively poor mechanical and physical and Teranishi,l970.
properties. Conversely, the carbon fiber pro-
ducer can pretreat the pitch to develop a
9.3 PITCH PRECURSOR TREATMENTS
continuous anisotropic phase (similar to a
mesophasic liquid crystal) or a two phase mix- A typical pitch precursor material is obtained
ture that becomes highly oriented during the from either the distillation products involved
subsequent spinning process. In contrast to the in the chemical treatment of decanted oil or as
chemical changes occurring in PAN, physical a by-product of the production of metallurgi-
changes are responsible for the final properties cal coke from coal. In a conventional
of pitch-based carbon fibers. Essentially, the as-received pitch, basic structural units (BSUs)
precursor isotropic pitch is pretreated to pro- are already present to a degree that pitch can
duce a two phase mixture that is be considered a random suspension of highly
predominantly anisotropic. During spinning aromatic molecules similar to coronene (mole-
and drawdown, this mixture is very strongly cular weights between 600 and 900)
oriented both parallel and transverse to the surrounded by a liquid of smaller molecular
fiber axis. Oxygen added during stabilization weight. Heating such a system initially
tends to crosslink these large molecules in a reduces the viscosity. Eventually, however, the
simple way before being released on car- viscosity increases as the BSUs grow and coa-
bonization as CO, CO, and H,O. More recent lesce to form larger entities (molecular weights
interest has centered on producing fibers from between 1000 and 4000) with a specific long
synthetic pitches. These require no extensive range anisotropy called 'mesophase' (Brooks
pretreatment and they stabilize faster at a and Taylor, 1965). Continued heating eventu-
given temperature. Fibers made from these ally causes an inversion in which the
pitches should cost less to produce. mesophase spheres become the continuous
Precursor materials that have been used to anisotropic phase within which are suspended
produce carbon fibers include: polyamides, spheres of the isotropic low molecular weight
polyesters, polyvinyl alcohol, polyvinylidene material. The rate of viscosity increase is very
chloride, poly-p-phenylene, phenolic, naptha- slow at low temperatures, but accelerates as
lene, naphthalene-phenanthrene, alkylbenzenes, the temperature is increased. At temperatures
rayon, polyacrylonitrile (PAN) and various greater than 350°C, the pitch begins to form
petroleum, coal tar and synthetic pitches coke by a process of thermal degradation and
(Ezekiel, 1969; US Patent 3 533 741, 1970; gas evolution. The variation in viscosity with
Shindo, Nakanishi and Soma, 1969; Boncher, temperature for numerous pitch fractions has
Cooper and Everett, 1970; French Patent 1535 been documented (Bathia, Fitzer and
800, 1968; Kawamura and Jenkins, 1970; 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-
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- A 1980 patent (US Patent 4 208 267, 1980)
cosity of any pitch is greater the more discussed a different method of producing
anisotropic phase it contains. By cooling after isotropic/anisotropic pitch mixtures. The
partial reaction, it is possible to produce a two method essentially consists of dissolving part
phase pitch with a viscosity appropriate for of the original isotropic pitch in an organic sol-
spinning or infiltration. vent such as benzene, toluene, xylene, etc. The
A number of experiments have been carried material that is insoluble can then be con-
out designed to accelerate the process of pro- verted, by heating, into a material that is
ducing two phase pitch mixtures. These greater than 75% anisotropic. The efficiency of
involved heating, stirring, bubbling an inert this process is quite poor however, since only
gas through the liquid (sparging), or the com- a \Tery small amount of this 'neomesophase'
bination of stirring and sparging (US Patent can be produced from a given pitch. For
3 629 379, 1971; US Patent 3 919 383, 1975; US instance, using Ashland A260 pitch, about
Patent 3 974 264, 1976; US Patent 4017327, 75-90% of the initial pitch will dissolve.
1977). In this way, an appropriate anisotropic Using Ashland A240,80-905:1 of the pitch dis-
concentration can be produced in much shorter so1v es.
time periods (hours instead of days) with Variations of the gas-sparge process fpossi-
improved spinning characteristics. This latter bly associated with a chemical fractionation)
characteristic seeins to be associated with the can be made to change the characteristics of a
smaller molecular size existing within the two resultant pitch. Lafdi, Bonnamy and Oberlin
phase mixtures formed by stirring and sparg- (1991a; 1991b; 1991c; 1992) and Lafdi and
ing and the smaller variation of molecular size. Oberlin (1994a;1994h) have indicated that
Spinning conditions 175
some pitches exposed to a nitrogen sparge at acetamide before extruding it into a ’coagula-
atmospheric pressure or a hydrogenation tion’ bath through a spinneret. In the
treatment at high pressure produce a continu- wet-spinning process, the fiber is solidified by
ous strongly anisotropic material that contains using a coagulant (such as ethylene glycol)
small particles of a weakly anisotropic mater- which extracts the solvent from the polymeric
ial. During spinning, the second phase fiber. In a manner similar to the dry spinning
becomes completely absorbed (or trans- process, the rate at which the solvent is
formed) to produce a uniformly anisotropic extracted from the polymer as it passes
fiber. They believe that sparging disturbs the through the coagulation bath governs the final
formation of an anisotropic phase that shape of the fiber. The temperature, concentra-
exhibits large differences in molecular weight. tion and circulation rate of the fluid in the
Indeed, they suggest that the spheres of coagulation bath are known to affect the struc-
anisotropic material contain BSUs that are ture and hence the physical and mechanical
only weakly associated. In contrast to the properties of as-spun fiber. Many companies
strong molecular orientation exhibited by the have added a supplemental stage to the spin-
Brooks and Taylor type of ’mesophase’ ning process that is designed to reduce the
(Brooks and Taylor, 1968), the common orien- water content. This additional step tends to
tation of this new anisotropic material results increase the molecular orientation within the
from the statistical orientation of small units. fiber (US Patent 3846833, 1975; US Patent
The pitch then behaves as a two component 3 841 079,1974).
gel which exhibits a long range anisotropy in A typical acrylonitrile-based precursor con-
the bulk. The short range change in orientation tains several percent of various co-monomers
of the carbon units produces sharp changes in such as methyl acrylate or vinyl acetate which
orientation similar to grain boundaries. Such improve the precursor’s spinnability or fabric
regions produce a zig-zag nanotexture in the properties. Though not added to aid car-
resultant carbon fiber that prevents inter-sheet bonization specifically, they have been found
gliding and provides a crack inhibiting func- to influence the properties of the resulting car-
tion that contributes to relatively high ultimate bon fiber. Many modified PAN polymers such
strength values. as acrylonitrile-hydroxyethylene, acryloni-
trile-vinyl chloride-itaconic acid (French
Patent 2 328 723), polyacrylomidoxium (US
9.4 SPINNING CONDITIONS Patent 3 767 773,1973) have been investigated
to obtain a suitable as-spun fiber capable of
9.4.1 POLYACRYLONITRILE
producing a fiber with a large carbon yield
Dry and wet spinning of polyacrylonitrilepre- after carbonization.
cursors have been used. In the dry process the
polymer is solubilized and spun into a current
9.4.2 PITCH
of hot air that removes the solvent.
Unfortunately, solvent removal tends to be According to Singer (US Patent 3919383
quite rapid and can cause the outer portion of (1975)), in order to spin a fiber, pitch must be
the fiber to solidify before the solvent can dif- heated to produce a viscosity between 10 and
fuse from the fiber’s center. The large diffusion 200 poise (1-20 Pa s). However, temperatures
gradient that develops can seriously affect the greater than about 35OOC cannot be used to
final shape of the fiber (Edie and Diefendorf, obtain the required viscosity because thermal
1993). The more common wet spinning decomposition of the pitch will occur. In addi-
method involves solubilizing the polymer tion, spinning should be carried out above a
with a polar solvent such as dimethyl minimum temperature of about 200°C since
176 Carbon fibers
this determines the maximum temperature The spinning of two phase mixtures is not
that can be used in the subsequent stabiliza- an easy commercial operation since the phases
tion step. These temperature requirements exhibit different viscosities and densities. The
define a processing window into which suit- strongly anisotropic continuous phase con-
able pitches must fall. Using literature data tains within it a less anisotropic (or isotropic)
(Lewis and Nazem, 1987a;Mochida et al., 1988; phase which exists as spheres. If the diameter
Yanagida et al., 1991), White (1992) has shown of the spheres is large relative to the spinning
that the smallest window exists for 100% orifice, localized weak sections of extrudent
anisotropic pitches processed from coal or can be produced that can break and make it
petroleum. A larger window exists for material difficult to maintain a continuous fiber thread.
partially transformed from the same precur- In addition, since the stabilization rates of each
sors; however, as shown in Fig. 9.5, the largest phase differ, one phase may be over stabilized
window exists for synthetic pitches. 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
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.
Stabilization of polyacrylonitrile 177
carbonization (Lavin, 1992; Yooh, Korai and 260°C for a period of time that varies between
Mochida, 1994).The operation is identical for thirty minutes and several hours. During sta-
both PAN and pitch based fibers. However, bilization, several interdependent chemical
the stabilization of anisotropic pitches reactions occur. The reaction that dominates is
involves simple cross linking of plate-like primarily determined by the chemical compo-
molecules whereas the stabilization of PAN sition of the initial precursor, the spinning
involves many different chemical reactions. history, the final composition of the as-spun
Stabilization of both PAN and pitch is an fiber and the stabilization heating schedule.
exothermic process, so great care must be A PAN polymer mainly consists of acry-
taken to control the rate of reaction and to lonitrile entities -CH,CH(CN)- which are able
avoid thermal runaway which melts the fiber to cyclize (Johnsonet al., 1972)with the help of
and is a fire hazard. an initiator into a presumably linear ’ladder
Commercial stabilization is carried out by polymer’ similar to that shown in Fig. 9.7. In
heating the PAN fiber in air between 200 and general, the pendant nitrile groups of PAN
I
CN CN CN
PAN
CYCL’ZATloN
Fig. 9.7 The process of PAN stabilization and subsequent carbonization (Fitzer and Heine, 1988).
Stabilization of polyacrylonitrile 179
first become crosslinked to form a ladder poly- A balance should be kept during stabiliza-
mer. Initiation of this process is catalyzed in tion as to hydrogenation degree. A large
some cases by the presence of a small amount hydrogen content can result in a small N/C
of reactive copolymer such as itaconic acid. ratio which increases the temperature at which
Oxygen is then incorporated into the ladder the local molecular ordering occurs.
polymer under a number of possible schemes Conversely, increasing the available oxygen
which have been described by Watt and decreases the size of and the temperature at
Johnson (1975) and by Clarke and Bailey which the units of local molecular order
(1973) and are shown in Fig. 9.8. Cyclization (LMOs)are formed. In addition, since the vis-
and stabilization induce tremendous shrink- cosity increases as crosslinking (stabilization)
age into the polymer. Longitudinal shrinkage proceeds, the mobility and growth rate of the
is resisted mechanically; however, the diame- LMOs decrease; hence their final size remains
ter of the fiber is allowed to decrease. 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 mal product, i.e. forming the LMOs at the
the properties of the fiber. In order to ensure smallest reasonable temperature, retaining the
appropriate N/C ratios at reasonable temper- largest nitrogen content beyond the tempera-
atures, stabilization should result in only a ture of LMO formation and incorporating an
moderate degree of crosslinking. In addition, optimum amount of oxygen during stabiliza-
slow heating rates during precarbonization tion to prevent polymer melting without
should permit hydrogen and delay nitrogen inducing too small a LMO size.
emissions; both of these effects lower the tem- It is known that the overall oxygen content
perature at which extensive formation and should be between 8 and 12 wt.% in order to
growth of LMOs occur. completely stabilize PAN fibers (US Patent
A commercially acceptable rate of stabiliza- 4069 297, 1978). Less than 8 wt.% oxygen
tion requires the use of as high a temperature gives a large weight loss on carbonization due
as possible. However, since the reactions that to excessive evolution of gases from the
occur during stabilization are exothermic, it is incompletely stabilized central core; more than
most important to limit the oxidation rate and 12 wt.% oxygen degrades surface layers and
to prevent uncontrollable temperature the properties of the final fiber (Johnson, Rose
increases. These conflicting requirements have and Scott, 1970). Exactly what an average
resulted in the development of alternative value of 8 wt.% translates into for the specific
methods of stabilization. These include stabi- oxygen content of the surface layers and the
lization in: hydroxylamine solution (US Patent core region is unknown, but it would obvi-
3 767 773, 1973), aminophenoquinones (US ously depend on fiber diameter and the
Patent 4 004 053, 1976), aminosiloxanes (US kinetics of the stabilization process (diffusion
Patent 4 009 248,1977), amine salts (US Patent or reaction controlled). A large diameter PAN
4 009 248, 1977; US Patent 4 024 227, 1978; US fiber containing an average of 8 wt.% oxygen
Patent 4 031 288, 1978) or stabilization in gas exhibiting diffusion controlled stabilization
phases such as mixtures of NO and NO,, Br, kinetics would probably be composed of
and 0,, or HC1 and 0,. Other stabilization highly degraded surface layers with perhaps
processes have been proposed that are an under-stabilized central core. Conversely, a
designed to reduce the cost and/or decrease very thin fiber exhibiting reaction controlled
the stabilization time. It seems possible to stabilization kinetics might be completely and
reduce the time by stabilizing the fibers in per- homogeneously stabilized with an average
sulphate (US Patent 3 650 668, 1972), cobalt oxygen content of less than 8wt.%.
salt (US Patent 3 656 882,1972), nitric acid (US Presumably a similar statement can be made
Patent 3814377, 1974; US Patent 3 656 883, for the stabilization of pitch fibers. In the sta-
1972), or to control the final quality of the fiber bilization process, the effect of fiber diameter
by stabilizing in carboxylic acid (US Patent on the rate of oxygen uptake is important. The
3 814 377, 1974; US Patent 3 656 883,1972), or three curves shown in Fig. 9.9 illustrate the
nitrophenol. Processes designed to produce slower rate of oxygen uptake exhibited by fat-
fibers of larger modulus have also been devel- ter fibers. In addition, larger diameter pitch
oped. These involve stretching the precursor fibers tend to exhibit a diffusion controlled sta-
during stabilization (US Patent 3 917 776,1975; bilization that produces an under-stabilized
US Patent 3 677 705,1976). central core and an over-stabilized fiber skin.
Fiber manufacturers attempt to fit the Smaller diameter pitch fibers appear to exhibit
physico-chemical conditions of the various reaction controlled stabilization since no skin-
operations cited above (nature and proportion core type microstructures are observed.
of the co-monomers, cyclization, stretching,
stabilization, carbonization) to obtain an opti-
Chemical changes during carbonization 181
.................... ________---------
=
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
fibre axis
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)
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.)
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
,,
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
Mechanical properties offibers 189
(a)
I I I I iil
scale factor, w is the distribution shape factor tion of the same fiber by a shear process. The
and a is a function of the length/diameter length of matrix required to do this defines a
(L/d) ratio of the fiber (Corten, 1967). bundle of short fibers (or segment of compos-
If many fibers are tested of different length ite) which must break in order to break the
I, then a graphical method can be used to composite. Such bundles can be modeled as
deduce w, a and a. and, the mean strength and analogous to a link within a chain; failure of
the strength of a bundle of fibers can be com- the weakest link defines the failure load of the
puted from composite. Nevertheless, since shorter fiber
bundles are stronger than longer, shorter links
om=oo(i/d)-lw(i + i/c~), (9.3)
are stronger than longer links.
where r is the gamma function and The link length, 6, has been discussed by
Rosen (1964) and, for purposes of this discus-
Gb=oo(acl)e)-'lY (9.4) sion can be approximated by,
Bundles of twisted fibers would exhibit lower
strengths. 6=~ d / 2 ~ (9.5)
where o = obthe stress in the fibers at failure of
the composite, d is the diameter of the fiber
9.10 COMPOSITES FABRICATED FROM
and z is the shear strength of the matrix or
CARBON FIBERS
matrix-fiber bond as it exists in the composite.
Carbon fibers are very strong, stiff and light- For a given fiber strength distribution, the
weight materials. In addition, their small stronger composites will all exhibit smaller
diameter (8-12 p)makes them extremely ineffective (link) lengths. This is accomplished
flexible. Unfortunately, they exhibit little com- by using small diameter fibers, well bonded
pressive strength and they exhibit a poor using high strength glue.
abrasion resistance. A solution to these prob-
lems, and to the problem of brittleness, is to
9.10.1 SURFACE TREATMENT
bond large numbers of fibers together to form
a composite solid. In this case, the glue or A freshly prepared fiber does not bond well to
bonding agent forms a continuous phase that a polymeric glue (or to anything else for that
is usually defined as the matrix. The matter); however, the tendency to bond can be
matrix-fiber mixture is called a composite significantly increased by subjecting the fiber
material. The function of the matrix is to sup- surface to a controlled oxidation. As discussed
port and separate the fibers, to protect them by Eggs, Shuford and Lewis (1982) in the ear-
from reaction with the environment and to lier edition of this handbook, this treatment
transfer load. In a composite, the tensile and essentially etches the surface, cleans it,
compression properties parallel to the fibers increases its surface area and produces polar
are much better than those measured on bun- hydrophilic oxygen-containing groups which
dles. The transverse properties are also bond to it. The process can be carried out in a
optimized, since the matrix serves to improve liquid or gaseous environment; for example,
the fiber-matrix connectivity. This function is heating in air or oxygen-nitrogen mixtures,
important since it affects the mechanical and CO,, C1, NOz-NO, NH, and plasma-ionized
thermal properties in the transverse direction. inert gases oohnson 1969; US Patent 3 754 957,
Fortunately, although the strength of individ- 1973a; US Patent 3 723 150, 1973b; British
ual fibers exhibits a pronounced size effect, no Patent 1341 161, 1973; U.S Patent 4 374 114,
size effect is exhibited by composites. In effect, 1983; US Patent 3 627 466, 1971; US Patent
load is transferred around fiber breaks into 3767774, 1973; US Patent 3780255, 1973).
adjacent fibers and back into the unbroken sec- Direct wet chemical oxidation has been tried
Mechanical properfies of unidirectional composites 191
using aqueous nitric acid, hypochlorite, chlo- crack by interaction with low strength
rate and dichromate in sulfuric acid. fiber-matrix bonds; strengthening depends on
Treatments have also been investigated using load being transferred from the matrix to the
electrolytes of hypochlorite, ammonium fibers through a strong fiber-matrix bond.
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 9.11 MECHANICAL PROPERTIES OF
Patent 3 859 187, 197513; US Patent 3 746 450, UNIDIRECTIONALCOMPOSITES
1973; US Patent 3989802, 1976; US Patent
The properties of unidirectionally reinforced
3832297, 1974; US Patent 3671422, 1972;
composites are strongly orthotropic.
British Patent 1371621, 1974; British Patent
Specifically, properties measured parallel to the
2 071 702,1981) .
fibers are quite different from those measured
During oxidation, the strong carbon-oxy-
at right angles to them. More importantly per-
gen complexes which are formed bond
haps is the sensitivity of property
tenaciously to the fiber surface and will subse-
determination with respect to the direction of
quently react with a matrix resin. In order to
the measurement. For example, Fig. 9.21 illus-
preserve this reactivity a thin layer of the final
trates the change in elastic properties exhibited
matrix resin is applied to the surface of the
when a unidirectionally reinforced composite
fibers as a finish or size. This layer does dou-
is loaded at some angle to the fiber axis. In this
ble duty in both protecting the fiber surface
case, it can be observed that the stiffnesses of
against damage during transportation, further
the composite (Qll,etc.) begin to change signif-
processing and handling and in promoting
icantly when the load is misaligned only fifteen
wetting when the sized fibers are bonded
degrees to the fiber axis.
together with the matrix resin.
Poor bonding is a sensitive function of the
surface morphology, anisotropicity, hetero-
9.11.1 MICROMECHANICS
geneity and the nature of the interphase layer
between the fiber and the matrix. For example, Using micromechanics, various equations can
it has been found that the greater the degree of be used to estimate the properties that might
graphitization and the better the alignment of be exhibited by well bonded composites. For
the microstructure with respect to the fiber example, parallel to the fibers, the modulus
axis, the poorer the fiber will bond. and Poisson's ratio y2are
(E,), strength (0,)
Essentially, the higher modulus carbon fibers given by;
will not bond easily in the absence of a surface
E , =Vf E, + Vm Em (9.6)
treatment. In some composites where the fail-
ure strain of the matrix is smaller than the ol=vfof+ vm0, (9.7)
failure strain of the fibers (as it is for ceramics
or carbon), poor bonding is an asset since the '12 = Vfv12 + 'mum (9.8)
largest fiber-matrix bond strength is not o2z om (9.9)
required. Conversely, if the failure strain of the
matrix is larger than that of the fibers, a strong where V is the volume fraction of fibers (0 or
bond is desired. The reason for this apparent matrix (m) respectively, ofis the strength of a
dichotomy involves the fact that fibers are bundle of fibers with length equal to the inef-
added to brittle matrices primarily to toughen fective length (usually, due to lack of statistical
them; only tough matrices (large failure strain) data ofis taken as the mean strength supplied
can be strengthened. The mechanism of tough- by the fiber processor). Also,
ening depends on the blunting of a running
192 Carbonfibers
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
or (9.15)
1.2 160
1.o
a 0.8 120
a .-
(I)
(3 0.6 80 x-
LL' 0.4 LX
g 0.2 40 g-
m
F! = o O E
5 -0.2 -40 i5
-0.4
-0.6 -80
-0.8
0 10 20 30 40 50 60 70 80 90
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 Of particular interest is the quasi-isotropic
are usually fabricated from multiple layers, composite which is often specified for com-
each arranged at some angle to their neighbor. mercial structures. The in-plane engineering
The angles that are used can be arranged to elastic constants of these materials are identi-
bring the fiber axes at some optimum angle to cal in all directions and there is no shear
the expected loads; however, there is a require- coupling. Examples of such composites are
ment for each lamina to be oriented very symmetric arrangements of [0/60/-601 or
precisely with respect to one another in order [0/ +45/90] layers.
to avoid tensile-shear effects and coupling
between in-plane loading and out-of-plane
9.12 TESTING TECHNIQUES
deformation (tensile loads can be made to pro-
duce bending and twisting deformation, for A knowledge of the behavior of the constituent
example). Various rules of angle-ply materials phases allows the mechanical properties of the
have been worked out in order to avoid the resulting composites to be computed. These
cross-coupling terms. For example, symmetric calculations are made with the use of expres-
laminates exhibit no coupling between sions (9.6)to (9.11).The results of the following
in-plane loading and out-of-plane deforma- tests should provide input to and in some cases
tion. (Symmetric laminates define a composite confirm these calculations. The following was
in which for every lamina oriented at some adapted from the excellent (and much more
angle there is another layer of identical thick- extensive) discussion contained in Chapter 8 of
ness and orientation placed at an equal the book Engineering Mechanics of Composite
distance from the mid-plane of the composite.) Materials (Daniel and 0.Ishai, 1994).
And, composites which exhibit no shear cou-
pling are 'balanced laminates' (pairs of
9.12.1 PROPERTIES OF FIBERS AND MATRICES
identical layers oriented at a positive and an
equal negative angle with respect to the lami- Determination of the elastic and failure prop-
nate reference axes). 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
structures. These include short fiber reinforce- can be made with modulus values much larger
ment of cement mortar and continuous than can be obtained from PAN precursors.
reinforcementof concrete. Some attempts have Unfortunately,rather sophisticated and expen-
been used to provide earthquake resistant sive pitch pretreaments must be applied to a
structures and fiber reinforced ropes and some petroleum or coal tar pitch in order to produce
successes have been reported in fabricating a high performance fiber. The pitch softening
structures with carbon fiber reinforced alu- temperature is much higher than PAN; thus
minum and copper. Carbon fiber reinforced stabilization can potentially be carried out
carbon has been considered for high tempera- quickly at higher temperatures. Nevertheless,
ture load bearing structures and heat shields stabilization of both PAN and pitch materials
in spacecraft and supersonic aircraft. And, is exothermic and, in order to avoid overheat-
finally, similar materials are considered useful ing, thermal runaway and decomposition of
in nuclear applications and disc brake materi- the precursor, a less than advantageous tem-
als for aircraft, high speed trains and racing perature of oxidation must be used. Future
cars. At the present time, there is a growing developments in these areas should therefore
interest in the use of very high thermal con- involve methods to increase the stabilization
duction properties to manage local rate and the development of new precursor
temperatures in sensitive electronic equip- materials. Specific topics might include stabi-
ment. Nevertheless, despite all these apparent lization in thermally stable environments
successes, it is vitally important to realize that (fluidized beds, liquids, etc.) and the develop-
the expanded use of high performance carbon ment of alternative synthetic precursor
fibers depends very sensitively on the lifetime materials (polymers and/or pitches).
costs involved in substituting carbon and its Cost of the final component, while very sen-
composites for competing metals, ceramics sitive to the cost of raw materials, also
and polymers. involves all of the design, fabrication and test-
It has been recognized for many years that ing costs. All of these component costs must be
market penetration of carbon fibers will tightly controlled if economically viable per-
always be limited to rather sophisticated formance increases are to be realized. When
structures if the cost remains at the present using composites, it has been found to be
high level. However, the precursor PAN mate- vitally important to pay strict attention to
rial presently costs about $5/kg; thus, taking detail design if a maximum expected weight
into account the weight loss and processing saving is to be realized. Designers must opti-
costs involved in converting PAN to carbon, it mize the total vehicle weight and not simply
is unlikely that large amounts of carbon fiber substitute a carbon composite for a metal one.
made from such material will ever be less than It is rumored for instance that, due to overly
$10/kg. Conversely, the cost of the pitch pre- conservative design (i.e., the use of metallic
cursor material is almost insignificant, since it joining and fabrication techniques etc.), the
is the byproduct of a commercial process resulting weight of some composite structures
established to produce other end products: has, in the past, turned out to be as heavy as
gasoline, metallurgical coke, etc. In addition, similar components built from aluminum.
since the fiber is fabricated using a melt spin-
ning process, the production rate can be much
9.14 CONCLUSION
faster than the wet or dry process used to pro-
duce PAN based fibers. The carbon yield from Many people appear to believe that despite
pitch precursors can average up to 85%, nearly thirty years of development, carbon
whereas the carbon yield produced from PAN fibers are still an evolving space age material.
averages about 65%. Pitch based carbon fibers Until very recently, there was a production
198 Carbon fibers
over-capacity in the carbon fiber industry. For At the present time, downsizing of the
example, in 1995 it was estimated that industry, increasing use of low cost fibers and
10 000 000 kg of carbon fibers were sold from the resurgence of orders for new commercial
an estimated capacity of 16 000 000 kg. Exactly aircraft that now use increased quantities of
how accurate these estimates were is difficult carbon fiber has brought industrial capacity
to assess; however, it can be concluded that the and market requirements closer together.
market is small and cannot accommodate Indeed, some fiber types are now difficult to
many producers. For this reason, many pro- obtain. Nevertheless, any major growth of the
ducers have seen fit to evaluate their position carbon fiber industry depends on the discov-
in the industry. For example, Table 9.3 is a list- ery of a method to produce fibers for one-half
ing of carbon fiber processors taken from or one-third of the present projected large vol-
Chapman and Hall's directory, 'Carbon and ume price and the development of new
High Performance Fibers' which was pub- inexpensive fabrication methods for struc-
lished in 1991. In 1996, only the first eight of tures. These developments will initiate major
these were still producing significant commer- new transportation based markets for the
cial quantities of PAN-based carbon fibers. material. At the present price, however, the
Table 9.4 is a similar listing for pitch-based use of carbon fibers will always be limited to
fibers. In this case only the first five appear to competitive performance driven applications.
be active.
Riggs, D.M., Shuford, R. and Lewis, R. 1982. US Patent 3 894 884,1975. Druin.
Handbook of Composites. New York: Van US Patent 3 917 776,1975. Mitsubishi Rayon.
Nostrand Reinhold. US Patent 3 919 383,1975. Singer.
Riggs, D.M., 1979. Doctoral Thesis. Rensselaer US Patent 3 972 984,1976. Nippon Carbon Co.
Polytechnic Inst., Troy, New York. US Patent (8) 3 974 264,1976. McHenry.
Robson, D., Assabghy , F.Y.I. and Ingram, D.J.E. US Patent (8) 3976729, 1976. Lewis, McHenry,
1972. J. Phys. D, 5: 169. Singer.
Rosen, B.W. 1964. AIAA 2: 1985. US Patent 3 989 802,1976. Loo.
Schwartz, M.M. 1984. Composite Materials Handbook. US Patent 4 004 053,1976.
New York: McGraw-Hill. US Patent 4 005 183,1977. Singer
Shindo, A., Nakanishi, Y. and Soma, I. 1969. Appl. US Patent 4 009 248,1977.
Polym. Symp. 9: 305. US Patent (4) 4 017 327, 1977. Lewis, McHenry,
Singer, L.S. 1978. Carbon 16:409. Singer.
Tanabe, Y., Yasuda, E., Machino, H. and Kimura. S. US Patent 4 024 227,1978.
1987. Ann. Mtg Jpn Ceramic Society, Nagoya, US Patent 4 031 288, 1978. Minnesota Mining and
77. Manufacture Co.
Temovoi, K. S., Zemskov, V. S., Kolesnikov, E. B. US Patent 4 039 341, 1976. National Research
and Mashkov, 0. A. 1985. Sorbitsionnaya Development Corp.
Defoksikatsiya v Khirurgicheskoi Klinike US Patent 4 069 297,1978. Toho Beslon Co. Ltd.
(Detoxification Sorption in Surgery) Kishinev US Patent (6) 4 208 267,1980. Diefendorf and Riggs.
(USSR):Shtiintsa. US Patent (5) 4 331 620,1982. Diefendorf and Eggs.
Tsai, S.W. and Hahn, H.T. 1980. Introduction to US Patent 4 374 114,1983. Kim.
Composite Materials, Technomic Publishing Co., US Patent (3) 4 376 747,1982. Nazem.
Inc., Westport, CT. US Patent 4 504 454,1985. Riggs.
US Patent 3 107 152,1963. Ford and Mitchell. Watt, W. 1972. Carbon 10: 121.
US Patent 3 533 741,1970. Courtaulds Limited. Watt, W. and Johnson, W. 1975. Mechanism of oxi-
US Patent 3 627 466,1971. Steingiser. dation of polyacrylonitrile fibres. Nature 2 5 7
US Patent (12) 3 629 379, 1971. Otani. 210-212.
US Patent 3 650 668,1972. Celanese. White, J.L. 1992. ONR Report for Contract No.
US Patent 3 656 882,1972. Celanese. 88-K-0424 and 89-J-3056.
US Patent 3 656 883,1972. Celanese. Wright, M.A., 1989. NASA Conference Publication
US Patent 3 656 903,1972. Celanese. 3054: 17.
US Patent 3 660 140, 1972. Scola. Wright, M.A. and Iannuzzi, EA. 1973. J. Comp. Mat.,
US Patent 3 671 411,1972. Ray. 7: 430.
US Patent 3 677 705,1976. Celanese. Wright, M.A. and Wills, J.L. 1974. J. Mech. Phys. Sol.
US Patent 3 723 150,1973b. Druin. 22: 161.
US Patent 3 746 450,1973. Goan. Wright, M.A. and Palmer, K.R. 1994. Research into
US Patent 3 746 506,1973. Aitken. Structural Carbons, Materials Technology
US Patent 3 754 957,1973~~ Druin. Center Publication, SIUC, Carbondale, Illinois,
US Patent 3 767 773,1973. Turner. 62901.
US Patent 3 767 774, 1973. Hou. Yanagida, K., Noda, M., Sasaki, T. and Tate, K. 1991.
US Patent 3 780 255,1973. Boom. 20th Conf Carbon, Extended Abstracts, American
US Patent 3 814 377,1974. Monsanto. Carbon Society, p. 160.
US Patent 3 832 297,1974. Paul, Jr. Yoneshoga, I. and Teranishi, H. 1970. Japanese
US Patent 3 841 079,1974. Celanese Patent Specification 2774/70.
US Patent 3 846 833,1975. Celanese. Yooh, S.H., Korai, Y. and Mochida, I. 1994. Carbon
US Patent 3 859 187,1975. Druin. 32: 281.
ORGANIC FIBERS 10
Linda L. Clements
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
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
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
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 fibers in the mid-l980s, aramid fiber composites
removed (DuPont, 1992a). The lower thermal had the highest specific strengths of all compos-
conductivity of aramids compared to inor- ite materials. Although composites from newer
ganic fibers can improve the fire resistance of fibers have taken over that position, aramids
their composites, since aramids do not readily still offer outstanding combinations of proper-
conduct heat into the more volatile matrix. ties, such as high specific strength, toughness,
creep resistance and moderate cost, for specific
applications.
Mechanical properties
Table 10.2 compares the mechanical proper-
Composite materials are most commonly used ties in axial tension of several commercially
because of their superior strength and/or stiff- available aramid fibers.
ness at a given weight as compared to Aramid fibers have some definite limita-
conventional structural materials. Figure 10.4 tions. They are weak in bending and show
compares the specific strengths and specific obvious damage if subjected to kinking or
stiffnesses of various reinforcing fibers. (The buckling. As a result, they are also weak in com-
strengths and stiffness in Fig. 10.4 are expressed pression (where microbuckling is inevitable)
in units of grams per denier (gpd). This is a tex- and in transverse tension (wherebond-by-bond
tile term often used for organic fibers which breakage of hydrogen bonds is likely). In addi-
measures specific strength and/or stiffness. This tion, even though the para-aramid chain is
term is further explained in the appendix to this quite polar in nature, almost all of the polar
chapter.) As can be seen, aramid fibers perfonn groups are fully involved in hydrogen bonding
very well. In fact, until the emergence of high to other aramid molecules. As a result, para-
strength intermediate modulus carbon fibers aramid fibers do not form strong bonds with
and the commercialization of polyethylene other materials such as composite matrices,
208 Organicfibers
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/or prepared using other fabrication
and compressive properties of the fiber itself. processes, the general trend is valid: aramid
The basic chemical structure differences fiber composites have poor off-axis properties.
between the aramid fibers produce many of In axial tension, both aramid fibers and
the mechanical property differences seen in their composites are linear to failure. In spite
Table 10.2. The ether (-0-) linkages in the of this fact, the same microstructural charac-
backbone of the Technora copolymer fiber pro- teristics which lead to the weakness of aramid
duce a lower modulus than that of Kevlar and fibers in buckling also make them very tough.
Twaron PPTA-based fibers. On the other hand, During failure, the widespread bending, buck-
the additional cyclic ring in the SVM PBIA- ling and other internal damage to the fibers
based fibers produces a higher basic modulus. absorbs a great deal of energy. Similarly, the
However, heat treatment and other fabrication strength of aramid fibers is not very strain rate
steps can also alter mechanical properties sig- sensitive: an increase in strain rate of more
nificantly, as is seen in the property differences than four orders of magnitude only decreases
between the various Kevlar fibers. the tensile strength by about 15%. (Abbott et
The mechanical properties of aramid com- al., 1975) This property alone provides design
posites are illustrated in the data of Table 10.3. advantages over all inorganic and many other
For this filament-wound composite the longi- organic fibers.
tudinal compressive strength was about The mechanical properties of aramid fibers
one-eighth that in longitudinal tension, the in- decrease with increasing temperature. Figure
plane shear strength was one-seventy-fifth and 10.5 shows the fiber elastic modulus as a func-
the transverse tensile strength over two hun- tion of temperature for several organic fibers.
dred times smaller. While the relative values of At 177°C (350°F) the modulus of para-aramid
properties may change for composites made fibers is about 80% of that at room tempera-
from other aramid fibers and/or other matrices 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 -
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
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 (DuPont, 1986). Para-aramids also can be
these conditions, but the phenomenon of stress expected to perform better than carbon fibers in
rupture must be considered in any design fatigue (Teijin, 1989; Yang, 1992). Technora
where long term loading is anticipated. para-aramid co-polymer is found to have even
Strength retention cannot be used to estimate better fatigue resistance than the para-aramid
the remaining life of aramid fibers or compos- homopolymer fibers (Teijin, 1989).
ites under long term load (Chiao, Sherry and
Chiao, 1976),so estimates of long term behavior
Chemical and environmental properties
must be derived from actual data, or acceler-
ated testing methods (Chiao and Chiao, 1982). PPTA fibers are quite stable chemically; their
Para-aramid fibers and their composites per- resistance to neutral chemicals is usually very
form very well in fatigue. For aramids, high. They are, however, subject to attack by
tension-tension fatigue generally is not of sig- acids and bases, especially by strong acids.
nificant concern in applications where an Because the spin process used for Teijin's
adequate static safety factor has been used Technora para-aramid co-polymer produces a
(Yang, 1992). Aramid composites have been very pure polymer, the chemical and environ-
found to be superior to glass fiber composites in mental resistance of Technora is superior to
both tensile-tensile and flexural fatigue load- that of the PPTA fibers. Table 10.5 reports the
ing. For the same lifetime (cycles to failure), resistance of Kevlar and Technora fibers to
Kevlar 49/epoxy composites can operate at a various chemicals. Technora has better acid
significantly larger percentage of their static and alkali resistance than PPTA and its steam
strength than can glass-reinforced composites resistance is also superior.
214 Organicfibers
Para-aramids are strong ultraviolet (W) in the para-aramid homopolymers and thus
absorbers. Upon exposure, the yellow or gold improved electrical properties. Technora fiber
fibers turn first orange and then brown, due to has a resistivity of 5 x lo’* Q/cm (Teijin, 1989).
degradation. The degradation occurs only in The dielectric constant of PPTA is 3.85 (Allied,
the presence of oxygen and is not enhanced by 1989).
either moisture or atmospheric contaminants The refractive index of Kevlar 49 fiber is 2.0
(DuPont, 1992a). Extended exposure may parallel to the fiber axis and 1.6 perpendicular
cause a loss of mechanical properties. Bare (DuPont, 1986).Aramid fibers are opaque and
1667 dtex (1500 denier) Kevlar 29 was found to are yellow to gold in color.
have 71% strength retention after 1 month of
outdoor exposure in Wilmington, DE and 43%
10.2.5 TREATMENTS
after 4 months (Yang, 1992).In both processing
and applications, para-aramids must be pro- Unlike inorganic fibers, few surface treatments
tected from W exposure, such as by painting are used on aramid fibers to promote matrix
or coating. However, since para-aramids are adhesion. One reason is the futility of increas-
self-screening, UV protection may also be ing the matrix bonding to the surface of a fiber
effected simply by dense packing of the fiber which readily fails by defibrillation. Most dra-
itself, with or without a matrix. Thus, bare matic improvements in fiber/matrix bonding
12.7mm (0.5 in) 3-strand Kevlar 49 rope was give only modest improvements in off-axis
found to have 90% strength retention after 6 strengths since they simply move the locus of
months outdoors in Florida and 69% strength failure from the surface to the interior of the fil-
retention after 24 months (DuPont, 1986). ament. In other cases, longitudinal tensile
Unlike inorganic fibers, aramid fibers absorb strengths are adversely affected by otherwise
water. For some aramid fibers the equilibrium successful surface treatments. Not all attempts
moisture content (see appendix on page 241 for at designing surface treatments have been
defirution) is quite high (5% for SVM, 7% for unsuccessful, but for the most part the surface
Kevlar, Kevlar 29 and Twaron), moderate for treatment used on commercial fibers is mini-
others (3.5% for Kevlar 49 and Twaron HM) mal compared to that used for inorganic fibers.
and reasonably low for some (2% for Armos Finishes - lubricants which aid in subse-
and Technora and about 1% for Kevlar 149) quent processing steps - are applied to aramid
(Akzo, 1991; Kaiser VIAM, 1993a; Teijin, 1989; fibers for some applications. Available finishes
Yang, 1992). The equilibrium moisture content are designed for such purposes as lubrication
is directly proportional to the relative humidity, during weaving operations, improving abra-
rising for Kevlar 49 to 6.2% at 96% r.h. (DuPont, sion resistance for cable applications or better
1992a). Absorbed moisture has only a small performance in rubber goods. If the fiber is to
effect upon the tensile properties of the fibers, be used in a high performance composite,
but a significant effect upon the transverse ten- however, the user will usually wish to avoid or
sile, compressive, shear and flexural properties remove any finish before impregnating the
of the composite. The gain of moisture is com- fiber with a matrix.
pletely reversible and once removed produces Commercial aramid fibers may also be
no permanent property changes. twisted. Twist may be quite useful in some
applications and a small amount of twist will
increase the strength of bare yarn or cord.
Electrical and optical properties
[This optimum twist for Kevlar fibers occurs at
Aramid fibers are electrical insulators. The a twist multiplier of 1.1.At about this value,
process used to make the Technora fiber, how- the strength of bare yarn is the highest and the
ever, leaves it with fewer ionic impurities than modulus is only slightly decreased from the
2 16 Organic fibers
untwisted level (DuPont, 1992b).] Twist will staple, pulp and in various fabrics.
make the fiber easier to handle, make subse- While the meta-aramid fibers are not usu-
quent weaving or braiding operations easier ally used as fiber reinforcements in
and will improve the abrasion resistance of the composites, they are used extensively as rein-
fiber. It is also required for rope and cable forcements for honeycomb sandwich core
applications. However, once the fiber is used materials. The use of such materials along
in composite matrix fiber, twist is not desir- with composite face sheet panels has greatly
able. This is because twist interferes with full extended the overall usage of composite mate-
impregnation of the fiber with resin and with rials, particularly in the aerospace industry.
stress transfer between adjacent fiber bundles. Information about the availability and
It also increases stress concentrations, particu- package sizes of the fibers shown in Table 10.6,
larly at higher twist levels. For this reason, about other products and about special formu-
most of the aramid fiber manufacturers supply lations can be obtained from Table 10.7. At the
most or all of their fibers untwisted or with time of this publication, Kaiser VIAM’s Armos
minimal twist. and SVM fibers are just being imported from
Russia. For this reason, information on the
fibers and their availability is limited in this
10.2.6 FORMS AND AVAILABILITY
chapter, but should be readily available later
Table 10.6 lists most of the commercial types of from the contact given in Table 10.7.
para-aramid fibers. Some of these fibers are
readily available in a variety of fiber deniers,
Pricing
package sizes, finishes and so forth, while oth-
ers are available only in limited quantities for Para-aramid fibers are currently priced from
specific applications. Due to constant changes about $20 per pound for the larger denier fibers
in market conditions and other factors, the to about $60 per pound for most of the small
user is advised to check with the fiber manu- denier, higher modulus fibers. (However, some
facturer concerning current availabilities. The of the very fine denier specialty fibers from
mechanical properties of fibers with different some manufacturers cost hundreds of dollars
deniers and/or finishes and other treatments per pound.) Prices can vary significantly for
will vary somewhat from each other and from similar fibers of different deniers or from dif-
the nominal values given in Table 10.2. ferent manufacturers and thus price quotes
In addition to the yarns, tows and rovings should always be obtained before any decision
listed in Table 10.6, DuPont’s Kevlar fibers are is made upon use of a specific fiber.
also available as staple (short fibers), floc (pre-
cision cut fibers of very short lengths) pulp
10.2.7 DESIGN CONSIDERATIONS
(very short and high fibrillated fibers) and in
specialty compounded forms (DuPont, 1992a, In the 1970s and early 1980s aramids began to
1993h).A variety of fabrics are also produced. replace carbon and glass fibers in many appli-
In addition, DuPont produces a colored fiber, cations. However, the development of high
Kevlar 100, in sage green, yellow, black and strength intermediate modulus carbon fibers in
royal blue (Yang, 1992).Both Teijin’s Technora the mid-1980s and the commercialization of
and Akzo’s Twaron fibers are available as sta- tough, high strength polyethylene fibers
ple and chopped fiber (very short lengths) and reversed this trend. Today aramid fibers are
in a variety of fabrics (Teijin, 1989;Akzo, 1991). used mainly in applications where they offer a
Technora is also marketed in black as well as unique combination of properties, such as high
natural color. Kaiser VIAM‘s Armos and SVM specific strength combined with toughness and
fibers are also expected to be offered as tape, creep resistance.
Aramidfibers 217
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 Aramids are strong UV absorbers and dete-
often the reason they are used over cheaper, riorate when exposed to ultraviolet light.
stiffer or even stronger fibers. Unlike glass and Protective coatings or the self-screening ability
carbon composites, aramid composites loaded in of the fiber should be used to avoid deterio-
compression, flexure or shear fail in a non-brittle ration.
manner, with significant work being required to Aramid fibers are opaque and thus the pen-
fail the composite. Their fatigue resistance is also etration of resin into the fiber bundles cannot
excellent. If other concerns such as cost or stiff- be determined visually for a aramid compos-
ness preclude the use of aramid composites, ite as it can for those made with glass fibers.
aramids are often used as a hybrid with another In fabric applications the weave used is
fiber to improve the toughness of the composite. important to the resulting properties. The
The poor off-axis and compressive proper- same is true for sandwich construction. In
ties of aramid fibers must be considered in any these cases, the fiber, fabric, or honeycomb
design. However, because of their high strength supplier can provide design assistance.
in axial tension and their toughness, aramid The choice of resin system for use with
fibers are often outstanding in applications aramid fibers is an important one. Epoxy resins
such as pressure vessels where the loading is give better translation of fiber properties than
almost totally in longitudinal tension. do polyesters, producing better shear strength
Aramid fibers absorb moisture. Where and flexural properties, but lower impact resis-
either the physical swelling of the fiber or the tance. Vinyl ester resins give both good shear
amount of moisture absorbed is of significant strength and impact resistance. Thermoplastic
concern, one of the lower absorption aramids, matrices are also used, particularly in chopped
such as Kevlar 149, Armos, or Technora should fiber composites, because of their improved
be considered. impact resistance over thermosets. However,
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
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
can be seen in Fig. 10.4, these fibers offer very very poorly to a matrix. Although gas plasma
high specific stiffnesses and specific strengths, surface treatment can improve the interfacial
equivalent or superior to all of the aramid bond strength significantly, polyethylene fiber
fibers and to most of the carbon fibers. This composites will still have poor off-axis proper-
superior performance is offered at a lower ties.
price than that of competitive fibers. Table 10.9 gives mechanical properties for
Table 10.8 compares the mechanical proper- Spectra fiber composites, including those
ties of representative commercially available made from plasma-treated fibers.
polyethylene fibers. In spite their weak transverse strength, but
Like aramid fibers and for similar reasons, because of the non-stick nature of polyethylene
polyethylene fibers have poor compressive and thus its low coefficient of friction, polyeth-
and off-axis properties. Since the fiber is held ylene fibers perform much better than aramids
together internally by only very weak van der in abrasion resistance and polyethylene fabrics
Waals bonds, the transverse strength of the are much less easily damaged than are those of
fiber is even worse than that for the aramids. aramid fibers. The abrasion resistance of poly-
In addition, the inertness of the polyethylene ethylene fibers can be up to ten times that of
fiber means that the untreated fiber bonds aramids (Dyneema, 1987)and can be improved
Table 10.9 Mechanical properties of Spectra polyethylene fiber composites” (Allied, 1989)
even further by the use of lubricants. exposure is 20-30%. The loss in both modulus
Because of their high strength, polyethylene and strength are reduced if annealing is per-
fibers exhibit very high energy to break. On a formed under tensile loading.
per-weight basis, the impact energy absorp- Unlike aramid fibers and their composites,
tion of polyethylene composites is superior to polyethylene fibers and composites show very
that of all other fiber composites. little or no loss of properties, axial or off-axis,
Polyethylene fibers are more affected by when exposed to moisture.
temperature than are higher melting point Creep resistance of extended-chain polyeth-
fibers. The loss in modulus as function of tem- ylene is of concern. Because of its low melting
perature is shown in Fig. 10.9 for Tekmilon temperature, the resistance of the fiber to creep,
multifilament fiber and Spectra fibers. Fig. 10.10 even at room temperature, is less than ideal.
shows the loss in strength as a function of tem- This is significant, since the creep of carbon,
perature for Tekmilon multifilament, Spectra glass and aramid fibers is minimal. Spectra
900 and Spectra 1000 fibers. Because of their 1000 is a 'stabilized' version of the fiber, which
very high specific strength at room tempera- shows better creep resistance than the Spectra
ture, however, polyethylene fibers still 900 fiber. Figure 10.11 shows the creep
outperform most other fibers to about 100°C response of the two Spectra fibers at room, ele-
(212°F). vated and low temperatures. At low load levels
Room temperature strength retention of at room temperature and/or at low tempera-
polyethylene fibers following annealing at tures the creep encountered is not severe,
temperatures of up to 125°C (260°F) is excel- especially for the Spectra 1000 fiber, but at
lent, while modulus loss following such 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
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
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
.___
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 ment (Jaffe, 1989). It shows superior chemical
fibers does not preclude their use in applica- resistance to PPTA in hydrochloric, nitric and
tions such as sailcloth or structural sulfuric acid (Dyneema, 1987).Table 10.10 com-
reinforcement, but does require that the creep pares the chemical resistance of Spectra
demands of an application be carefully evalu- polyethylene fiber to that of aramid fiber.
ated. Because of their relatively poor creep Polyethylene fibers also show good resis-
resistance, polyethylene fibers are often tance to UV exposure. After 100 hours UV
hybridized with other, more creep resistant exposure in a fadeometer, Dyneema SK60
fibers in applications where prolonged loading retained 70% of its original strength and after
is anticipated. 1500 hours, retained 25% strength. This latter
The fatigue resistance of polyethylene fibers exposure is equivalent to about 2 years of out-
is excellent. In one test of loading and unload- door exposure (Dyneema, 1987).
ing of ropes, polyethylene fiber ropes Polyethylene fibers are hydrophobic and
withstood approximately eight times the cycles thus absorb very little moisture. The moisture
before break as aramid fiber ropes (Weedon and regain of polyethylene fibers is less than 1%.
Tam, 2986). T ~ indicates
E a superiority in ten- Their weatherability is excellent: after 600
sile fatigue even to aramid fibers, which are hours exposure in a Weatherometer, Tekmilon
known for their excellent fatigue resistance. fiber retained 80% of its strength and 90% of its
modulus. Following similar exposure, an
aramid fiber had only 40% strength retention
Chemical and environmental properties
(Mitsui, 1989).Because of their excellent chem-
Polyethylene is inert. It is stable in almost all ical and moisture resistance, articles made
organic solvents and in a variety of other chem- with polyethylene fibers can be cleaned in
icals. It is also biologically inert. It is the best of soap and water.
all high modulus fibers in an alkaline environ-
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
Allied-Signal’s Spectra 1000, which has signifi- Polyethylene fibers can be damaged by
cantly improved creep resistance compared to rough handling and should be handled with
Spectra 900. Polyethylene fibers are often care before and during processing. They pre-
hybridized with other more creep-resistant sent minimal safety or environmental concerns
fibers in applications where prolonged loading and most are biocompatible, offering another
is anticipated. Without hybridization polyeth- potential design advantage.
ylene fibers must be limited to applications
where long term, high load level, or elevated
10.3.8 APPLICATIONS
temperature loading is not anticipated, or
where creep is otherwise not of concern. Most of the current applications of polyethyl-
As with aramids, the poor off-axis and com- ene fibers are not in structural composites.
pressive properties of polyethylene fiber One of the main uses is in ropes and cables,
composites may also be concern. This is not a particularly in marine and off-shore applica-
problem, of course, in applications where the tions. The fibers are used because of their high
loading is mainly in axial tension. strength, outstanding abrasion resistance (up
The X-ray and radar transparency of the to ten times that of aramids), low density
fiber can present significant design advan- (since they float), good UV stability, resistance
tages. The UV resistance of the fiber is very to seawater and high durability. The fibers are
good and thus does not present a design prob- also used as marine sewing threads.
lem in most applications. In another major application, UV- and
Because of its chemical inertness, polyethyl- water-resistance are again important. Both
ene fibers are almost impossible to dye, Spectra and Dyneema fabrics are used, typi-
although color can be added during the fiber cally with a film coating, in sails. Unlike
spinning process. As with aramids, polyethyl- aramids, polyethylene sail can be folded and
ene fibers are optically opaque, so resin repacked numerous times without damage.
penetration within a composite cannot be This latter quality also led to the selection of
determined visually. Spectra fabric for the anchor balloon of the
Polyethylene fibers can be used with a vari- Hilton Earthwinds round-the-world balloon
ety of resins, including polyurethanes, flight project and to their usage in lightweight,
epoxies, vinyl esters, polyesters and thermo- durable backpacks.
plastics, so long as the composite can be Polyethylene fabrics are used as filter
processed below 120°C (250°F).Polyesters are cloths, where the excellent chemical resistance
economical, vinylester resin systems provide is a tremendous advantage. Spectra fabric has
outstanding impact properties and epoxies been used in oil containment and recovery
give better translation of structural properties. systems following the Persian Gulf war. The
The preferred thermosetting matrix cure tem- fabric is treated so that water passes through it
perature is 93-104°C (200-220°F) (Allied, but oils and other floating pollution do not.
1990). The fiber manufacturers can be very Because of their excellent biocompatibility,
helpful in choosing an appropriate resin sys- polyethylene fibers are used as sutures and as
tem for an application. artificial ligaments. They are also used in sur-
As with aramids, polyethylene fiber com- gical gloves, because of their excellent cut
posites are relatively hard to machine and resistance, biocompatibility and low absorp-
producing a smooth final machined surface tion of fluids. While the poor temperature
requires special techniques. Machining tech- resistance rules out the use of polyethylene
niques developed for aramid composites can fibers in thermal protection, they are used in
be used successfully, as can hot knife or hot industrial protective clothing and in ballistic
wire cutting (Allied, 1989). protection and impact shields, with or without
234 Organic fibers
p:
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.
Y
Current hybrid applications range from bike
frames to impact shields.
Fig. 10.12 General structural formula of Vectran.
aromatic polyester fiber.
Other organic fibers 235
cost. Hoechst Celanese was successful in pro- over a broad temperature range and excellent
viding a fiber with the desired performance, chemical resistance.
but unfortunately the resulting cost was even The density of Vectran HS is 1.41 g ~ m - ~
hgher than the aramids. Shortly thereafter, (0.0509 lbs in") (Hoechst Celanese, 1990). It
Hoechst Celanese stopped marketing Vectran melts at 330°C (636°F). Like aramid fibers,
fiber and marketed Vectran resin instead. Vectran HS has a negative axial coefficient of
Vectran resin quickly became the material of thermal expansion. From 20°C (68°F) to 145°C
choice in the electronics and computer indus- (293°F) its longitudinal linear thermal expan-
tries for small, very close tolerance connectors, sion coefficient is 4 . 8 x lo4 /"C ( - 2 . 7 ~
plugs and other components. Based upon this /OF). The coefficient increases to -14.6 x 10"
success, in 1989 Hoechst Celanese reintroduced /"C (-8.1 x lo4 / O F ) from 145°C (293°F) to
Vectran as a fiber product. Since the fiber is 200°C (392°F) and to -26.7 x lo4 /"C (-14.8 x
more expensive, by 1.5to 3 times, than aramids, / O F ) from 200°C (392°F) to 290°C (554°F)
the marketing focus is on areas where aramids (Beers and Ramirez, 1990).It has good temper-
do not meet the performance requirements ature resistance, although not as good as
(Adams and Farrow, 1993a). aramid fibers since it melts at high tempera-
Vectran is a polyester-polyarylate fiber. ture. Its shrinkage in hot air at 177°C (350°F)or
Unlike the aramids, Vectran melts at high tem- in boiling water is less than 0.5%.
perature. It is melt spun on conventional Vectran HS fiber is outstanding in its
polyester spinning equipment and the as-spun mechanical properties. Its axial mechanical
fibers are then heat treated in a sequence of properties are summarized in Table 10.13.
steps (Adams and Farrow, 1993b).It is the only Vectran displays no creep when tested for 2760
commercially available melt-spun liquid crys- h at 50% of its ultimate tensile strength. This
talline polymer fiber (Hoechst Celanese, 1990). behavior is significantly better than both
aramid and polyethylene fibers. Vectran also
has excellent vibrational damping characteris-
Properties
tics, better than aramids. Vectran HS has
Vectran HS offers a unique combination of superior abrasion resistance to Kevlar 29,
properties: high strength, no creep, low mois- although not as good as polyethylene fibers. In
ture absorption, negative coefficient of flexural fatigue, Vectran HS braid exhibited a
thermal expansion, good property retention 10% reduction in strength after one million
Table 10.13 Axial tensile mechanical properties of representative non-aramid, non-polyethylene organic
fibers
cycles (and maintained this strength level to glasslvectran M products, the glass fibers are
five million cycles), while a Kevlar 29 braid producer-sized.) (Hoechst Celanese, 1990).
showed a 30% strength reduction under the More information on Vectran can be
same conditions (Beers and Ramirez, 1990). obtained from the source listed in Table 10.14.
Vectran absorbs very little water, having a
moisture regain of less than 0.1%. It is
Applications
hydrolytically stable. It has excellent chemical
resistance being resistant to organic solvents, As with aramid and polyethylene fibers, ropes
to acids at less than 90% concentration and to and cables are an important usage. Marine
bases at less than 30% concentration (Hoechst cables, fish nets, towing ropes, cargo tie
Celanese, 1990). downs, slings, sails, bicycle brake cables and
Vectran's dielectric constant is 3.3at 1 kHz optical fiber reinforcement all have been made
(Hoechst Celanese, 1990). from Vectran HS. Olympic target archers use
Like aramid and polyethylene fibers, bow strings from Vectran HS having a propri-
Vectran is difficult to cut and its composites are etary abrasion resistant finish. The result is
difficult to machine. Typical aramid composite increased arrow speed with no creep of the
machining techniques can be used successfully. 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
Forms, availability and treatments stretch far less than either aramid or polyeth-
Vectran is produced in the USA by Hoechst ylene and they have four to six times the life of
Celanese Corporation and in Japan by the aramid sails (Adams and Farrow, 1993a).
Kuraray Corporation under license from Safety materials and protective garments
Hoechst Celanese. It is available as Vectran have also been made of Vectran in industries
HS, a high strength reinforcement fiber, ranging from meat packing to metal working.
Vectran M, a high performance matrix fiber, In these applications, Vectran is superior to
and as engineered, commingled combinations aramids, which have poor resistance to bleach,
of Vectran HS with Vectran M and S-2 Glass and to polyethylene fibers, which are sensitive
fiber with Vectran M. to the high temperatures used in drying laun-
Vectran HS fiber is available in dtex (deniers) dered garments.
of 222 (200),833 (750), 1000 (900)and 1667 Vectran composites have been used in aero-
(1500).These fibers are composed of 40,150,180 space applications and in recreation and
and 300 filaments respectively, with the fila- leisure applications such as canoes, golf clubs,
ments being 23 pm (0.91x 10" in) in diameter. baseball bats, hockey sticks, tennis rackets,
Vectran HS fibers are offered with or without a bicycles, skis, ping pong paddles, paragliders
standard textile finish to assist in processing and stereo speaker cones. Vectran properties of
and/or to provide (dramatically improved) importance in these applications include the
abrasion resistance. Commingled Vectran HS or low moisture absorption, the excellent damp-
M fibers have no finish. (In the commingled S-2 ing characteristics, high stiffness, lack of creep
PBO is one of the most thermally and tions include composites loaded in tension,
thermo-oxidatively stable organic polymers such as pressure vessels, missile cases and ten-
known. No weight loss was observed for PBO sile beams. PBO fiber composites may also be
held at 316°C (600°F) (Wolfe, 1990)and weight used in non-load-bearing applications where
loss of only O.O6%/h was observed at 370°C high temperature exposure or harsh chemical
(700°F) (Burk, 1993). Its decomposition tem- environments are anticipated, such as rocket
perature is 600°C (1110°F) (Burk, 1993). insulation systems and brake and transmis-
Exposed to flame, PBO chars, but does not sion systems. The high strength could also
support combustion. (Wolfe, 1990) Dow's PBO lower the weight of composites used in space-
fiber has a longitudinal coefficient of thermal craft and in recreation and sporting goods.
expansion of -6 x 104/OC (-3.3 x lO"/"F) PBO also has significant potential application
(Burk, 1993). to ballistics, where, as a fabric or composite, it
PBO fiber has a significantly higher tensile performs equally well at half the weight of an
strength and modulus than any other known aramid. PBO composites could provide out-
organic fiber. PBO fibers have been produced standing containment systems for high speed
with tensile moduli of as high as 470 GPa rotors and turbines where high temperature
(68 Msi). Dow's current pre-production fibers exposure is of concern. The fibers also have
do not achieve these high levels, but do potential for bomb containment systems, for
nonetheless have excellent axial mechanical fire resistant and cut resistant apparel and fire
properties, as shown in Table 10.13. However, blocks, as well as ropes and cables (Burk,
like all other high performance organic fibers, 1993).
PBO fibers are quite weak in compression, More information on PBO can be obtained
with a fiber compressive strength comparable from the source given in Table 10.14.
to that of aramids (Burk, 1993).They also bond
poorly to epoxy matrices, so their off-axis
10.5 CONCLUSIONS
properties are also poor (Wolfe, 1990). For
these reasons, as with other organic fiber com- While high performance organic fibers are not
posites, PBO composites are limited to competitive with inorganic fibers in all of their
applications where structural loading is properties, they offer certain properties and
mainly in axial tension. combinations of properties that are unavail-
Moisture regain for Dow's PBO is 2.0% for able with inorganic fibers. All suffer from
the standard fiber and less than 0.570 for the certain limitations, such as poor off-axis and
high modulus version. The moisture resis- compression properties and/or temperature
tance is significantly better than aramids limitations. However, if these limitations are
(Burk, 1993).PBO is highly resistant to hydrol- properly considered, high performance
ysis, acid chemical attack, bases, solvents, organic fibers can make possible designs that
electron bombardment and laser radiation. Its can be achieved in no other way.
UV stability is outstanding (Wolfe, 1990).
Dow's PBO fiber has a lower and more stable
REFERENCES
dielectric constant than that of aramids, 3.0 at
100 kHz (Burk, 1993). Abbott, N.J., Donovan, J.G., Schoppee, M.M. and
The price for commercial PBO will be vol- Skelton, J. 1975. Some mechanical properties of
Kevlar and other heat resistant, nonflammable
ume dependent, but will be higher than that
fibers, yarns, and fabrics. Technical Report
for aramids. PBO fiber will be used where AFML-TR-74-65, Part 111. Wright Paterson Air
aramids and other fibers do not meet the per- Force Base: Air Force Materials Laboratory.
formance needs, particularly for strength, Adams, P.M. 1993. Private communication. 10-28-93.
modulus and flammability. Potential applica- Charlotte, NC: Hoechst Celanese Corporation.
References 239
fibers. In Encyclopedia of Materials Science and as the weight in grams of 1000 meters of the
Engineering, Vol. 3, ed. Michael B. Bever, pp. material. A related term is decitex (dtex),0.1
213940. Cambridge, MA: MIT Press. tex, which is often used in order to be com-
Weedon, G.C. and Tam, T.Y. 1986. New PE fibers for parable to the US quantity 'denier.'
high-end composites. Modern Plastics.
63(3):64-68. Equilibrium moisture content: moisture
Wolfe, J.F. 1990. Polybenzothiazoles and polyben- absorbed by a fiber after it has been dried at
zoxazoles. In Encyclopedia of Polymer Science and 50°C (122°F)for 2 h and then equilibrated at
Technology, Vol. 11, ed. J.L. Kroschwite, pp. 20°C (68°F)and 55% relative humidity
601-635. New York: John Wiley. Strength retention: percent of room tempera-
Wu, E.M. 1980. Strength degradation of aramid- ture strength retained following exposure
fiber/epoxy composites. AMMRC-TR-80-19.
to the conditions indicated
Watertown, MA: Army Materials and
Mechanics Research Center. Tenacity: the ultimate failure strength of a fiber
Yang, H.H. 1992. Kevlar Aramid Fiber. New York: per unit original area per unit weight. The
Wiley-Interscience. most commonly used units are 'grams per
Yang, H.H. 1989. Aromatic High-Strength Fibers. New denier' (gpd) and 'newtons per tex'
York Wiley-Interscience. (N/ tex).
Feldspar and nepheline syenite are not con- amorphous phase, of silica has very high sur-
sidered to be a health hazard or toxic and these face area. When added to liquid systems, this
minerals have been recommended as suitable type of product can provide a thixotropic
for use in composites that contact food. effect and reinforcing properties in cured rub-
Feldspar is obtained from white granite by bers or polymers. Flocculated varieties of the
quarrying the rock and crushing it. Nepheline colloidal form give flatting characteristics and
is the mineral derived from syenite rock and is composite properties different from the partic-
referred to as nepheline syenite. High-grade ulate colloidal phase. The synthetic forms are
deposits consisting of millions of tons are so fine in particle size that they offer little in the
mined and processed northeast of Toronto, way of hardness in the finished composites.
Canada. Natural silica products, as in the case of the
low quartz phase, come from quartzite and
tripolitic forms, which are generally termed
11.2.3 KAOLIN (CLAY)
natural, microcrystalline quartz. These are
Kaolin is the common term for the mineral usually less expensive than the synthetic, col-
kaolinite, a hydrous aluminosilicate mineral, loidal forms. They offer excellent electrical
one of a number of minerals called clays. It is insulation, good mechanical properties and
available in two primary grades: the natural lower surface area, hence better rheological
hydrous form and a calcined, anhydrous form. flow. Drawbacks are increased wear of pro-
The larger average particle sizes consist of cessing equipment and the lack of reinforcing
mixtures of blocky and platy particles. The properties.
finer fractions are almost entirely thin plates. Fused silica is manufactured by subjecting
Clay is a rock term applying to soft, earthy high purity quartzite to temperatures in excess
ores which are plastic when mixed with water. of 2200°C (4000°F).Finely divided fused silica
The hydrous forms are non-abrasive, chemi- has a very low coefficient of thermal expan-
cal resisting and have relatively high surface sion. This is desirable in composites subjected
area, which results in high viscosities in liquid to wide variations in temperatures.
polymer systems. They disperse readily in most Silica surfaces can be modified to offer
plastics, especially with the aid of dispersants organofunctionality,hydrophobicity and non-
or surfactants. In reinforced and thermoset functionality. commercial activity in surface
plastics, they control flow properties to provide modification is limited now, but the future will
more uniform composite properties. surely see more functional particulate silica
Calcined kaolin is considerably harder and materials with the interface tailored to specific
provides improved electrical properties in ther- end uses.
mosets and thermoplastics. Many surface-
treated types of each grade are available to pro-
11.2.5 ANTIMONY OXIDE
vide outstanding water resistance, electrical
properties and reinforcement, in a variety of Antimony oxide is an opaque white mineral
systems. powder which has been used as a pigment
because of its good color and high hiding
11.2.4 SILICA power. It is no longer competitive with more
economical white pigments and its high cost
There are over 20 distinct phases of silica and and density makes it unattractive as an ordinary
each is chemically SiO,. A number of them are filler or extender. The major use now is as a
useful as fillers in plastics. These different flame retarder.
phases offer advantages and disadvantages, Synergism between antimony oxide and
for example a synthetic colloidal form, or halogens accounts for the widespread use of
Common particulate fillers 245
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.)
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.
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
Titanates and zirconates vary widely for the many different types and
grades of particulate fillers.
Titanates and zirconates produced by
Kenrich Petrochemicals Inc., Bayonne, New
Jersey, have received much attention in recent 11.5.2 OIL ABSORPTION NUMBER
years and show promise of affording some
The oil absorption number is an important
remarkable improvements in processing
characteristic of a particulate filler. An analo-
characteristics and final properties of many
gous situation exists in the paint and coatings
composites systems. These coupling agents
industry, where two ASTM specificationshave
are analogous to the silanes. Each product has
been used to determine the oil absorption of
organic functionality and an inorganic back-
pigments. The objectives of these tests are 'to
bone, so that one end can interact with the
obtain information about the vehicle demand
matrix resin and the inorganic component will
of the pigment when it is used in a pigment
have an affinity for the filler or reinforcement
paste.' In ASTM D1483, linseed oil is added in
surface.
drops to the gently stirred pigment. The
amount of oil required to form a paste is used
Miscellaneous coupling agents to calculate an oil absorption value. In ASTM
D281, linseed oil is added dropwise to a small
There have been many polymer additives and
quantity of pigment, while rubbing vigorously
modified polymers that have been used to
with a spatula. The end point occurs upon
improve the properties of particulate filled
obtaining a 'stiff, putty-like paste, that does
polymer composite^.^
not break or separate.' ASTM D281 refine-
Polypropylene has been grafted with
ments, which can involve the use of
acrylic acid and this modified polypropylene
appropriate liquids other than linseed oil,
has provided improved bonding to mica and
have been described for determination of oil
talc in polypropylene composites. Copolymers
absorption or packing fractions of fi1lers.l" In
of styrene and maleic anhydride have been
most applications, it is desirable to choose
shown to have improved mechanical proper-
fillers with low oil absorption values, since
ties in filled thermoplastics compared to a
these fillers will cause the minimum increase
polystyrene matrix. Dupont produces a line of
in viscosity of the matrix material.
fluorosurfactants, with the trade name Zonyl,
that have been recommended for use as a
polymer additive to improve wetting and 11.5.3 HARDNESS
bonding with fillers.
The particulate fillers that are commercially
available have a wide hardness range. They
11.5 REPRESENTATIVE PROPERTIES OF are usually rated by use of qualitative scale in
PARTICULATE FILLERS which the hardness of a mineral was deter-
mined by its ability to scratch or be scratched
11.5.1 PROPERTIES OF PARTICULATE FILLERS
by another mineral. The scale was set up by a
In considering the use of particulate fillers all mineralogist, Friedrich Mohs. In the Mohs' rat-
factors should be evaluated including chemi- ings, the standard hardness minerals are: talc, 1;
cal and physical properties, surface gypsum, 2; calcite, 3; fluorite, 4; apatite, 5;
characteristics, particle size and size distribu- feldspar, 6; quartz, 7; topaz, 8; alumina, 9 and
tion. Among physical properties are specific diamond, 10. The hardness can be important
gravity, bulk density, specific heat, coefficient in the choice of a particulate filler. In the case
of linear expansion, index of refraction and of a polymer matrix cast part that must be post
Mohs' hardness value. These properties can machined, it will usually be advantageous to
252 Particulatefillers
choose a soft filler such as talc or calcium car- much higher ratio of resin/filler to fill the voids
bonate, since an alumina filler may result in before the system becomes sufficiently fluid for
severe abrasion of standard machining tools. most processing or molding procedures. Many
Also, in the extrusion or injection molding of applications will benefit from the use of a par-
polymer composites, a quartz or alumina filler ticulate filler and the proper packing of the
may cause severe abrasion of processing filler, filler blends or filler and fiber combina-
equipment or molds. tions will be useful to optimize the physical
properties of the composite.'l
11.7 TYPICAL END USES FOR PARTICULATE carbide fillers. Flexible and rigid plastic mag-
FILLERS nets contain about 90 wt.% loading of ferrite
The traditional source for particulate filled powder. These magnets are used in many
plastics has been from plastics compounders. automotive and appliance applications, such
There are many custom compounders with as door seals and refrigerator gaskets.
appropriate equipment such as Banbury mix- Mica-reinforced polypropylene has been
ers and twin screw extruders that are used to used in many automotive applications, such as
obtain a uniform blend of the filler and matrix. fan shrouds, seat backs, glove compartment
Various filled polymer compounds, usually in moldings and inner fender linings.
the form of small pellets that have been Among the many end products that are
chopped from extruded rods, are available made by use of particulate filled composites
from these compounders. In addition, large are electronic components, toys, marine com-
resin producers have introduced filled grades ponents, grinding wheels, display items, tools,
of their compounds. Among the many prod- housewares and cameras.
ucts that are commercially available are Nylon
and PBT resins filled with talc or mica from REFERENCES
GAF; Nylon filled with kaolin from Hoecht-
1. Katz, Harry, S., and Milewski, John V., Handbook
Celanese, Dupont (Minlon), or Monsanto of Fillers for Plastics, New York: Van Nostrand
(Vydyne); and GE’s Valox 700, which is a PBT Rheinhold (now Chapman & Hall), 1987.
resin filled with mica. GE’s Valox HV7000 2. Fillers and Extenders f o r Plastics, Norwalk, CT
series resins are PBT composites that are Business Communications Co., 1995.
highly loaded with mineral filler. Grade 7075 3. Canova, L.A., Effect of surface treatments in
has 68 wt.% filler. mica-filled polypropylene, Plastics Compounds,
1990, July/August, 3843.
Most commercial particulate filled plastics
4. Davis, et d.,US Patent 2 460 977,1949.
have had a maximum filler loading of about 5 . Searight, et d., US Patent 3 138 444, 1964.
40 wt.% because the physical properties have 6. Bland, et d., US Patent 3 150 947, 1964.
usually fallen dramatically when this level of 7. Schmidt, et d.,US Patent 3 190 737,1965.
filler has been exceeded. However, as the art 8. Plueddeman, E.P., Silane Coupling Agents, New
and science of compounding progresses, it York Plenum Press, 1982.
may be anticipated that future composites will 9. Skeist, I., Handbook of Adhesives, New York: Van
Nostrand Reinhold, 1989.
effectively use much higher average loadings 10. Ferrigno, T.H. in Handbook of Fillers for Plastics,
of mineral fillers. This trend is apparent from New York: Van Nostrand Reinhold (now
the high loading of minerals in GE’s HV7000 Chapman & Hall), 1987, pp. 17,19-20.
series mentioned above. Synthetic marble, 11. Milewski, J.V. and Katz, Harry S., Handbook of
which is used to fabricate bathroom sinks, is Reinforcements for Plastics, New York: Van
usually formulated by use of polyester resins Nostrand Reinhold (now Chapman & Hall),
that have been highly loaded with calcium 1987, pp. 14-33.
SANDWICH CONSTRUCTION 12
Andrew C. Marshall
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- amounts of ’B’ staged resins; high strength
dential construction materials, interior resins; tough, high peel adhesives requiring
partitions, doors, cabinets and a great many lower cure temperatures and pressures; as
other everyday items. well as the discovery of the resistance of sand-
Although the employment of sandwich wich to sonic fatigue.
design to produce lightweight or special pur-
pose load-carrying members is thought to
12.2 FACING MATERIAL
have originated as early as 1820, routine com-
mercial use of the idea did not occur until The primary function of the face sheets in a
about 110 years later. What started this sudden sandwich structure is to provide the required
acceptance was the successful commercial pro- bending and in-plane shear stiffness and to
duction of structural adhesives, starting in carry the edgewise and bending loads, as well
both UK and USA in the 1920s and 1930s. as the in-plane shear loading. In the aerospace
This early production began with the use of field, facings most commonly chosen are resin
casein glue and later urea-formaldehyde and impregnated fiberglass cloth or a laminate of
phenolics, with wood facings and cores. The unidirectional fibers (commonly called
search for better adhesives subsequently ’prepreg’), graphite prepreg, 2024 or 7075 alu-
resulted in the development of the rubber- minum alloy, titanium alloy, or any of several
phenolics and the vinyl-phenolics, which were stainless steel or refractory metal alloys. Even
suitable for use with metals. Commercial the most economical of these products repre-
adhesives such as ’Cycleweld,’ (from Chrysler sents a substantial cost and customary practice
Motors), ’Plycosite,’ (from US Plywood) and is to choose among them very carefully on a
’Redux’ (from Bonded Structures, in Duxford, value engineering, or lowest lifetime cost,
UK) adhered well to both wood and metals basis.
and possessed rather high and predictable
strength.
12.2.1 SUITABILITY OF MATERIALS
The result was the beginning of a revolution
in bonding technology. Many further develop- When choosing facing materials (as well as the
ments followed in only a few years. They core, adhesive, or other materials) for an appli-
included improved cleaning methods for cation, it is wise to examine the less obvious
metal skins; low weight, high strength/stiff- properties of the material, such as toughness
ness honeycomb core materials; ‘B’ staged or brittleness, mode of fracture, durability and
tape adhesives which could be stored for long weatherability, compatibility with rivets and
times; glass fabrics and collimated tapes bolts and other such attributes which may
preimpregnated with accurately measured directly affect the usability or success of the
256 Sandwich construction
end product, even though not directly applications such as boat hulls, large tanks and
involved in stress analysis or weight savings. airborne pallets and containers. This broaden-
An understanding of these requirements has ing usage is also prompted by its excellent
resulted in a switch from aluminum to fiber- compressive strength and modulus properties
glass skins and from fiberglass to aramid when compared to all but the aramid paper
(Nomex, from DuPont) cores for most aircraft honeycombs, which are much more expensive.
cabin interior panels. Complete information can be obtained from
the leading producer of these materials,
BaltekI3,or Balsa Ecuador Lumber Company.
12.3 CORE MATERIALS
exception to this statement lies in the extensive foams, even though this value is needed for
use of polystyrene foams as cores in several sandwich panel design. This property, even
thousand amateur-built composite aircraft. where listed, cannot be considered to be a reli-
This application was pioneered by Burt Rutan, able value. The actual value for an application
in his ’moldless construction’, used in his at hand must be determined for the actual
series of high performance small aircraft and materials and conditions of use in order to be
the many similar designs offered by others in considered reliable. When a value for shear
subsequent years. strength is not available, it may be roughly
The polyvinyl chloride (PVC) foams, which estimated to be about 0.7 times the compres-
made an impact on the transport aircraft sive strength shown. Even the compressive
industry as flooring cores, have been largely strength cannot be considered to be reliable,
replaced by the more efficient high density however, as many differing methods of mea-
aramid honeycombs. suring this value are commonly used and each
The foam-in-place system of producing results in a substantially different value
sandwich structures has been used for more reported.
than 35 years, because of its simple concept.
However, users of this system have always
12.3.2 HONEYCOMB
had difficulty with the continuing problem of
producing uniform properties from one mix to Honeycomb types in common usage include
the next and in achieving uniformly high core products made from uncoated and resin-
and bond strengths to the metal or pre-cured impregnated kraft paper, various aluminum
glass fiber skins. The use of systematic incom- alloys, aramid paper and glass or carbon fiber
ing inspection, automatic mixing and reinforced plastic in a number of cloth weaves
dispensing equipment and, in the case of criti- and resin systems. Honeycombs based on tita-
cal airframe parts, test coupons, produced nium, stainless steel and many others are used
integrally with the basic part, have all helped in lesser quantities. Most honeycomb cores are
to keep the problems under control. constructed by adhesively bonding strips of
It will be noted that Table 12.1 does not list thin material together, as shown in Fig. 12.3.
the shear strength of many of the various In the case of aramid paper honeycomb, the
Roll c T r
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
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-
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 )
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
2
I
HEXAGON' C E L L S
3
I I
4
used to confirm actual values obtained, as the CORE THICKNESS (INCHES J
Density
All mechanical properties increase with higher the loads anticipated. Figure 12.7shows typical
density, as shown in Fig. 12.6. 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
Cell shape
strength/weight ratio. This attribute can be of
All honeycombs are anisotropic and the result- great importance in manufacturing curved
ing directional properties should be adapted to parts of appreciable thickness.
1 PCF
I L Fig. 12.6(b) Typical 'L' shear
0 20 40 60 80 100 120 140 160kglm'
Density strengths.
C D
E F
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.
employed as decoration - and are still fre- Some of the above alloys are also available as
quently seen today as seasonal decorations in corrugated, corrugated and reinforced, over-
department stores in the form of expanded expanded and flexible cell configurations.
bells, spheres and so forth. Some have also been produced in a specially
Current materials used as sandwich cores tailored geometry to make all the cell axes lie
are different, in that much stronger kraft paper on a true radius of a cylinder, a sphere, or
is employed and 11-35% phenolic resin is fre- other unique configurations. These same alloy
quently used to improve mechanical foils can also be wound as a corrugated spiral
properties, as well as moisture and fungus to form a cylinder or tube for very light energy
resistance. Many variations are available in absorption applications.
cell sizes of 10,13 and 19 mm (%, X and % in) or The aluminum honeycomb cores remain
even larger sizes. The higher strength versions the most used, as well as the most versatile of
are only produced in the smaller cell size, with the various core materials obtainable and are
the 10mm (% in) cell available as a water- often found to possess the most favorable per-
migration resistant grade meeting military formance/cost ratio available. Expanded
specification MIL-H-2104Q. aluminum cores commercially available
Most applications are found in non-aircraft ranges from a low of about 32 kg/m3 (2 lb/ft3)
uses, where cost saving is the one primary to a high of 192kg/m3 (12.0Ib/ft").
objective. Usage is growing rapidly in recre- Corrugated aluminum cores, however, start at
ational vehicles; for doors, walls and under 128kg/m3 (81b/ft3) and can be pur-
partitions; for factory produced kitchen cabi- chased up to 880 kg/m3 (55 lb/ft3). At
nets; in packaged patio room additions for densities below 128 kg/m3 (8 lb/ft3) corru-
homes; in curtain wall panels; and in bearing gated core suffers a serious penalty in shear
walls for commercial building. properties when compared to expanded core.
This family of materials has been in produc- This family of materials is most commonly
tion and growing since about 1947.Aluminum used in electrically sensitive parts, such as
honeycomb now includes four alloys, at least radomes and antennae, or where a heat resis-
five cell shapes and many foil gauges to pro- tant resin and low thermal conductivity make
vide a range of densities. The alloys generally it a natural choice. It has also seen distin-
available are: guished service as a matrix for retaining
non-structural ablative materials, such as soft
0 3003-H19, the lowest strength of the group, silicone rubbers or syntactic rigid epoxy
usually used for non-aircraft applications; foams, which otherwise could not have been
0 5052-H39, the most often used aircraft used effectively as ablative heat shields on the
grade, available with a corrosion resistant Gemini and Apollo re-entry vehicles.
surface treatment. Mechanical properties Only high temperature phenolic and poly-
are listed in Table 12.2; imide cores are generally produced. They are
0 5056-H39, the strongest of the regular air- commonly available in cell sizes of 5, 6.3 and
craft grades, available with a corrosion 10 mm (K, X and X in) with a 3 mm (% in) cell
resistant surface treatment; available in a bias weave glass reinforcement.
0 2024-T3 or T81, the most heat-resistant alloy Densities range from 32 to 192 kg/m" (2 to 12
and slightly stronger in some properties lb/ft3). Mechanical properties of several com-
than 5056-H39. Available with a corrosion mercially available glass fiber-reinforced cores
resistant surface treatment. are shown in Tables 12.3-12.6.
Core materials 269
__
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.
in typical panels result in low volumes of space vehicles. In addition to this small usage,
smoke and gases given off in fire tests. Typical however, carbon fiber honeycomb is now used
applications make use of these properties very as the structural core for nacelle assemblies in
effectively.As a consequence, they have grown the Boeing Model 777 transport aircraft. The
to a commercial volume nearly as large as that constant pressure for lighter structures in such
of aluminum, for use in aircraft structures. designs has led to the use of carbon fiber fac-
Uses outside the aerospace industry are lim- ings, which have a potential corrosion
ited due to the high cost of the material, but problem when used with aluminum cores.
despite this it has seen some application in This concern for corrosion problems has sub-
boat hulls up to 10.2 m (40 ft) in length, as well sequently led to the adoption of a new class of
as in skis, racing shells and several other prod- carbon fiber honeycomb materials for this air-
ucts. craft and will possibly lead to further use in
Aramid core is normally produced in cell other future designs.
sizes of 3, 5, 6.5 and 10 mm (%, 36,X and % in), Two types of carbon fiber cores are now
in densities of 24-192 kg/m3 (1.5-12 lb/ft"). being produced. One is for purely structural
Densities higher than 64 kg/m3 (4 lb/ft3) are applications, while the other has a require-
almost entirely used for aircraft flooring. ment for heat transfer through the thickness of
Mechanical properties of some of these core the panel. The former type uses only the usual
materials are shown in Table 12.6. pan based carbon fibers, while the latter
employs pitch based carbon fibers, which
duplicate the heat transfer properties of the
Carbon fiber honeycomb
aluminum core which it replaces. Although
Reinforced plastic honeycomb has for many neither of these materials is as yet in large vol-
years employed glass fabric reinforcement,b u t ume production, the economic impact is
only rarely employed other fibers. In the past substantial, since these honeycombs are
few years, however, both Kevlar and carbon markedly higher in price than the aluminum
fiber have become much more common as or Nomex cores they replace.
reinforcing fibers for honeycomb. Carbon Little data is yet available on these new
fibers only now are beginning to be used in cores, but it is likely they will see substantial
Adhesive materials 271
use and public scrutiny in the next several be understood by the designer and fabricator
years. in order for the otherwise inevitable problems
to be avoided. Some factors which merit atten-
tion are discussed below.
Kevlar honeycomb
This honeycomb has been in use for a number
of years as a core for space vehicle antenna 12.4.1 PRODUCTS GIVEN OFF DURING CURE
reflectors. The purpose of the Kevlar honey- Some adhesive types, such as phenolic, give
comb is to allow transmission of radio signals off a vapor as a product of the curing reaction
through the panel, while at the same time the and the presence of these secondary materials
Kevlar facing acts as a partial reflecting antenna can lead to several problems:
for a different wavelength of a different signal.
Kevlar honeycomb, based on one of several 0 internal pressure, resulting in little or no
fabrics woven from Kevlar yarn, is usually bond in some areas, or 'blisters';
produced in cell sizes of 6.3-9.5 mm (%-% in) . 0 core splitting, as the gas forces its way
Usual densities available range from 16 to through the core to a lower pressure area;
64 kg/m3 (14 Ib/ft3). 0 core movement, sometimes several inches,
resulting in an unusable cured part;
0 subsequent corrosion of core or skins by the
Kevlar paper honeycomb chemical action of the vapor or its residual
In addition to Kevlar honeycomb made from condensate.
woven fabric, DuPont has recently introduced
a new honeycomb, based on a Nomex-like 12.4.2 BONDING PRESSURE
paper, which is entirely composed of fibers
derived from Kevlar. This material has rather Adhesives such as the phenolics and some
surprising mechanical and physical proper- others actually require more than atmospheric
ties, with strengths well above both glass and pressure in order to prevent excessive poros-
Nomex honeycombs and dielectric properties ity. Certain forms may be suitable for solid
somewhat superior to Nomex. This material is cores like balsa, but cannot be used at all in
trade named 'Kortex' and is available in the open cores such as honeycomb or large cell
usual range of cell sizes and densities. foams. Also, most core materials will not alone
Because the material is somewhat more withstand compressive bonding loads exceed-
expensive than Nomex, no large scale replace- ing a few atmospheres and consequently
ment of Nomex honeycomb appears likely, cannot be used with any adhesive system
although many special purpose applications requiring higher pressures.
have been developed in both air and space
craft.
12.4.3 FILLET FORMING
In order to achieve a good attachment to an
12.4 ADHESIVE MATERIALS
open cell core, such as honeycomb, the adhe-
Adhesives, as they apply to sandwich struc- sive must have a unique combination of
tures, constitute a somewhat different family surface tension, surface wetting and controlled
of materials than those required to bond an flow during early stages of cure. Controlled
open cellular core to a stiff and continuous fac- flow prevents the adhesive from flowing
ing. Although these differences are less down the cell wall and leaving a low strength
important with some of the newer modified top skin attachment and an overweight bot-
epoxy materials, they remain basic and must 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.
The peel test is used to control quality 12.4.9 NITRILE RUBBER MODIFIED EPOXIES
throughout the sandwich industry. Values
These make up a broad group of more recent
obtained, provided the adhesive weight and
materials which provide much of the flow and
core material are in balance, will give indica-
toughness shown by the nylon-epoxies, along
tions of tooling or cure problems and of
with the durability and weather resistance of
adherend surface preparation problems. It is
the vinyl-phenolics. They are the most com-
particularly useful for this when an environ-
mon of the 'toughened' thermosetting
mental exposure involving both elevated
adhesives and are usually limited to about
temperature and high humidity is interposed
149°C (300°F) service temperature. Some of
between manufacture and test. It is also adapt-
these materials routinely achieve shear
able to use with nearly any skin material,
strengths of 34500 kPa (5000psi) and most
except that it becomes impractical with very
can be cured over a wide range of tempera-
thick or very stiff skins.
tures and pressures.
It can be readily seen that a number of points
of difference separate the sandwich adhesives
from other structural adhesives. Fortunately for 12.4.10 URETHANES
the sandwich user, many adhesives are avail-
able which satisfactorily meet both sets of Urethane based adhesives are used in
requirements. me types available, along with commercial structures. Both moisture-cured
some salient features, are as follows. and two-part systems are available.
216°C (420°F) for some of the materials All the above forms of adhesive are in cur-
intended for service at elevated temperatures. rent use at substantial volume and most are
available from many sources.
Supported films
12.5 DESIGNING A SANDWICH
Films or tapes having a carrier of light glass
fiber, cotton, nylon, or polyester fabric, or The usual objective of a sandwich design is to
spunbonded synthetic fiber are provided save weight or to increase stiffness or to use
either dry or with slight to moderate ’tack’ or less of an expensive skin material, or perhaps
stickiness, so that the parts of the assembly all three. Sometimes other objectives, such as
stay in place as they are being assembled. reducing tooling or manufacturing costs,
achieving aerodynamic smoothness, reducing
reflected noise, or increasing durability under
Unsupported films, containing only the
exposure to acoustic energy, are also involved.
adhesive
The designer’s problems sift down to rela-
The very low weight films are nearly always tively few, such as getting the loads in, getting
furnished without a carrier, as the weight of the loads out and attaching small or large
the carrier itself becomes quite appreciable in load-carrying members, under constraints of
very light sandwich structures. They are often deflection, contour, weight and cost.
hard to handle and sometimes have bond line
Understand the fabrication sequence and meth-
control problems.
ods. The cost of a sandwich structure is
fundamentally fixed at the design stage and
Reticulating films a considerable difference in cost can result
from alternate solutions to the design prob-
These are intended for use at very low
lem. Both of the edge close-out details
weights, with the adhesive being melted by
shown in Fig. 12.12 perform essentially the
hot air after placing on the core, so that it
same job at the same weight. Placing the
draws back to the cell edge and provides
legs of the channel facing outward instead
material to form the largest possible fillet
of inward saves the cost of two relief cuts
without wasting any on the inside facing sur-
into the core and the very difficult step of
face in the middle of the cell.
sliding the edge of the core and adhesive
into the channel. Another alternative at
Cell-edge adhesive even lower cost for either fixed or simply
supported edges is shown in Figs.
This is a material pre-placed on the cell edge
12.13-12.16.
by the honeycomb manufacturer to provide
Use the right core. Several densities of core
the same results as those produced with retic-
can be used in a single panel, each appro-
ulating films.
priate to the load carried in the area and
adhesively bonded to its neighbor, as
Self-adhesive skins shown in Fig. 12.17. In many cases, how-
ever, the weight saved in lower density
These skins are usually structural fabrics of
areas of core is added back in the form of
glass, graphite, quartz, or aluminum coated
core splice adhesive weight. Core splices,
glass fibers, pre-impregnated with a resin,
such as those shown in Fig. 12.18(b)or (c),
which is then cured so that the fiber-filled
have been used to produce ablative matrix
resin becomes both the face structure and the
structures for large re-entry heat shields,
attaching material.
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
''2
METAL
F O RMEO RING ---.
Fig. 12.14 Several common edge treatments.
278 Sandwich construction
Fig. 12.15 Several suggestions for corner designs, edge close-outs and splices.
Ex trurion,
f Weldd
b
\
Locking Bar
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- 5. Use doublers where needed, instead of a heavier
duce for splices more than a few inches facing over the entire part. The use of doublers,
long. although adding labor cost in assembly,
Do not hesitate to use several joining methods often improves the part quality. Where
in the same part. Fittings to be included in a skins are formed of glass or graphite
bonded sandwich may be produced from prepreg, the problem is even simpler, since
weldments, forgings or riveted assemblies, extra plies can be added to carry extra loads
or may themselves be bonded assemblies. exactly where and as needed.
Available adhesives permit secondary 6. Use external doublers rather than infernal dou-
bonding to be performed at temperatures blers wherever possible. The use of internal
from 16°C (60°F) up to 177°C (350°F) with- doublers usually means that a relief cut
out degrading the integrity of the must be made in the thickness dimension of
previously bonded sub-assemblies. the core to prevent bridging and a conse-
Use bolts and rivets for carrying loads (not for quent unbonded area where the doubler
soothing fears). Where space is not available ends. Figure 12.19 shows a panel where the
for progressive doublers or wide-area loads which can be carried are the same at
bonded overlaps to carry high loads, the each end of the panel. The design detail on
addition of rivets or bolts is sometimes the the left end can cost substantially more to
only solution. Their use, however, often manufacture than that on the right end.
results in lower (sometimes dramatically Figure 12.20 shows the same panel with
lower) fatigue life of the structure, in addi- both ends produced at low cost, while still
tion t o increased weight. The use of achieving an unbroken outer skin line on
'chicken rivets', added for the sole purpose one side. In the case of some skin materials,
of appearance, is to be particularly avoided, such as 0.25mm (0.010in) aluminum, or
since they often defeat much of the advan- most weights of pre-impregnated glass or
tage which would otherwise result from use graphite cloth, it is feasible to use thin dou-
of the bonded structure. blers without a relief cut in the core, since
280 Sandwich construction
I
1
Fig. 12.20 Low cost doubler treatment.
the gap caused by bridging is small enough 12.6 STRUCTURAL ANALYSIS FOR SPECIFIC
to be within the capacity of the adhesive to CASES
fill. Sometimes an extra layer of adhesive The following notations are used in sandwich
film is added to help. An example of a dou- design formulas.* This chapter’s formulas are
ble skin splice using this method is shown only for honeycomb beams and columns
in Fig. 12.21. which have the same facings on each side of
the core.
Structural analysis for specific cases 281
Facing failure
Initial failure may occur in either
compression or tension face. caused Of =
M
t, hb
~
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.
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
I I
I
Simple support
A
IP
Center load
P
-
2
E
4
“ I +
192
I I I
Cantilever Uniform load
P = ql
lrrrrrrr
I I 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
-[I
2E, t,
ufcnt. = 1 ,
Skin, t,: Try t = 0.090 in
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 = ~
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
Table 12.7
Subject MIL-HDBK-23 *
CHAPTER
~~
_ _ ~ ~~~ ~~~
1. Make sure the core is properly sized to fit much more slowly, resulting in warpage
the space it is intended to occupy. If it has problems upon cool-down. Warpage on
been stretched a little, to make the distance very light parts can also be caused by one
from one edge member to the opposite one, side cooling down too fast as a result of
it will probably shrink back as the cure having one side removed from the still-hot
cycles starts, leaving mysterious voids next tooling, while the other side continues to
to an edge member. If it is undersize in stay at the temperature of the tool. Also one
thickness at an edge, the adjoining edge side, next to the bag may be heating faster
member or fitting will hold the facing away or to a higher temperature than the oppo-
from the core and result in an unbonded site face, which is in contact with a massive
area. and still cold tool. Slower heat-up rates or
2. If a honeycomb core is being used, remem- better heat distribution in the tool design
ber that the adhesive between the core and will help prevent these problems.
the faces will end up much thinner than the 6. Be sure to provide a route for the escape of
same adhesive between the edges or solid trapped air and gases from a totally enclosed
inserts and the facings. For this reason, it is part while it is being cured. This is particu-
common to require the core to be as much larly important in parts which are vacuum
as 0.25 mm ( 0.010 in) thicker than adjoining bagged to a female tool and cured in an auto-
solid parts in the same assembly. clave. A coarse cloth 'breather' should be
3. The elevated temperatures which most enclosed inside the bag to prevent the bag
core-to-facing adhesives require for curing from sealing off portions of the assembly as
are often inaccurately measured. A good pressure is being applied. Critical or expen-
point to remember is that only the adhesive sive assemblies should have several vacuum
being cured can give you the cure tempera- lines attached at different points of the bag,
ture you are trying to measure. Some shops with each monitored separately by a pres-
insert thermocouples directly into the bond sure recorder.
line to determine temperature and then 7. Caul plates should be carefully matched to
leave the thermocouple permanently in the the job they are expected to perform. These
part after cure is completed. tooling aids are often used to cover the top
4. Most adhesives flow at an early point in the of an assembly containing several different
cure cycle. At this time, the bond lines will pieces of core, inserts, edges, etc., so that a
change in thickness by substantial amounts. thin skin will not push each detail to the
The tooling employed to establish the shape minimum bond line thickness and result in
of the part and hold details in place must an uneven outer surface. When the caul
also allow the details to move into their plate is moderately stiffer than the top skin,
final cured position. Simple examples are a the bonding pressure is transmitted more to
hot platen press, in which the platens close the thicker inserts and less to the under-
on the sandwich as the bond lines grow sized inserts, allowing all of the details to
thinner, or an autoclave, in which a flexible 'float' in the adhesive before cure, resulting
bag follows the details as the adhesive in optimum relative placement of all the
flows, continuously transmitting the auto- internal details in the sandwich. If the caul
clave pressure to the shrinking assembly. plate is extremely stiff or thick, this effect is
Keep in mind that most adhesives are very changed to one of simply bridging over the
weak and crack-prone as they go through most oversized details and the danger of
the gel point. producing voids or unbonded areas over
5. Inserts or heavy members being cured as a the thinner details is substantially
part of a very light assembly will heat up increased. Generally, the caul plate should
Manufact uring sandwich structures 289
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
Fig. 12.27 Nose radome core assembly, assembled Office, Washington, DC,
by edge-bonding together several post-formed sec- 8, Hexcel Corporation, TSB-120.
tions of glass fabric-phenolic honeycomb. Nomex 9. Hexcel Corporation, TSB-123.
core may also be formed in this manner. 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.
I
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
Fig. 12.28 Effect of roll-forming on aluminum hon- Command, Dover, New Jersey. The publication
eycomb. The core on the left has been roll-formed in MIL-HDBK-23 was abandoned some years ago.
sheet metal forming rolls, while the piece on the However, because the information it contained con-
right has not been pre-formed at all. Note the anti- tinues to be needed by designers of spacecraft
clastic, or ‘saddle shape’, which the unformed piece structures, the entire publication will in future be
assumes when forced to a cylindrical form. included within MIL-HDBK-17.
METAL MATRIX COMPOSITES 13
V. I. Kostikov and V. S. Kilin
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.
Carbon fiber coating methods 293
of reduced clearances between fibers in zones Coatings of refractory metals applied to car-
difficult to access and stagnation and poor bon tows and tapes by thermal decomposition
solution exchange take place. In these zones, of volatile carbonyls in the gaseous phase have
the solution is fully depleted, while in other the following advantages: low temperature of
decomposition of carbonyls of some commer-
zones, the nickel plating may continue. The
addition of 0.01 g1-1 lead sulfide to the soh- cially important metals (Cr, Mo, W, Rhs etc.);
tion slows the process of electroless nickel high reaction velocity; uniformity of coating
plating and eases the conditions of the forma- thickness on each individual carbon fiber; ease
tion of uniform coating thickness. Reducing of adjustment of structures and properties of
the number of individual fibers in carbon tows coatings as a result of change of the deposition
to 100 and the number of ends in tows also conditions.
help to provide better uniformity of coating The thermal decomposition of the metal
carbony is carried out as follows:
thickness. When 300-fiber, 6 pm equivalent
diameter, twisted tows of bean shaped cross Me(CO)n= Me + nCO
section were coated, the coating thickness on
the fibers was uneven and varied from In addition to the main reaction, side processes
0.2-0.6 pm up to 0.5-1.0 pm at nickel gain in that cause the presence of admixtures of metal
weight from 0.5 to 1.0 g. (Editor's note: Carbon carbides in the coating can take place. As the
fiber tows are not generally twisted and are all temperature is increased, the possibility of
single end in the USA and other countries.) obtaining pure metal layers without admix-
The thickness of nickel coatings, used for tures of free and fixed carbon occurs11. To
subsequent impregnation of carbon tows and obtain pure metals with a minimum content of
tapes with aluminum melts, is usually about admixtures, the process should be run at the
0.5-1.0 pm. The nickel coating obtained by highest possible temperature and sufficiently
chemical deposition from solutions does not high vacuum. Some characteristics of coatings
diminish the fiber strength. by precipitation from the gaseous phase are
The chemical deposition of copper is shown in Table 13.1. The type of substrate
accomplished at 20°C in alkaline solution that heating is usually determined by temperature
contains sodium sulphate, formalin, caustic requirements, and may be performed by con-
soda, potassium sodium tartrate, and diethyl duction, induction, radio frequency or
sodium carbonate. At a holding time of 3-6 infra-red radiation.
min, the coating thickness reaches 0.1-0.4 pm. During the vapor phase of carbonyl decom-
Before application of copper coatings, the position there are a number of subsequent
fibers are subjected to the same preliminary processes: vaporization (sublimation) of car-
treatment as the nickel coating. bonyls, heat transfer, chemical process in the
The more rapid electrolytic method of gaseous phase and substrate, adsorption-des-
deposition should be a more efficient tech- orption on the substrate, formation of nuclei
nique to obtain thick nickel or copper coatings. and growth of coating crystals12.Successively
However, the electrolytic method may be used changing the carbonyl vapor feed velocity
only for building up of the coating layer on (growth of the coating layer from 0.3 to 6-8 pm
previously electrolessly coated carbon fibers. h-l) and the temperature of substrate heating
Otherwise, the fiber tows will be coated with a from 300 to 900°C can result in denser coatings,
crusty layer from the outside. 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
~.... ~~~~~~ ~~
Fig. 13.2 Relation between tensile strength of titanium carbide and zirconium carbide coated CF and coat-
ing thickness.
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. Deposition of nickel and aluminum coat-
The degree of aluminum-carbon interaction ings on a Sic barrier layer substantially affects
was estimated in terms of quantity of the the carbon fibers-aluminum interaction. These
obtained aluminum carbide, using the alu- coatings, dissolving in the aluminum melt,
minum carbide-water reaction. ensure impregnation of the carbon fiber tows.
The results of determining the aluminum However, in the presence of nickel, the resid-
carbide content on carbon fibers with various ual aluminum content on the fibers after
coatings, and their tensile strength after annealing at 720°C is increased. This increase
annealing (the aluminum matrix is etched obviously is associated with a nickel-silicon
away) are shown in Table 13.2. carbide interaction that results in opening the
These results suggest a strong alu- fiber surface.
minum-carbon fiber interaction. The However, the surface layer increases the Sic
quantity of aluminum carbide is sharply barrier properties. The quantity of aluminum
increased with annealing temperature and carbide measured after annealing under the
exposure time. However, a Sic coating with a same conditions is decreased down to the level
thickness of only 28 nm decreases the alu- which can be obtained for Tic coating. This is
minum carbide formation by a factor of 1/5. associated with the fact that silicon dissolving
Doubling the Sic coating thickness inhibits in aluminum saturates it and suppresses the
the reaction resulting in the aluminum car- following reaction:
bide formation by an order of magnitude.
Subsequent increases of the coating thickness
(4) Sic +A1 + (Sic) +Al,C,
affect the aluminum carbide formation at a To summarize, based on the estimated
lesser degree. 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
nickel, it can be concluded that titanium and shapes, by rolling in dies and extrusion. The
zirconium carbides are preferred for a nickel hot extrusion, and consolidating in autoclaves
matrix, and that silicon and titanium carbides are used for manufacturing cylindrical cases
are preferred for an aluminum matrix with the and tubes with longitudinal and circumferen-
coating thickness of no more than 100 nm. tial reinforcement.
Typical cross sections of MMC composite Preformed composite MMC with constant
structures are shown in Fig. 13.6. Many types cross section can be manufactured by contin-
of continuous length composite structure can uous casting or drawing of fibers through
only be produced by continuous casting. In melt. The principal advantages of continuous
some cases, it requires a preliminary applica- casting are continuity, reduced time of con-
tion of a barrier coating on the fibers by means tact of the fibers with molten metals and
of chemical deposition from solution or minimum unstable period. This method also
vapor-gaseous mixtures. It is convenient to results in a high production system, effi-
prepare a unidirectional tape for composite ciency and reduced capital investment. The
structures by plasma spraying of matrix alloys basic expenditures are for control equipment
on rows of monofibers or taped fibrous since the process only requires a common
prepegs. In some cases, use is made of a varia- melting furnace and a foundry crucible,
tion of a hot extrusion treatment compression molding fixture, a magazine of spools with
method to obtain a taped foil composite struc- fibers and a system for transportation of
ture reinforced by one or several rows of fibers fibers and handling products. During opera-
and infiltrated tows, as well as of plasma tion the melting furnace must be filled with
sprayed or infiltrated tapes. Sheets and plates argon or evacuated. As a result, the cost of the
are obtained by rolling in a die and extrusion. MMC produced by continuous casting is
The simplest sections can be produced by close to the cost of the initial fibers and
bending of rolled strips, and more complicated matrix.
1 2 3 4
@
4
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.
Infiltration under pressure 299
The continuous casting method has a num- operations with fibers and the procedure for
ber of advantages from a metallurgical testing of fiber volume fraction are shortened.
standpoint since the composite is prepared The production of aluminum carbon fiber
without formation of typical oxide inclusions for MMC is complicated due to several fac-
which are common in plasma spraying and tors associated with the carbon fibers. Their
hot molding. Most investigators have used small diameter (6-10 nm), friability, high
vertical techniques of continuous casting, but reactability and poor infiltration characteris-
there are versions of horizontal drawing of the tics with aluminum melts at temperatures
fiber through the melt. Before being sub- below 1030°C are all contributory factors. The
merged into the melt, each fiber is detached latter two are most important. The danger of
from the other fibers to ensure intimate contact chemical degradation and reduction of fiber
with the molten metal. Then the fibers pass strength due to graphitization and formation
through the drawing die that determines the of carbides increases with greater contact
cross section of the preform. The fibers are time of the fiber with the melt and with
drawn with a rate necessary for solidification higher temperatures.
of the matrix to fill up the inner space of the
composite preform. For example, in produc-
13.6 INFILTRATION UNDER PRESSURE
tion of cast boron aluminum cable, the
drawing rate could reach 900 m/h, but cannot lnfiltration of fibrous preforms makes it possi-
exceed 450 m/h due to fiber defects. ble to obtain intermediate preforms and
The continuous casting process can consist composite structures of limited size.
of two stages: the first stage involves the pro- Infiltration is accomplished by various means:
duction of the composite preform with a small by heating the mold containing the fibers and
cross section, essentially a wire, bar or band; in matrix material in the form of a foil, powder
the second stage, the previously produced or coating on the fibers up to above the melt-
composite preform is integrated into a more ing temperature of the matrix material with
complicated structure with a larger cross sec- the subsequent shaping of the mold; by sub-
tion. For example, in the course of production merging the fibers into the melt or filling
of a boron-aluminum MMC, the most popular molds with the melt in vacuum, protective
form of the initial composite structure is a bar atmosphere or air; by vacuum suction of the
of a circular section, containing 16-19 fibers. In melt; by feeding the melt into the mold under
the second stage, the amount of matrix added pressure; and by centrifugal casting. In all
into the MMC can be very small to keep a high types of infiltration, the common denomina-
volume fraction of reinforcing fibers in the tor is the presence of the mold with the fixed
final product. The two stage process is used fibers. Because the process is long compared
for the production of such profiles as rods, with continuous casting, the fibers should
angle bars, T-beams, I-beams, and lenses. have high thermal stability in metal melts.
The composite resulting from cast lamina Experiments on infiltration with uncoated
may be obtained in one, two or more steps. To carbon fibers and with nickel plating by suc-
form profiles, particular attention must be tion or by filling with melted aluminum or
focused on the first stage since it determines magnesium in vacuum have been unsuccess-
the basic physicomechanical properties, espe- ful due to the failure of the fiber to be
cially specific strength. Because of the infiltrated at the melt temperatures without
organization of the liquid phase process by extensive carbide formation. Common draw-
stages, the amount of manual labor can be backs of vacuum infiltration of carbon fibers
reduced, the equipment simplified and the with aluminum or magnesium alloys are
dead time due to fiber breaks shortened. Also, incomplete infiltration because of nonuniform
300 Metal matrix composites
penetration of the matrix material into the braids of carbon fibers with aluminum melts
interfiber spaces, nonuniform package config- at lower temperatures and higher pressures. It
uration and touching and burning of the has been reported that a two layer coating pro-
fibers where there is no protective coating. duced the best results'l; the first layer of
These drawbacks are especially evident in silicon carbide protects and the second layer of
infiltration of multifilament braids and bands. such transition metals as chromium, molybde-
Uneven distribution of fibers results in defects num, tantalum or tungsten which are properly
in the form of isolated groups of filaments not infiltrated with aluminum improves infiltra-
separated from each other by matrix, thus tion. They also have a lower affinity for carbon
serving as stress concentrators. The result is compared to silicon.
that with an increase in volume fraction of
carbon fibers to more than 30-35%, which 13.7 ROLLING IN VACUUM
does not increase the strength of the compos-
ite material but starts to reduce it, due to the Nondeforming process methods, including
greater number of groups of filaments not ionic and plasma spraying and spontaneous
infiltrated with the matrix. infiltration make it possible to obtain the high
To improve infiltration of the carbon fibers physical and mechanical properties of car-
with aluminum melts with metal coatings bon-aluminum MMC. However, these
(especially nickel plating), conditions must be methods are characterized by low productiv-
chosen to ensure a high rate of flow and to ity and high labor input. The formation of the
considerably shorten the duration of time of structure and properties of carbon aluminum
contact of the coating with the melt13.The rela- that has been vacuum rolled within the solidi-
tionship between the capillary and excessive fication range of the matrix aluminum-
pressure and the infiltration angle and volume magnesium alloy has also been studied.
fraction of carbon fiber in the molten alu- Rolling of the initial billets of carbon alu-
minum matrix on the other, taken at a minum was performed on a vacuum rolling
temperature range 925-1083"C, shows that the mill with residual pressure Presid = 6.5 x lo-' Pa.
melt penetrates the braids of the fibers only at Powder alloys were used as the matrix, the
a pressure less than 1.1x lo5 Pa. Experimental carbon band, grade 'Kulon' with two-layer
testing shows that, under appropriate pres- coating (silicon carbide and free silicon) was
sure, the rate of infiltration of fibers with used as reinforcement.The temperature condi-
aluminum melt with an 1%(mass) titanium tions of the rolling were characterized as
additive moves at 0.5 m/s. follows:
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 where T is the rolling temperature within the
strength values of the carbon/aluminum solidificationrange of the matrix alloy; TIlqand
MMC with V , = 4040% are not in excess of Tsolare the temperatures of the liquidus and
700-800 MPa, whereas the higher values solidus of the matrix alloy.
(1000-1200 MPa) would be expected from rule The amount of reduction of porosity in the
of mixtures. initial porous billets of carbon aluminum was
To eliminate the strength drawback, it is determined by considering the maximum
necessary to determine the nature of barrier spread and extraction of the part of the matrix
ceramic and process metal coatings which alloy from the billet in compliance with the
ensure protection (compared with the nickel following formula:
plating) and allow effective infiltration of
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
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
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.
uniformity is 78-94%; and the number of the rolling must be accomplished at a vacuum
defective fibers is 4-10%. High quality rolled of 6.65 x lo-' Pa, and compacting of the initial
carbon aluminum is most dependent on the powder-like billets of the carbon aluminum
percentage of defective fibers. In a 45% Vf must be performed with rigid, plastically
composite, the properties in the direction of undeformed casings.
reinforcement are as follows: tensile strength, However, this technology is unsuitable for
825 MPa; bending strength, 1300 MPa; and production of combined composites. For
the modulus of elasticity is 200GPa. A two example, during production of Ti-A1-C by this
layer protective coating on the carbon fiber, technique, intimate contact of the layers of
with a small amount of aluminum carbide titanium with carbon-aluminum is not real-
(- 0.1./0), retains the transverse strength of the ized; whereas, during rolling of fibrous
reinforced composite (a, = 55 MPa). material A1-B-C, an intensive interaction of
Application of a protective chromium coating the boron fibers with the molten aluminum
on the carbon aluminum by condensation ion takes place. Thus, in the production of com-
bombardment also increases its resistance to bined composites, the criterion requirements
corrosion. are necessary with at least an additional
However, carbon aluminum is somewhat requirement for intimate connection of the
unsatisfactory in economic terms because of its separate hybrid components. To produce a
inherent problems with soldering, welding and diverse combination, such as MCM AIB-MCM
mechanical connection with other materials. A1-C, the number of requirements doubles.
These drawbacks can be eliminated by However, research shows the requirements
using combined composites of the following can be met by non-traditional manufacturing
systems: boron-aluminum - carbon-ah- approaches.
minum (high compressive strength, good The combination Ti-A1-C is an example of
resistance to erosion); titanium - carbon-alu- the product of such an approach. The bimetal
minum, dispersively reinforced aluminum titanium-aluminum composite can be success-
(filling agent: Sic, A1,CJ carbon-aluminum fully produced by rolling at temperatures of up
(high hardness, transverse strength). to 500°C (932"F), with high degrees of defor-
There are specific criteria for production of mation. The requirement for preservation of
such composites using the method of rolling fiber continuity and the elimination of the car-
along the fibers. It is advisable to use some of bon-aluminum reaction decreases the
these criteria to optimize the manufacturing probability of formation of an intimate connec-
process15. The basic requirements for carbon- tion between titanium and aluminum layers
aluminum are: sealing of the porous billets during production of the combined composite.
during extrusion; 100% filling of the interfiber Also, during compaction of carbon-aluminum
spaces with matrix alloy; provide for compati- within the solidification range of the matrix
bility; and prevent component oxidation. alloy, the probability of formation of friable
Research considering the influence of intermetallic layers between titanium and alu-
rolling manufacturing parameters on meeting minum is very high. Thus, the application of
criteria requirements makes it easier to select liquid phase methods (infiltration, soldering,
an optimum technology for production of car- and rolling above the alloy solidus tempera-
bon aluminum. The main feature of this ture) makes it possible to obtain a high quality
technology is that rolling is performed over combined composite. For the combined com-
10-12 steps at a temperature corresponding to posite, the following manufacturing methods
the median value of the solidification range of were used. The pack billet consisted of layers
the matrix alloy (- 40-50 vol. YOof the liquid of the matrix alloy, titanium foil, and carbon
phase). After solid phase additional sealing, bands and was heated to a temperature
304 Metal matrix composites
exceeding the liquidus temperature in the vac- the braids of the carbon fibers, as well as the
uum chamber of the rolling mill. Preferred infiltration of the porous monolayer of boron
evaporation of magnesium from the aluminum aluminum with molten melt, but without direct
alloy with subsequent deposition on the con- contact with the boron fiber, takes place. After
tact surface of titanium, as well as cooling below the solidus point of the carbon-
simultaneous infiltration of the carbon bands aluminum additional reverse rolling results in
took place. After treatment, the billet was preferred sealing of the boron-aluminum.
cooled down to the carbon-aluminum com- Analysis of the microstructure and mechan-
pacting temperature and was vacuum rolled. ical properties of the obtained material shows
Deposition of the protective magnesium coat proper weldability and filling of separate
does not form chemical compounds with tita- monolayers, with a minimum number of the
nium. The infiltration of the carbon framework broken fibers. This combined composite
with subsequent welding-soldering of tita- shows better mechanical properties than car-
nium with matrix alloy during rolling ensures bon-aluminum. Thus, for a one step filling
that bonding bridges are formed during the technique, the combined composite has
liquid phase high temperature contact of com- 10-15% greater tensile strength than the car-
ponents at the moment the infiltration is bon- aluminum composite and the transverse
completed. strength was increased by a factor of 2 (20% B).
Plate and layer reinforced carbon aluminum Combined fibrous dispersively-reinforced
with high resistance to corrosion, with trans- composites AIM-Sic and Al-C-Al,C, have
verse strength exceeding that of the aluminum been obtained by careful selection of the matrix
by 1.5-2.0 times, has been obtained by this tech- alloy or by using an alternative manufacturing
nology. m s composite can also be successfully processes. For these composites, adherence to
attached to titanium structures by soldering or the criterion requirements is relatively simple.
welding. The strength of the titanium to matrix It is possible to produce sealed monobands
alloy bond is higher than the strength of the from the dispersively reinforced composites
bond between the carbon fibers and the matrix (AI-Sic, Al-C-AI,C,) with subsequent com-
(attempts to peel the titanium result in fracture pacting of the composite using the techniques
between the aluminum and the carbon). developed for compacting carbon-aluminum.
To obtain the combined composite A 1 - K , Data developed on compatibility of carbon
the following ground rules have been estab- fibers with barrier (protective) coatings and
lished: compacting of plasma porous aluminum and nickel matrixes, as well as data
semifinished boron aluminum items should be on strength as a function of a barrier coating
performed in the solid phase at temperatures thicknesses, have facilitated the development
exceeding 560°C (1040"F)15; and carbon-alu- of a number of MMCs.
minum should be compacted in the middle of Properties for some of these MMCs are pre-
the solidification range of the matrix alloy. An sented in Table 13.3. These materials were
alloy of A1 with 10% Mg with a solidus temper- made with 'Kulon' carbon fibers with Russian
ature of 510°C (950°F)was used as a matrix for production barrier coatings. Data on these
carbon-aluminum, but a higher temperature fibrous materials both coated and uncoated
alloy was used as a matrix in the boron-alu- are shown in Table 13.4. Figures 13.9 and 13.10
minum. The assembled pack billets of show articles made of aluminum-carbon and
boron-aluminum and carbon-aluminum uni- nickel-carbon composites. Although MMC
directional lamina were rolled at a temperature properties are excellent, higher strength car-
of 540-550°C (1004-1022°F) for 9-10 steps (the bon fibers will permit further increases of both
compacting mode for carbon-aluminum). With specific and absolute strength of the newly
tlus procedure, filling of the interfiber space in created MMC.
Rolling in vacuum 305
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
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
Fig. 13.9 Various types of shaped articles made of alu- Fig. 13.10 Ring made of the composite
minocarbon composites material: (1) shell; (2) tube; (3) material nickel-carbon fiber.
gas-turbine blade; (4) T-profile.
analysis will show that the p,, can be calculated studies are critical to developing proper com-
by multiplying the failure strain of the fiber by posite fabrication methods since almost all
the radius of the fiber. Thus high strength, low processing techniques require high tempera-
elastic modulus and fine diameters produce the ture processing. Both FP and PRD166 fibers
most robust fibers. The first successful alumina can be heated to 1000°C before any serious
based textile fiber was DuPont FP fiber. This reduction in strength occurs3.The boria modi-
fiber has a very high elastic modulus but its low fied alumina-silica (Nextel 312) and mullite
strain to failure results in very large critical compositions (Nextel 440 and Nextel 480) are
bend radius which has limited its application. A also degraded with high temperature heat
modification of the all alumina fiber by adding treatments as seen in Fig. 14.24.The high tem-
partially stabilized zirconia, the DuPont FP 166 perature degradation in strengths and elastic
fiber, has reduced the critical bend radius by moduli of the boria modified alumina silica
one third. However, only the silica modified bases fibers are summarized in Table 14.3. The
alumina based fibers such as the 3M Nextel retention of properties at high temperatures
fibers and the Sumitomo Altex fiber have criti- following the relative degree of crystallinity
cal bend radii of about 0.5 mm. among the three grades with Nextel 312 being
Numerous studies have been performed on the least crystalline and Nextel 480 being the
these fibers to determine their strength and most crystalline.
modulus retention after heat treatment. These 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
been measured by Bunsel15u p to 1200°C. Both of a silicon carbide based textile fiber for com-
the strength and elastic modulus begin to posite reinforcement. All commercially
degrade at 800°C while above 1000°C the available fibers in this category contain oxy-
properties drop significantly. gen but can also contain nitrogen and
During the last 20 years there have been titanium. Nicalon fiber manufactured by
significant advancements in the development Nippon Carbon Company and marketed in
Constituent materials 311
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
the large agglomerates must be broken down (5 % or lower) sintering may produce satisfac-
by mechanical action or chemical treatments if tory results. For complete densification of
the agglomeration is due to surface forces. If even low fiber volume fraction composites,
the whiskers are robust or some degree of sintering may impractical due to excessive
whisker breakage can be tolerated, both temperatures and durations. For high fiber or
agglomerate reduction and constituent mixing whisker volume fractions, hot pressing and
can be accomplished simultaneously by ball hot isostatic pressing are the only effective
milling. methods for densification. Table 14.6 shows
Organic binders are usually mixed with the the effect of hot pressing time and temperature
particle-whisker mixture for near-net-shape at 31 MPa pressing pressure on the theoretical
processing by a variety of cold forming opera- density of Sic whisker-Al,O, composites for
tions including uniaxial pressing, cold various vol.% whiskers. Theoretical densities
isostatic pressing, tape casting, extrusion, of over 99 vol.9'0 can be achieved in unrein-
compression molding and injection molding. forced A1,0, at 15OO0C, in lO%SiC whisker
The ceramic preform after cold consolidation composites at 1650°C and in 2O%SiC whisker
is referred to as the 'green' form. The part in composite at 1800°C10.
the green form can usually be machined with-
out damage. In this state additional
14.3.2 LIQUID PROCESSING
near-net-shape processing can be applied such
as gate removal and machining. When high temperatures and mechanical
Final consolidation and densification is per- forces are used to consolidate composites from
formed at high temperatures. Three of the the powder, the optimum strength properties
most common methods are sintering, hot (uni- can be sacrificed. Reducing processing tem-
directional) pressing and hot isostatic perature, time and pressure can minimize
pressing. For low fiber or whisker contents damage to the reinforcements but fully dense
Processing methods 315
or near-fully dense composites cannot gener- SrO~Al,O;SiO, were infiltrated into Sic pow-
ally be produced. Processing by infiltration der preforms with and without Sic whiskers
with a molten matrix would be an ideal way of with resulting open porosity of about 1%12.
minimizing mechanical damage and still Recently considerable attention has been
achieve fully dense structures. The melting applied to directed melt gas-metal reactions
temperatures of ceramics used as matrices in which produce ceramic matrix composites
composites limits the general use of melt infil- directly from the liquid metal13.14. Both metal
tration as a viable processing route. However, oxide matrix and metal nitride matrix com-
by careful tailoring of the matrix and the use of posites have been produced by this technique.
innovative in situ reaction techniques, melt Net shape composites can be processed at tem-
infiltration has been successfully utilized to peratures of the melting temperature of the
fabricate ceramic composites. metal. The commercial development of this
Glass and glass-ceramic matrices have been processes is called the DIMOXTMprocess of the
successfully infiltrated in the liquid form into Lanxide Corporation. In this process oxidation
fiber preforms by 'matrix transfer mold- or nitridation occurs on the surface of the
ing'".The high temperatures required to molten metal forming a layer of solid ceramic.
achieve the appropriate fluidity of the matrix The layer thickens as the molten metal wicks
limjts the available fiber-matrix compositions up between the grains of the ceramic. A
to only those with low mutual reactivity. Other schematic representation of the process is
matrix materials such as CaSiO,, SrSiO, and 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
The main drawbacks for processing com- gases are forced through the fiber preform
posites by CVI are the high processing time retained in a graphite holder with a sharp
and costs. Since the deposition occurs most thermal gradient maintained by water cooling.
rapidly on the outer surfaces, the internal pas- A schematic diagram of the forced flow/ther-
sages can be blocked off long before full mal gradient method is shown in Fig. 14.8.
densification is complete. It is usually neces-
sary to interrupt the infiltration process to
14.4 DESIGN CONSIDERATIONS
grind the surfaces in order to reopen the gas
access to the fibers or preform in the center of The approach to designing ceramic matrix is
the part. Residual porosity of 10-20% with less constrained by the brittle nature for both the
than 10% open porosity are typically matrix materials and reinforcements used.
obtainedz1. Unlike polymer matrix composites and even
Two basic methods of CVI are isothermal metal matrix composites, the rationale for
processing and forced flow/thermal gradient design of ceramic composites is to impart
processing. In isothermal processing the fiber toughness in a structure that would have unac-
preform is heated by radiation from the walls ceptable toughness as a monolithic ceramic”.
of the furnace (so called ’hot wall reactor’) or Design methods are unique to the form of the
by inductively heating a carbon mandrel on composite, depending on whether continuous
which the preform is placed. In both cases the unidirectional reinforcements, discontinuous
decomposing gases are allowed to diffuse reinforcements or multi-layer, multi-directional
through the fiber preform. In the forced reinforcements are being considered. As a start-
flow/ thermal gradient method the reactant ing point in the design of continuous
Exhaust aas
Heating element
Perforated lid
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
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
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 ,
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
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.
"
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 ~
Table 14.8 Mechanical properties of polycrystalline A1,0, and Sic whisker /A1,0, matrix composites3’
Table 14.9 Room temperature strength and fracture toughness of Sic whisker (Silar-SC-9)/A120,
composites (Adapted from Reference 2 )
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
. . . . 1 30 5 10 15 20 25 30 35 40
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
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
.-
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
Washington, DC, Government Institute Inc. 55. Rhodes, J.F., Whisker reinforced ceramic com-
Washington DC, 749-756,1988. posites, in Proc. Fifth Ann. Conf. Maferials
54. Billman, E.R., Mehrota, P.K., Shuster, A.F. and Technology, Materials Technology Center,
Beegley, C.W., Machining with A1203-Sic Southern Illinois University, Carbondale, IL,
whisker cutting tools, Bull. Am. Ceram. Soc, 205-219,1988.
1988,67,1016-1019.
CARBON-CARBON COMPOSITES 15
John D. Buckley
15.1 INTRODUCTION n
E a
Reference directions
Fig. 15.2 Tightly bonded, hexagonally arranged carbon layers held together by weak van der Waals forces.
I
LC
:rdo02
Fig. 15.3 Comparison of (a) carbon turbostratic structure with (b) 3-D graphite lattice (Bokros, 1969).
Carbon fibers 335
The anisotropy of the graphite single crystal three precursor materials: rayon, polyacryloni-
encompasses many structural forms of carbon. trile (PAN)and petroleum pitch. Fibers having
It ranges in the degree of preferred orientation a low modulus (27.6 GPa (4 x 106 psi)) are
of the crystallites and influences porosity, formed using a rayon precursor material that
among other variables. A broad range of prop- may be chemically pretreated by a sequence of
erties is the result of this anisotropy. In CC heating steps. First, the fiber is heated to
composites, this range of properties can >400"C (752°F) to allow cellulose to pyrolyze
extend to both constituents. Coupled with a (decomposition or chemical change during
variety of processing techniques that can be thermal conversion of organic materials to car-
used in the fabrication of CC composites, great bon and graphite). Carbonization (continued
flexibility exists in the design of and the resul- heating of organic material to >lOOO"C (1832°F)
tant properties obtained from CC composites. to initiate ordering of the carbon structures
The wide range of properties of carbon produced by pyrolysis) is completed more
materials can be shown when comparing the rapidly at >lOOO"C (1832°F).Upon completion
tensile modulus of commercially manufac- of carbonization, the fiber is graphitized (con-
tured carbon fibers that range from 27.6 GPa tinued heating of carbonized organic materials
(4 x 106psi) to 690 GPa (100 x lo6psi). In fabri- to the 2000-3000°C (3632-5432°F) range of
cation, the fibers can be used in either produce 100% graphite-ordered crystal struc-
continuous or discontinuous form. The direc- ture) by heating to >2000"C (3632°F);the fiber
tionality of the filaments can be varied ranging is now, for all practical purposes, 100% carbon.
from unidirectional lay-ups to multidirec- High-modulus carbon fibers from rayon pre-
tional weaves. Fiber volume fraction cursors are obtained by the additional process
constitutes another variable. The higher the of stretching the carbon fibers at the final heat
volume fraction of a specific high-strength treatment temperature. Nigh-modulus (344
fiber in a matrix, the greater the strength of the GPa (50 x 106 psi)), high-strength (2.07 GPa
composite. The matrix can be formed via two (300 x lo3 psi)) carbon fibers are typically
basic approaches: (1) through the carboniza- made from PAN or, in some cases, mesophase
tion of an organic solid or liquid, such as a pitch precursors. These fibers are processed
resin or pitch, or (2) through the chemical similarly in a three-stage operation (Fig. 15.4)
vapor deposition (CVD) of carbon from a (Diefendorf, 1987).The PAN fibers are initially
hydrocarbon. A range of carbon structures can stretched from 500-1300% and then stabilized
be obtained by either approach. Finally, heat (cross-linked) in an oxygen atmosphere at
treatment of the composite material at graphi- 200°C (392°F)to 280°C (536°F) under tension.
tization temperatures offers additional Carbonization of the fibers is conducted
variability to the properties that can be between 1000°C (1832°F)and 1600°C (2912°F).
obtained. Typically, there is an optimum Finally, graphitization is accomplished at
graphitization temperature at which the high- >2500"C (4532°F). Mesophase pitch fibers
est strength can be obtained for a given undergo the same processing procedure as
composite composition of fiber and matrix PAN fibers but do not require an expensive
(Edie et al., 1986; Stoller et al., 1974). stretching process during heat treatment to
maintain preferred alignment of crystallites
(Fig. 15.4) (Diefendorf, 1987). Control of fiber
15.2 CARBON FIBERS
shape has resulted in improved fiber strength
The properties of carbon fibers can vary over a (4.1 GPa, 600000 psi) (Cogburn et al., 1987)
wide range depending on the organic precur- when produced from melt-spun, mesophase
sor and processing conditions used. At petroleum pitch (Fig. 15.5) (Cogburn et al.,
present, graphite fibers are produced from 1987). Round fibers using the same method
336 Carbon-carbon composites
PAN process
Pitch process 1
tCarbonize
z z I I Graphitize
zim
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 2. achieve a more nearly isotropic material;
et al., 1986).Of the shapes studied, the C-shape 3. increase the composite interlaminar tensile
and hollow fibers were found to be superior in strength;
strength to round solid and trilobal cross sec- 4. along with continuous filament substrates,
tions (Edie et al., 1986; Cogburn et al., 1987). obtain a stronger composite by providing
additional nucleation sites that serve to
reduce composite porosity.
15.2.1 CARBON FIBERS IN CARBON MATRIX
The most widely used starting materials are a
Addition of a matrix to carbon fiber, either
carbonized, rayon felt substrate with a
through the carbonization of an organic pre-
pyrolytic carbon matrix and short, chopped
cursor or by the deposition of pyrolytic
fibers in a pitch-based matrix. Felt is produced
carbon, is conducted at 800°C (1472°F) to
through the mechanical carding of viscous
1500°C (2732°F).Subsequent heat treatment of
rayon fibers to produce a continuous web of
the composite material may involve tempera-
fibers. The webs are folded one on top of
tures to 3000°C (5432°F).
another to produce a batt. The batts are then
cut, stacked and needled to produce the
15.2.2 DISCONTINUOUS FIBER COMPOSITES required felt. The rayon felt is subjected to a
controlled carbonization cycle in an inert
Fabrication of discontinuous fiber composites
atmosphere or vacuum; the maximum temper-
uses short carbon fibers combined with either
ature determines such factors as shrinkage,
a pyrolytic carbon or pyrolyzed organic
weight loss and chemical composition of the
matrix. This approach to CC composites gen-
felt. A maximum carbonization temperature of
erally does not have true fiber reinforcement
1200°C (2192°F) is a nominal standard; the
as an objective. Rather, discontinuous fiber
length of the carbonization cycle and rate of
substrates have been used to:
temperature rise are dictated by the thickness
1. increase fabrication capability of large-scale of the felt. Carbon content in the fibers is
structures; ~ 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 oriented substrate, usually with no interlock-
isotropic casting, flocking lay-up, spray lay-up ing between layers. Woven fabrics are used to
and pulp-molding techniques (Fig. 15.6) form a two-dimensional laminate with no
(Cook, Lambdin and Trent, 1970; Lambdin, interlocking between layers. Helical filament
Cook and Marrow, 1969; Lambdin and Cook, winding, which is directional, results in con-
1971.).The rationale for using these short fibers tinuous, adjacent layer interlocking.
is to reduce composite anisotropy (Lambdin, Multilayer locking is achieved through com-
Cook and Marrow, 1969). plex weaving patterns or yarn placement
resulting in 'multidirectional' substrates (Fig.
15.7).
15.3 CONTINUOUS FIBER COMPOSITES
Fig. 15.7 Interlocking approaches of continuous filament substrates: (a) tape wrapped, shingle; (b) filament
wound, helix; and (c) multidimensional.
Carbonized organic composites 339
3 t o 5 times I cure I
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 To summarize, a typical manufacturing cycle
(347°F) with curing pressures on the order of of a 2-D CC part is shown in Fig. 15.10.First, a
2.76 MPa (400 psi). The reinforced resin lami- woven graphite fabric that is preimpregnated
nate is then post-cured at 200°C (392°F) to with phenolic resin is laid up as a phenolic-
275°C (527°F).As pyrolysis is initiated, shrink- graphite laminate in a mold and is autoclave
ing occurs as the organic phase decomposes. cured. Once cured, the part is pyrolyzed to
Simultaneously the release of vapors from form a carbon matrix surrounding the graphte
pyrolysis expands the composite material. A fibers. The part is then densified by multiple
slow release of these volatile by-products is furfural alcohol reimpregnations and pyrolyza-
required to minimize structural damage to the tions. The resulting CC part then is ready for
char. Finally, as higher temperatures are use in inert or vacuum environments. This
reached, thermal expansion of the carbon char process is very time consuming. A single pyrol-
itself occurs after pyrolysis is complete. After ysis may take >70 h in a low-temperature,
the initial carbonization, the material is then inert-atmosphere furnace.
subjected to a series of reimpregnation and Although CC materials can withstand tem-
carbonization cycles until the desired density peratures >3000"C (5432°F) in a vacuum or in
or the maximum density is achieved. The an inert atmosphere, they oxidize and sublime
reimpregnation process is usually conducted when in an oxygen atmosphere at 600°C
under vacuum and pressure to aid in maxi- (1112°F). To allow for use of CC parts in an
mizing the pore filling. If graphitization is oxidizing atmosphere, they must be com-
desired, the high-temperature heat treatment pounded with materials that produce
may be used after each carbonization step or at oxidation-protective coatings through thermo-
the end of the reimpregnation and recar- chemical reaction with oxygen at >2000"C
bonization cycles. (3632°F) (Buckley, 1967) or they must be coated
Manufacturing 341
and sealed to protect them (Strife and Sheehan, RCC Seal strips
1988). For applications such as the Space (22) LH
Shuttle CC leading edges and nose caps, sur- (22) RH Wing L.E. RCC panels
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 Nose cap (1)
that enhance the sealing capability of the exist- RCC Seal strip
(1) LH, (1) RH and
ing coating-TEOS system. (3) Lower
RCC ExDansion seal
(1) LH, (1) RH and
15.6 MANUFACTURING (3) Lower
The fabrication process of the Space Shuttle Fig. 15.11 Leading edge structural subsystem
Orbiter nose cap and wing leading edge com- (Curry, Scott and Webster, 1979).
ponents (Fig. 15.11) (Curry, Scott and Webster,
1979) is a multi-step process typical of the
technology used to produce CC composites. furnace and submitting it to a 7-day cycle dur-
The process steps are illustrated in Figs. ing which it is taken to 260°C (500°F) very
15.12-15.16. slowly to avoid distortion and delamination
Initial material lay-up is similar to conven- (Fig. 15.12).
tional practices with fiberglass-reinforced The next step is initial pyrolysis as shown in
plastic parts. Square-weave graphite fabric Fig. 15.13 (Curry, Scott and Webster, 1979).
impregnated with phenolic resin is laid-up in Pyrolysis tooling composed of graphite
an epoxy/fiberglass mold cavity shaped to the restraining fixtures containing the part are
desired configuration (Fig. 15.12) (Curry, Scott loaded into a steel retort that is packed with
and Webster, 1979).Lay-up thickness for these calcined coke. The retort and its contents then
components varies from 19 plies in the exter- undergo a 70 h pyrolysis cycle at 815°C
nal skin and web areas to 38 plies in the (1500°F)converting the phenolic resin to a car-
attachment locations. Upon completion of lay- bon state. During pyrolyzation, the resin forms
up, the part is vacuum-bagged and cured in an a network of interconnected porosity for the
autoclave to 150°C (300°F) for 8 h (Fig. 15.12). escape of volatile matter. This stage is
The cured part is rough trimmed, X-rayed and extremely critical since, during controlled char-
ultrasonically inspected for irregularities fol- ring of the cured resin matrix, the parts are
lowing the cure cycle. Post-cure of the weak and delamination can easily occur if ade-
component involves placing the part in a quate escape paths and time are not ensured.
graphite restraint fixture loading it into the 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 AUTOCLAVE 0 REMOVE BAG LOAD IN POST CURE
COLD I LAY.UP 0 APPLYVACUUM CURE 0 ROUGH T R I M RESTRAIN-
STORAGE I CLOTH 0 CHECK FOR DRILLHOLES ING
j PLIES LEAKS 0 X.RAY AND/OR 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
Fig. 15.13 Initial pyrolysis (Curry, Scott and Fig. 15.14 Densification impregnation and cure
Webster, 1979). (Curry, Scott and Webster, 1979).
Manufacturing 343
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
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
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
Ohlhorst, 1984; Webb, 1985; Gray and Engle, ulus values for the TEOS material are shown
1985; Johnson and Finley, 1985; Sawyer and in Fig. 15.19 (Curry, Scott and Webster, 1979).
Moses, 1985; Maahs and Ransone, 1985; The effect of temperature on the as-fabricated
Ohlhorst and Ransone, 1985). tension strength properties is shown in Fig.
CC components on the Space Shuttle are 15.20 (Curry, Scott and Webster, 1979). As
required to have adequate strength at design shown in Figs 15.17 and 15.20, the strength of
temperatures to withstand the aerodynamic CC composite material does not decrease sig-
loads of flight and to continue to do so for the nificantly with temperature. Typically, above
operational life of the component. Minimum 1425°C (2600°F) there is an increase in
mechanical properties are guaranteed through strength.
statistical analysis of a data sampling having The effect of substrate mass loss through
at least 99% probability and 95% confidence. oxidation on tensile strength is shown in Fig.
The primary variables affecting the structural 15.21 (Curry, Scott and Webster, 1979). Mass
design allowables are temperature, material loss results in a significant reduction in design
thickness, coating thickness, biaxial stress con- allowable stress, emphasizing the value of the
ditions and substrate mass loss due to additional oxidation protection provided by
oxidation through the mission life of the com- the TEOS treatment.
ponent (Table 15.2) (Curry, Scott and Webster,
1979). 15.8 THERMAL PROPERTIES
Figure 15.18 (Curry, Scott and Webster,
1979) illustrates the typical effect of ply thick-
15.8.1 THERMAL OXIDATION
ness on the allowable stress values for tension,
bending, compression and shear used for A critical requirement when using CC com-
design. As fabricated, room temperature mod- posites is the ability to withstand numerous
346 Carbon-carbon composites
Table 15.2
Simultaneous cycling - - 3 18
Mission cycling
Tension 3 36 - -
Flexure 3 24 - -
Compression 3 27 - -
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 flaws were performed over a wide range of
re-entries of the Space Shuttle into the earth's pressures and temperatures in both plasma arc
atmosphere. Although CC Space Shuttle com- jets and radiant-heating test facilities. Arc jet
ponents have an oxidation-inhibiting silicon tests on CC specimens ranged in temperature
carbide coating, they can lose mass over an from 815°C (1500°F) to 1870°C (3400°F) and
extended temperature range without apparent atmospheric pressures from 0.01 Pa to 0.10 Pa.
surface recession. Photomicrographs of CC Radiant-test conditions ranged from 420°C
specimen surfaces show minute fissures and (800°F)to 1425°C (2600°F)and pressures rang-
thermal microcracks, some of which terminate ing from 0.01 Pa to 1.0 Pa. Mass-loss data for
at the coating substrate interface. Specimens the CC shuttle specimens exposed to the arc jet
exposed to convective and radiant heat trans- and radiant-heating tests are presented in Figs
fer tests micrographically have shown the 15.22 and 15.23. Figure 15.22 (Curry, Scott and
presence of voids at the coating substrate sur- Webster, 1979) shows mass loss at 980°C
face. Tests to characterize the effects of these (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).
Applications 349
14.5 7
11.1-
,- SPECIFIC HEAT
THERMAL CONDUCTIVITY
\
'F ai.
PARALLEL TO PLY
B
E
1
8
i'
5'8'
2.9.
-THERMAL CONDUCTIVITY PERPENDICULAR
TO PLY
a
f
-0
-28(1
+T
-OTAL
-18 280
EMISSIVITY
538
TEMPERATURE "C
818 1094
-
1372 16sO
Fig. 15.24 Reinforced carbon-carbon thermal properties (Curry, Scott and Webster, 1979).
thermal conductivity is dependent upon the CC material systems using coatings, TEOS
mass loss experienced by the CC composite, and additions to the basic CC recipe have
resulting from subsurface oxidation. improved the oxidation resistance of products
Results of thermal conductivity studies for made of CC composites by an order of magni-
shuttle CC composite shuttle materials are tude. These composites are being used in
shown in Fig. 15.24 (Curry, Scott and Webster, products such as the nozzle in the F-100 jet
1979).To simplify thermal modeling, no differ- engine afterburner, turbine wheels operating
entiation has been made for conductivity at >40 000 rpm, nonwetting crucibles for
variation resulting from the number of plies in molten metals, nose caps and leading edges
the substrate. Results for conditioned speci- for missiles and for the Space Shuttle, wind-
mens having a mass loss of 0-5 Pa (0.1 lb/ft2) tunnel models and racing car and commercial
suggest that thermal conductivity decreases disk brakes (Klein, 1986).
with mass loss. Figure 15.24 also shows that Pushing the state of the art in CC compos-
neither specific heat nor emittance was ites is the piston for internal combustion
affected by material or mass loss conditioning. engines (Miller and Grimes, 1982; Taylor,
1985). The CC piston (Fig. 15.25) would per-
form the same way as any piston in a
15.9 APPLICATIONS
reciprocating internal combustion engine
An example of the state of the art in CC com- while reducing weight and increasing the
posite applications is a one-piece, bladed mechanical and thermal efficiencies of the
turbine rotor that, in service, is coated to pre- engine. The CC piston concept features a low
vent oxidation. The rotor offers higher piston-to-cylinder wall clearance; this clear-
temperature performance without cooling; ance is so low, in fact, that piston rings and
low weight and use of low-cost, non-strategic skirts are unnecessary. These advantages are
materials (Miller and Grimes, 1982).Other gas made possible by the negligible coefficient of
turbine engine applications using CC compos- thermal expansion of this kind of CC (0.54 x
ites include exhaust nozzle flaps and seals, /OF). (Carbon-carbon composites can
augmenters, combustors and acoustic panels. have a range of thermal expansion coefficients,
350 Carbon-carbon composites
REFERENCES
Beatty, R.T. and Kipplinger, D.V., 1970, Gas pulse
impregnation of graphite with carbon. Nuclear
Application and Technology, 8(6):488495.
Bokros, J.C., 1969, Deposition, Structure and
Properties of Pyrolytic Carbon. Chemistry and
Physics of Carbon-A Series of Advances, (ed.
Philip L. Walker, Jr.) pp. 1-118. Marcel Dekker,
InC.
Buch, J.D., 1984, Graphite Crystals - A General
Model for Diverse Carbon Forms. Metal Matrix,
Carbon and Ceramic Matrix Composites, (ed. John
D. Buckley) NASA CP-2357, pp. 119-135.
Buckley, J.D., 1967, Statis, Subsonic and Supersonic
Oxidation of JT Graphite Composites, NASA TLN
D-4231.
Fig. 15.25 Carbon+arbon automotive piston. Cogbum, J.W., Fain, C.C., Edie, D.D. and Leigh,
H.D., 1987, Processing C-Shape Pitch-Based
Carbon Fibers. Metal Matrix, Carbon and Ceramic
Matrix Composites, (ed. John D. Buckley) NASA
depending on the processing techniques.) CC (2-2482, pp. 185-200.
material maintains its strength at elevated Cook, J.L., F. Lambdin and P.E. Trent, 1970,
temperatures allowing the piston to operate at Discontinuous Carbon/Carbon Composite
Fabrication. Carbon Composite Technology - With
higher temperatures and pressures than those Special Emphasis on Carbon/Carbon Systems. Proc
of a comparable metal piston. The high emit- 10th Ann. Symp. New Mexico Section of ASME
tance and low thermal conductivity of the CC and University of New Mexico, pp. 143-171.
piston should improve the thermal efficiency Curry, D.M., Scott, H.C. and Webster, C.N., 1979,
of the engine because less heat energy is lost to Material Characteristics of Space Shuttle
the piston and cooling system. The elimination Reinforced Carbon-Carbon. Paper read at the
of rings reduces friction, thus improving 24th National SAMPE Symposium, 1-9 May,
1979, at San Francisco, CA.
mechanical efficiency.
Diefendorf, R.J., 1987, Carbon/Graphite Fibers.
Besides being lighter than conventional pis- Engineered Materials Handbook 1: 49-53.
tons, the CC piston can produce cascading Dienes, G.J., 1952, Mechanism for Self-Diffusion in
effects that could reduce the weight of other Graphite. Applied Physics 23(11): 1194-1200.
reciprocating components such as the crank- Edie, D.D., Fox, N.K., Barnett, B.C. and Fain, C.C.,
shaft, connecting rods, flywheels and 1986, Melt-Spun Non-Circular Carbon Fibers.
balances, thus improving specific engine per- Carbon 24(4): 477482.
Gray, P.E. and Engle, G.B., 1985, Wettability of
formance (Taylor, 1985). Carbon/Carbon Composites and Carbon Fibers
by Glass Sealants Used in Oxidation Inhibition.
ACKNOWLEDGEMENTS Metal Matrix, Carbon and Ceramic Matrix
Composites, (ed. John D. Buckley) NASA
The author acknowledges Mr. D.M. Curry of 0-2406, pp. 149-162.
NASA Johnson Space Center and H.C. Scott Johnson, A.C. and Finley, J.W., 1985,
and C.N. Webster of the Vought Corporation Carbodcarbon Composites for Advanced
Spacecraft. Metal Matrix, Carbon and Ceramic
for the data, as referenced, on which a portion
Matrix Composites, (ed. John D. Buckley) NASA
of the present paper is based. (3-2406, pp. 175-190.
Acknowledgement is also given to Mrs. H.A. Kanter, M.A., 1957, Diffusion of Carbon Atoms in
Coombs for her valuable contribution in Natural Graphite Crystals. Physics Review 107
assisting in the formatting of this paper. (3):655-663.
References 351
Klein, J., 1986, Carbon-Carbon Composites. Ransone, P.O. and Maahs, H.G., 1985, Effect of
Advanced Materials and Processes 130 (5):64-68. Processing on Microstructure and Mechanical
Kotlensky, W.V. and Pappis, J., 1969, Mechanical Properties of 3-D Carbon-Carbon. Metal Matrix,
Properties of CVD Infiltrated Composites. Proc. Carbon and Ceramic Matrix Composites, (ed. John
95th Biennial Conf.Carbon Defense Ceramic D. Buckley) NASA CP-2406, pp. 289-303.
Information Center, Compilers, pp. 76-80. Ransone, P.O. and Ohlhorst, C.W., 1984, Interlaminar
Lambdin, F. and Cook, J.L., 1971, Fabrication of Shear and Out-of-Plane Tensile Properties of
Carbon-Carbon Composites Electrostatic Fiber Thin 3-D Carbon-Carbon. Metal Matrix, Carbon
Deposition (Flocking). Y-1786 (Contract No. and Ceramic Matrix Composites, (ed. John D.
W-7405-eng-26), Y-12 Plant, Union Carbide Buckley) NASA CP-2357, pp. 137-148.
Corp. Rummler, D.R. and Sawyer, J.W., 1984, Properties
Lambdin, F., Cook, J.L. and Marrow, G.B., 1969, and Potential of Advanced Carbon-Carbon for
Fiber-Reinforced Graphite Composite Fabrication Space Structures. Metal Matrix, Carbon and
and Evaluation. Doc. Y-1684, "ID4500 (Contract Ceramic Matrix Composites, (ed. John D. Buckley)
W-7405-eng-26), Nuclear Division, Union NASA (3-2357, pp. 149-170.
Carbide Corp. Sawyer, J.W. and Moses, P.L., 1985, Effect of Holes
Maahs, H.G. and Ransone, P.O., 1985, Mechanical and Impact Damage on Tensile Strength of Two-
Property Evaluation of 2-D Carbon-Carbon Dimensional Carbon-Carbon Composites.
Panels Fabricated From a Specialty-Weave Metal Matrix, Carbon and Ceramic Matrix
Fabric. Metal Matrix, Carbon and Ceramic Matrix Composites, (ed. John D. Buckley) NASA
Composites, (ed. John D. Buckley) NASA (3-2406, pp. 245-260.
CP-2406, pp. 261-276. Stoller, H.M., Butler, B.L., Theis, J.D. and Lieberman,
Miller, T.J. and Grimes, H.H., 1982, Research on M.L., 1974, Carbon Fiber Reinforced-Carbon
Ultra-High-Temperature Materials-Monolithic Matrix Composites. Composites: A State of the Art,
Ceramics, Ceramic Matrix Composites and (eds. J.W. Weeton and E. Scala) Metallurgical
Carbon/Carbon Composites. Advanced Society of the American Institute of Mining,
Materials Technology, (eds. Charles P. Metallurgical and Petroleum Engineers, Inc., pp.
Blankenship and Louis A. Teichman) NASA 69-136.
CP-2251, pp. 275-291. Strife, J.R. and Sheehan, J.E., 1988, Ceramic Coatings
Ohlhorst, C.W. and Ransone, P.O., 1985, Effects of for Carbon-Carbon Composites. Ceramic Bulletin
Thermal Cycling on Thermal Expansion and 67(2):369-374.
Mechanical Properties of Advanced Taylor, A.H., 1985, Carbon-Carbon Pistons for
Carbon-Carbon Composites. Metal Matrix, Internal Combustion Engines. NASA Tech
Carbon and Ceramic Matrix Composites, (ed. John Briefs 9 (4):156-157.
D. Buckley) NASA (3-2406, pp. 289-303. Theis, J.D., Jr., Taylor, A.J., Rayner, R.M. and Frye,
Pierson, H.O., 1968, Development and Properties of E.R., 1970, Filament Wound Carbon/Carbon
Pyrolytic Carbon Felt Composites. Advanced Heatshield SC-11FW-Y12-7, A Process Histoy.
Techniques for Material Investigatioiz and SC-DR-70425, Sandia Labs.
Fabrication 14, National Symposium and Webb, R.D., 1985, Oxidation-Resistant
Exhibit, Society of Aerospace Material and Carbon-Carbon Materials. Metal Matrix, Carbon
Process Engineers, Paper II4B-2. and Ceramic Matrix Composites, (ed. John D.
Buckley) NASA CP-2406, pp. 149-162.
HAND LAY-UP AND BAG MOLDING 16
D.R. Sidwell
are competitive with alternate types of con- tional and woven product forms (fiberglass,
structions that result from optimization of graphite and aramid) were developed for com-
process controls, design refinements and mercial applications; aerospace structures were
improved materials. Composite designs and the prime users of 100%graphite materials.
bag molding processes are interrelated by pro- The fabrication of a 1979 Ford LTD with a
duction goals, the desire to control finished weight of 1138 kg (2504 lb) proved
manufacturing costs and by service or mission that graphite could be used as reinforcement
requirements. The responsibilities shared by for just about any automotive component
fabricators and designers include: including bumpers, hoods, frames, doors and
drive line. The major drawback to automotive
0 reproducibility and knowledge of process-
use of these composites was the processing
ing characteristics of candidate materials;
cost. During the 1990s, processing times were
knowledge of requirements for facilities
reduced to acceptable levels (less than 5 min)
and tooling including provisions for assem-
for automotive components, using resin trans-
bly, inspection and quality control;
fer and resin injection molding. Improved
0 reduction of total part count;
mechanical properties, lower costs and
0 avoiding design as replacement for sheet
improved resin systems allowed for greater
metal;
inroads for fiber-reinforced plastics in the
0 selecting the best material for the applica-
automotive industry.
tion.
The use of ultra high modulus pitch-based
carbon fiber in modern communication satel-
16.2 HISTORY
lites has led to refinement in the art of hand
lay-up and vacuum bag molding. The primary
Composite materials first arrived in the New structural element of some communications
World with the early Spanish explorers who satellites is a central cylinder. A typical cylin-
produced adobe bricks for the building trades der is about 180 kg (80 lb) and supporting a
from a mix of straw and adobe clay. Modern 13 000 kg (6000 lb) payload at launch. A typical
day users developed the chopper gun and cylinder consists of 520GPa (75msi) pitch
fiberglass roving that use low cost inexperi- fiber skin laminates and aluminum honey-
enced labor; many fabrications utilize ’wet’ comb core, the structure is oven co-cured
lay-up for making bath tub enclosures and utilizing a nylon vacuum bag. The require-
truck hoods. Early use of carbon fiber compos- ments for ever lighter structures created the
ites was primarily for secondary structure need for ultrathin unidirectional prepregs.
aerospace applications. In the early 1970s, the Solar array panels for a modern communi-
first woven graphite fabric was developed for cations spacecraft required the use of
aerospace structural applications. 0.0004 cm (0.001 in) thick unidirectional
Complex and highly detailed hybrid (unidi- 520 GPa (75 msi) graphite prepreg. Solar array
rectional and woven carbon materials) panels, made with three-ply skins bonded to
structures were developed for an interconti- an ultralight honeycomb core, are manufac-
nental ballistic missile (ICBM) program. It did tured on a regular production basis, utilizing
not take long to integrate the woven graphite vacuum bag molding process and oven cure.
prepregs into mainstream production, reducing An example of what can be involved in a
labor costs over 70% from that of the previous high visibility composite materials application
unidirectional tape structures. During the was the 1992 America’s Cup Challenge, the
1980s, composite hybrids were developed first application of graphite composite materi-
using the best of all material forms available. als for the America’s Cup racing yachts. The
The hybrid structures utilizing both unidirec- example utilized here is the ’Spirit of
354 Hand lay-up and bag molding
Australia’ program entered by the Darling ial from the supplier, to the freight forwarder,
Harbor Yacht Club, Sydney, NSW, Australia. airline, customs, importer clearing house and
(See section 16.7.2.) Design and analysis were then delivered to the manufacturing facility.
performed by Ian Murray and Associates, This effort can go astray; the shipment can be
yacht designers; the design parameters were off-loaded at an intermediate stop or off-
established by the America’s Cup Rules loaded at the incorrect destination. Sea
Committee. The program objective, deter- shipping requires 30 days to get material from
mined in large part by available funding, was the manufacturer to a sea forwarder, provid-
to manufacture one America’s Cup racing ing the container is off-loaded as scheduled.
yacht. A program of this magnitude requires a All of these considerations combined with
substantial amount of material. The ’Spirit of availability of funds and tight fabrication
Australia’ was a relatively small program schedule play a primary role in design and
compared with some of the other syndicates. fabrication decisions.
Twenty-seven America’s Cup yachts were fab-
ricated, representing eight countries, with a
16.3 MATERIALS
total investment of over $600000000. The
material combinations utilized in the hull con- Fiber reinforced composite materials are now
struction of the various entries included being used to satisfy the high strength and/or
Spectra, aramid, graphite and wood. The over- stiffness-to-weight requirements of aerospace
all goal was to acheve the specified minimum structures. Fibers of extremely high strength
laminate density and still retain the required are incorporated into a relatively weak matrix
load carrying capabilities. that is used to bind the fibers; the combination
Various hybrids of Spectra/graphite, results in a light, extremely strong structural
aramid/graphite and graphite/wood were material. Experience and theoretical studies
utilized to achieve the design results. The pro- have shown that fibers will always be stronger
gram for ’Spirit of Australia’ required much than bulk materials. Some of the properties
dedication from supporters and suppliers to that can be improved by combining the con-
make it to the elimination trials with competi- stituents into a composite are strength,
tors. There were significant other concerns in stiffness, wear resistance, corrosion resistance,
addition to the normal decision factors in fatigue life, temperature resistance and electri-
selecting composite materials for a program, cal and thermal conductivity.
such as mechanical properties, tack, resin flow The relationship between resin viscosity and
and gel. These other concerns can have a large the cure cycle can be used to obtain maximum
influence on the program outcome and require performance in a composite structure. Figure
planning the materials’ delivery schedule, 16.1 shows the relationship between resin vis-
testing, packaging, export license, custom for- cosity and a stepped autoclave cure cycle. The
malities and shipping method. If the program curves shown are for a typical 121°C (250°F)
is within a few hours flight time, the prepreg is curing epoxy resin system. The viscosity will
usually packed with dry ice and shipped on vary with a change in heat-up rate and tem-
the next available aircraft. On international perature. This information relating the effect of
programs, the weight of just the dry ice can rate and temperature is available from the
equal the material cost and delivery takes 3 4 material suppliers. Using this information as a
days. Scheduling becomes the critical path in starting point, a cure cycle can be defined for a
overall planning. In the case of ’Spirit of specific composite structure. The cure cycle
Australia’, America’s Cup challenge 1993, air production capability becomes increasingly
shipments were a minimum of three days. The important as the complexity of the composite
three days were a best effort to get the mater- structure increases. To help in planning a
Materials 355
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
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
temperature of the lay-up room. Sometimes, individual plant fabrication conditions. Air
tack is increased by increasing resin and conditioning minimizes local temperature and
volatile content, less prepreg advancement, or humidity sensitivities; reducing the tempera-
a slight increase in lay-up room temperature. ture makes heavy tack manageable. Judicious
At other times, tack can be modified by the use of hot air guns can improve dry tack.
prepreg manufacturer by changes in resin for-
mulations or new additives blended into the
Flow controls
resin. Alterations to the formulations should
not be accepted without prior requalifications Flow measurements indicate resin capabilities
by the user. Often, properties are severely to fuse successive plies in a laminate and bleed
affected for a cured laminate; therefore, per- out the void producing gas reaction by-prod-
formance and durability must be verified. ucts. Flow is also an indicator of prepreg age
Prepregs with excessivelyheavy tack gener- or advancement. It is often desirable to opti-
ally cannot be handled without grossly mize resin content and tack to attain adequate
disrupting resin distribution and fiber orienta- flow but, in some cases, flow is controlled by
tion or causing a roping (fiber bundling) of the thickening additives in a resin.
composite laminate. Excessive tack makes it
difficult to achieve reproducibility in compos-
Gel times
ite structures since undetermined amounts of
resin are always removed when the release Gel time is an indicator of the degree of cure of
film or backing is separated from the prepreg. resin systems. The amount of staging or
In general, all the disadvantages of wet lay-up advancement limits gel time for prepregs.
systems are inherent in the excessively tacky Most prepregs are formulated to attain a use-
prepregs. ful life (out time) of 8 days or more at standard
Prepregs with no tack are either excessively atmospheric conditions. Out time can be pro-
advanced or have exceeded their normal stor- longed by storage at -18°C (O'F), but each time
age life. Such materials cannot attain adequate the prepreg is brought to equilibrium at room
cured properties and should be discarded. temperature, the useful life is shortened. Gel
Exceptions are silicones and some polyimides time measurements can be used as quality
that can only be prepared with no tack. Lay- control verifications. Criteria based on those
ups with these materials are limited to those results determine whether to initiate more
occasions where lower mechanical properties costly property testing or to dispose of an
can be tolerated in exchange for improved overage prepreg.
heat resistance or electrical properties.
Thermoplastic prepregs typically do not
Storage
exhibit much tack.
Most prepregs are staged to attain more Most advanced composite hand lay-up mate-
manageable tack. The tack qualities should be rials that are utilized today are
adequate for adhering the prepreg to prepared time/temperature critical. Precautions must
molding surfaces or preceding plies for a lay- be taken in handling, storage and processing.
up and still light enough to release the backing During the initial processing, where resin is
film without loss of resin. Provided that cured impregnated onto the reinforcement fiber, the
laminates will not be adversely affected, tack degrading of the materials starts the moment
qualities can be specified to require the the resin is applied to the reinforcement.
prepreg to remain adhered to the backing until However, cases exist where material has been
a predetermined force is applied to peel it off. stored at -18°C (0°F) for as long as 5 years and
Tack requirements can be modified to suit was capable of molding a commercially
358 Hand lay-up and bag molding
16.3.2 REINFORCEMENTS
Carbon fiber reinforced composites
In continuously reinforced composites, the
fibers carry nearly all of the load applied to the Carbon/graphite fiber is an attractive material
system, with the matrix transferring the load because it has the best balance of material
into the fibers. In chopped fiber reinforced characteristics to compete with metals. Carbon
plastics, the load is distributed between the fiber is the end product of a series of manufac-
fibers and matrix, depending upon the nature turing processes that begin with the basic PAIV
of the constituents,percentages of each and the precursor that is carbonized and graphitized.
orientations of the fibers. Selection of the It is then collimated, woven or, chopped to
proper fiber for a specific application depends become tape, cloth, or molding compound
upon the type and magnitude of loading, oper- when prepreged with an appropriate matrix
ating temperature and cost limitations. The material. Carbon composites offer many
following are attributes of several applicable advantages over conventional materials.
fibers: Major advantages are:
0 high specific strength and stiffness;
PAN-based carbon fiber 0 can be woven into cloth;
0 high strengths; 0 dimensional stability at temperature;
0 improved strain to failure; 0 tight product control;
0 workable; 0 ease of manufacturing;
0 available in many forms. 0 high fatigue resistance;
0 extremely complex structures can be fabri-
Pitch-based carbon fiber cated.
0 high to ultra high modulus;
0 low strain to failure; While offering significant advantages, carbon
0 high cost; fiber does present the following problems rel-
0 can be difficult to handle. ative to conventional materials that must be
Materials 359
considered when designing for specific appli- Some are better than others; some have appli-
cations: cation only to specific needs of a particular
structure. Some of these are presented to show
low strain to failure compared to most metals;
the basic selection process that is required in
relatively low impact resistance;
the initial design phase and the manufactura-
potential for galvanic corrosion;
bility of each product form into a successful
potential matrix bonding problems;
composite structure.
low interlaminar shear;
All fibers can be obtained in many different
high cost;
forms: unidirectional tapes, Unidirectional
chemical resistance.
tows or yarns, woven cloth, chopped and in
hybrid Combinations. The combinations are
Non-woven and collimated tape unlimited in hybridizing fibers together. The
During lay-up with unidirectional tape, there following list shows some of the hybrid rela-
are several techniques that will help achieve a tionships and Table 16.2 shows some of the
cost effective structure. As soon as unidirec- properties of composite material forms.
tional tape has been selected, start preliminary Carbon/fiberglass
planning as to ply orientations and develop 0 high impact strengths;
basic patterns for the initial fabrication. The 0 high modulus;
results of this preplanning will be that wastage 0 high performance;
will be minimized and better quality can be 0 cost effective.
built into the finished part,
Using unidirectional tape on contoured sur- Spectralcarbon
faces presents a number of lay-up problems. 0 improved bond interface;
0 little improvement in overall properties;
As the tape is placed on the mold surface, the
0 low density.
orientation can change dramatically during its
application. In order to minimize angle Aramid,@ergIms
changes, narrow pieces of unidirectional tape 0 reduced overall costs;
can be used. Scrap material can be used for 0 limited applications.
local reinforcements and to fill gaps between
pieces of unidirectional tape. Gay filling pieces Aramid/graphite
0 limited applications;
up to 3.2mm (1/8 in) wide are generally
0 high costs;
acceptable,
0 highly resistant to cracking;
0 better impact resistance.
Woven fabric
Joints with woven materials can be more of a 16.3.3 EXPENDABLE MATERIALS
challenge than those with unidirectional tape.
On a highly stressed composite structure, the Supporting materials can contribute to a pro-
selvage edge must be removed to minimize gram’s success as much as the composite
the discontinuities in the lay-up joints. Joints structures. If there are problems with the vac-
in succeeding plies must not be adjacent but uum bag, release film, or sealant tape, the final
staggered by a minimum of 51 mm ( 2 in). product quality can be compromised although
the overall unit cost of most of these materials
is low. Specifications to control support mate-
Hybrid materials
rials have been slow to develop with the
Many combinations of composite materials industry. There have been problems with
have been developed over the past 15 years. expendables such as release coating of porous
360 Hand lay-up and bag molding
Teflon fabric where there was insufficient coat- encounters a problem utilizing support mate-
ing material to provide an effective release, rials, contact the supplier who can provide
resulting in a bond between the Teflon fabric technical assistance on its products. During
and the composite structure and when using a the lay-up of composite structures, care must
perforated release film, the perforations were be taken to insure that all areas are covered
torn rather than pin pricked, allowing exces- with a release or separator film. The bleeder
sive resin bleed. and/or breather will bond nicely to composite
Specifications would help limit the incon- laminates if there is no separator.
sistency of some of these products. If one
Tooling 361
are made of many materials: wood, plaster, the inside contour of the hull is constructed
plaster/metal and other combinations. Almost from stanchions and stringers and covered
any material can be considered as a pattern with strips of wood, with a laminate of 2 45”,
material if it holds its shape. 90” layers. The tooling plug is finished and
It is assumed that when only one large com- covered with mold release.
posite structure is required, such as a 23 m
(75ft) America’s cup yacht hull, the cost of
16.4.5 INTEGRATING INSPECTION AND
making a pattern and a mold in order to make
MACHINING
the hull may not be justified. However, the
construction of a pattern that becomes a male A machine tool is for machining. If it isn’t mak-
plug can be cost effective for high performance ing chips, it’s wasting time, so keep non-cutting
composite structures. To avoid excessive cost time to an absolute minimum. That’s the stan-
with this tooling approach, one must remem- dard philosophy most shops try to live by. In
ber that it is the total cost of the end product fact, many shops are investing in pallet shuttles,
not just the cost of the pattern (plug) that must quick-change fixtures, tooling systems, rapid
be considered. A limited use plug for a large transverse fixtures, programming and schedul-
marine hull 14-23 m (45-75 ft) in length would ing systems to keep spindles turning and
be made as follows: a simple wood frame to 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.)
Tooling 365
from it. Using dynamic display of the tool the composite materials. For complex shapes
path, programmers can visually verify the NC with integral stiffeners, each block of silicone
program, check clearances and make sure rubber is wrapped on all but one side, the side
gouges are avoided. in which the tooling rubber is removed (see
The inspection path will be generated from Figs 16.4(c) and (d)). In tooling a thermal
the same surface geometry. By referencing the expansion molding, it is best to avoid using
soft gauge, the inspection path will be sure to rubber on both sides of a laminate as illus-
include checks of all critical features. The path trated in Fig. 16.4(e)unless straight edges are
of the probe can be visually verified in the not critical. Vacuum bag assist (see Fig. 16.4(f))
same way as the NC program. provides an alternate method.
After executing the NC program, the work- The linear thermal coefficient of most sili-
piece can be inspected immediately using the cone rubbers that have been measured fall into
touch probe in the spindle (see Fig. 16.3). This the range of 1-2.1 x This range is consis-
inspection can be considered in-process, tent over a 23-246°C (75480°F) temperature
because the workpiece is still fixed on the range. The rubbers are said to have a linear
machine tool and can be remachined without expansion of approximately 17 times that of
being moved or refixtured. This approach is carbon steel which is why they are used to
called closed-loop machining. mold composites by thermal expansion mold-
Results of this inspection routine are auto- ing techniques. Precautions in mixing some
matically used to create a 3D model of the silicone rubber compounds are required if full
features checked. By comparing this model to potential is to be achieved. During prolonged
the soft gauge, any out-of-tolerance conditions storage, the catalyst tends to separate and set-
can be identified. It will also show where addi- tle to the bottom of the container. Mixing the
tional machining passes will be required. catalyst prior to adding it to the base rubber
Final inspection can performed on the will allow correct mixtures and long tool life.
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 (a) Compression molding
can be reduced by 30%.
when the separate plies of prepreg in the lay- up assemblies. When the presses are closed,
ups and other adherents are bonded together. the sealed chambers are pressurized and
Densifications result in reduction of voids and heated to attain molding conditions similar to
removal of excess resin. Other results desired those of an autoclave. Unlike the specialized
of bag molding methods during cure include pressure bag molds, the modified presses are
prevention of blistering in the composites, used to cure many different composite con-
increased controls of pressure and heat appli- structions.
cation and control of the fiber/resin ratio. Autoclave and pressure bag molding condi-
Consolidations and densifications of vac- tions to 177°C (350°F) and 1379 kPa (200 psi)
uum bag moldings can be achieved by are routinely attained. Newer, customized
atmospheric pressure alone as the bagged lay- autoclaves attain cure conditions that exceed
ups are evacuated throughout the cure cycles. 260°C (500°F) and 3447 kPa (500 psi). Fire haz-
The pressure-bagged and autoclaved-cured ards are greatly increased at elevated
composites are pressurized by hot gases. Vents temperatures and pressures. Pressure vessel
to the atmosphere or vacuum provide for the fires are minimized by uses of fire retardant
escape of the volatilized reaction by-products processing materials and inert pressurizing
and the entrapped air from the curing com- gas. Fire prevention measures include uses of
posites. If the pressures within the bag are not silicone rubber, nylon or Tedlar bags. Before
reduced from those applied to the bag, the cure cycles are initiated, the pressure vessels
membrane remains inert and there is no com- are purged of all enclosed air. After the ther-
paction. Of the three methods, vacuum bag mal cure is completed, the pressure vessels
molding is least limited as to the size of con- and their contents are cooled to 68°C (150'F)
structions that can be processed. On a few before the pressure is relieved and the auto-
occasions, 'wet' lay-up vacuum bag molded clave is opened.
composites are room-temperature cured. Most
are thermally cured to produce improved
16.5.1 EXPENDABLE VACUUM BAGGING
properties. Thermal cures are best attained in
TECHNIQUES
air circulating ovens/autoclaves, but can also
be achieved in infrared heated and passive Bleed-out systems are devised to maintain
type convection ovens. reduced pressures within the bags' contents.
Pressure bag molding methods are efficient The bagged lay-up includes the bleed out sys-
for producing both deeply contoured struc- tem designed for the composite part. Bagged
tures and shallow composites. Sonar domes, lay-ups can be bled in two ways: vertically or
radomes and antenna housings are examples edge bled. The classical differences between
of deeply contoured composites.Architectural the two can be seen by comparing Figs 16.5
panels, door panels and aircraft fairings are and 16.6. Many of today's resin systems are
examples of shallow composites. Heavy mostly 'net resin' and do not require any resin
molds are built to reproduce deeply con- bleed during cure. This allows for better con-
toured structures. Each specialized mold is trol of the resin content of the composite
constructed to withstand the elevated temper- structures. If a resin bleed sequence is pre-
atures and increased pressures required for ferred, the following sequence can be used as
the cures. a guide.
Shallow items may often be bag molded in
0 The surface of the mold is prepared with
modified compression presses. The lower
the release agent.
press platens contain vents and vacuum lines.
0 The composite plies are applied and rubbed
The upper press platens are made hollow to
out to remove entrapped air.
enclose the mold plates together with the laid
368 Hand lay-up and bag molding
ATMOSPHERIC
OR VACUUM
VENT
CAUL PLATF
RAG
A perforated release film is applied over the In a typical vacuum bag lay-up, there are
composite laminate and extended approxi- several methods available; some use double
mately 3.2 mm (1.25 in) beyond all edges. sealant tape side/side, some single and some
A predetermined number of bleeder plies one on top of the other. The best system is the
are applied over the release film and one that works. The side/side method is used
extended to the perimeter of the lay-up. to provide some insurance during cure that
A perforated release film is applied over the the bag will not shrink, pulling an edge off,
bleeders and extended 3.2 cm (1.25 in) from causing loss of vacuum. The over/under
edge. method is used to provide ease of placement
One or two layers of a non-woven breather of ears to allow some movement of the vac-
is placed over the lay-up and extended over uum bag. No matter which method is chosen,
the release film. it is important to remember that vacuum bags
Sealant tape is applied around the perime- tend to pull down more than expected and
ter of the bleeder. can puncture, if bagging is over a sharp
The vacuum bag is positioned and sealed. object. During the application of a vacuum
The contents are evacuated and smoothed bag, 'ears' are required to facilitate the uni-
and the bag is checked and sealed against form application of vacuum to the composite
leaks. laminate.
The bagged lay-up is ready to be cured. Vacuum bag bridging is one of the leading
causes of resin rich and excessive voids in cor-
In any bagging sequence, the types of release
ners of composite laminates. Figure 16.7
film, bleeder, breather and bagging materials
illustrates this common problem. One method
used vary from company to company and from
of eliminating bridging of the vacuum bag is
supplier to supplier. Each supplier has typical
presented in Fig. 16.8by means of 'ears' in the
data sheets on expendable materials to acheve
bag. Another method to help reduce resin rich
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).
370 Hand lay-up and bag molding
fSEAMNT TAPE
VACUUM BAG
4- INCH HIGH PLEAT OR FOLD
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
Design 373
will not follow the mold surface and will Changes in thickness
develop voids and resin rich areas in the lami-
To change thickness in open mold construc-
nate in the vicinity of the angle. For instance,
tion is to add or remove plies of material. An
in inside right angle corners without radius,
abrupt change means that the plies must be
(Fig. 16.12(a))the laminate will not pack into
carefully laid up in a precise pattern. An
the corner. When there are sharp outside cor-
abrupt change in thickness (Fig. 16.13(a))
ners, the laminate (Fig. 16.12(b))will not wrap
results in a stress concentration and should be
tightly over the corner. The solution to such
avoided as delamination is sure to occur at
problems is to design with a generous radius,
such a point. The solution to this problem is
preferably 4.75-12.75 mm (0.187-0.500 in)
not to have abrupt changes but to gradually
inside and out. The laminate will then follow
change by stepping back or 'shingling' the lay-
the contour. Abrupt changes in direction are
up (Fig. 16.13(b)).
high stress areas and tend to delaminate and
crack. They should be avoided and moderate
self reinforcing curvatures used. 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)).
L I
Fig. 16.12 Corner lay-up techniques (a) radius cor- Fig. 16.13 Changes in ply lay-up (a) abrupt
ner; (b) no radius corner. changes; (b) stepped piles; (c) hole reinforcement.
374 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
Applications 377
1-
.k&
- ---- -
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.
I
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
I * cure, required a maximum of 21 days. The
I
selected carbon/epoxy resin system was
workable for this limit. The mast, spinnaker
t pole and rudder stock utilized variations of
pressure bag molding with integrally heated
Fig. 16.15 'Spirit of Australia' laminate laydown fiberglass tooling.
(top) 45" ply laminate; (bottom) 0" ply laminate.
These two tooling approaches allowed for
some of the largest one-piece structures to date
two or three stages and culminating with a to be fabricated in the commercial marine mar-
final coat of good grade epoxy or urethane ket. Logistics can become a major role player
marine paint. This step is often postponed in the planning required in that not only the
until the boat is completely assembled and support materials are on hand but that power
ready for fitting out. Then, the hull was is available; materials handling is taken into
inverted and placed in a fitted saddle; the male account and there is sufficient crew available
plug was removed. Additions of bulkheads, to complete the lay-up within the material out
flooring and interior completed the work. time limits.
The manufacture of the carbon/epoxy mast As seen in the above examples, the one
for the 'Spirit of Australia' presented some major factor for all the programs was the
unique challenges. The major program chal- material out time. With the development of
lenge was how to obtain a mast that would new resin matrixes, the design of complex
provide the required performance at affordable structures can be achieved.
MATCHED METAL COMPRESSION 17
MOLDING OF POLYMER COMPOSITES
Enarnul Haque and Burr (Bud) L. Leach
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
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 17.2.3 THICK MOLDING COMPOUND (TMC)
chemistry of glass fibers, development of a
TMC was developed by Takeda Chemical
chemical thickening system and thermoplastic
Industries, Ltd (Osaka, Japan). TMC is suited
low profile additives help BMC to attain to compression, injection and transfer mold-
strength, chemical resistance and to overcome
ing and is usually processed on the same
surface irregularities. Consequently, BMC was equipment as SMC and BMC materials. TMC
accepted for use in the electrical, chemical and composites are usually produced up to 51 mm
appliance industries.
(2in) thick and glass fiber length can vary
Today, BMCs are accepted as high perfor-
from 6.4 to 50.8 mm (0.25 to 2 in). In TMC,
mance engineering thermoset molding continuous impregnation and high sheet
compounds and used extensively in the elec- weight result in complete wet-out of resins,
trical, automotive and consumer goods
fillers and reinforcing fibers. Better wet-out
industries. BMC is increasingly injection
results in improved mechanical properties
molded to take advantage of the automation and reduced porosity. TMC is usually used in
and reproducibility afforded by the process,
business machine housings, appliance com-
although it is also both transfer molded and
ponents and other consumer related
compression molded. industries.
ZMC was developed in 1979 in France to SMC is a type of fiber reinforced plastic which
improve BMC performance. BMC suffers primarily consists of a thermosetting resin,
from glass fiber degradation during injection glass fiber reinforcement and filler. Additional
molding and ZMC was developed to keep ingredients such as low-profile additives, cure
shear forces as low as possible during mold- initiators, thickeners and mold release agents
in$. A special type of injection molding are used to enhance the performance or pro-
machine developed by Billion in France com- cessing of the material4.
bines the advantages of both a screw machine The development of SMC started in the
and a plunger machine. The ZMC injection early 1950s after the finding that the viscosity
machine uses a screw to homogenize and pre- of unsaturated polyester resins increases with
cisely measure the shot. The injection is made the addition of Group IIA metallic oxides,
like a plunger by the displacement of the hydroxides, or carbonates5. The first pub-
screw and inner barrel inside the main barrel. lished report on SMC was presented at the
In a ZMC, the different components are Cleveland Section of the Society of Plastics
mixed in conventional mixers like BMC. The Engineers meeting. The report involved work
compound viscosity is usually low and done in Germany using fiberglass mat
adapted to injection machine characteristics. impregnated with a resin mixture containing
The design of the mold plays a key role in the magnesium oxide6.At the same time a num-
processing phase and ZMC parts cannot be ber of US patent^^,^ were published on the use
successfully made unless part design and of Group I1 metal oxides, hydroxides, or car-
mold design are combined upfront. bonates for use on adhesives. The early
Compared to SMC, ZMC parts have lower applications of SMC materials were in electri-
mechanical properties, but higher perfor- cal and industrial goods. During the next two
mance when compared to conventional decades, growth in commercial usage of SMC
injection molded BMC. 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
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
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
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;
0 aesthetics and marketing;
0 shipping limitations;
0 weight requirements;
0 strength and stiffness requirements;
0 flexibility requirements or limits;
0 process limitations.
Draft angle
(1’ recommended)
1Ae” Minimum
Recommended
Radius Determined
‘By Part Thickness
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.
4- 0.5"draft
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
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).
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
building and finishing allowances Fig. 17.16).
All matched metal compression molds use Knife edge shears are to be avoided as they
telescoping shear edges around the perimeter create a thin mold section which can bend or
of the part. The shear of the mold halves is break under molding pressures (Fig. 17.17).
never in contact but bypass each other as the Shear edges should be flame hardened to a
mold closes, leaving a thin amount of flash Rockwell C of 55-60.
(0.154-0.254 mm, 0.006-0.01 in). The bypass-
ing feature allows the mold cavity to be fully
17.8.3 HEELBLOCKS
filled regardless of small variations in charge
weight. Compression molds should have heel blocks
A minimum of 3" of draft is preferred for and wear plates suitable to withstand all lat-
return flanges. A minimum of 1.0 mm (0.04 in) eral forces at 12.41 MPa (1800 psi) molding
nominal flat clearance should be provided to pressure. The heel blocks should be an integral
keep the cavity and core halves of the mold part of the mold and flame hardened to a
from contacting each other. A surface normal to Rockwell C of 50-55. Bronze wear plates
die draw should be provided at the edge of the should be bolted opposite the heel blocks and
part. A nominal angular tolerance of QO" and a have a minimum of 3.18 mm (1/8 in) chamfer
1.5 mm radius should be allowed for mold lead in to avoid shearing off the wear plate.
Acknowledgements 395
l.0mm (0.04")
min flat
Normal to die
draw +/- 200 -1I t
+0.15mm (0.006")
flash
Fig. 17.16 Shear edge design; part design requirements to maintain sufficient tool strength at the shear
edges.
Vacuum Impregnation
K
Vacuum Infiltration
Composite
Design and Product
material system
selection
Liquid Impregnation
When combined with high performance Svedova, 1990). For more specific references
fibers, matrices and properly tailored one can examine the book by Goswami et al.
fiber/matrix interfaces, fiber architecture (1977) on yarns (linear fibrous assemblies);
promises to expand the design options for the Lord et al. (1973) on weaving; Spencer (1983)
manufacturing of tough and reliable structural and Raz (1987) on knitting and Krcma (1971)
composites. With an integrated network of on nonwovens.
structural cells in two- and three-dimensional
arrangements, textile structures not only pro-
18.1.1 THE ROLE OF TEXTILE PREFORMS
vide a mechanism for structural toughening of
composites but also facilitate the processing of The final goal of manufacturing a composite
composites into net or near net shape struc- structure is to meet design requirements
tural parts. including performance and cost. How success-
Considering the important role which tex- fully the goal can be met depends on the
tile preforms play in the chain of composite effective use of the reinforcement material and
manufacturing processes, there is a worldwide the cost of manufacturing a quality product.
revival of interest in the technology and sci- Preform fiber architecture plays a key role
ence of the processing of textile preforms for in composite manufacturing by facilitating
composites. The serious interest in the subject processing steps including forming and resin
of textile composites can best be illustrated in infiltration. The properties of the composite
the two recent publications on textile compos- will also vary depending on the fiber architec-
ites, one in English (Chou and KO, 1989) and ture. Fiber orientation (13)and volume fraction
the other in Russian (Tarnpolski’i et al., 1987). (V,)are key engineering parameters for textile
These two books have been translated respec- composite formability, permeability and per-
tively into Russian and English. Special formance. Accordingly, after reviewing the
journal issues have been devoted to the subject experimental evidence of the dynamic interac-
of textile composites as well (for example, tion of process-structure-performance, this
Jouvnal of The Textile Institute, 1990, No. 4, article will examine textile preforms through a
Textile Institute). This article intends to pro- unit cell based analysis relating the preform
vide a quick reference to textile preforming geometric parameters of V, and I3 and their
from the point of view of composite process- relationship to textile preform performance.
ing science. To facilitate discussion, textile
preforms are classified into linear, planar and
Formability
three-dimensional fibrous assemblies. After a
brief introduction of the processing technol- The manufacturing of composites often
ogy of textile preforms, discussion will focus requires transformation of the fiber reinforce-
on the processing kinematics of the preforms ments into various structural shapes through
and the geometric parameters which control net shape fabrication or formed shape process-
two of the most important parameters in com- ing. While 3-D textile preforming is more
posite design: fiber volume fraction (V,) and suitable for the creation of net structural
fiber orientation (0). The role of fiber archtec- shapes, 2-D textile preforms are usually
ture in the forming, resin infiltration and the formed into shapes by molding or stitching.
translation of fiber properties to the composite One of the earlier studies of fabric formability
is also discussed along with experimental evi- in composite manufacturing (Potter, 1979)
dence. For readers interested in further showed that total available deformation could
pursuing the technological aspect of the sub- be imposed on the fabric uniformly and that
ject, there are several outstanding general the modes of deformation are important para-
references on industrial textiles (Kaswell, 1963; meters for fabric formability. Potter
In trod uction 399
Q)
sidered. g 600
W
z
Permeability - 400
(L
IL
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
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
structures. The drawback of this fiber architec- While weaving, braiding and knitting can
ture is its intra- and interlaminar weakness produce planar or 3-D structures, nonwoven
due to the lack of in-plane and out-of-plane fabrics can be a 2-D planar system with ran-
yarn interlacing. dom or organized fiber orientation, as well as
A third category of fiber reinforcement is the orthogonal 3-D system. The 2-D and 3-D
the planar interlaced and interlooped system. fabrics are distinguished by yarn orientation
Although the intra-laminar failure problem distribution and the number of yarn diameters
associated with the continuous filament sys- in the thickness direction. A 2-D fabric consists
tem is addressed with this fiber architecture, of two to three yarn diameters in the thickness
the interlaminar strength is limited by the direction with fibers oriented in the x-y plane.
matrix strength due to the lack of through A 3-D fabric, consisting of three or more yams
thickness fiber reinforcement. in the thickness direction, is a fibrous network
The fully integrated system forms the wherein yarns pass from surface to surface of
fourth category of fiber architecture wherein the fabric in all three directions.
the fibers are oriented in various in-plane and
out-of-plane directions. With the continuous
filament yarn, a three dimensional network of 18.2 YARN PREPARATION FOR TEXTILE
yarn bundles is formed in an integral manner. PREFORMING
The most attractive feature of the integrated
18.2.1 CLASSIFICATION OF YARNS
structure is the additional reinforcement in the
through-thickness direction which makes the In addition to preforming methods and para-
composite virtually delamination-free. meters, the physical properties of textile
Another interesting aspect of many of the fully preforms, such as thickness, fabric tightness,
integrated structures such as 3-D woven, knits fiber orientation, etc., are also affected by the
and braids is their ability to assume complex characteristics of yarns. Linear fibrous assem-
structural shapes. blies can be composed of filaments of discrete
Another way of classifying textile preforms (staple yarns) or continuous lengths (filament
is based on the fabric formation techniques: yarns). Staple yarns are held together by an
through fiber entanglement or yam twisting, appropriate level of twist, whereas filament
interlacing, interlooping, intertwining or mul- yarns may or may not have twist. Larger fila-
tiaxial placement. While most textile preforms ment bundles that have little or no twist are
are converted from fiber to yarn or yarn to fab- called rovings; yams are usually smaller than
ric structures, some preforms, such as fiber rovings and some level of twist is generally
felts, are converted directly from fiber to fab- added. The majority of high performance
ric. In Table 18.2, the four basic yarn-to-fabric yarns are continuous filament yams having
formation techniques are compared. single or multiple strands.
Table 18.2 A comparison of fabric formation techniques
~ ~~~
Fig. 18.7 Idealized fiber packings: (a) open packing; (b) square packing; (c) close packing.
404 Textile preforming
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).
Fig. 18.11 Structural geometry of biaxially woven fabrics: (a) plain weave; (b)twill weave; (c) satin weave.
406 Textile preforming
geometry: warp, web, fill and surface weave When surface weave yarns are employed in
yarns. Warp yarns are the system of yarns the fabric, there are two yarns for every warp
which run in the machine direction and have plane of the fabric. This system of yarns con-
no crimp. These are also called ’stuffer’yarns tributes the least to the mechanical properties
or ’longitudinals’. Because of their very low of the composite.
crimp, these yarns provide the primary
strength and stiffness in the longitudinal (x)
18.3.3 DESIGN METHODOLOGY
direction of the material. Web yarns run in the
machine direction and provide the interlacing Figure 18.16 gives the unit cell geometry for
necessary for fabric integrity. These yarns con- plain biaxial weave, as proposed by Dow and
tain crimp in the through thickness direction, Ramnath (1987). In their analysis, Dow and
providing the z-directional properties of the Ramnath assumed circular yarn cross-section,
system. These yarns are sometimes called the same yam diameter and pitch length for
’weavers’. The ‘weave angle’ of the web yarns both fill and warp yarns. The expression of the
(6) refers to the angle of orientation of the web fiber volume fraction was derived:
yarn with respect to the warp direction. Fill
yarns are perpendicular to machine direction I
2-+46
and interlace with the web yarns. These yarns (18.9)
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. where K is the fiber packing fraction, d is the
These yarns provide the transverse (y) direc- yarn diameter, L is the pitch length, T is the
tional properties of the composite system. fabric thickness, I is the dimension shown in
Surface weave yarns run in the machine direc- Fig. 18.16. The yarn inclination angle to the
tion and form what is essentially a fabric plane, 6, is given by:
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.
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
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()
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).
Knitting 409
J ’Djrection of knitting
Fig. 18.18 Yarn feeding and loop formation: (a) weft knitting; (b) warp knitting (Spencer, 1983).
Stitch (loop) formation is similar in both weft technology can be found in Spencer (1983)and
and warp knitting. The formation of the Raz (1987).
stitches in a single wale is illustrated in Fig. Knitted 3-D fabrics are produced either by
18.19. In Step 1, the needle rises through loop weft or warp knitting. An example of a weft
A from its lowest position; in Step 2, yarn slips knit is the near net shape structure knitted
under the tip of the needle and onto the stem; under computer control by the Pressure Foot@
in Step 3, ascending hook catches the new yarn process (Williams, 1978). In a collapsed form
at the top of its rise and begins to descend; in this preform has been used for carbon-carbon
Step 4, the new yarn slips under the tip and aircraft brakes. While weft knitted structures
into the hook; in Step 5, the needle moves have applications in limited areas, multiaxial
down until the tip slides under loop A and the warp knit (MWK) 3-D structures are more
hook pulls the new loop through. After the promising and have undergone a great deal
completion of five steps, loop B is formed and more development in recent years. Schematic
the process is repeated. In a knitting operation, of a MWK LIBA system is given in Fig. 18.20,
each of the needles is controlled by a cam to in which up to six layers of insertion yarns
rise and fall in synchronization with the other plus one layer of non-woven can be stitched
needles. Detailed description of the knitting together.
,Hook
Ti
1 2 3
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
Knitting 411
stitch patterns and laid-in insertions. To illus- illustrated in Fig. 18.23(b).For untwisted fiber
trate the use of the unit cell method for bundles under compression applied during
relating fiber volume fraction, yarn orientation preforming or composite processing, they
and processing variables, a plain weft knit as have a ribbon-like cross-section similar to a
shown in Fig. 18.18(a) is selected as an exam- race-track with a width-to-thickness aspect
ple. The unit cell geometry identified for the ratio off > 1 as illustrated in Fig. 18.23(a).For
plain weft knit is shown in Fig. 18.22, having a composite applications, untwisted fiber bun-
dimension of x (course width), y (half wale dles are usually used in knitting, which have
width) and z (fabric thickness). 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.
In this analysis, the knit thickness is assumed relative course width (x/w), relative half wale
to be approximately equal to two yarn thick- width (y/w) and yarn aspect ratio (f)under
ness (t)for computational purposes, i.e. compression is depicted in Fig. 18.24, using the
geometric model developed. In the calculation,
z = 2t (18.14)
we use the fiber packing fraction k = 0.8, which
The yarn orientation angle (e), which is the is within the range for tightly packed yarn bun-
angle made by the fabric axis (in x direction) dles according to experimental observation.
and the yarn path projected to the fabric sur- Also, to show the processing window of fiber
face plane ( x - y), is given by: 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).
(18.15) 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 =
The fiber volume fraction (V,),which is defined 2-10. When y/w is beyond 10, the fiber vol-
as the ratio of volume of total fibers to the over- ume fraction slightly increases and soon
all composite volume, can be derived as: 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
Y = 3, y/w = 2 and k = OB), its maximum fiber
(18.16) volume fraction is only about 0.274.
1+tan - To increase the fiber volume fraction, a com-
pression in the fabric thickness direction is
necessary. The effect of the compression is the
where k is the fiber packing fraction within increase in yam aspect ratio (i.e. yams within
yarn bundles and a is the shape correction fac- the knitted structure become wider in x-y plane
tor defined as:
(18.17) 060
1 2 2 (18.19) ooo
W 10 100 1000
Ylw
The processing window of fiber volume frac-
tion for knitted structures within the possible Fig. 18-24 Processing window of fiber volume frat-
ranges of key processing parameters, such as tion for the plain knitted structure.
Braiding 413
but thinner in z direction).As a result, the yarn tal. A schematic of a horizontal braider is
coverage over the fabric increases, whereas the shown in Fig. 18.25.Although braiding is simi-
volume of the preform decreases due to the lar to filament winding in many ways, the
decrease in fabric thickness. These two factors, major difference between braiding and fila-
the increased yarn coverage and decreased pre- ment winding is that braids are interlaced
form volume, raise the fiber volume fraction to structures having as many as 144 or more inter-
a much higher level. As shown in Fig. 18.24, at lacing per braiding cycle (or pick).
a maximum aspect ratio f = 12, the fiber vol- Three-dimensional braiding technology is
ume fraction can be as high as 0.475. an extension of 2-D braiding technology in
A series of studies on the technology, struc- which the fabric is constructed by the inter-
ture and properties of the MWK preforms and twining or orthogonal interlacing of yarns to
composites have been reported by KO and his form an integral structure through position
co-workers (1980,1982,1985,1986,198813).In a displacement. A unique feature of 3-D braids
recent study, a unit cell based geometric model is their ability to provide through the thickness
of the four-layer MWK structure as shown in reinforcement of composites as well as their
Fig. 18.21was developed by Du and KO (1992). ready adaptability to the fabrication of a wide
Based on the experimental observations, the range of complex shapes ranging from solid
unit cell geometry of the MWK fabric is iden- rods to I-beams to thick-walled rocket nozzles.
tified and a geometric model is developed Three-dimensional braids have been pro-
relating the fiber volume fraction and fiber ori- duced on traditional Maypole machines for
entation in terms of structural and processing ropes and packings in solid, circular or square
parameters. cross-sections. The yarn carrier movement is
activated in a restricted fashion by horn gears.
A 3-D cylindrical braiding machine of this form
18.5 BRAIDING was recently introduced by Albany with some
modification that the yarn carriers do not move
18.5.1 PROCESSING TECHNOLOGY
through all the layers (Brookstein, 1991). 3-D
Braiding is an old textile technology, tradition- braiding processes without using the horn
ally used for the manufacture of a wide variety gears, including Track and Column (Brown et
of linear products ranging from cables, electri- al., 1988) and 2-Step (Popper and McConnell,
cal insulators and shoelaces to surgical sutures. 1987),have been developed since the late 1960s
Recognizing the high level of conformability in the search for multidirectionally reinforced
and the damage resistance capability of composites for aerospace applications.
braided structures, the composites industry A generalized schematic of a 3-D braiding
had found structural applications for braided process is shown in Fig. 18.26. Axial yarns, if
composites ranging from rocket launchers to present in a particular braid, are fed directly
automotive parts to aircraft structures.
Two-dimensional braided structures are Axial yarns, /Carrier track
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 Fig. 18.25 Schematic of tubular braider with gantry
majority of the composite braiders are horizon- system.
414 Textile pyeforrning
-
braiding methods differs from the traditional
horn gear method only in the way the carriers
Forming point are displaced to create the final braid geome-
Convergence point 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
Fig. 18.26 Schematic of a generalized 3-D braider. as T-beam and I-beam, is accomplished by
proper positioning of the carriers and the join-
into the structure from packages located below ing of various rectangular groups through
the track plate. Braiding yarns are fed from selected carrier movements. The track and col-
bobbins mounted on carriers that move on the umn braiding machine can also be used to
track plate. The pattern produced by the create 2-step braids and other similar 3-D
motion of the braiders relative to each other structures by simply adding a certain number
and the axial yarns establish the type of braid of axial yarns and removing most of the braid-
being formed, as well as the microstructure. 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
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)
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
0.006
Braid Axis Pressure drop: 60 psd
s2
-r?
e.-x 0.004-
c
-
._
L2
0.002-
6- Limiting fiber
2
architecture
0.000 _1
0 3 6 9 12 15
Fiber diameter (pm)
0, , , . , .~ , , , . , . . .
0 5 10 15 20 25 30 35 40 45 50 55 60 Fig. 18.39 Effect of fiber volume fraction and diam-
Braid angle, 8 (") eter on preform permeability.
Fig. 18.38 Stiffness properties of 3-D braided car-
bon-carbon composite. Fiber packing and tightness can be quantified using the Kozeny-Carman
factor are assumed as IC = 0.785,~= 0.573; Young's equation, as shown in Fig. 18.39, noting that
moduli and Poisson's ratios of fiber and matrix are the permeability is in the unit of mass flow
given as E , = 33.5 Msi, Em = 1.3Msi, z),= 0.3, urn= 011.
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
The other example of the application of the fabric thickness of 0.5 in.
fiber architecture models to the composite pro-
cessing is to predict the permeability of fabric
preforms. As suggested by the well known REFERENCES
Kozeny-Carman equation, there are two Brookstein, D.S. 1990. Interlocked Fiber
major geometric parameters which greatly Architecture: Braided and Woven. Proc. 35th
affect permeability of fibrous materials, i.e. Intern. SAMPE Symposium, Society for the
porosity of fabric preforms E and characteristic Advancement of Material and Process
Engineering, Vol35, pp. 746-756.
dimension of fibers @D,where @ is the shape
Brown, R.T., Patterson, G.A. and Carper, D.M. 1988.
factor and D is the fiber diameter. Other para- Performance of 3-D Braided Composite
meters which also affect the permeability are Structures. Proceedings of the Third Structural
flow properties, pressure drop and part thick- Textile Symposium, Drexel University,
ness. These parameters have been shown to be Philadelphia, PA.
independent of preform fiber architecture. Chou, T.W. and KO,F.K., eds. 1989. Textile Structural
From geometric analysis, one can construct Composites. New York Elsevier.
the V f 4 relationship and determine their Dow, N.F. and Tranfield, G. 1970. Preliminary
Investigations of Feasibility of Weaving Triaxial
dependence on the process parameters. The Fabrics (Dow Weave). Textile Research Journal,
fabric porosity can easily be calculated from V , pp. 986-998.
( E = 1 - V,), whereas the shape factor of fibers Dow, N.F. 1985. Woven Fabric Reinforced
@ is related to the fiber orientation 8 and the Composites for Automotive Applications.
flow direction in composite processing. From Technical Final Report, NSF Grant No. DMR-
our experiments, we have observed that @ = 8212867, MSC TFR 1605/8102, December.
1.5 when most of the fibers are aligned paral- Dow, N.F. and Ramnath, V. 1987.Analysis of Woven
Fabrics for Reinforced Composite Materials.
lel to the flow direction and @ = 0.75 when the NASA Contract Report 178275.
fibers are perpendicular to the flow direction. Dow, R.M. 1989. New Concept for Multiple
The effect of the fiber volume fraction and Directional Fabric Formation. Proc. 21st Intern.
fiber diameter on the permeability of air flow S A M P E Tech. Conf., September 2.528.
References 423
Du, G.W., Popper, P. and Chou, T.W. 1990. Process Applications. J. Industrial Fabrics 4(2).
Model of Circular Braiding for Complex- KO, F.K., Pastore, C.M., Yang, J.M. and Chou, T.W.
Shaped Preform Manufacturing. Proc. Symp. on 1986. Structure and Properties of
Processing of Polymers and Polymeric Composites, Multidirectional Warp Knit Fabric Reinforced
ASME Winter Annual Meeting, Dallas, Texas, Composites. In Composites '86: Recent Advances
NOV.25-31. in Japan and the United States, eds. Kawata, K.,
Du, G.W., Popper, P. and Chou, T.W. 1991. Analysis Umekawa, S. and Kobayashi, A. Proceedings,
of Textile Preforms for Multi-directional Japan-U.S. CCM-111, Tokyo, pp. 21-28.
Reinforcement of Composites. 1. Mater. Sci. 26: KO, F.K., Pastore, C.M., Lei, Charles and Whyte,
3438-3448. D.W. 1987. A Fabric Geometry Model for 3-D
Du, G.W. and KO, F.K. 1992. Analysis of Multiaxial Braid Reinforced Composites. Intern. S A M P E
Warp Knitted Preforms for Composite Metals Conference: Competitive Advancements in
Reinforcement. Proc. Textile Composites in Metals/ Metals Processing.
Building Construction 2nd Inter. Symp., Lyon, KO, F.K. 1988. Braiding, Engineering Materials
France, June 23-25. Handbook, Vol 1, Composites, ed. Reinhart, T.J.
Du, G.W. and KO,EK. 1993a. Unit Cell Geometry of Metal Park, OH: AMS International, pp.
3-D Braided Structures. J. Rein. Plus. Comp. 12 519-528.
(2): pp. 752-765. KO, F.K., Whyte, D.W. and Pastore, C.M. 1988a.
Du, G.W. and KO, EK. 1993b. Analysis And Design Control of Fiber Architecture for Tough Net-
Of 2-D Braided Preforms For Composite Shaped Structural Composites. MiCon '86:
Reinforcement. Proc. ICCM-9, Madrid, Spain, Optimization of Processing, Properties and Service
July 12-16. Performance Through Microstructural Control,
Fukuta, K., Aoki, E. and Nagatsuka, Y. 1984. 3-D ASTM STP 979, eds. Bramfitt, B.L., Benn, R.C.,
Fabrics for Structural Composites. 15th Textile Brinkman, C.R. and Vander Voort, G.F.
Res. Symp., The Textile Machinery Society of Philadelphia: ASTh4 pp. 290-298.
Japan, Osaka, Japan. KO,F.K. and Kutz, J. 198813.Multiaxial Warp Knit for
Fukuta, K., Onooka, R., Aoki, E. and Nagatsuka, Y. Advanced Composites. Proc. 4th Ann. Con$ Adv.
1982. Application of Latticed Structural Composites, ASM International, pp. 377-384.
Composite Materials with Three Dimensional KO, F.K. 1989. Preform Fiber Architecture for
Fabrics to Artificial Bones. Bull. Res. Inst. Polym. Ceramic Matrix Preforms. Ceramic Bulletin 68
Textiles. 131(2)2:151. (2): 401414.
Geoghegan, P.J. 1988. DuPont Ceramics for KO, F.K. and Du, G.W. 1992. Processing and
Structural Applications - the SEP Noveltex Structures of Textile Preforms for Composites.
Technology. 3rd Textile Structural Composites Proc. Science and Innovation in Polymer
Symp., Philadelphia, PA. June 1-2. Composites Processing, MIT, Cambridge, MA,
Goswami, B.G., Martindale, J.G. and Scardino, EL. July 16-17.
1977. Textile Yarns, Technology, Structure and Krcma, R. 1971. Manual of Nonwovens. Manchester,
Applications. New York John Wiley and Sons, UK Textile Trade Press.
pp. 273-337. Li, W., Hammad, H. and El-Shiekh, a. 1990.
Hearle, J.W.S., Grosberg, P. and Backer S. 1969. Structural Analysis of 3-D Braided Preforms for
Structural Mechanics of Fibers, Yarns and Fabrics, Composites, Part I: The Four-Step Preforms. I.
Vol 1,New York: Wiley-Interscience. Text. Inst. 81:491-514.
Kaswell, E.R., ed. 1963. Wellington-Sears Handbook of Lord, P.R. and Mohamed, M.H. 1973. Weaving:
Industrial Textiles. New York: Wellington-Sears. Conversion of Yarn to Fabric. Durham, UK:
KO, F.K., Bruner, J., Pastore, A. and Scardino, E 1980. Merrow Technical Library.
Development of Multi-Bar Weft Insertion Warp Loos, A.C., Weidermann, M.H. and Kranbuchi, D.E.
Knit Fabric for Industrial Applications. ASME 1991. Processing of Advanced Textile Structural
Paper No 90-TEXT-7, October. Composites by RTM. Proc. 5th Textile Structural
KO, F.K., Krauland, K. and Scardino, F. 1982. Weft Composites Symp., Drexel University,
Insertion Warp Knit for Hybrid Composites. Philadelphia, PA, Dec. 4-6.
Proc. 4th Intern. Conf. Composites. McCarthy, S. and Kim, Y.R. 1991. Resin Flow
KO, F.K., Fang, P. and Pastore, C. 1985. Multilayer Through Fiber Reinforcement During
Multidirectional Warp Knit Fabrics for Industrial Composite Processing. Proc. 5th Textile
424 Texfilepreforming
Structural Composites Symp., Drexel University, Raz, S. 1987. Warp Knitting Production. Heidelberg,
Philadelphia, PA, Dec. 4-6. Germany: Melliand.
Mohammed, M.H., Zhang, Z. and Dickinson, L. Scardino, F.L. 1989. Introduction to Textile
1989.3-DWeaving of Net Shapes. Proc. Zst Japan Structures. In Textile Structural Composites, eds.
Intern. SAMPE Symp., Nov. 28-Dec. 1. Chou, T.W. and KO, F.K. Amsterdam: Elsevier,
Pastenbaugh, J. 1988. Aerospatiale Technology. Proc. pp. 1-26.
3rd Textile Structural Composites Symp., Drexel Scardino, EL. and KO, EK. 1981. Triaxial Woven
University, Philadelphia, PA, June 1-2. Fabrics. Textile Research Journal 51(2).
Pastore, C.M. and Cai, Y.J. 1990a. Applications of Smith, B.F. and Block, I. 1982. Textile In Perspective.
Computer Aided Geometric Modeling for Englewood Cliff, New Jersey: Prentice-Hall.
Textile Structural Composites. Proc. 2nd Intern. Spencer, D.J. 1983. Knitting Technology. New York:
Conf. Computer Aided Design in Composite Pergamon Press.
Material Technology, Brussels, Belgium, April Stover, E.R., Mark, W.C., Marfowitz, I. and Mueller,
25-27. W. 1971. Preparation of an Omniweave-
Pastore, C.M. and KO, F.K. 1990b. Modeling of Reinforced Carbon-Carbon Cylinder as a
Textile Structural Composites, Part I: Candidate for Evaluation in the Advanced Heat
Processing-Science Model for Three- Shield Screening Program. AFML TR-70-283,
Dimensional Braiding. J. Text. Inst. 81: 480-490. Mar.
Popper, P. and McConnell, R. 1987. A New 3-D Svedova, J., ed. 1990. Industrial Textiles.Amsterdam:
Braid for Integrated Parts Manufacturing and Elsevier.
Improved Delamination Resistance - The 2-Step Tampol’skii, Y., Zhigun, I.G. and Polikov, B.a. 1987.
Method. 32nd Intern. SAMPE Symp. Exhib., pp. Spatially Reinforced Composites. Pennsylvania:
92-103. Teknomic. (English translation, 1992).
Potter, K.D. 1979. The Influence of Accurate Stretch Williams, D.J. 1978. New knitting methods offer
Data for Reinforcements on the Production of continuous structures. Advance Composites
Complex Structural Mouldings. Composites, 10, Engineering, Summer, pp. 12-13.
pp. 161-167, IPC Business Press Ltd, July.
TABLE ROLLING OF COMPOSITE TUBES 19
John T. K a m e and Jerome S. Berg
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,
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.
Fig. 19.5 Photograph of vertical tape wrapping Mandrel pullers are generally hydraulic or
machine. (Courtesy of Century Design pneumatic. Hydraulic pullers offer a con-
Incorporated.) 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.
19.2.5 HORIZONTAL TAPE WRAPPER
The type of mold release used, correct size
This machine represents an alternate to the of the stationary block and the mass plus
vertical tape wrapper. It is used frequently for integrity of the cured part must be carefully
longer, heavier parts and also for very flexible evaluated or end crushing of the part will
mandrels such as fishing rods. The mandrel is occur. Also, thin walled tubes or tubes with a
affixed to a chuck or mechanical coupling high degree of longitudinal plies can crack
which rotates the parts while tape is applied. during mandrel extraction.
The rollers provide support for the part while
motion is in place. The single or even dual tape
19.2.7 CURING OVENS
feed spools move with the tape carriage and
return to restart position (Fig. 19.6). Ovens used for curing the composite tubes can
After cure, the wrapping tapes are removed be either electrically or gas heated and of batch
by slitting the tape longitudinally and peeling or conveyorized design. Temperatures rang-
the tape away from the cured part. Wrapping ing from 121-191°C (250-375°F) are most
tapes are then discarded. common for roll forming prepregs. Consult
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
Fig. 19.7 Photograph of pneumatic mandrel puller. metallurgy. They can select the materials and
(Courtesy of Century Design Incorporated.) 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-
the prepreg supplier for recommendations on drels generally provide a longer life since
appropriate cure profiles. Fine tuning of the scratched or dented surfaces will hamper
cure profile is often needed to optimize partic- mandrel removal.
ular roll forming operations and specific
products. Ovens with thermocouples are use-
ful in determining hot and cold spots, which 19.3.2 STEEL RULE DIES
may indicate oven regulation for uniform tem- These dies incorporate multiple blades
perature control. This ensures a uniform gel embedded in a rigid backing (usually marine
within the part. grade plywood) which cut the material in the
roller press. The prepreg tape (up to 20 layers)
19.2.8 CENTERLESS SANDER OR GRINDER is cut between the cutting die blades and a
polyethylene sheet sandwiched between the
The wrapping tapes can leave a series of spiral rotating press wheels. Dies with one piece
indentations approximately 0.5 mm (0.002 in) blades provide the best and most continuous
deep in the composite tube surface. If a cuts (Fig. 19.8(a)). Dies which include weld-
smooth surface is desired for cosmetic reasons ments (as in a triangular shape flag) generally
or for geometry requirements the part can be dull faster since the weldments soften the cut-
surface sanded or ground. A centerless sander ting edges (Fig. 19.8(b)) Ramps can be used
basically removes a user defined controlled between the cutting blades in die designs to
amount of surface material. A centerless keep the roller pressure off the blade ends. The
grinder provides a more accurate finish die builder can recommend blade height and
dimension. Centerless grinders are common cutting edge type best suited for the task.
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 19.4 MATERIALS
golf shaft manufacture, these surface finishing 19.4.1 MOLD RELEASES
techniques are also used to tailor the product
stiffness by incrementally removing material Generally, mold releases for table rolling man-
along the shaft length. This changes the shaft drels consist of two components: a primary
stiffness characteristics. 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
19.5.1 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 Warm lay-up and rolling tables can help
finish. Resin content and formulation can be increase material rolling ability and are gener-
adjusted to suit the manufacturing environ- ally adjusted for slight material and
ment. Temperature and humidity control are environmental changes. Off angle plies are dif-
very helpful in maintaining consistent material ficult to roll adjacent to the mandrel and the
tack in the manufacturing shop. Avoid leaving difficulty is magnified by the higher modulus
cut patterns exposed since moisture in the air fibers. Tack tape is a narrow strip of reinforced
greatly affects the material surface tack and adhesive designed to aid the adhesion of bias
sometimes renders it useless. Consuming the plies to the mandrel. Also, solvent based 'tack
material within two days is a good rule to resins' can be applied to the mandrel to ease
follow. 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
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
ISOCYANATE POLYOL
HYDRAULICS
MACHME MODE
HEAD
sively. In addition, many mold materials can design stage. The usefulness of such design
be used. tools is discussed in detail, giving the relevant
0 Inserts: Ribs, bosses, cores, inserts and spe- advantages and disadvantages.
cial reinforcement can be added easily.
0 Labor saving: The skill level of operator is
20.2 RTM PROCESS
less critical.
0 Low tooling cost: Clamping pressure is low The RTM process can be viewed as seven unit
compared to other closed mold operations. operations. The general practice and process-
Low volatile emission: Volatile emissions ing issues are described for each unit
are low because RTM is a closed mold operation.
process. The worker is not exposed to
chemical vapors as with the lay-up process.
20.2.1 FIBER REINFORCEMENT
Disadvantages are:
Selection of the proper reinforcement type
Mold design: The mold design is critical should take into consideration loading condi-
and requires good tools or great skill. tion, part geometry (size, thickness),
Improper gating or venting may result in mechanical properties and surface finish. The
defects. quantity of parts demanded also determines
Mold filling: Control of flow pattern or the selection. The reinforcement normally car-
resin uniformity is difficult. Radii and ries 90% of the load in a composite and
edges tend to be resin-rich. provides over 90% of the stiffness. The rein-
Properties are equivalent to those with forcement in a composite can be designed to
matched-die molding (assuming proper match the strength requirements of the part.
fiber wetout, etc.), but are not generally as The following characteristics should be con-
good as with vacuum bagging, filament sidered when selecting fiber reinforcements:
winding or pultrusion.
Volume fraction: ratio of the volume of a
Reinforcement movement during resin
given mass of reinforcement to the volume of
injection is sometimes a problem.
the same component after molding;
In the following sections, the resin transfer
Wash resistance: ability of a reinforcement to
molding process is discussed in terms of the
withstand movement due to fluid motion or
unit operations involved, to familiarize read-
solvation of the reinforcement binder by the
ers with the basic steps of the RTM process.
resin;
The discussion covers details such as materials
of construction, mold design, preforming, cur- Wettability: ability of a reinforcement to reach
ing, and demolding. Processing issues are a condition wherein all voids in the reinforce-
mentioned in each individual unit operation. ment are filled with resin;
Relevant variations of RTM such as vacuum
Sizing: most fibers are coated with size for
assisted resin transfer molding and flexible
better wettability and bonding but the size
molding tools are summarized. may influence the cure kinetics during the
Process physics is described with emphasis
manufacturing.
placed on the principles that govern the RTM
process; these are applied in the use of com- Most standard reinforcement materials for
puter simulations. Through the design tools composites can be used, but fiberglass, carbon
such as simulation codes for mold filling and aramid are the most common in RTM.
analysis, engineers are able to predict or diag- One requirement is that the reinforcement
nose the problems in gating and venting in the should hold its shape during the injection
436 Resin transfer molding
phase. Therefore, the reinforcements are gen- mally have 4-6 wt.% of thermoplastic binder
erally stitched, woven or bonded together. added. They are thermoformable and can
Reinforcement build-ups in certain areas can therefore be used for highly complex shapes or
easily be included. For example, woven roving when the anticipated volume of production
and fabric can be combined with continuous makes them economical.
strand mat and chopped strand mat in appli- Different sizings can be obtained on many
cations where higher strengths are required. reinforcements. Sizings can be tailored to the
Hybrid systems composed of high perfor- type of resin system. Sizings are available that
mance reinforcements such as carbon fiber and are compatible with epoxy, vinyl esters or poly-
aramid fiber can also be incorporated in RTM esters. The strength variation with type of
laminates. Surfacing materials called veils can sizing can be as much as 20%, so this factor
be used in the preforms to hide the imprint of needs to be considered in the choice of rein-
fibers, for improved surface finish. Another forcement.
application of surfacing veil is to achieve a
resin-rich skin to improve corrosion resistance. 20.2.2 PREFORM
Stitched fabrics (Fig. 20.3(a))reduce stresses
inherent in the woven roving design and lead For a flat part, the preform can be as simple as
to higher compressive strengths in the com- a stack of reinforcements that fit in the mold
posite. However, other constructions such as cavity. As preforms become more versatile,
8-HS style of weave (eight-harness satin various means of producing preforms are
weave) in Fig. 20.3(b)have been used because available. Currently cut-and-sew is commonly
of improved wetting characteristics and com- used to assemble preforms of various shapes
pressive strength compared to bidirectional for aerospace applications. Other near net
woven fabrics. shape techniques include braiding, spray-up
Continuous strand mat is multi-stranded, and thermoforming (Fig. 20.4).
laid in swirled configuration. The mats nor-
I I t I
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
I
heatingcuring
resinbinder
1
1 cooling
A
t+ Vayum source
I N M '
demolding 1 forming
screen
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-
Fiber distribution:Uniformity of fiber content
tional reinforcement is subjected to washing
(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
than this critical value, dramatic movement of (Fig. 20.6) is necessary to conform to the con-
the fibers to the inside of the radius occurs. As tours of the tool. This drapability problem,
a result, channeling becomes dominant in the therefore, has a two-fold significance in RTM.
mold filling stage and induces irregular flow Because of the fiber rearrangement, the
patterns. nonuniformity of fiber distribution should be
The edge of a preform is another source of accounted for in the design of the composite.
the race tracking of resin. In order to avoid Fiber volume fraction and orientation are no
the channeling effect, the preform edge longer that of the unreformed reinforcement.
should be cut to fit the edge of the mold cav- Further, such preforms exhibit different char-
ity. The task of obtaining a good edge acteristics to resin flow. Designers should
definition is normally difficult because of the account for this change in determining the
bulkiness of the layers and inter-layer move- location of vent ports relative to an injection
ment (sliding, rotating) during the mold port.
closing when prefabricated preforms are not In practice, to modify the permeability of
used. preforms, various flow inducing media or
Preforming of fabrics over tool geometry mechanisms have been suggested. Application
other than simple flat type will induce shear of such high porosity to the preform or inclu-
deformation in the fiber reinforcements. For a sion of a runner system in mold design can
biaxial reinforcement, shearing of the weave alter the mold filling pattern.
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
volume and high temperatures dictate metal steps. Therefore, the mold designer should
molds. incorporate this rule in the design of the mold
Steel, the most suitable mold material, pro- cavity. Instead of joining several substructures
vides superior face life. Aluminum is good for or onto a major structure after molding, it is
construction of prototype molds since the structurally more effective and efficient to
metal is easy to machine, is lightweight and incorporate them into the part before fabrica-
has a reasonably high heat transfer rate, but tion. This can be easily achieved by joining
also galls easily. Cast aluminum and spray- substructure preforms when practical.
metal tooling are currently available and can In production the number of molds or cavi-
be used for higher volume applications. Cast ties required is determined by needed
copper alloys are being considered for use in throughput. This should take into account the
RTM molds due to the potential for increased cycle time. For small parts, the designer can
throughput via heat management and better incorporate several cavities in a mold.
durability. High surface quality with excellent dimen-
Composites, for example reinforced poly- sional control can be achieved by
ester and epoxies, are most frequently used for electroplating the mold face with nickel. The
making RTM molds. They can be expected to appearance surface of a part is usually placed
last for approximately 2000 parts (Isorca, on the bottom of the mold. Pinholes are more
1992).Higher production volumes may justify likely to collect on the top surface. Mold
the use of higher cost spray-metal or metal preparation is similar to that used for hand
tools. lay-up. Anew tool must to be treated with sev-
In some cases, the mold must be backed up eral coats of release agent.
in order to maintain its shape. Conventionally New mold materials provide flexibility in
the backup can be done cost-effectively with mold design for RTM. For example, to demold
core material or steel frames to add rigidity to a part with vertical sides, it is common to
the cross section and to support composite allow several percent draft in the vertical
mold faces. The closure of the mold is dimension. Flexible silicone rubber has been
achieved by mating of the mold surfaces used for RTM molds in the form of a bladder
against a perimeter gasket. Therefore, guide mold half which is capable of being inflated or
pins are usually employed to align the mold deflated depending on the process require-
halves both laterally and vertically to keep ment. During mold filling, the flexible mold
resin from leaking. wall is pressed against the rigid wall by inflat-
Advancement in adapting composite tool- ing the bladder with a pre-determined
ing to the needs of RTM is underway. For pressure. During the injection cycle, the mold
example, lengthening the life of the composite can deform to enhance resin flow. Upon com-
tool face is desirable and effective to maintain pletion of mold filling, the flexible tool can be
quality while keeping costs low. The factors further inflated to consolidate the composite
that cause deterioration of the mold face are component. Part removal in this case is easy
temperature fatigue and attack by solvents or since the flexible half can be deflated. %s
mold release agents. An electrolytically or technique allows fabrication of complicated
vapor deposited nickel shell is a new tech- parts that are not ordinarily possible to
nique that will extend face life. demold.
may be critical. The location of inlet ports must when vacuum is used. Sealing the mold to
allow the resin to reach all areas without achieve cavity pressure of 690 kPa (100 psi) or
bypassing part of the reinforcement. Air vents higher is necessary if the void content of the
help control internal pressure, bleed out air part is to be kept low. The only practical way to
and provide a visual indication of mold filling. accomplish this is to use O-rings. Machining
Race tracking, or channeling, in the mold is the face of the mold to close tolerances is pro-
usually the reason why the resin bypasses hibitively expensive. It is also usually
areas of the reinforcement. Since the resin will impossible to maintain the mold absolutely flat
not flow backwards, this tends to create dry to achieve a metal-tight seal.
patches. The engineering way to ensure com- O-ring design is well established. The slot
plete initial wetout is to gate the mold has to be cut so that the O-ring can deform
correctly in the design. This may be difficult when the mold is closed and maintain a seal.
even for an experienced mold designer. Use of Either square or round O-ring grooves can be
computer simulations as a design tool has used. The type of O-ring material used
become popular in conventional injection depends on the maximum temperature the 0-
molding. Without an engineering design tool, ring will experience during the fabrication
gates and vents can be put in the mold after cycle and the type of solvent used to clean the
molding some trial parts, but many trial runs mold. Nitrile rubber material can be used sat-
may be prohibitive in some applications. In isfactorily up to 120°C (250°F). Over 120°C
the next section, new engineering tools silicone rubber can be used to temperature
adapted for RTM mold filling will be dis- approaching 177°C (350°F). If help is needed
cussed to overcome the problem. in sealing around inlet or outlet tubes, tacky
Mold designers have found that RTM sealant can be used. This type of sealant is use-
molds must be vented to allow the air within ful for making an O-ring where grooves do not
the mold to be pushed out by the resin. Gate at exist.
the lowest point and vent at the highest point
is generally a good design practice.
20.7 HEATING AND COOLING DESIGN
Experienced designers may use symmetry to
design the inlet ports and outlet vents to The mold should have good temperature con-
remove entrapped air. Venting ports must be trol. The RTM mold should be able to heat and
placed to draw the resin through sections of cool the part during the fabrication cycle. Most
the part that are difficult to wet out. They are resin systems cure faster at elevated tempera-
best placed at dead ends where the resin tures. During demolding, lowering the
would not flow by itself. temperature is sometimes helpful in removing
After the resin has finished bleeding, both the part. Even molds that are intended for
injection and venting ports must be sealed off. room temperature-cured resins should be well
This allows pressure to build up in the mold, insulated so that environmental conditions do
and forces the resin to further wetout other not change the gel times and viscosity of the
sections of the part. This packing stage allows resin. Some molds are heated or designed to
the part to gel under pressure, decreasing void go into ovens to achieve faster cures at higher
content in the finished part. temperatures.
Normally, the mold is heated and cooled
using either hot water or oil. The mold is con-
20.6 SEALING THE MOLD
structed to allow the heating/cooling fluid to
The perimeter gasket seals the edges of the flow through channels (Fig. 20.8) in its interior.
mold to prevent loss of resin and injection pres- The fluid is heated and cooled by conventional
sure. In addition, it is an absolute necessity means, such as a gas-fired heater and heat
444 Resin transfer molding
heating
channel -
//////////////
TCO hh
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 mold is filled, the pumping system is shut off
cooling times will be longer if the heat transfer and immediately flushed, and the part is
area does not increase in proportion to the allowed to cure.
weight. At some point, the production cycle Successful configurations demonstrated in
time becomes limited by the rate at which heat the industry show a common factor: that is,
can be added or removed, and becomes inde- the flow of resin is symmetrical about the vent
pendent of the curing characteristics of the ports, in a manner such that the volume of air
resin system. left in the reinforcement decreases. This com-
Under development is low thermal inertia pression effect helps sweep the remaining air
technology that allows the tool face to be out of the part.
heated by electric wires buried in the face. The When the flow path is arranged in such a
construction of the mold face is such that the way that the resin flows into a configuration
heat flows into the mold face and not outward with increasing volume, there is a tendency to
toward the mold support structure. This is bypass part of the reinforcement. This situa-
accomplished by use of a foam core that insu- tion can happen when core material is used.
lates the bulk of the mold from the tool face. For example, when there is reinforcement on
This novel technology, if successful, will allow either side of a core, it is possible that slight
a more instantaneous transfer of heat where it misalignment in the core thickness will cause
will do the most good - at the mold face. dry spots in the part. To overcome this prob-
lem, the resin must be introduced on either
20.8 MOLD FILLING side of the core simultaneously. Holes may be
drilled through the core to allow the resin sys-
Resin injection is to pump the base resin sys-
tem to flow to the other side. When this is
tem to a mixing head through either a single or
done, the core floats on the wet reinforcement
two pot system. Impingement mixing of the
and equalizes itself.
components occurs in the mixing head. The
When the injection pressure is too high or
catalyzed mix is then pumped through a static
reinforcement tends to move in the mold, the
mixer which completes the mixing of the two
following remedies must be considered:
components. The injection nozzle is attached
to the injection port on the mold and the resin Multiple gates: partition the mold along the
system is injected into the mold to pack the flow path such that travel distance for resin is
mold to a predetermined pressure. When the reduced.
Curing 445
Runner system: allows the delivery of resin to ing (Mosher, 1995). Note that the tooling must
various parts of the reinforcement quickly be large enough to accommodate the perime-
without using high injection pressure. ter gasket, air vents, injection ports and guide
pins.
Flexible mold wall: allows the deformation of
the bladder wall to facilitate mold filling.
20.9 CURING
There are several techniques to modify the
flow patterns. Application of high porosity To convert a resin system into useful products
media on the preform or inclusion of a runner it must be cured or cross-linked by chemical
system in mold design can alter the mold fill- reaction into a three dimensional network. The
ing pattern. This is helpful in reducing reaction usually involves either a step growth
injection pressure or displacing air. polymerization, a chain growth polymeriza-
All resin movement must be accomplished tion, or a combination of both. The
within the time allowed before the onset of accompanying rheological change in the
gelation. Additionally, the resin injection process is shown in Fig. 20.9 (Macosko, 1989).
process should not cause movement of the The curing step constitutes a major portion
reinforcement and should be done at low pres- of a typical RTM cycle. During curing, rheo-
sure so that the mold will maintain its shape logical property changes of the resin system
without requiring massive backing. and heat transfer between the mold wall and
Vacuum may be used to facilitate filling the the resin dictate the cure cycle.
mold and simultaneously assist in removing Simultaneously, modulus and strength begin
air from the laminate. This requires good mold to build up at a rate depending on the type of
sealing and the use of a vacuum pump. resin and catalyst used and the chemical kinet-
Vacuum up to 740-760 mm Hg (29-30 in Hg) ics of the resin system. Curing can continue
has been reported in assisting RTM mold fill- after the part is demolded.
Matrix
Time
Fig. 20.9 Rheological change during the curing process. (Reproduced from Macosko.)
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
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. 20.12 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
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
PP Slnglegnfr s2nglegate
pressure. If only one injection gate is used, the 20.11.6 MOLD FILLING WITH RESIN DELIVERY
pressure under the constant flow rate bound- SYSTEM
ary condition will reach a maximum.
Compared to the sensor controlled injection Conventionally, an injection port serves as a
with four gates, the pressure at the gate is only point source where fluid is pumped. The
48% of the pressure reached by the single gate drawback of a point source is that the pressure
injection. In terms of filling time, the two value tends to rise rapidly to an extent that
molds are subject to a constant pressure could be detrimental to the preform. By
boundary condition. Results show that the extending the point source into other forms
mold filling for the single gate injection takes proves to be effective in reducing the pressure
almost three times that for the sensor-con- build-up. To implement this concept, one can
trolled injection. use multiple point sources as discussed previ-
An example is shown in Fig. 20.17, which ously. A line source has been popular in
elaborates on how one can utilize a sensor to vacuum assisted RTM because of its ability to
eliminate a dry spot during molding. In Fig. fill the mold using 1 atm of pressure.
20.17(a), where no sensors are implemented A line source may be modified to serve as a
and the injection gate is at the location as runner by allowing more fiberfree space in this
shown, a dry spot will appear in the middle of delivery system. This is the channeling effect,
the part. However, an extra gate in the middle now used to advantage in mold filling. Further
as shown in Fig. 20.17(b), if triggered at the extending the fluid source may possibly yield
point the fluid reaches the midframe, can pre- a 'plane' source. The actual implementation of
vent this void, as indicated by Fig. 20.17(c). a plane source may include a high-porosity
This feature is incorporated in a numerical layer in the stack-up of the reinforcement
simulation such as LIMS and can be systemat- mats. The layer can possess a permeability
ically studied for a given geometry to decide several orders higher than that of the fiber pre-
the best strategy when in situ sensing capabil- form. The result of this is a three-dimensional
ities are incorporated in the fabrication phase mold flow with fluid propagating rapidly
(Liu et al. (1995)). through the spreading plane or surface first
t Vent 1Vent
Fig. 20.17 Use of sensors to eliminatedry spots: (a) no sensor; (b) extra gate sensor; (c) void prevented.
454 Resin transfer molding
followed by percolation of the resin through of Application Support Laboratory, Fiber Glass
the thickness of the preform. For three-dimen- Reinforcements Division, Vetrotex CertainTeed
sional flow, venting the mold may become less Corporation, 1991.
Chou, T.W., 1992, Microstructural Design of Fiber
intuitive. In practice, vacuum assistance can Composites, Cambridge: Cambridge University
provide part of the solution. Press, UK.
Isorca Inc., 1992, Introduction to Resin Transfer
Molding, Society of Plastics Industry,
20.12 CONCLUSIONS Composites Institute.
Fong, L., J. Xu, and Lee, L,J., 1994, Analysis of ther-
Resin transfer molding is a practical process moformable fiber mat preforming in liquid
for much of the composite industry. The qual- composite molding: study of deformation
ity of RTM molded parts can equal that by modes and reinforcement characterization,
conventional autoclave processes and its eco- Polym. Comp., 15, 134.
nomic advantages are obvious. Although the Fong, L. and Advani, S.G., 1994, The role of drapa-
underlying principles of RTM appear at first to bility of fiber preforms in resin transfer
be simple, this is often not the case. The chal- molding, Amer. SOC.Comp., Proc. 9th Tech. Conf.,
1246.
lenge for RTM is to bring together the Fong, L., and Lee, L.J., 1994, Analysis of fiber mat
disciplines of preforming, mold design and preforming in liquid composite molding, pre-
process development with existing fibers and forming induced effects on mold filling, J. Reinf.
resins. This can be best achieved through an Plas. Comp., 13, 637.
understanding of the physics governing RTM Fong, L., Varma. R.R. and Advani, S.G., 1994, Use of
and by current simulation technology. process models and simulations as design tools
in molding polymer and polymer composites,
The Pacfic Conference on Rheology and Polymer
REFERENCES Processing (PCR’94), Kyoto, Japan.
Fong, L. and Advani, S.G., 1994, The role of dual
Advani S.G., Bruschke, M.V. and Parnas, R., 1994, permeability of fiber preforms in mold filling
Resin Transfer Molding, in Flow and Rheology in simulation of resin transfer molding, Proc. Zst
Polymeric Composites Manufacturing (Ed S.G. Intern. Conf. Comp. Engng, New Orleans, LA, 17.
Advani,) Amsterdam: Elsevier Publishers, Ch Fong, L., Liu, B. and Advani, S.G., 1995, Modeling
12, pp. 465-516. and simulation of resin transfer molding with
Advani S.G., Bruschke, M.V. and Liu, B., LIMS 3.0: flexible mold walls, 50th Ann. Conf., SPI, Comp.
Liquid Injection Molding Simulation, User Inst., Session 3-A.
Manual, CCM Report, University of Delaware, Krolewski, S. and Busch, J., 1990, The competitive
Newark, DE 19716. position of selected composites fabrication tech-
Bruschke, M.V. and Advani, S.G., 1994, A numerical nologies for automotive applications, Proc. 35th
approach to model nonisothermal, viscous flow Intern. SAMPE Symp., pp. 1761-1771.
with free surfaces through fibrous media, Intern. Lee, S.M. International Encyclopedia of Composites,
J. Num. Methods Fluids, 19,575-603. 1991, New York: VCH, 1991.
Bruschke, M.V. and Advani, S.G., 1991, RTM: Filling Liu, B., Bickerton S. and Advani, S.G., 1994,
simulation of complex three-dimensional shell- Modeling and simulation of RTM - venting and
like structures, SAMPE Quarterly, 23(1), 2-11. void formation, Proc. Intern. Conf. Comp. Engng,
Bruschke, M. and Advani, S.G., 1990, A finite ele- p. 17.
ment/control volume approach to mold filling Lucey, A.D. and Carpenter, P.W., 1992,J. Fluid Mech.,
in anisotropic porous media, Polym. Comp., 11, 234, 121.
398-405. Macosko, C.W., 1989, RIM, Fundamentals of Reaction
Bruschke, M.V. and Advani, S.G., 1990, Mold filling Injection Molding, New York: Karl Hanser
of generalized newtonian fluids in anisotropic Verlag.
porous media, Transport Phenomena in Material Mosher, I?, 1995, An introduction to vacuum-
Processing, ASME Trans. HTD 132, 149-158. assisted resin transfer molding (SCRIMP), 50th
Carvalho, R.L., Personal communication, Manager Techn. Conf., SPI, Comp. Inst., Session 8.
References 455
Pillai K. and Advani, S. G., 1994, The role of dual Vanwest, B.P., Pipes, R.B., Keefe, M. and Advani,
permeability of fiber preforms in resin transfer S.G., 1991, The draping and consolidation of
molding, Proc. 9th Am. SOC.Comp., p. 17. commingled fabrics, Comp. Manufng, 2, pp.
Potter, K.D., 1979, Composites, lg 161. 10-21.
Ranganathan, S., Wise, G.M., Phelan, F.R., Jr., Young, W.B., Rupel, K., Han, K., Lee, L.J. and Liou,
Parnas, R.S. and Advani, S.G., 1994, A numeri- M.J., 1991a, Polym. Comp., 12, 30.
cal and experimental study of the permeability Young, W.B., Han, K., Fong, L., Lee, L.J. and Liou,
of fiber preforms, Proc. 10th ASM/ESD Adv. M.J., 1991b, Flow simulation in molds with pre-
Cornp. Con$, 309. placed fiber mats, Polyrn. Comp., 12,391.
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.
FILAMENT WINDING 21
Yu.M. Tarnopollskii, S.T. Peters, A.I. Bed’
TENSIONING
ARTICLE
W
SEMIFABRICATED
MATERIAL
INITIAL STRESSES
process may include specifymg fiber tensioning to the geodesic line, against the static friction or
and extra compaction pressure (internal or viscous resistance of the binder, or mechanical
external), or geometric parameters (configura- obstacles, such as pins, to keep the filaments on
tion of reinforcement lay-up along the length non-geodesic curve.
and through the thickness of the article). The Larger components will result in changes to
reinforcement configuration is determined by the system of residual stresses. To calculate,
the design requirements of the article and can analyze and control the values of residual
be achieved with high accuracy. Winding, as a stresses, it is necessary to find the interrelation
way of obtaining preset reinforcement configu- between the winding parameters (mainly ten-
rations, is restricted in terms of available sioning) and the properties of the finished
winding angles. Filament lay-up on geodesic product. By controlling filament tensioning
lines on an external surface is easy. (A geodesic and the reinforcement configuration, it is pos-
line is a line linking two preset points of the sur- sible to control strength and stiffness of the
face along a shortest path.) In non-geodesic material, residual stresses and pressures on
winding, filament tension can shift the filament the mandrel or previous layers.
458 Filament winding
shrinkage analogous to chemical and thermal Winding of more complex shapes aggra-
shrinkage in the curing and cooling of ther- vates the problem of pattern closure. To obtain
mosetting plastics. The analysis of winding a continuous layer, it may be necessary to vary
techniques and general engineering winding the bandwidth during winding. Also, it may
theory for thermosetting plastics are surveyed be advantageous to vary the fiber volume and
in detail6. thickness by alternate compaction techniques.
t is the basis vector directed along the tangent of pressure. The pressure p on the convex sur-
to the curve and P is the normal surface reac- face comes from tension of the wound
tion related to a length unit of filament. material and is unique to filament winding; p
Equation (21.l) describes the redistribution = P / b , where b is the width of the material to
of tension along the filament length due to fric- be wound. For the simple case of circumferen-
tion, viscous resistance from lower-lying tial winding of cylinders with a radius R, this
circuits, viscous resistance of above-lying cir- pressure is calculated according to the for-
cuits and inertial effects. Equation (21.3) mula:
represents the force, which tends to shift the fil-
N
ament onto a geodesic line and viscous
resistance of both the lower-lying and above-
P=m (21.5)
lying circuits. In the simplest case of the If this pressure is insufficient (if R is high), it is
friction law I Fg I 5 kP where k is the friction necessary either to increase the fiber tension to
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 of the fiber band or tows or to employ addi-
relationship can be derive& tional methods. For helical angle winding (at
an angle t to the axis) of a cylinder, it follows
-Rn
=tanv<k (21.4) from equation (21.2) and the relationship
Rg
The ultimate permissible angle of geodesic Rn = Rc = R / sin'p
deviation is equal to v Iarctan k.
To obtain a monolithic (fully compacted) that
material with successful chemical processes
(matrix crosslinking) in any type of composite p = N sin2
- (21.6)
bR P
processing, some pressure must be maintained
through the completion of the curing stage of The greater the angle deviation from the cir-
the matrix. There are several potential sources cumferential the less the compaction pressure
Technology of winding 461
pattern is generated (Fig. 21.4). This process instead of translation motion of a wind eye,
enables the fabrication of vessels with differ- there is a reciprocating motion along a curvi-
ent sized polar openings or closed ends. There linear trajectory. One version of winding with
are a number of alternative techniques. First, a whirling arm-type winder is when a wind
the wind eye executes a rotational motion in eye rotates and moves along some curvilinear
two planes. It is a very complex technique and trajectory.
is used only for unique articles. Second, the Fourthly, there is a group involving two
rotational motion of the mandrel is in two rotational motions executed alternately (a pla-
planes (Fig. 21.5), sometimes supplemented by nar-polar winding). Applications of this
a reciprocating motion of a wind eye or turn- method include chord winding (Fig. 21.6) of
ing of its head. composite flywheels.
3 1’
Fig. 21.8 6-Axis computer controlled filament winding machine. Machine motion indicated by arrows.
(Courtesy of McClean Anderson, Inc.)
Fig. 21.9 20-Spindle golf shaft filament winding machine. (Courtesy of ENTEC, Salt Lake City, UT, USA.)
Water-soluble mandrels are primarily used account these fields, their analysis, develop-
in rocket motor cases and pressure vessels ment and application of the methods of
where mandrel removal through small open- controlling the fields are important aspects in
ings is desired. The sand/polyvinyl alcohol the manufacturing of defect-free structures,
(PVA) mixture is cast into female molds that especially thick-walled components.
have preassembled components, such as insu-
lation, wind axis, lightening tubes and polar 21.4 THIN-WALLED STRUCTURAL
bosses. The sand mixture is cured and the two ELEMENTS
mandrel ends are assembled and bonded.
Spider/plaster mandrels are often used to pro- 21.4.1 TYPICAL ARTICLES
vide a high-tolerance mandrel surface. The
plaster is cured, then overwrapped with tetra- The basic problems in the design and manufac-
fluoroethylene tape or other separator film. ture of thin-walled composite shells are related
Following cure, tooling is removed, the plaster to the optimization of shape and reinforce-
is chipped or washed out and the release tape ment configuration^'^. Fibrous composites
is removed, leaving the desired inside dimen- show their best performance under tensile
sions. Metal-supported plaster is generally load acting strictly along the fibers, while the
used for relatively large parts of 3-6 m. matrix serves only to distribute the load uni-
Segmented collapsible mandrels, used for long formly among fibers. A rational reinforcement
tubes, are specialized and expensive, but the configuration for a thin-walled composite
advantages of their reusability and the continu- structure is similar to that of a guyed structure
ous winding process renders expensive tooling working under the same loads. The winding
worthwhile for high-production applications. technique is a natural process and is the most
The main considerations for mandrels are widespread production process for thin-
stiffness, hardness, strength, coefficient of walled structural elements.
thermal expansion and heat resistance. The most widely used elements are cylin-
Mandrel removal from the part is equivalent drical shells, such as pipelines which operate
to application of the pressure of opposite sign under a combination of external or internal
and new shearing stresses at the interface pressure, bending and axial tension-compres-
between the part and the mandrel and must be sion. Cylindrical sections of missiles,
done with some care. cylindrical shells with semi-spherical closed
ends used as tanks or pressure vessels,
toroidal shells for electrical applications; and
21.3.7 RESIDUAL STRESSES
conical shells, which include nose fairings of
The residual stresses caused by the tension of aircraft and rocket motors, are also common.
the reinforcement and compaction undergo
essential changes during elevated temperature
21.4.2 SHAPE CONFIGURATIONS OF WOUND
exposure. The thermoelastic stresses as a result
PARTS
of the difference in thermal expansion of the
mandrel and composite article and the Filament-wound shapes generally include
anisotropy of thermal expansion of composite cylindrical, spherical, conical, or dome-end
in a statically indeterminable type of structure configurations.These bodies of revolution best
are added to the system of residual stresses. exploit the advantages of high-speed winding.
The majority of wound articles end up with Spherical shapes contain the maximum
these stresses. The resulting fields of residual possible volume with minimum surface area.
stress in wound articles are comparable in Hence this shape is commonly used for pres-
scale to fields of allowable stresses. Taking into sure vessels. Because the radius of curvature is
Thin-walled structural elements 467
equal in all directions, the best reinforcement 21.4.3 SPECIFIC FABRICATION FEATURES
pattern is an isotropic combination of wind
angles. This pattern is readily obtained by One of the main problems in obtaining the
winding a series of great circles, each stepped designed shape for thin-walled composite
out from the preceding pattern by the width of structures is the problem of warpage. The
one winding band. bending stiffness of structure is proportional
Cylinders and shafts can be wound on a to the cube of the thichess, while residual
cylindrical mandrel by providing an adequate stresses, as a function of thickness, increase
pattern reversal length at each end. The cured more slowly. Therefore, warpage can be a
part can be removed from the mandrel by problem with thin-walled articles. The reasons
using a stripping die. Winding patterns consist for warpage are :
of hoops or helical patterns as desired to react Inhomogeneity of material properties in
to design loads. For torsion-type loading, k45" structures can be ascribed to local imperfec-
helicals provide the most efficient load path. tions, inaccuratewind angles, inhomogeneity
Thick-wall effects are a major consideration in of temperature field during cure and
the design of composite shafting. changes in binder composition or volume
With flat cylinders, the width is just a frac- within the wall.
tion of the thickness. These parts can be Mandrel removal; pressure and shearing
fabricated using hoop windings alone. A typical stresses on the interface between the man-
application is in flywheels. Thick-wall effects drel and article can be distributed
and delaminations are potential problems that nonuniformly as a result of different ther-
must be carefully considered. Fabrication tech- moelastic behavior of the mandrel and
niques using programmed winding tension, composite article, especially for complex
high strain resin systems and low temperature shapes.
cures help to overcome these problems. Anisotropy of composite shrinkage and dif-
The combination of cylinders with domes ferent relaxation rate of components of
is typical of rocket motor cases and pressure residual stresses can cause inhomogeneity
vessels. The winding patterns and dome and anisotropy of relaxation characteristics.
shapes must be carefully chosen to prevent
fiber slippage and to react adequately against In the production of thin-walled articles it is
the pressurizing forces on the domes. Ideal, most important to have a high degree of wind
or isotensoid, domes or end closures for fila- angle fidelity.
ment-wound vessels have a general surface
of revolution that requires a numerical solu- 21.4.4 SANDWICH AND COMPOUND THIN-
tion. The two types of dome contours WALLED STRUCTURES
generally considered are geodesic (constant
stress) and polar (planar) ones, each of which Sandwich structures incorporate a low density
requires its own derivation. The only geomet- filler to increase bending stiffness to increase
ric variables affecting the dome shape are the bending moment of inertia. Foam and honey-
radius of the cylindrical portion of the pres- comb plastics are most often used as low
sure vessel and the radius to the center of the density fillers. These materials serve not only
filament band at the polar opening. There are to increase the separation between the load-
several winding considerations. Winding pat- bearing layers, but also to act as sound and
terns must be stable, the dome must be heat insulation. Sandwich structures are
shaped with properly sized openings and widely used in aviation and construction.
there must be balanced stress fields in a cylin- Typical design problems are associated with
drical section. optimization of the thicknesses of load-bearing
468 Filament winding
layers and the filler and selection of the rein- material properties. To define these changes, a
forcement angles. When winding the outer simplified hypothesis about the progression of
load-bearing layer the winding tension has to the stress state has been developed.
be low enough to avoid damage to the low Experiments with tensometric (instru-
density filler. Stress distribution during wind- mented) mandrels have served as an impetus
ing depends essentially on the compliance of for the development of an engineering theory
the mandrel6.In sandwich structures the outer (Fig. 21.11). The distinction between the wind-
load-bearing layer of the filler serves as the ing process of a semifabricated composite
mandrel for the outer skin lay-up. article and that of an isotropic metallic tape was
made by examining an 'integral force parame-
ter' - the dependence of the pressure - on the
21.5 THICK-WALLED STRUCTURES
mandrel related to the number of circuits n
being wound. A sigruficantpart of the applied
21.5.1 ENGINEERING THEORY OF WINDING
pressure is consumed in the deformation
The development of engineering winding process of the lower-lying circuits. By using
mechanics must involve the study, description instrumented mandrels it has been possible to
and sequential consideration of the peculiari- evaluate the variation in winding pressure for
ties of composite behavior under loading every stage of the process. In the curing
perpendicular to the plane of reinforcement. process, constant pressure on the mandrel is of
During the winding process the physical- special interest and makes it possible to
mechanical properties of the composite develop several variations of the theory of
undergo great changes. The composite proper- residual stresses, omitting the polymerization
ties remain linear and practically do not change stage. It establishesthe dependence of the resid-
in the reinforcement direction. The compliance ual stresses d,and 0 : on the geometry of the
in the transverse direction is essentially nonlin- article h / R , material anisotropy p2 = E, / E ,
ear during the stages of winding, heat build-up winding angle p(x, Y), the number of circuits n,
and curing of the article and can vary by three winding tension N(x, r ) and parameters of the
orders. The possibility of applying a universal curing process (q is contact pressure, T is tem-
rheological model to such a material is beyond perature and t is curing time).
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
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
required in concert with multiple compaction loads. The advantage of this technology has
and cure cycles due to the thickness of the ves- been demonstrated in high resistance to
sel. Composites combining low density, impact loads. The impact failure is localized
stiffness and high strength with superior within several spatial cells of the structure.
sound damping properties are very promising
materials for submarines and deep-submer-
21.6.5 THICK-WALLED STRUCTURES LOADED
gence devices. Filament wound composites
IN TORSION
offer cost savings in terms of materials and
process both for primary and secondary struc- Progress has been made in the development
tures on submarines. of thick-walled wound rods loaded in torsion.
A characteristic example is shafting for
shipd5. The advances in the mechanics and
21.6.3 NETTED-RIBBED SHELLS
technology of winding of thick-walled large-
The middle layer of a sandwich composite scale elements have substantially solved this
structures is usually fabricated by an alterna- problem. It is well known that fibrous com-
tive technology. Winding technology can be posites behave poorly when loaded in torsion.
used not only to manufacture facing layers, Ways of increasing load-carrying capacity
but also for middle layers by winding a net- involve increase in shear strength of a ply and
work of helical ribs. Netted-ribbed composite the adherence to the optimal law of shear
shells (Fig. 21.16) are widely used in aerospace stress distribution over the radius of a rod.
because of low dead weight, a9 antenna Increase in the strength of a ply is accom-
frames, solar batteries, etc.I4. plished by properly selecting the optimal
angle in the plane of fiber lay-up and the
number of starts and crossovers during wind-
21.6.4 WINDING WITH BRAIDING
ing. Shear strength in torsion zuLT= 400 MPa
Winding with braidingi0 allows the manufac- has been attained and a shaft was fabricated
ture of articles of complex shape with with wall thickness equal to the inner radiusi6.
sophisticated reinforcement techniques. These Thick-walled wound structures can also be
structures possess high resistance to bending, manufactured by multidirectional braiding of
torsion, tension, compression and to local 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
Fig. 21.16 Carbon-epoxy filament wound isogrid hyperboloid can be governed by the wind
space structure. angle of the applied fibers, which are originally
474 Filament winding
Fig. 21.17 A full-scale specimen of the hull of underwater vessel of reinforced plastic before test in a pres-
sure chamber19.
References 475
FiberPkementHead r
T i Restart Rollers
ControlledHeat
tow to independently conform to the surface normal to the surface while the machine is
of the part. For example, when the head lami- laminating tows. The machine also has 24 pro-
nates a curved path, the outer tows of the fiber grammable electronic bidirectional tensioners,
band pull more length than the inner tows. which are mounted in a creel. These tensioners
A rolling compaction device, combined provide individual tow payout and maintain a
with heat for tack enhancement, laminates the precise tension. The fiber placement head is
tows onto the lay-up surface. This action of mounted on the end of the wrist. The head
pressing the tows onto the work surface (or a precisely dispenses, cuts, clamps and restarts
previously laid ply) adheres the tows to the individual prepreg tows.
lay-up surface and removes trapped air, mini- To increase productivity some machines are
mizing the need for vacuum debulking. equipped with dual mandrel stations (Fig.
Figure 22.2 is a diagram of a Cincinnati 22.3). This setup allows two sets of lay-up
Milacron 'Viper' Fiber Placement System tools to be placed on the machine, ensuring a
(FPS). This system has seven axes of motion constant supply of work for the head. During
and is CNC controlled. The machine consists routine manual operations such as hand lay-
of three position axes (carriage, tilt, crossfeed), ing small plies, inspecting plies, or vacuum
three orientation axes (yaw, pitch, roll) and an debulking on one part set, the head simply
axis to rotate the mandrel. All of these axes are shifts to the other mandrel and picks up the
necessary to make sure the processing head is program where it left off.
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
22.4 PLY SHAPE length. The exterior ply boundaries can the
Fiber placement is used to fabricate simple extended in the areas where there are mini-
parts such as flat panels or complicated parts mum cut length problems. These extended
such as an inlet duct, which is square on one areas can later be cut off. Interior plies must be
end and round on the other (Fig. 22.6).The ply reshaped to match the fiber angles.
shapes can be any size or geometric form. A The designer must also consider the end
ply shape can also include interior ply bound- locations of the tow. Each tow is cut at a 90"
aries which create holes. angle; because of this the ending angle of the
When generating ply shapes, the designer tows may not match the angle of the ply
must consider the shortest tow length the boundary. Figure 22.8 shows three different
machine can lay down. This length is the dis- ply boundary conditions for a 45" ply. The
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 Outer Pb bunday 45'
Fig. 22.6 Fiber placing an inlet duct. Fig. 22.7 Ply boundary adjustments.
aircraft structure. The black areas are the areas amount the tows can cover the ply bound-
that cannot be fiber placed because the length aries is specified by the percent of ply
of the required tow is less than the shortest boundary coverage. A 100% value is typically
allowable fiber length. These areas could be used on the larger ply boundaries that are
laid in by hand, or the ply shape could be later trimmed to shape. This makes sure that
adjusted, as in Fig. 22.7, so that the required all of the fibers go to the edge of the bound-
fiber length
" is longer" that the shortest cut arv. A 50% value is used on interior plv I d
482 Fiber placement
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
TRIANGULAR GAP
\
/'
,' 0% OVERLAP
/'
a
,'
'.
'. '.
u
50% OVERLAP
TRIANGULAR OVERLAP-/'\ /
u
100% OVERLAP
'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
SURFACE NORMAL
2 COLLISION POINT
NO COLLISION AVOIDANCE
SURFACE NORMAL 7
C"
1
'-,a I-
I O " COLLISION AVOIDANCE
TOOL SURFACE
7
contact with the surface. The part can still be describing the tool surface matches the actual
fiber placed but the number of tows in the tool surface. It also verifies that the transfor-
fiber band should be reduced to match the mation matrix, used to associate the part's
compaction line width. On the concave sur- electronic data coordinate system to the tool's
face the radius should be increased to allow position in the machine's coordinate system, is
the compactor to contact the surface, other- correct. This is accomplished by watching the
wise the tows will bridge over the small compactor as it follows the part surfaces. Dry
radius of curvature. running also verifies that collision avoidance
worked properly.
Further reading 487
The next step in first article inspection is to scale and lay it on the ply normal to the fiber
load the machine with tows and fiber place direction.All the gaps along the 30.5 cm (12 in)
each ply. After each ply is fiber placed, the ply distance are measured and summed. If this
is inspected for the correct fiber angle, ply loca- value exceeds a pre-determined design crite-
tion, band-to-band overlap and for missing rion the area is reworked.
tows. The easiest way to inspect for fiber angle
and ply location is to have a Mylar template FURTHER READING
that has the ply boundary plotted onto it and a
line for the fiber angle. The template needs to Barth, James R. 1990. Fabrication of Complex
be located with alignment marks or pins that Composite Structures Using Advance Fiber
Placement Technology. 35th Intern. SAMPE
are part of the tool. A Mylar template will not Symp., 2-5 April 1990.
work on surface geometries with curvatures in Enders, Mark L. and Hopkins, Paul C. 1991.
both directions. For these geometries, a formed Developments in the Fiber Placement Process.
inspection tool should be fabricated. 36th Intern. S A M P E Symp., April 1991.
After the first article inspection, subsequent Enders, Mark L. 1991. The Fiber Placement Process.
parts need to have each ply visually inspected Intern. Conf: Comp. Mater., (ICCM/8), July 1991.
for excessive gaps and overlaps, lost tows, Evans, Don O., Vaniglia, Milo M. and Hopkins, Paul
C. 1989. Fiber Placement Process Study. 34th
twisted tows, wrinkled tows and bridging Intern. S A M P E Symp., 8-11 May 1989.
tows. Table 22.1 is an example of a typical in- Evans, Don 0. 1993. Design Considerations for
process inspection criteria. Another criterion Fiber Placement. 38th Intevn. S A M P E Syrnp.,
used to evaluate gaps is to take a 30.5 cm (12in) 10-13 May 1993.
PULTRUSION 23
Brian A. Wilson
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.)
The basic process 489
that it takes advantage of the strength of the curing energy in the heated die to cure the com-
longitudinal fibers in the section to pull the posite into a hard structural product and using
extruded shape through the forming die and the resulting shape as a unidirectional strength
the heated curing die to create a constant cross element for commercial structures.
section structural element from a composite The primary advantages of pultrusion are
materials system. Hence the name pultrusion. as follows:
Use of this-processhas now expanded both in
the USA and around the world with many ~roductioniscontinuous~
manufacturers equipped to produce the simple 0 labor requirements are low;
structural elements which are the main pultru- 0 material scrap rate is low;
sion products. The process was labeled for the 0 the requirement for support materials is
first 30 years or so of its existence as a com- eliminated, i.e. breathers, bleeder cloth, sep-
mercial production method. This was owing to arator film, bagging film, edge tape.
the nature of the method, using longitudinal
fibers and a simple thermoset resin system to
23.2.1 VARIATIONS IN PROCESSING
produce a structural shape which had its pri-
mary strength in the longitudinal direction and The original process of pulling a bundle of
properties in the transverse and third axis unidirectional fibers through a curing die
relating only to those of the resin system. The remained without variation until the middle
ability to incorporate three-dimensional of the 1960s. At this point, pultruders, both in
strength first occurred in the mid 1960s when it Europe and the USA, developed the process of
became possible to include layers of mat/fab- adding fabric in strip or sheet form and fiber
ric and circumferentially wound layers of fiber mat to the pultrusion system in order to pro-
both w i t h the body and on the surface of the vide transverse strength and shear strength in
structural shapes. Multi-directional reinforce- the corner sections of complex pultruded
ment was used extensively starting in the shapes. In addition, the concept was devel-
1970s2,3 . These developments, plus the intro- oped for a filament winding head to be added
duction of thermoplastic resin matrices, have to the pultrusion machine to provide a hoop
brought the pultrusion process into the manu- wrap around a pultruded form. This process is
facturing arena of the aerospace, defense and known as 'pull winding' and is primarily used
aircraft businesses as a relatively inexpensive with tubular or rod shapes. It is not feasible to
and repeatable method of producing a constant add the filament winding process to a struc-
cross-section structural element48 *. tural shape that has a concave curvature, such
In this chapter, the basic process, variations as angles, channels and I-beams. A typical
on the process, pultrusion equipment, materi- process of pull winding is shown schemati-
als including fiber, fabric, resin matrices, cally in Fig. 23.212.
additives, tooling, curing, structural connec- During the 1970s, the concept of pull form-
tion methods, equipment manufacturers, ing was developed by Brandt Goldsworthy.
pultrusion fabricators and potential markets Three versions of this forming process were
and applications will be reviewed"". developed.
The first was actually named 'curved pultru-
sion' by Goldsworthy Engineering. The method
23.2 THE BASIC PROCESS
was developed under a NASA contract and
The basic pultrusion process as originally con- resulted in a pure, constant radius section with
ceived consisted of creating a cured composite a constant cross section. A curved die was used,
shape by pulling a bundle of resin impregnated with a reduced radius, smaller than the
fibers through a heated die, providing sufficient required part radius. This allows for a degree of
490 Pultvusion
COUNTER-ROTATING
MANDREL
AND
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
Pull forming 491
Fig. 23.3 Curved pull forming process. (Courtesy of W. Brandt Goldsworthy and Associates Inc.)
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
Fig. 23.4 Schematic of pultrusion process. (Courtesy of W. Brandt Goldsworthy and Associates Inc.)
Process equipment 493
mobile system. The casters are provided with a plied on 'way wound' packages on standard
foot locking device to enable them to be locked diameter cardboard cores. A typical carbon
in place when this is required. The glass roving fiber package mounted in a payoff creel is
is pulled vertically from the package through shown in Fig. 23.5. These fiber packages are
ceramic-lined holes in the shelves above. The designed to provide fiber payoff from the exte-
roving is collected above the creel and turned rior of the fiber package and hence avoid
90" by means of a ceramic textile type thread twist. While fiberglass is normally supplied in
guide and then moved forward to the material the heavy center pull spools, it can also be
accumulating section just prior to the resin obtained in the outside payoff type package.
bath and forming die. A series of ceramic All of the cardboard cores are a standard three
guides or rollers can be provided in the fiber inch diameter with the exception of the aramid
path in order to tailor the tension in the fibers which is 90 mm (3.5 in) inside diameter.
to the required level. The pulling of fiber from This style of package requires the use of a
the center of the package will automatically multiple spindle creel design in which the
insert a twist in the fiber as it is led into the pul- packages are oriented normally horizontal but
trusion machine. To eliminate this, some usually with a slight upward camber. Creels
fiberglass rovings are provided in a center pull are available with package positions up to
twistless condition where the natural twist has 1500 or 2000 on a single creel or combination
been off-set by a 'built-in' reverse twist. of creel frames. A loaded multiple spindle
Continuous fibers of fiberglass, carbon, creel is shown in Fig. 23.6. Ceramic guides are
aramid and polyethylene are normally sup- used to move the fibers to the front of the creel
Fig. 23.5 Carbon fibre spool on package holder with quick braking action. (Courtesy of Texkimp Ltd.)
494 Pulfrusion
materials remain in the correct relationship to bath is frequently used which matches the pre-
each other and are placed in the correct zone of form shape or orientation of materials which
the pultruded product according to the prod- pass through it. These types of tailored chan-
uct design requirements. This can be best nels or baths can also be used to orient the flat
accomplished by the use of orifice plates, creel materials properly. This method permits the
cards combs and rollers (grooved and flat) to resin impregnation to take place without mov-
precisely and accurately place all the materials. ing the reinforcements away from their
The materials commonly used for these guides optimum path or shape.
and rollers are primarily titanium oxide
ceramic, stainless steel, tool steel alloys and
23.4.3 VERTICAL PULTRUSION
chrome plated steel. These materials are also
used for the various rollers associated not only The vertical pultrusion process should be men-
with guiding the sheet materials but also with tioned at this point since the primary difficulty
controlling them during their passage through in creating a vertical pultrusion is the place-
the resin impregnation zone. ment and use of a resin bath. In the
arrangement for vertical pultrusion the equip-
ment used is essentially similar to that for the
23.4.2 RESIN IMPREGNATION
horizontal methodI8.Most equipment operates
Virtually all pultrusion processes utilize a in the vertical position with the exception of the
resin impregnation bath to facilitate the resin bath and roving creels which are generally
impregnation of the resin into the fiber struc- positioned horizontally and the roving is fed in
ture. The position of the resin impregnation the regular manner, horizontally through the
bath in the production line can be varied and resin impregnation bath. This bath is located
the manner in which the resin is applied to the above the entrance to the forming die and the
fiber can have many different versions. A resin fibers exiting from the bath are turned 90"
dip bath is most commonly used. During this across a roller and then proceed vertically into
process the fibers are passed over and under a the forming die. The advantage of using this
series of rollers or bars which both spread the vertical procedure is that a uniform arrange-
fiber to more easily accept the resin and also ment of impregnated fibers can be achieved
provide a massaging effect which 'kneads' the across the section being formed. The effects of
resin into the fiber bundles and structure. gravity are removed from the fiber arrange-
The wetting speed of the fibers depends ment. During the horizontal process, gravity
upon their pretreatment and on the resin for- plus any nonuniform tensioning across the
mulation. Wetting is also affected by the type fiber group will result in some fibers sagging
of sizing agent on the fiber, the possible pres- under their weight with resin and hence not be
ence of remaining lubricant on woven fabric properly located as they enter the forming and
and finally the type of binder which is used in curing dies. An additional advantage of the ver-
mat and veil products. The resin bath is uni- tical process is that it is possible accurately to
formly used for products that utilize all roving locate the internal mandrels whch are neces-
in their construction or for products that are sary for hollow shapes and tubes. This is
easily formed from the flat fiber ply which particularly important in the fabrication of
emerges from the resin bath. However, in heavy, thick wall tubes. In the horizontal
many of the more sophisticated products process, these internal mandrels will frequently
which are now made from pultrusion, it is deflect under their own weight and cause a
impractical to dip all of the materials in the nonuniformity of wall thickness around the
resin bath. When vertical mats are required or hollow profile or tube. In addition, the vertical
hollow profiles are produced, a tailored resin process allows the use of several different fiber
496 Pul trusion
entry points to the forming process with multi- fabricators to provide pultruded tubular struc-
ple resin baths. In the horizontal procedure, the tures both round and square23,24. The process
multiple entry points have to come from the side combines the standard continuous unidirec-
of the main fiber path and it is not as easy to coa- tional fibers of the pultrusion process with
lesce the fibers into a single merged preform. hoop wound continuous fibers. The longitudi-
nal fibers are used for axial and bending
resistance while the hoop fibers are used for
23.4.4 USE OF THERMOPLASTIC MATRIX
hoop tension and compression resistance. The
RESINS
combination of the two processes of pultru-
Thermoplastics cannot be applied to roving sion and winding provides virtually unlimited
easily using the standard resin bath, even with possibilities. However, the increasing com-
heating. Thermoplastic resins impregnated on plexity of the process limits these
roving are generally available as preimpreg- combinations. Normally, longitudinal fibers
nated (prepreg) materials and are supplied by are positioned at the inside and outside sur-
specialty companies who are experts in the faces of the tube with one or two hoop wound
prepreg process. Thermoplastic matrices layers positioned internally in the tube wall.
improve the toughness of the composite and These hoop wound layers are not truly 90"
this is their major end use advantage. In gen- hoop wound layers because of the slightly
eral they have high softening temperatures helical nature of the winding and the lateral
and high physical properties coupled with a movement of a wound roving, one band width
low fluid viscosity in their melted form. The of advance with each circumferential pass.
prepregs are normally prepared using solvents Depending on the diameter of the tube, the
and this provides some difficulty against envi- winding angle is typically anywhere from
ronmental regulations in order to remove and 80-87". The winding can be performed in
dissipate the majority of the solvent. Some sol- both clockwise and counterclockwise direc-
vent has to be retained in the process in order tion and in addition to the hoop tension and
to have the material be sufficiently pliable for compression resistance can also provide a
machine and manual handling. In addition to degree of torque strength to the tubing.
the improved toughness of the thermoplastic Single and double head pull winders are used
composite, an important advantage of thermo- with these techniques. The pull winding
plastic pultrusions is the ability to heat and process is shown in Fig. 23.2 and the proce-
reshape the product after f ~ r m i n g ' ~ - ~ ~ . dure for the use of these systems is self
explanatory. The important control feature of
the pull winding process is the control of the
23.4.5 RESIN BATH LIFE
winding speed and position with respect to
In a continuous pultrusion process, the pot life the linear motion of the pultruded form
of the resin should be several days. However, through the machine. This is achieved by
if the volume of the resin bath can be kept sensing the speed of the longitudinal motion
small in relation to the resin being withdrawn, accurately and using a microprocessor con-
shorter pot-life resin, i.e. 3 4 h can be used. trol to coordinate the speed of the rotating
Shorter pot-life resins result in smaller batches head motor. This relationship defines the
and mixing becomes time consuming. pitch of the winding which is defined as the
linear distance moved during one revolution
of the head. With the microprocessor control
23.4.6 THE PULL WINDING TECHNIQUE
the pitch can be varied, thus providing varia-
The pull winding process was developed in tions in fiber content and angular position, as
Europe and was used frequently by European 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.)
the rate of polymerization of the resin system Use of the platen system will allow change out
and the position of the resin gel point front of dies with very little system down time.
w i t h the die. It also influences the degree of During start up and also during shut down
resin exotherm profile throughout the various periods it is necessary to provide a cooling
wall thicknesses of the pultruded structure. method at the front of the die to prevent early
The curing dies are typically heated with elec- gelation of the resin system. During these
tric strip heaters or hot oil jackets. The thermal phases, the entire die will heat up rapidly
curing using these two methods of heating is without the composite being pulled through it
slow, owing to the fact that the tool steel of the and acting as a heat sink. The cooling can be
die is a poor conductor and limits the rate of done dynamically through cold air impinge-
heat injection to provide a uniform cure. The ment or by using a water jacket or tubes
thermal energy which is required to cure the through which cold water will be pumped.
composite material must all be applied Instead of these dynamic methods, a simple
through the outer surface of the composite static method would be to provide an
shape. The heat input is required to produce unheated zone at the beginning of the die to
gelation of the resin throughout the composite act as a heat sink and conduct away the excess
part. When the composite structure being pul- heat during start up or shut down actions.
truded has thick sections, this necessarily These same unheated or cooled sections may
requires a longer heat input which slows also be useful at the exit of the die to remove
down the pultrusion rate. Increasing the rate contained heat from the product prior to its
of heating to permit a faster pulling speed will exit.
not necessarily solve this problem and may It has been mentioned that the heating pro-
result in premature curing of the outside skin file within the die is the primary factor which
of the profile with early onset of the exotherm controls the speed of throughput of material in
in the resin system and potential overheating the process. This was recognized early in the
and cracking of the exterior surface of the part. development of the pultrusion process by W.
Temperature conditions of the die are con- Brandt Goldsworthy and he added a radio fre-
trolled by the internal placement of quency preheated system to his pultrusion
thermocouples and this can result in individ- machine designZ6rz7. The use of radio frequency
ual control of heating rates in various heating in conjunction with the traditional die
segments of the die. heating methods can significantly increase
Instead of using strip heaters or hot oil jack- running speeds. This technique is basically
ets, it is possible to heat the curing die by limited to unidirectional reinforced rods, bars
means of heated platens and a press. These and shapes and cannot be used if carbon fibers
heated platens will usually have several zones comprise the reinforcement. Data from
of heating control with imbedded thermocou- Goldsworthy Engineering Inc. shows speed
ples to sense the platen temperature. T h s increases of up to 400% based on a 2.54mm
method provides a uniform heating condition (0.1 in) wall thickness pultrusion. Speed
to the die. However, since the thermocouples increases of 100% (i.e. doubling the speed) are
are sensing the platen heating temperature accomplished at wall thicknesses of 2.54 mm
rather than the die or product temperatures, (0.1 in).
the temperature differential between these During recent years it has become possible
zones must be well documented. This permits to evaluate the internal die profile with regard
the platen heating temperature to be set to pro- to both temperature and pressurez8.The sen-
vide an adequate heating level in the sors which are used to provide that data are
composite product and absorb all of the con- essentially similar to strain gages with output
duction and radiation losses from the system. 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
Design features and materials 501
profiles to a relatively large radius for a large pultruded profile remains stationery until the
and complex composite profile particularly puller returned to the beginning of its stroke.
where the fiber content is high. The bell mouth Because of the alternating pull and pause
is polished and the finished die is hard chrome mechanism this system was known as the
plated to a thickness of 0.025-0.050 mm 'intermittent puller'. This system is still used
(0.0014.002 in) with a Rockwell C hardness of on some very early machines, however, it is
approximately 70. The dimensions and surface certainly not in widespread use.
quality of the pultruded product are a direct A modificationof the clamping/pulling sys-
reflection of the condition of the die. Dies will tem has become popular which provides a
thus not be removed from production to be continuous pull. The clamping, pulling and
inspected unless the shape or quality of the unlocking cycles of this system are coordinated
product begins to change. Chrome plated dies by the control system of the machine. The drive
will normally have a life of 61 000-150 000 m system used can be either a hydraulic cylinder,
(200 000-500 000 ft) of product run with their a threaded ball screw such as is used on lathes,
initial chrome plate application. Up to 305 000 m or a chain drive mechanism. The clamping
(1x lo6ft) of product have been produced from pads are still formed to match the contour of
some hard chrome plated dies. Chrome plated the profile being pulled. The two puller heads
dies require frequent inspection to insure that must operate in the space originally designed
their internal shape and dimension is main- for the single puller. Consequently, limited lat-
tained. They should also be inspected for wear eral movements of approximately two feet
of the chrome plated surface since the wear each are sustained by the two pullers. The two
process will proceed much more rapidly if the puller system is shown in Fig. 23.10.
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.
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-
Table 23.1 Typical properties of the major fibers used in the pultrusion process
All the rovings discussed will yield the highest is porous and its use on the exterior surface of
possible longitudinal properties. Fibers as rov- a pultrusion might well leave porosities or
ings result in the maximum fiber content to be voids in the surface. To counter this problem, a
achieved in pultrusion. If the longitudinal rov- very fine filament, E-glass mat, commonly
ings are used under near perfect conditions, a known as veil, can be used as the surface ply.
65% fiber volume percent level should be Its presence during the pultrusion process will
achieved. In a product which utilizes 100% tend to bring more resin to the surface of the
roving this material is normally in the longitu- pultrusion and this will achieve a smooth, uni-
dinal direction or axis of the pultruded form surface, devoid of porosity or voids. The
product. Properties in the other two directions veil mats can also be placed internally in the
are dependent upon the resin system and the composite and recent improvements in their
mechanical properties of the matrix resins are structural properties have made this possible.
much lower than fiber properties. Transverse The random fiber mats in E-glass are used
strength problems are overcome by inserting in weights of 0.15-0.6 kg/m2 (0.5-2 oz/ft2).
transverse fiber materials into the pultrusion. The inclusion of these mats in the pultruded
This is done either by using fabric or continu- structure means that some of the longitudinal
ous strand mat. The latter is most commonly fibers will have to be removed to allow for the
used. While the fabric is a standard woven tex- volume of the mat, veil or fabric. With the use
tile form, the continuous strand mat has fibers of fabric or mats in the structure, the resin con-
oriented in a random mode, bonded with a tent by volume will increase in order to fill the
thermoset resin binder which holds the mat openings in the mat or fabric. Thus while the
together adequately for processing in the pul- transverse strengths increase, the longitudinal
truded section. While mat is available in any of strengths usually decrease. Mats are also avail-
the fibers which have been previously dis- able in carbon fiber.
cussed, the most common available mat is an The random fiber structure of strand mat
E-glass version that has coarse fibers in an provides fibers in all directions. However, this
open or porous construction. This mat can be random orientation does provide some prob-
used either as a center ply in a pultruded lems in that the fibers may not provide a
structure or on the outer surface of the struc- symmetrical balance within the structure. The
ture. Use of the mat greatly improves the initial solution to this problem was the use of
transverse physical and mechanical proper- woven fabric. However, the lack of tension in
ties. It should be noted, however, that the mat the fabric results in a lower strength capability
504 Pultrusion
of the pultrusion since under load, the fibers 23.6.1 MATRIX RESINS
in the fabric will have to straighten and Of all of the technology considerations in the
become tensioned prior to being able to pultrusion process, the most critical material is
accept load. One way of solving this diffi- the resin system and its f~rmulation~"~~. Resin
culty is to use non-woven biaxial fabrics selection controls mechanical characteristics,
which are stitched or knitted together at the electrical insulation, corrosion resistance,
crossover points. Because of the nature of fab- operating temperature and flame and smoke
rication of these nonwoven materials, any properties. It also has a significant effect on the
ratio of fibers in the two directions can be process speed because of the required cure
provided. It is also feasible to utilize k45" cycle for any particular resin. The selection of
fibers in conjunction with the 0 and 90" fibers. a resin system will also affect the production
The biaxial fabrics are normally used as inter- cost of the process. The two most commonly
nal plies and not on the external surface. This used resin types in pultrusion are the isoph-
is due to the nature of the nonwovens in that thalic polyester and the vinylester. These two
their transverse fibers will tend to be dis- comprise over 90% of all resins used in pultru-
placed by friction with the walls of the die sion. Epoxy resins and phenolic resins are also
during pulling. Fabrics using a +45" orienta- being increasingly used. Phenolic resins were
tion without any longitudinal fibers are traditionally avoided by pultruders because of
usually impractical for the pultrusion their condensation reaction during cure.
process. It should be noted that hybrid com- Condensation reactions produce large vol-
posites with tailored properties are possible umes of water vapor and this typically causes
using combinations of the fiberglass, carbon voids, channels, delaminations and porosity
and aramid materials. The designer will read- when there is no provision to remove it. While
ily determine the mechanical properties the pultrusion die does have an entrance and
which are required from the nonwoven or an exit, nonetheless the system is essentially a
woven fabrics. The rule of mixtures will closed, pressurized volume. Table 23.2 pro-
apply for combination proper tie^^^. vides typical mechanical properties for resin
When pultruded composites are used in systems most generally used in pultrusion and
outdoor weather conditions, the surface of several other chapters discuss the broad range
the composite may be degraded with time by of matrix materials39.
sun, wind, rain and ultraviolet exposure. In
order to solve this problem, additional resin
needs to be provided at the exterior surface of 23.6.2 PHENOLICS
the pultrusion. This is done by incorporating
the very fine filament veil mats which are In consideration of the use of phenolic resin
typically fabricated from polyester or nylon34. systems, the disadvantage of the condensation
These veil fabrics are available in a variety of type reaction was certainly sufficient to cause
weights and weaving patterns. They help the delays in the potential use of phenolic resin in
pultruder by providing a tough surface mate- the pultrusion process. The amount of water
rial which will protect the die wall from the vapor which is generated in the condensation
abrasive nature of the fiberglass or aramid. In process is very large and it has always been
addition, the resin rich surface is created assumed that a phenolic pultruded structure
without any obvious fiber weaving patterns, would look somewhat like a sponge. However,
plus the veil materials can be screen printed phenolic systems have been pultruded in
with company identification or decorative recent years and a phenomenon has occurred
effects35. 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
~~
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.)
Materials 507
increased processing rate, or line speed, is the die and is proportional to the speed of pro-
result of increasing shear forces over the cessing. Hunter provided evidence that the
length of the die. In the case of the catalyzed pressure loss in zone 3 of the die occurs well
resin and referring back to Fig. 23.12, viscous before the material cools. Thus it is not thermal
shear forces are generated only in the front contraction but volumetric shrinkage due to
portion of the die, i.e. zone 1. Within the gel the cure of the resin. The coefficient of thermal
zone, cohesive forces come into play for a expansion of the steel material of the die also
small length of the die which is followed by enters into this equation. For a differential
the transition to the rubbery cured material temperature of 121°C (250"F),the hottest tem-
which provides substantial friction forces. As perature section of the die for a 12.7 mm
the resin hardens and shrinks away from the (0.5 in) diameter pultrusion will be 0.3% larger
surface of the die, the frictional forces are than the entrance. Thus pressure and volumet-
reduced significantly. It is obvious that the ric shrinkage together play a major role in
pull load is significantly higher for the cat- pultrusion dynamics. Insufficient pressure
alyzed resin system, particularly as the line causes sloughing problems and insufficient
speed increases. This proves that the major shrinkage can cause excessive pull loads. The
portion of the pultrusion loads are generated resin rate of shrinkage affects the rate of pres-
in the gel zone and are cohesive forces and sure decay and is controlled linearly by the
frictional forces resulting from the interface of cure rate of the resin. Thus a delicate balance
the resin and the die. between pressure, cure rate and shrinkage
Sumerak showed that a significant part of must be obtained for a clean pultrusion
the internal pressure does develop inside the process to take place.
B
4
-1- -
---
INITIAL CURE CYCLE
SECOND HEAT CYCLE
0
>
-2-
STARTING VOLUME - 9.098 ML
NET VOLUME LOSS - 0.<5 ML
VOLUMETRIC SHRINKAGE - 6.04 %
-3-
1 . r l r . l : 1 1 1 . 1 I ,
Fig. 23.14 Volume change of polyester resin during cure. (Courtesy of Shell Development Company.)
508 Pultrusion
-2-
NET VOLUME LOSS - .32 MLS.
VOLUMETRIC SHRINKAGE - 3.57 %
-3-
Fig. 23.15 Volume change of epoxy resin during cure. (Courtesy of Shell Development Company.)
Materials 509
00
50
00
50
I I I I
75 100 125 150 175 200
GEL TIME TEMPERATURE, DEG. C
Fig. 23.16 Gel time compared with temperature of epoxy and polyester resin. (Courtesy of Shell
Development Company.)
510 Pultrusion
content may be to reduce the pot life. Hunter 23.6.6 REINFORCEMENT VOLUME
ran experiments to provide data on gel times The general relationship of glass fiber content
of epoxy resin at different accelerator levels. to pull loads in epoxy resin system is shown in
In addition, he checked on the gel times of Fig. 23.18. These data were derived from an
polyester resin using two different curing experiment in the Shell laboratories where the
agents. Figure 23.16 shows the data which reinforcement volume was decreased and the
resulted from these two evaluations. The data pull loads were recorded until sloughing
on the epoxy resin system shows that signifi- The fiber volume was then
cantly more heat is required to generate the increased until the sloughing was eliminated
same gel times even though the accelerator and was increased further until pull loads
content is doubled. Figure 23.17 shows the became too large. The data shows that there is a
viscosity versus time of the epoxy resin at two plateau in the pull load curve spanning approx-
accelerator levels and two temperatures. This imately 2% of the glass fiber content range. This
graph clearly indicates that pot life is sacri- is the optimum level for pultruding the
ficed by increasing the accelerator level. Pot 12.7mm (0.5in) diameter epoxy rod used in the
life is also affected by temperature and Fig. test program. Below the optimum range,
23.17 illustrates that a small increase in tem- sloughing occurs owing to the insufficient
perature will reduce the time to double the hydraulic pressure at the gel point. Above the
initial viscosity by almost half. Heat can be optimum level, the pull loads rise owing to the
generated during the mixing process of the high pressure both during and after the gel
epoxy formulations and because of this it is zone (referring back to Fig. 23.12). Both poly-
important to minimize the mixing times when ester and epoxy systems respond similarly to
using high shear mixers that generate heat the different types of reinforcement materials
within the body of the resin system. The which are contained within the pultruded
implication of the experimental data pre- structure. For both of these resin systems, the
sented in these figures is that the most minimum reinforcement level to prevent
efficient method of increasing cure rate in the sloughing when using a continuous mat and
epoxy resin is to increase the die temperature. roving is somewhat less than that for an all rov-
4 0 0 0 ~0- P T D . A C C E L E R A T O R LEVEL AT 2 l . C
3500 -
W
u)
0 3000-
n
2500-
2
w
0 2000-
>.
1500-
u)
2 1000-
-
u)
5 500-
01 I I I I I I 1 1 1 1 1 1 I J
0 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3
TIME, H
Fig. 23.17 Epoxy resin viscosity compared with time and temperature. (Courtesy of Shell Development
Company.)
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
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 23.6.7 DIE TEMPERATURE CONTROL
volumes for the epoxy system for a variety of In polyester pultrusion, there is a wealth of
reinforcement systems. These values were gen- prior experience7 which can be used to pro-
erated by following the same procedure as for vide a temperature set point to produce the
the data in Fig. 23.18. The data shown in Table desired surface and internal quality of the part
23.3 are qualitative rather than quantitative val- with the controller being a thermocouple
ues. They may be used to estimate the required located some short distance from the entrance
reinforcement volume. to the die. This creates a situation which is
Table 23.3 Target fiber volume ranges for epoxy
independent of the actual exotherm tempera-
pultrusion 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
All glass roving reinforced composites
region of the part and die. At this temperature
Multi-end type rovings 78 homopolymerization will take place within
Single end type rovings 77-81 the epoxy resin system and the resin does not
Glass roving and continuous mat need the curing agent to stimulate the cure.
reinforced composites The mechanical and physical properties of the
3.175 nun (1/8in) thick cross sections 6447 structure are degraded under these conditions
6.35 nun (1/4 in) thick cross sections 71-74 by the presence of the unused curing agent.
For most thin profiles (up to 12.7 mm (0.5 in)
Carbon fiber reinforced composites
thick), a single heating zone is sufficient. The
All unidirectional tows 67-74 thermocouple should be located in the center
(57-65VOlYO)
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
CIT
200c
Q
18' /MINUTE
r
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 initiated there may be potential for significant
batch of the resin can be mixed and set aside in build up on the surface of the die and this may
advance of the production run.This batch with- be difficult to remove. The most troublesome
out the curing agent will be stable for up to spots in the die are the low pressure, remote
three days. The curing agent can then be added areas such as a comer or a small radius. There
to a small make-up batch and mixed in just is a standard process used in pultrusion of
prior to the addition to the system resin bath. A purging the die with pure mold release just
typical formulation used in batch mixing is prior to entry of the resin. Experience and
shown in Table 23.4. recent tests have shown that the pure mold
Even with the best of conditions in terms of release is not necessary and may lead to
a small resin bath and frequent addition of related problems. The normal types and quan-
new batches, the resin mix will ultimately tities of mold release recommended for use
become too viscous for good fiber wetting. A with epoxy were determined by tests at resin
good tip is to provide a large hole in the resin suppliers. Any levels of mold release in excess
bath with an appropriate plug. This allows a of those recommended will not provide addi-
quick drain and a clean and refill with only a tional benefit to the process. A high
momentary pause in the process. With this concentration of mold release may result in a
step, the pot life of the resin bath will be reset 'squeeze off' at the die entrance which could
to zero. It should also be noted that the plug in work its way back into the resin bath. If a pre-
the drain hole should not be threaded since a lubrication step is used, this squeeze off resin
very small amount of resin can cure and lock quantity must not be allowed to get back into
up the threads. A preferred plug would be the resin bath.
hard rubber with a rim, similar to the knock Prior to the resin entering the bath, the die
out drain plugs in the floor of an automobile. 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-
23.7 START-UP PROCEDURE
mended until the cured stock is in the pullers,
A key factor in trouble free start up is to use to minimize loads imposed on the dry fiber.
the minimum required amount of reinforce- Process rate increase can then be made gradu-
ment. However, if too much reinforcement is ally and for epoxy resins the processing speeds
eliminated in start up, sloughing will take normally will not exceed 45.7 cm (18 in) per
place in the die because of insufficient total min. It would appear that 30.4-35.5 cm
pressure in the gel zone. Once the sloughing is (12-14 in) per min provides the best combina-
tion of processing parameters, pull loads and provide a mild scrubbing action that will clean
surface gloss. If RF preheating is used, perform the surface of the die.
the start up without it at a reduced speed
15.2-20.3 cm (6-8 in) per min to minimize pull
23.7.2 SHUT DOWN
loads. When cured stock is through the die and
in the pullers, the RF preheater can gradually Standard shut down procedures have been
be started up. The resin temperature entering developed for polyester resins. The key step is
the die should be monitored and as it reaches to remove the resin bath or bypass the rein-
about 71°C (160°F)gradually increase the pro- forcement around it. The dry reinforcement
cessing speed. Do not recycle the resin which is should be completely pulled through the die.
squeezed off at the die entrance. 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.
23.7.1 TROUBLESHOOTING
The resin drain from the bath should be
The standard problem encountered with placed in a container in an area with good ven-
epoxy resin pultrusions is poor surface finish tilation and spill protection. A metal or plastic
or sloughing. The reasons for this have been tray with a surrounding high lip will be satis-
discussed earlier in this chapter. If the rein- factory for spill protection. The resin containers
forcement level is low then the cure for this is should only be half full. Eventually when it
to obviously add some reinforcement. does exotherm, it will become hot, expand and
However, if the redorcement level is in accor- may overflow the container if it is too full.
dance with the specifications, then additional
reinforcement will increase the pull loads
23.8 ADDITIVES
beyond standard. In this case the die tempera-
ture profile is probably too low. There is an Inorganic fillers are used to reduce shrinkage at
instrument on the market known as the polymerization. They also extend the volume of
Gelstar Thermal Analyzer. The thermal ana- the resin phase to provide a low cost formula-
lyzer can be used to obtain a temperature tion. These are primary additives. Fillers can
profile within the die. From this, the size of the frequently constitute the largest proportion of a
gel zone can be estimated. This is proportional formulation, second only to the base resin.
to the lag time between the die and internal Fillers are classified according to their particle
temperature profiles. If the temperatures size, as either coarse fillers or fine. Coarse fillers
appear to be within limits but the lag time is have an average particle size in excess of 8 pm
too large then the processing rate is too fast for and are generally the nonfibrous type with low
the particular cross section within the die. At surface area and low oil absorptions. They can
this point either reduce the process rate or use be highly loaded into the resin and are easily
RF preheating to minimize the problem. These wetted out by the resin system. Their disadvan-
steps will reduce the size of the gel zone. tage is that they tend to provide poor
If sloughing is encountered, the part should compound cohesiveness and to introduce local-
automatically clean itself up. The typical ized resin rich pockets and possibly to increase
purge techniques that are common in the fiber agglomeration during secondary molding
industry can be used with epoxy resins. If a processes (as in pull forming).The large particle
portion of the die refuses to clean up, a trick is size filler can be filtered out by a high density
to insert a copper kitchen ‘Chore Boy’ in the roving preform which can lead to large voids in
area of the part which has the problem. This the interior of the pultruded structure.
will often push the offending plug out or catch The most common of these fillers are cal-
onto it and pull it out. The copper gauze will cium carbonate, aluminum silicate and
516 Pultrusion
normally required to make the color bright. 0 surface preparation of the composites is
Zinc sulfide is also a UV absorber which is fre- not required;
quently used in pigment systems. Both 0 inspection of the joint is relatively easy;
titanium dioxide and zinc sulfide seem to have 0 the joint can be assembled and connected
little effect on the ultimate mechanical and up to full strength rapidly;
physical properties of the pultrusions such as 0 ability to disassemble and reassemble.
the strength, moduli and impact resistance.
The disadvantages of a mechanically fastened
joint are:
23.8.2 STRUCTURAL CONNECTIONS
in preparing the joints, holes must be
Pultruded FRP composites can be joined using drilled and sealed, structural members
various methods of assembly including must be trimmed and any required gusset
mechanical fastening (with plastic or metallic plates must be fabricated;
bolts or screws or by doweling with dowels or drilling of holes cuts the longitudinal
rivets), mechanically interlocking connections strength fibers in the area of the hole. This
(where molded or laminated inserts lock into can cause high stress levels and stress con-
the sections being fastened), adhesive bond- centrations;
ing, or a combination of these methods50. strength of the joint is dependent upon the
When structural components are assembled bearing strength of the composite material;
special attention must be given to the rigidity, the strength of mechanically fastened
geometry, fabrication and assembly require- joints is also dependent upon the strength
ments involved. It has been determined that of the fastener.
mechanical fastening and/or mechanically
Fastener parameters include:
interlocking connections are most suitable for
structural connections. Some connections 0 clamping force/installation torque limits;
depending upon the geometry and the stresses 0 washer size for transmission of load;
developed in connection can be strengthened 0 fastener size;
by also adhesive bonding in addition to 0 hole size and tolerance;
mechanical fasteners. Each of these systems 0 joint type;
have their own advantages and disadvantages 0 geometry of the fastener layout;
which are discussed in the following para- 0 composite thickness;
graphs. 0 rate of loading and the direction;
0 static or dynamic loading;
0 failure criteria;
23.8.3 MECHANICAL FASTENERS
0 high stress concentrations around fas-
If properly designed and fabricated, mechani- tener.
cally fastened connections are the most
reliable method of joining pultruded struc-
23.8.4 ADHESIVE JOINTS
tural sections. In recent years a significant
amount of information through empirical test- Adhesive joints have become popular for the
ing and prototyping of connections has connection of the composite materials since
become available on the bolting and riveting there is not degradation of the composite itself
of composites. There are many standard refer- by the bonding process. Adhesives are usually
ences in this field51-53. available in solid, paste or liquid form and are
classified as either inorganic or organic materi-
The advantages of a mechanically fastened als. The majority of the structural adhesives are
joint are: derived from the organic group and can be
518 Pultrusion
thermosetting resins, thermoplastics, or elas- double or single lap joint. The stress can be
tomers. These adhesives are known for their particularly severe in thick, double lapped
properties of being strong, tough, insoluble and joints;
useable over a wide temperature rangeM.The 0 adhesive bonded joints take time to cure
primary advantages of an adhesive joint are: while the resin is setting up and hardening.
During the cure cycle, the component parts
0 the properties of the composite material must be restrained in a fixed position.
remain intact and are not degraded;
0 adhesives are generally stronger than the
23.8.5 MECHANICAL ADHESIVE
composite material being bonded, conse-
COMBINATION
quently any failure mode is usually forced
into the surrounding primary structural Some connections are stronger using a
material; mechanically fastened/adhesive bonded joint.
0 good distribution of joint stresses; Advantages of mechanically fastened/adhe-
0 adhesive bonding can be used to bond dis- sive bonded joints are:
similar materials;
0 higher overall capacities;
0 adhesive joints can be particularly forgiv-
0 greater resistance to environmental and
ing. Flaws in the joints do not generally
thermal deteriorations;
degrade the strength of the joint. The main
0 less subject to peel stress failure than
reason for this is that the critical stress
‘bonded only’ joint;
location in a bonded joint is usually at the
0 improved fatigue and impact characteris-
end of the overlap and flaws tend to occur
tics;
in the center of the joint where the stress
0 increased joint rigidity.
level is low;
0 good fatigue and impact loading charac- The disadvantage of mechanically fas-
teristics. tened/adhesive bonded joints is that they are
labor intensive.
Disadvantages of the adhesive bonded joints
are:
23.9 APPLICATIONS FOR PULTRUDED
0 surface pretreatment such as cleaning and PRODUCTS
etching must be carefully performed;
0 the preparation and mixing of the adhe- Applications for pultruded products are many
sive in the correct proportions is critical. and varied but generally are commercially ori-
Manufacturers instructions must be fol- ented. The process shows up in the consumer
lowed precisely; and recreation market, electrical equipment
0 there is a time limit or shelf life of the products, corrosion resistance, civil engineer-
adhesive following its preparation; ing and construction and transportation
0 the component parts must be carefully (automotive, truck, bus and rail).
located ;sing holding tools and fixtures
and maintained in position with pressure 23.9.1 CONSUMER/RECREATION
across the joint during the curing of the The combination of strength, stiffness, fatigue
adhesive; resistance and aesthetic design and coloring
0 while adhesive joints are normally makes pultruded products ideal for the con-
designed and stressed in shear, there is an sumer recreation market. Applications are:
additional failure mode owing to peel fishing rods, archery bows and arrows, hockey
stress. This is a tensile stress which devel- sticks, tent poles, ski poles, playground equip-
ops a maximum value at the free end of a ment, fence posts and baseball bats.
Applications for pultruded products 519
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. 23.26 Aberfeldy footbridge. (Courtesy of
Maunsell Structural Plastics Ltd.)
Fig. 23.24 Grating and handrail installation. two sections of a golf course. The bridge is a
(Courtesy of North West Fibre Mechanics Ltd.) 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.
23.9.5 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.
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,
References 523
1983, Session 6-A, p. 5, Confer. 627, SPI Process Variables, Mod. Plast., March 1985.
Reinforced Plastics/Composites Institute. 45. Sumerak, J.E. and Martin, J.D., Pultrusion
34. Browning, J., Synthetic Surface Veils for GRP Process Variables and their Effect Upon
Laminates, Int. Reinf. Plast. Ind., 1986, 5(5) 14/6. Manufacturing Capability, RP/C Reinforced
35. Werner, R.I., Improvements in Means of Plastics/Composites '84; Composites go to the
Evaluating Weathering Characteristics of Market; Papers presented at Technical Sessions
Pultrusions, Rising to the Challenge: 35th Ann. of the 39th Ann. Conf., New York. Jan 16-19
Conf. New Orleans, LA, Feb 1980, Section 4-E, 1984, Session 1-B, p. 7, Confer. 627, SPI
p. 6, Confer. 627. SPI Reinforced Plastics/ Reinforced Plastics/Composites Institute.
Composites Institute. 46. Sumerak, J.E., Understanding Pultrusion
36. Heritt, R.W., New, High Performance, Fast Process Variables, Mod. Plast., 1985,62(3),58-64.
Curing Epoxy Resin System for Composites, 47. Sumerak, J.E., Understanding Pultrusion
Composite Solutions to Material Challenges: Process Variables for the First Time, Conference,
38th Ann. Conf. Preprint, Houston, Tex., Atlanta, GA, January 28-February 1, 1985,
February 7-11,1983, Session 19-D, p. 7.627, SPI, Paper No 2-B, p. 8, Confer. 627, SPI Reinforced
Reinforced Plastics/Composites Institute. Plastics/Composites Institute.
37. Kershaw, J.A., New Epoxy Resin Systems for 48. Armstrong, R.F., Calcium Carbonate,
Pultrusion, Shell Development Co., Composite Encyclopedia of Chemical Technology, Vol. 4, 2nd
Solutions to Material Challenges: 38th Ann. ed., Wiley Interscience, New York, 1964.
Conf Preprint, Houston, Tex., February 7-11, 49. Anderson, R. and Riddel, R., Effects of Pigments
1983, Session 6-42, p. 4, 627, SPI Reinforced on Pultrusion Physical Properties and
Plastics/Composites Institute. Performance, Molded Fiberglass Co.; Morrison
38. McQuarrie, T.S., New Generation Resins for Molder Fiberglass Co., Composite Solutions to
Pultrusion, 33rd Ann. Conf., Washington, D.C., Material Challenges: 38th Ann. Conf Preprint,
Feb 1978, Section %E, p. 5, Confer. 627 SPI Houston, Tex., February 7-11, 1983, Session
Reinforced Plastics/Composites Institute. 6-H, p. 4, Confer. 627, SPI Reinforced Plastics/
39. Howard, R.D. and Sayers, D.R., Development of Composites Institute.
New Methacrylate Resins for Use in Pultrusion, 50. Rufolo, A., Design Manual for Jointing of Glass
RP/C Reinforced Plastics/Composites '85. 40 Reinforced Plastics, US Naval Material
Years of Innovative Technology;Proc. 40th Ann. Laboratory Report, Navship 250-6341, August
Conf., Atlanta, GA, January 28-February 1, 1951.
1985, Paper 2-A, p. 5, 627, SPI Reinforced 51. Hodgkinson, J.M., de Beer, D.L. and Matthews,
Plastics/Composites Institute. EL., The Strength of Bolted Joints in Kevlar R.P.,
40. Boinot, E and Daspet, Y., Phenolic Resins: A Proc. Composite Design for Space Application,
Boon to the Building and Transport Industries, The Netherlands, (esa SP-243) 15-18, October
Composites Plast. Renf. Fibres Verre Text, 26, 3, 1985.
May/June 1986,97-100. 52. Hollaway, L. and Baker, S., The Development of
41. Lo Scalzo, E., Phenolic Resins in Advanced Nodal Joints Suitable for Double Layer Skeletal
Composites, Mat. Plast. Elast., 1988, 3, p. 124-9 System made from Fibre/Matrix Composites,
(Italian). Part 7, Paper 21, Proc. 3rd Intern. Conf. on Space
42. Hunger, G.A., Pultruding Epoxy Resin, Structures (ed. Nooshin, H.), Barking: Elsevier
Reprinted from 43rd Ann. Conf. and Focus '88. Applied Science, 1984.
Proc. 43rd Ann. Conf. SPI Reinforced 53. Green, A.K. and Phillips, L.N., Crimp-Bonded
Plastics/Composites Institute End-Fittings for Use on Pultruded Composite
43. Kiernan, D., Tessier, N. and Schott, N., Sections, Composites, 1982,13(3),219-24.
Modification of Epoxy Resins for Improved 54. Hart-Smith, L.J., Adhesively Bonded Joints for
Pultrusion Processing, US Army Materials & Fibrous Composite Structures, Douglas paper
Mechanics Research Center, RP/C Reinforced 7740, Long Beach, California, 1986.
Plastics/Composites '85, 40 Years of Innovative 55. Anderson, R., Use of Pultruded Reinforced
Technology; Proc. 40th Ann. Conf., Atlanta, GA, Plastics in Energy Generations and Energy
January 28-February 1,1985, Paper 2 4 , p 6 627, Related Applications, Working Together for
SPI Reinforced Plastics/Composites Institute. Strength, 36th Ann. C o d , Washington, D.C.,
44. Sumerak, J.E., Understanding Pultrusion February 16-20, 1981, Session 22-B, p. 1-3,
524 Pultrusion
Confer. 012. SPI Reinforced Plastics/Composites 62. Starr, T.F., Structural Applications for Pultruded
Institute. Profiles, TECHNOLEX, Composite Structures 2;
56. Morara, F. and Eva, G., GRP Conduits and Proc. 2nd Intern. Conf. Composite Structures,
Poles, Agrosistemi, Macplas, 1985, 10(67), Paisley, September 1616,1983, p. 192-216,627.
136-9. 63. Tickle, J.D., Halliday, G.A., Lazzarou, J. and
57. Pultrusions for Cable Rack, Brockhouse Group, Riseborough, B., Designing Structures With
Eur. Plast. News, 1982, 9(4), p. 36. Pultruded Fibre Glass Reinforced Plastic
58. Mallick, P.K., Qiauw, L.K. and Fesko, D.G., Structural Profiles as Compared to Standard
Design and Evaluation of a Pultruded Hybrid Steel Profiles, 33rd Ann. Conf., Washington,
Beam, Working Together for Strength, 36th Ann. D.C., Feb 1978, Section SF, p. 8, Confer. 627.SPI
Conf., Washington, D.C., Febraury 16-20, 1981, Reinforced Plastics/Composites Inst.
Session 1 7 4 , p. 1-5, Confer. 012. SPI Reinforced 64. Owens-Corning Fiberglas Europe SA, Fiberglas
Plastics/Composites Institute. in Action: FRP Lighting Poles, Burssels, 1977,
59. Head, P.R., GRP Walkway Membranes for Publn, 13-Ch. 4-5, p / 4 12 ins. 16/2/77
Bridge Access and Protection, 13th Reinforced 6272-6R.
Plastics Congress, 1982, Brighton, November 65. Mutch, W., Composite Utility Pole, Plast. World
8-11,1982, Paper 20,97-91, BFP Publn. 293, BPF, 1987,45, (8), 43.
Reinforced Plastics Group. 66. Kliger, H.S., Yates, D.N. and Davis, G.C.R.,
60. Head, P.R., Pultruded Box Beams, Fibreforce Driveshafts: The Next Step for Composites?,
Composites, Ltd.; Maunsell Structural Plastics; Aufomot. Engng, 1980,88(3),1OC-3.
UK Dept. of Transport; Windfoil Ltd. 67. Roubinet, P. and Delacroix, B., Industrial
61. Anderson, R.A. and Thomas, C., Development Development of Composite Leaf Springs,
of Large Hollow Rectangular Tubes for Composites Plast. RenJ Fibres. Verre Text., 26,(3),
Structural and Electrical Markets - A Unique May/June 1986, p. 79-83 (French).
Application for Pultrusion, Rising to the 68. de Goncourt, L. and Sayers, K.H., Composite
Challenge: 25th Ann. Conf., New Orleans, LA, Spring Systems, Composites Plast., Rent Fibres
Feb 1980, Section &A, p. 5, Confer. 627. SPI Verre Text, 1988,28(3), 145-50 (French).
Reinforced Plastics/Composites Institute. 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
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
Table 24.1 Adducts in thermoplastic polymers’ cussed in detail shortly. As is apparent, fillers
and fibers increase the polymer processing dif-
Antioxidants ficulty. In certain instances, as with continuous
Antistatic agents reinforcing fibers, conventional thermoplastic
Colorants and pigments processing cannot be used.
Coupling agents Part geometry is one way of classifying suit-
Flame retardants able polymer processes, Table 24.56. This
Fillers
Foaming agents classification is further amplified in Table
Heat stabilizers 24.67. Again, not all these processes are suit-
Mold release agents able for processing all polymers with all
Odor suppressors combinations of fillers or reinforcements. As
Plasticizers noted in Fig. 24.1, the cost of the polymer is
Processing aids only one aspect of the overall economics of
Emulsifiers product manufacture. Table 24.7 gives a rela-
Lubricants
Reinforcing fibers tive comparison of the process costs for filled
Ultraviolet stabilizers and reinforced polymers8.
Viscosity depressants 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
thermoplastic polymers are given in Table molding thermoplastic composites, in the
24.23. Typical fibrous reinforcements used in 1950s esentially all injection molded thermo-
thermoplastic polymers are given in Table plastics were neat or unfilled and
24.34. Filled, reinforced and foamed thermo- unreinforced. By the early 1990s, filled,
plastics offer great breadth of solid mechanical foamed and reinforced polymers accounted
properties. In many cases, they offer substan- for,more than 25% (wt) of all injection molded
tial processing challenges, as well. Nearly all parts. In certain instances, blow molding and
thermoplastic processes shape the polymer in rotational molding are possible.
its fluid state (The most notable exception to Thermoforming or rubbery sheet deformation
this is thermoforming, where forming occurs is now being applied to continuous fiber rein-
when the polymer is in a rubbery state. forced polymers. These processes are
However, thermoforming depends on the pro- described below, with the objective of compar-
duction of sheet that is produced by ing general operating conditions of neat
calendering or extruding the polymer in its polymers with thermoplastic composites. The
fluid state.) Fillers and reinforcing fibers technical details of these processes are given
increase the viscosity of the polymer, making elsewhere9-I4.Two axioms apply:
it more difficult to shape. As expected, pro-
0 Axiom I: If the neat polymer is processed in
cessing difficulty increases with increased
filler or reinforcement loading. conventional polymer processing equip-
ment, composite versions of that polymer
There are more than twenty major types of
are usually processed in adapted or modi-
polymer processes5.Not all these processes are
suitable for thermoplastics and not all thermo- fied versions of that equipment.
plastic processes are suitable for filled, 0 Axiom 11: Processing is always more diffi-
reinforced or foamed thermoplastics. Table cult with composite versions of processable
neat polymers.
24.4 lists most of the thermoplastic processes
that are used with neat, filled or reinforced An important corollary also applies:
poIymers. Several of these processes are dis-
Rheology,fiber flow and fiber orientation 527
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
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
)
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
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
Table 24.9 Effect of filler particle shape and packing type on maximum
packing fraction, P, for uniformly sized particlesM
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- - if the extruder die is annular, the result-
mary polymer property is shear viscosity. ing product is a hollow pipe or tube. This
Other important properties are given in tube or pipe is also a parison for extru-
Table 24.10. sion blow molding;
0 Extruder die, where the polymer melt is - if the extruder die is irregular, the result-
shaped a n d presented to the take-up ing product is called a profile. Some of
equipment39. The extruder die shape the major polymer properties that are
depends on the product being produced. important in profile extrusion are given
For example: in Table 24.10.
- if the extruder die is slot-like, the result- Extrusion dies are dissipative. That is, the
ing product is a planar sheet; polymer exhibits pressure drop through the
- if the extruder die is cylindrical, the die equal to that provided at the tip of the
resulting product is a rod; extruder screw.
536 Processing thermoplastic composites
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 Fiber length degradation is much less influ-
in producing linear composite products. Figure enced by screw speed than mixing time. As a
24.7 is an illustration of a cylindrical intermesh- result, twin-screw compounding extruders
ing twin-screw d e ~ i g n ~ ~ lTwin-screw
~l. provide less fiber length degradation than do
extruders are classified according to the relative tandem compounding single screw extruders.
screw rotational directions, whether the screws In fiber-reinforced extruded products, the
intermesh and the relative screw speeds, Table average fiber orientation for discontinuous
24.11. Comparative twin-screw performance is fibers is up to about 20" from the axis4s.The
given in Table 24.12. Despite some important orientation is the result of converging flow
shortcomings, twin-screw extruders are desired from the extruder screw tip to the die end.
for low shear and controlled feed rates, impor- (Converging flow is one of the standard die
tant aspects of compounding composite design critia for neat polymer extrusion.
thermoplastics as well as extruding them into Accelerating flow allows molecuIar alignment
uniformly consistent products. in the axis direction and tends to minimize
Increasing time in the shear field results in a extrudate swell shear d e ~ e n d e n c y ~ ~ . )
linear decrease in fiber length (Fig. 24.847). 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
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 of hoop reinforcement is related to the channel
fiber orientation in the hoop direction. width expansion52.
Orientation in the extrusion direction is
desired for profiles that are designed for
24.5 INJECTION MOLDING FILLED AND
strength in the bending direction. For pipe and
REINFORCED THERMOPLASTICS
tubing, on the other hand, the strength in the
hoop direction is half that in the axial direction Injection molding is a means of producing dis-
for an isotropic polymer. Reinforcement and crete products on a cyclic b a ~ i s ~The ~,~~.
hence fiber orientation is desired in the hoop injection molding machine consists of two
or cross-extrusion direction. This is achieved major parts: the plasticating and pumping sec-
by using a diverging die section following the tion, and the clamping mechanism.
converging section (Fig. 24.1O5I).The amount
*-
24.5.1 THE PLASTICATING AND PUMPING
Annular Die 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
Fig. 24.10 Expanding mandrel extrusion die with of polymer is accumulated, the mold is closed,
converging section for extrusion of highly fiber- the nozzle abuts the sprue, the screw advances
reinforced polymers. (Redrawn from Ref. 50 by and the melt is pushed into the mold. Injection
permission of Society of Plastics Engineers.) molding screws have L / D ratios of 15:l to 30:l.
Hopper
f r l
\
Hydraulic Piston
Plasticating Screw
Nozzle
Non-Return Valve W
\
Frame Electromechanical Drive
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.)
Injection molding filled and reinforced thermoplastics 539
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- methods are common means although new
cating to melt pumping is 50:25:25. Injection electric drives are considered to need less
molding screw compression ratios are usually maintenance. In addition, means for ejecting
the same as those for extrusion. the part from the mold cavity are usually
attached to the moveable platen. The polymer
is transferred from the accumulator section of
24.5.2 THE CLAMPING SECTION
the screw into the mold cavity by ram-
Figure 24.1256shows a fully hydraulic clamp, advancement of the screw at relatively high
one method of holding the mold halves closed shear rates of 100-10000 s-l, with transfer
against the pressure of the injecting melt. The times of seconds. Since polymers are com-
clamp consists of a stationary platen and a p r e ~ s i b l eat~ ~injection pressures and exhibit
moveable platen. The platens are guided open decreasing density with increasing tempera-
and closed along tie bars. The polymer is intro- pressure is applied to the polymer in the
duced through the sprue, a hole in the mold cavity, runner system and transfer lines
stationary platen. The moveable platen con- after the cavity is filled, until the polymer cools
tains a means of applying pressure to hold the sufficiently to hydraulically seal the mold cav-
mold halves closed. Hydraulic and mechanical ity. This packing pressure is most important in
540 Processing thermoplastic composites
Tailstock Platen
Fig. 24.12 Schematic of hydraulic clamping portion of conventional injection molding machine. (Redrawn
from Ref. 56 by permission of Carl Hanser Verlag.)
the injection molding of all polymers, includ- result exhibit differential shrinkage values that
ing heavily filled and reinforced compounds. increase with increasing loading (Fig. 24.13j9).
A tabulation of polymer properties impor- As a first approximation, the flow of a filled
tant in injection molding is given as Table molten thermoplastic can be considered simi-
24.13. Note that many of these properties are lar to the flow of the neat polymer, regardless
important in extrusion, as well.
For filled and reinforced polymers, mold
design is critical. There are several elements to
a mold: Cross-Flow
?
size and location of the gate are critical to
injection mold part performance, as noted
below.
; Diameter
of the loading level. The amount of force mold system (Fig. 24.1463).(It has been mathe-
needed to transfer the polymer from the injec- matically shown that the fountain flow effect
tion molding machine to the mold cavity holds for cylindrical and planar flow field&.
increases with increase in apparent shear vis- Even at very high fiber loading, individual
cosity. Since the transfer pressure is usually fibers or fiber aggregates align themselves
fixed by the machine hydraulic system, the with the flow streamlines6z.)As is apparent
transfer rate usually decreases with increasing 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
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
-
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 Weld lines are particularly bothersome with
fibers is usually the result of continuing injec- fiber-reinforced polymers. The primary con-
tion as the flow channel freezes closed. The cern is the undesirable fiber orientation at the
resulting high shear orients the fibers in the interface between two advancing flow fronts
flow direction. This layer may not be apparent (Fig. 24.17”O). Trpically the reZative weld line
in all fiber-reinforced parts. In very thin parts, strength decreases with increasing filler load-
fibers are nearly always oriented parallel to ing and aspect ratio71(Table 24.14).
the mold surface67.The flow in an injection
- -
mold is mathematically modeled using
Hele-Shaw or creeping flow6*,69.
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^^*,'^
~~~
For neat polymers, thermoforming and com- Temperature dependent polymer hot strength
pression molding are different disciplines74,75. Elastic modulus at forming temperature
Elongational viscosity at the forming temperature
Thermoforming begins with a formed sheet of Strain-rate hardening at high elongation
plastic that is heated to the rubbery state of the Other properties that are important in extruding
polymer, usually a few degrees above its glass polymer sheet
transition or melting temperature. The rub- Temperature dependent thermal properties of
bery sheet is then pressed with relatively little rubbery solid polymer:
differential force into or onto a cooled single- Thermal diffusivity
Thermal conductivity
sided mold and held there until the polymer
Heat capacity
temperature is substantially below the form- Polymer density
ing temperature. (In traditional vacuum
forming, the space between the sheet and the
mold surface is evacuated, thus applying dif- form the composite from the planar state to a
ferential pressure of up to 0.1 MPa. In pressure useful product. Mechanical means such as
forming, air pressure is applied to the free sur- matched dies, or hydraulic forces using super-
face of the sheet, thus applying differential air plastic aluminum or polyimide films, replace
pressure of up to 1Ml'a76.) The desired part is pneumatic forces when the differential form-
then trimmed from the web. Compression ing pressures exceed 1 MPa. The foamed
molding is usually reserved for thermosetting polymer, on the other hand, cannot be heated
polymers, but certain thermoplastic polymers to the same forming temperature as the
such as UHMWPE, PTFE, and certain poly- unfoamed polymer without dramatic cell col-
imides are compression molded. These lapse. As a result, foamed polymers are
polymers are characterized as having very formed at temperatures substantially below
high viscosities even at temperatures hun- forming temperatures for the unfoamed poly-
dreds of degrees above their melting or mers. Mechanical forces, such as matched dies,
processing temperature^^^. A polymer of this are used for forming foamed polymer sheet
type is compressed as a powder into a pre- into useful products. Typically, the ratio of
form, heated in a convection oven to the polymer modulus at forming temperature to
processing temperature, and transferred to a applied pressure, E ( T ) / P , should be in the
compression molding press where it is com- range of 2-10 with a value of 5 most typical for
pressed between heated mold halves. Typical traditional thermoformingsO.As an example,
molding pressures are 7-35 MPa. The mold is the temperature-dependent flexural modulus
then cooled until the formed part temperature of glass fiber-reinforced polyetherimide is
is substantially below the polymer processing shown in Fig. 24.W. At 200°C (392"F), the
t e m p e r a t ~ r eTable
~ ~ . 24.15 gives polymer prop- modulus of neat PEI is 2 MPa. The pressure
erties important in thermoforming. required to thermoform this polymer at this
For filled, foamed and reinforced polymers, temperature is about 0.4 MPa. For 30% (wt)
the boundaries between thermoforming and glass fiber-reinforced PEI the modulus is
compression molding blur. Frequently, the 7MPa and the required pressure is about
composite sheet forming process is simply 1.4 MPa. Pneumatic pressures at this level are
called stamping79.Fillers and discontinuous possible, but mechanical forming is preferred.
fibers stiffen the polymer so that even at the In many cases, the elastic modulus of the com-
upper forming temperature of the polymer, posite exibits similar temperature dependency
substantial differential force is required to to the elastic modulus of the polymer matrix,
546 Processing thermoplastic composites
10, I I I
I I I I
Fig. 24.18 Temperature dependent
0 50 103 150 0 flexural modulus of glass fiber rein-
Temperature, "c forced Dolvetherimide. (Redrawn
from Rei. s'l by permission of Carl
0 xa zm 3M Hanser Verlag.)
Temperature. "F
with the isothermal value of the modulus of the rubbery sheet is key to the forming
increasing monotonically with increasing filler process. Figure 24.20 is a schematic of a temper-
or fiber loading (Fig. 24.19a2). ature-dependent stressstrain curve for a neat
Thermoforming is a surface-generating polymer that exhibits a yield at low tempera-
process. That is, the total area of the finished t u r e ~ The
~ ~ . effect of filler and discontinuous
part plus web is greater than the total area of fiber on the shape of this curve is shown in Fig.
the initial sheet. The dominant method of gen- 24.21M.Typically, the initial slope of the curve,
erating surface is biaxial stretching of the the tensile modulus increases, the yield point
rubbery solid polymer. The shape of the tem- disappears and the elongation at break
perature-dependent tensile stress-strain curve 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
oo 10 20
Elongation
Fig. 24.19 The effect of glass fiber loading on flexural Fig. 24.20 Schematic of temperature dependent
modulus of polysulfone at 25°C (77'F). (Redrawn stress-strain curve for a neat polymer exhibiting a
from Ref. 82 by permission of Carl Hanser Verlag.) yield point.
Thermoforming and compression molding 547
n n Drive Shaft
Cartrldge Heater
Bottom Platen
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.)
548 Processing thermoplastic composites
lntraply Shear
Resin Percolation Through Fiber Bundle
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.)
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
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
the parison to cool more quickly. As a result, ment of the mold and so rarely yield useful
parison wall thickness control must be products. Fibers with aspect ratios of 1000 or
changed radically when blow molding filled less can be successfully molded if the maxi-
or reinforced polymers. Table 24.16 gives a list mum fiber content is less than about 15% (wt).
of polymer properties important in blow Lower fiber loadings may be necessary for cer-
molding. tain mold geometries and certain types of
Rotational molding is an atmospheric polyethylenes. If the fiber loading is too high,
process in which polymer powder is charged the fibers orient at right angles to the mold sur-
to a metal clam-shell mold. The mold is rotated face, producing an unacceptable setaceous
about the polar or major and equatorial or inner surface104.One method of forming a hol-
minor axes (Fig. 24.261°3),while being heated in low composite is to impregnate nonwoven
a forced air convection oven for several min- fiber mat with up to 30% (wt) electrostatically
utes, until the powder sticks to the mold charged polymer powder, then sinter the struc-
surface, melts and densifies into a void-free ture to fuse the powder to the fibers. The hot
hollow object. The mold is then air- and/or structure is then manually pressed against the
water mist-cooled, the part removed, the mold mold surfaces prior to adding additional poly-
recharged and the process repeated. mer powder, closing the mold, rotating it,
Polyethylene is the major rotational molding heating it to the forming temperature, and
polymer, with particle sizes ranging between cooling it in standard fashion105.Evacuating
50 pn and 500 pm. Coarse particle fillers hav- the mold through the rotating concentric shafts
ing particle sizes of about 50 pm or more, such is helpful in minimizing voids but is usually
as CaCO,, milled glass and glass cullet are suc- quite difficult to achieve successfully. Table
cessfully molded to loadings of 30% (wt). Fine 24.17 gives a list of polymer properties needed
particle fillers such as TiO,, carbon black and for rotational molding.
talc fluidize readily in the tumbling environ-
8. Progelhof, R.C. and Throne, J.L., Polymer 27. Shenoy, A.V., Saini, D.R., and Nadkari, V.M,
Engineering Principles: Properties, Processes, and Rheograms of filled polymer melts from melt-
Tests for Design, Munich: Carl Hanser, 1993, flow index, Polym. Comp., 1983,453-63.
Table 5.5. 28. Han, C.D., Multiphase Flow in Polymer Processing,
9. Progelhof, R.C. and Throne, J.L., Polymer London: Academic Press, 1981, p. 113.
Engineering Principles: Properties, Processes, and 29. Tanaka, H. and White, J.L., Experimental inves-
Tests for Design, Munich: Carl Hanser, 1993, tigations of shear and elongational flow
Chapter 5. properties of polystyrene melts reinforced with
10. Throne, J.L., Plastics Process Engineering, New calcium carbonate, titanium dioxide, and car-
York: Marcel Dekker, 1979. bon black, Polym. Eng. Sci., 1980,20,949-956.
11. Middleman, S., Fundamentals of Polymer 30. Chan, Y., White, J.L. and Oyanagi, Y., A funda-
Processing, New York: McGraw-Hill Book Co., mental study of the rheological properties of
1977. glass-fiber-reinforced polyethylene and poly-
12. Tadmor, Z. and Gogos, C.G., Principles of styrene melts, J. Rheol., 1978,22,507-524.
Polymer Processing, New York: Wiley- 31. Kamal, M.R. and Mutel, A.T., The prediction of
Interscience, 1979. flow and orientation behavior of short fiber
13. Crawford, R.J., Plastics Engineering, 2nd Edn, reinforced melts in simple flow systems, Polym.
Oxford: Pergamon Press, 1987. Compos., 1989,10,337-343.
14. McCrum, N.G., Buckley, C.P. and Bucknall, 32. Progelhof, R.C. and Throne, J.L., Polymer
C.B., Principles of Polymer Engineering, Oxford: Engineering Principles: Properties, Processes, and
Oxford University Press, 1988. Tests for Design, Munich: Carl Hanser, 1993, p.
15. Bird, R.B., Armstrong, R.C. and Hassager, O., 165.
Dynamics of Polymeric Liquids. Volume 1: Fluid 33. Progelhof, R.C. and Throne, J.L., Polymer
Mechanics, New York: John Wiley & Sons, 1977. Engineering Principles: Properties, Processes, and
16. Larson, R.G., Constitutive Equations for Polymer Tests for Design, Munich: Carl Hanser, 1993, p.
Melts and Solutions, Boston: Buttenvorths, 1988. 166.
17. Han, C.D., Rheology in Polymer Processing, New 34. Progelhof, R.C. and Throne, J.L., Polymer
York Academic Press, 1976. Engineering Principles: Properties, Processes, and
18. Ferry, J.D., Viscoelastic Properties of Polymers, Tests for Design, Munich: Carl Hanser, 1993, p.
New York: John Wiley & Sons, Inc., 1961. 161.
19. Lenk, R.S., Plastics Rheology: Mechanical 35. Throne, J.L., Thermoplastic Foams, New York
Behaviour of Solid and Liquid Polymers, New Chapman & Hall, 1994, Fig. 9.108.
York Wiley Interscience, 1968. 36. Progelhof, R.C. and Throne, J.L., Polymer
20. Middleman, S., The Flow of High Polymers: Engineering Principles: Properties, Processes, and
Continuum and Molecular Rheology, New York: Tests for Design, Munich Carl Hanser, 1993, Fig.
Wiley Interscience, 1968. 5.3.
21. Brydson, J., Flow Properties of Polymer Melts, 37. Rauwendaal, C., Polymer Extrusion, Munich:
New York Van Nostrand Reinhold, 1970. Carl Hanser, 1986.
22. Han, C.D., Multiphase Flow in Polymer 38. White, J.L., Twin Screw Extrusion: Technology and
Processing, Academic Press, 1981, Fig. 3.14, p. Principles, Munich: Carl Hanser, 1990.
101. 39. Michaeli, W., Extrusion Dies: Technology and
23. Herschel, W.H. and Bulkley, R., Measurement Principles, Munich Carl Hanser, 1984.
of consistency as applied to rubber-benzene 40. Throne, J.L., Thermoplastic Foams, Hinckley,
solutions, Proc. Amer. SOC.Test. Mater., 1926,26, OH: Shenvood Publishing, 1996, Section 5.2.
621-674. 41. White, J.L., Twin Screw Extrusion: Technology and
24. Hershel, W.H. and Bulkley, R., Kolloid-Z., 1926, Principles, Munich: Carl Hanser, 1990, Chapter
39,291-299. 7.
25. Han, C.D., Multiphase Flow in Polymer 42. White, J.L., Twin Screw Extrusion: Technology and
Processing, London: Academic Press, 1981, Fig. Principles, Munich: Carl Hanser, 1990, p. 10.
3.22, p. 106. 43. Rauwendaal, Polymer Extrusion, Munich Carl
26. Han, C.D., Multiphase Flow in Polymer Hanser, 1986, p. 462.
Processing, London: Academic Press, 1981, Fig. 44. Throne, J.L., Thermoplastic Foams, Hinckley,
3.24, p. 108. OH: Shenvood Publishing, 1996, Table 5.4.
554 Processing thermoplastic composites
77. Anon., 1900 ultrahigh molecular weight poly- 93. O’Bradaigh, C.M. and Pipes, R.B., Issues in
mer compression molding techniques, Bulletin diaphragm forming of continuous fiber rein-
HPE-102, Himont U.S.A., Inc., Wilmington DE, forced thermoplastic composites, Polym.
undated. Compos., 1991,12,246-256.
78. Narkis, M. and Rosenzweig, N., Eds., Polymer 94. OBradaigh, C.M. and Pipes, R.B., Issues in
Powder Technology, Chichester: John Wiley & diaphragm forming of continuous fiber rein-
Sons, 1994. forced thermoplastic composites, Polym.
79. Fong, L., Xu, J. and Lee, L.J., Preforming analy- Compos., 1991,12,246-256, Fig. 2a-2b.
sis of thermoformable glass fiber mats - 95. Bigg, D.M., Hiscock, D.F., Preston, J.R. and
deformation modes and reinforcement charac- Bradbury, E.J., Thermoplastic matrix sheet
terization, Polym. Compos., 1995,15,134-146. composites, Polym. Compos., 1988, 9, 222-228,
80. Throne, J.L., Thermoforming, Munich: Carl Fig. 6.
Hanser, 1987, Chapter 4. 96. Progelhof, R.C. and Throne, J.L., Polymer
81. Domininghaus, H., Plastics for Engineers: Engineering Principles: Properties, Processes, and
Materials, Properties, Applications, Munich: Carl Tests for Design, Munich Carl Hanser, 1993, pp.
Hanser, 1993, Fig. 523, p. 564. 471475.
82. Domininghaus, H., Plastics for Engineers: 97. Shutov, F., lntegral/Structural Polymer Foams,
Materials, Properties, Applications, Munich Carl Berlin: Springer Verlag, 1986, Chapter 10.
Hanser, 1993, Fig. 457, p. 506. 98. Peters, D.L., Kowalski, R.C. and Hughes, J.K.,
83. Domininghaus, H., Plastics for Engineers: Blow molded reinforced HDPE for structural
Materials, Properties, Applications, Munich: Carl applications, SAE Tech. Paper No. 830077,
Hanser, 1993, Fig. 454, p. 506. 1983.
84. Domininghaus, H., Plastics for Engineers: 99. Rosato, D.V. and Rosato, D.V., Eds., Blow
Materials, Properties, Applications, Munich Carl Molding Handbook: Technology, Performance,
Hanser, 1993, Fig. 457. Markets, Economics. The Complete Blow Molding
85. Bigg, D.M., Hiscock, D.F., Preston, J.R. and Operation, Munich: Carl Hanser, 1989, p. 481.
Bradbury, E.J., Thermoplastic Matrix Sheet 100. Rathgeber, J., Evolution of an imaginative tech-
Composites, Polym. Compos., 1988,9,222-228. nology - double wall blow molding, in Blow
86. Wolpert, V.M., Synthetic Polymers and the Paper Molding Handbook: Technology, Performance,
lndusty , San Francisco: Miller Freeman, 1977. Markets, Economics. The Complete Blow Molding
87. d’A. Clark, J., Pulp Technology and Treatment for Operation, Munich Carl Hanser, 1989 (D.V.
Paper, San Francisco: Miller Freeman, 1978. Rosato and D.V. Rosato, Eds), pp. 828-829.
88. Cakmak, M. and Dutta, A., Instrumented ther- 101. Han, C.D., Multiphase Flow in Polymer
moforming of advanced thermoplastic Processing, London: Academic Press, 1981,
composites. 111: Relative performance of vari- Figure 3.26, p. 109.
ous prepregs in forming double curvature 102. Minagawa, N. and White, J.L., The influence of
parts, Polym. Compos., 1991,12,354-369, Fig. 3. titanium dioxide on the rheological and extru-
89. Throne, J.L., Thermoforming, Munich: Carl sion properties of polymer melts, J. Appl.
Hanser, 1987, p. 28, Fig. 1.22 Polym. Sci., 1976, 20, 501-523.
90. Berins, M.L., SPI Plastics Engineering Handbook 103. Throne, J.L., Rotational molding, in Polymer
of the Society of the Plastics Industry, lnc., 5th Powder Technology, (M. Narkis and N.
Edn, New York Van Nostrand Reinhold, 1991, Rosenzweig, Eds.), Chichester: John Wiley,
Figure 13-llb, p. 392. 1994, Fig. 3.
91. Dutta, A, Niemeyer, M. and Cakmak, M., 104. Ramazzoti, D.J., Rotational molding, in PZastzcs
Thermoforming of advanced thermoplastic Engineering Handbook of the Society of the Plastics
composites. I: Single curvature parts, Polym. Industry, Inc., (J. Frados, Ed.), 4th Edn, New
Compos., 1991,12,257-272. York Van Nostrand Reinhold, 1976, p. 353.
92. Cakmak, M. and Dutta, A., Instrumented ther- 105. Crawford, R.J., Rotational moulding of plastics,
moforming of advanced thermoplastic Prog. Rubb. Plast. Technol., 1990,6(1),1-29.
composites. 11: Dynamics of double curvature
part formation and structure development
from PEEK/carbon fiber prepreg tapes, Polym.
Compos., 1991,12,338-353.
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
initial issue of tooling for composites.
decisions regarding tolerances, heat up rates,
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.
Tool design basics 557
One of the effects that occurs as a function of the fabrication of composite details. One
these dimensional differences is called spring- method is careful selection of the appropriate
back. Composite details, when cured, hold the tooling material. Each of the commonly used
specific molded shape, as defined by the tool, tooling materials available has a specific CTE
as a result of the cured combination of resin value (Table 25.1). When selecting the appro-
and reinforcement. The springback, or more priate tooling material based on the issue of
accurately defined as a warpage condition, CTE compatibility only, first determine the
occurs when the composite detail is cured into CTE of the composite detail being fabricated.
a tool, that at a specific temperature has one The specific expansion rate will be determined
definite dimensional tolerance and then upon by the combination of the resin and reinforce-
cooling to ambient temperature, contracts to its ment utilized along with the particular fiber
original ambient dimensions. The composite orientation that is incorporated into the lami-
detail, based on the resin chemistry, cures dur- nate. For example, the CTE of the more
ing the specific period when tool expansion is common unidirectional carbon fibers used in
at it greatest. Warpage occurs when stresses are most composite epoxy laminates is approx. 4.5
induced to the composite as the tool begins to x 104/OC (2.5 x 10"/OF ). The strength of the
return to the ambient dimensions, because the reinforcement material lies along the direction
composite detail is being forced to conform to of the fiber, not perpendicular to it. If a lami-
the new dimensional range against the dynam- nate is balanced, quasi-isotropic, with
ics of the state it reached during cure. This individual laminate layers or plies equally dis-
condition will increasingly become greater as tributing loads throughout the laminate, the
the temperature difference between ambient CTE of the laminate will be consistently equal
and cure temperature increases and the dimen- in all directions. If one direction is dominated
sional size of the tool increases. A common by more material plies than any other direc-
method of minimizing the effects of springback tion, the CTE value will vary, with the
or warpage of quasi-isotropic composite dominant direction having the lower CTE.
details during and after cure cycling is to deter- Once the CTE of the laminate is determined,
mine the CTE of the composite part being using the appropriate chart select the tooling
fabricated and the CTE of the tooling material material with the closest match to the laminate
selected. During the design of the tooling, care- value.
fully match as closely as possible the The other method of accounting for CTE
appropriate tooling material CTE to that of the variations between the detail being fabricated
composite detail. and the associate tool, besides material selec-
Other conditions that might lead to a tion, is the use of shrink factors in the
warpage of the laminate include an unbal- calculation of dimensions prior to tool fabri-
anced laminate orientation where the number cation. If requirements dictate that when
of layers or plies of material are more domi- fabricating the tool, a material with an incom-
nant in one direction than another. This patible CTE to the detail being manufactured
condition is separate from any function of the must be used, steps may be taken to mini-
tool and must be considered during the design mize the effect of this variation. During the
of composite detail. design phase of the tool, accurate estimates of
the actual tool size at its greatest expansion
point or at the highest temperature during
25.2.2 USING CTE IN THE DESIGN OF
the cure cycle must be made. The percentage
TOOLING FOR COMPOSITE
difference between this calculation and the
Two methods are commonly used to minimize dimensions at ambient must be applied to the
the effect of CTE when designing tooling for base design as a 'shrink factor' reducing the
558 Toolingfor composites
size of the tool by that same percentage. For sions. Since the composite detail was cured
example, if a specific tool at 177°C (350°F) has while the tool was at the larger dimension, if
a growth factor equaling 1.27mm (0.050 in) of the detail is confined to the tool surface or
growth over ambient dimensions, this same restricted from movement due to complexity
factor would be applied as a reduction of the in the tool surface, the composite detail could
overall tool dimension while at room temper- become entrapped, resulting in dimensional
ature. This method of applying a shrink abnormality in the laminate and possible
factor to allow for variations of CTE between damage to the composite detail or the tooling
tools and details must be approached cau- surface. A variety of other factors should also
tiously when complex shaped surfaces are be considered such as tool durability, tool
involved. This is due to the potential for the usage rates, thermal conductivity of the mate-
composite details to become entrapped rial and machinability or fabrication cost.
within the geometry of the tool as the tool Each of these factors must be weighed indi-
returns to the ambient temperature dimen- vidually before final selection is made.
Tool design basics 559
25.2.3 MATERIAL CHOICES IN THE DESIGN OF machining the final tool surface directly from
TOOLING FOR COMPOSITE a computer model can be accomplished using v
The use of CTE is not the sole determinant for a material capable of the final cure tempera-
selection of a tooling material. For example, as tures. Monolithic graphite and a variety of
defined in Table 25.1 monolithic graphite epoxy and polyester tooling boards would
which as a tooling material has a CTE value of allow this with monolithic graphite offering
2.2 x 104/OC (1.2 x 1O4/'F) has good machin- the highest quality and lowest CTE at a com-
ability at a relatively low cost compared to parable cost to the board stocks available.
other tooling materials, but exhibits poor These costs would be similar to laminated
durability when utilized in the high usage of tooling without the intermediate and time
production environments. InvaP 36, however, consuming steps necessary to complete the
displays a similarly low CTE value, displays a laminated tool. However, in a high usage pro-
much higher level of damage resistance but duction program, these materials can be
has poor machinability and also has a high damaged more easily than the composite lam-
acquisition cost. Careful selection of the inate or metallic tools currently in use.
appropriate material for tool use must include Continued advances by the suppliers of com-
review of the following criteria: posite tooling prepregs have drastically
increased the ability of composite laminate
0 anticipated tool usage (expected life of tool); tools to support a high number of cycles at
0 cost available for tool fabrication; cure temperature.
0 materials available for tool construction; Another factor directly affecting the
0 available methods of tool manufacturing; longevity of tooling fabricated from composite
0 level of dimensional tolerances required materials is the effect of proper employee
from composite detail. training in the care required of such tooling.
Improper handling techniques will drastically
Anticipated tool usage shorten the expected life of composite tooling.
Employee caused damage such as cutting on
The life expectancy of any tool fabricated for the surface of the tool, using sharp instru-
the lay-up and cure of composite details is ments to facilitate the removal of details after
dependent on a variety of factors. Material cure and improper application of release
selection, shop handling procedures and cure agents are the most readily identified causes of
cycle times all affect the ability of the tool to shop induced damage. Special handling pro-
withstand long usage. Certain materials dis- cedures and employee indoctrination can
play characteristics that allow longer tool life, minimize this type of damage. While all tool-
however the advantage and disadvantage of ing, both metallic and non-metallic, is
each material must be analyzed prior to selec- susceptible to damage, tooling fabricated from
tion. In addition, each of the tooling materials composite materials is especially sensitive to
presently used is sensitive to damage specific surface damage caused by employee careless-
to that material. If short term usage is antici- ness.
pated, temporary tooling such as wet lay-up
epoxy or polyester tooling (dependent on
Cost available for tool fabrication
detail cure temperature) may be acceptable,
however master models and intermediate Cost of tool fabrication is difficult to quantify
transfer tooling would be necessary to main- since material procurement and labor cost
tain the correct surface tolerances. To vary widely throughout the industry.
minimize the costs associated with master However, comparisons can be made between
models and intermediate transfer tooling, the different tooling materials and methods
560 Toolingfor composites
In the early days of advanced composites, result in dimensional changes occurring dur-
applications were limited to aerospace, which ing this process.
invoked strict dimensional requirements for The highest level of tolerances available are
both tooling and detail parts. These require- obtained by machining the tooling surface
ments continue within aerospace today. With directly from the computer model. Certain
the expansion of composite usage into other master model materials such as plaster and
areas, such as sporting goods and automotive some board stock materials have a limited
applications, the range of acceptable dimen- temperature exposure level which inhibits the
sional variations has increased but visual ability to pull composite laminates directly off
requirements are much more stringent than their surface. Intermediate tooling must be
before. The variation of CTE between differ- fabricated either to obtain the correct surface
ent materials for tooling has a major effect on level from the master or to be capable of with-
dimensional tolerances. In addition, some standing elevated temperatures within an
materials display sensitivity to environmental autoclave or oven, above that of the original
conditions that have an adverse effect on model. By machining directly from the engi-
dimensional stability. Tooling, such as refer- neering database, the need for intermediate
ence patterns or master models manufactured surface splashes to obtain the correct surface is
from urethane board stocks or plaster models, eliminated. Each time a splash or the original
are hygroscopic and may absorb moisture surface model is duplicated, a 'stackup' or
from the atmosphere. This condition will, at a accumulation of the tolerances for each model
minimum, cause dimensional changes related is combined, resulting in a much greater range
to the level of moisture absorbed. Also, this of tolerances in the final tool. For example, if a
condition could be excaberated if the moisture plaster master is fabricated to k0.25 mm
contamination is extensive and the model is (a.010 in) tolerance and each of two addi-
taken to elevated temperatures. At higher tional splashes have the same tolerance range,
temperatures, the moisture will expand and prior to fabrication of the final lay-up mold,
may result in possible significant changes in the beginning tolerance range is now d . 7 6
structural integrity. Urethane or epoxy board mm (4.030 in). If a tool is machined directly
stock materials have greater resistance to from NC data, the tolerance stackup is elimi-
moisture. However, if machined and used for nated and only the range of the individual
reference patterns they are both still suscepti- machine tool applies. Machine tools, depen-
ble to contamination, which could result in dent on the condition and environment of
dimensional changes and possible failures in machining, are capable of providing 4.128
the bond joints between the block surfaces. mm (4.005 in) accuracy or greater.
Additional steps must be taken to protect all
models manufactured from these materials to
25.2.4 DESIGNING TOOLS FOR RESISTANCE TO
prevent these types of contamination. Sealers
FAILURE
must be applied and the items must be segre-
gated from potential sources of Because of the abusive environment experi-
contamination. Monolithic graphite offers enced by tooling during the fabrication of
advantages over these materials because it is composite details, life expectancy of tooling
inert and resists contamination from the envi- will always be short of anticipation. Repetitive
ronment. Lay-up molds manufactured from cycling from ambient to over 177°C (350"F),
both ferrous and nonferrous materials must inadequate care and handling procedures,
be protected from oxidation. Failure to main- incorrect fabrication techniques have all led to
tain a nonoxidized lay-up surface will require a variety of defects resulting in premature
restoration of the tooling surface which could temporary or permanent failure of the tool.
562 Toolingfor composites
Failure modes common to composite lay-up laminating the initial tool, apply additional
tools fabricated by both wet lay-up and plies of pregreg in the area of the bushings to
prepreg methods generally involve fiber sepa- increase support in those areas to resist move-
ration. This is due to a variation in CTE ment during part removal.
between the resin matrix and the fiber. Another possible solution to the problem of
Generally, the neat resin systems used in most delamination between layers of prepreg tooling
composite tooling systems have a CTE of 65 x is the application of glass transition tempera-
104/"C (36 x 104/"F) The graphite fibers used ture values (TJ to extend the life expectancy of
in most prepreg tooling systems have a CTE of a tool. Most tooling resin systems are formu-
around 4.5 x 104/"C (2.5 x 104/"F). During lated with a Tg value at or slightly above the
exposure to cure cycles where temperatures maximum use temperature of the resin system.
will vary from ambient to 177°C (350°F) and As a function of the resin chemistry, glass tran-
above, the difference in CTE between the sition temperatures decay or reduce with each
fibers and the resin will eventually cause dis- exposure to the cure temperature that the sys-
bonds between laminate layers resulting in tem was designed for. This decay, in
leaks internally within the tool. In addition, incremental steps will continue until well
the expansion of the resin is somewhat con- below the cure cycle temperature that the tool
trolled by the fiber reinforcement in the x and was intended to be cycled at. When this point is
y axis. Because no reinforcement exists in the z reached, the resin will begin to break down
plane linking the individual layers together, with a mechanical failure of the bond between
the difference in CTE between the resin and the resin matrix and the fiber reinforcement.
reinforcement becomes more pronounced. The solution to this problem is to use a
Failures between the individual plies increase resin system with the highest possible Tg
because of the lack of reinforcement restrain- value available. For example, if the tool is
ing the resin from the repeated expansion and intended to be cycled repeatedly at 177°C
contraction. (350"F), a T value of the resin system in the
Furthermore, when laminating layers of 220°C (425"h) range will allow more cycles. It
either prepreg or wet lay-up tooling, by cut- is common among some aerospace compa-
ting each of the plies into pieces 304-457 mm nies to now fabricate composite tooling for
(12-18 in) square, no continuous fiber path epoxy laminates from a bismaileimide or a
will pass through the tool. By discontinuing cyanate ester resin system with Tg values
these pathways, leaks occurring along the higher than 260°C (500°F). This allows the
fiber path will be minimized. In addition, inevitable decay of the Tg value to span a
because each layer or ply consists of sections greater difference allowing the life of the tool
without any continuous fiber path, stresses to be extended. The same principle may be
within the laminate will be lower, minimizing applied for any prepreg system from poly-
warpage during use. A majority of failures in esters to the higher temperature resin
composite tooling may be directly tracked to systems. One consideration in using this
leakage around tooling holes or plumbing fit- method requires the selection of a master
tings. Tooling hole fittings are exposed to model material capable of exposure to the
repeated shocks during the removal of cured elevated temperatures that the higher tem-
composite details. If steel bushings are used, perature systems require during cure. Plaster
the difference in CTE will possibly lead to and most of the board stocks available are not
cracks in the tool surface which will become capable of these higher temperatures and
potential leak paths. One solution is to install intermediate splashes or surfaces would have
Invar 36 bushings in laminated tools which are to be provided. Monolithic graphite does pro-
closer in CTE to the parent tool. Also, when vide a surface capable of exposure to higher
Master models 563
temperatures in addition to having the lowest struck with a hard object. Carriers designed to
CTE available, allowing tools fabricated from transport the tool to and from work station
these resin systems to be taken directly off the must also function as a protective barrier to
model surface without need for intermediate prevent the tool from striking walls or beams
surfaces. within the shop environment. Support tool-
Employee-induced damage of tooling can ing, where applicable, must be designed to be
play a much greater part in the reduction of as lightweight as possible to prevent injury to
expected tool life. Correct indoctrination into the employee and damage to the tool surface
the importance of the tool to the fabrication of when handled.
accurate details must be stressed. Most of the
employee-induced damage will occur either
25.3 MASTER MODELS
during the lay-up procedures, the removal of
cured composite details from the tool surface, A master model is considered to be just that -
or preparation of the tool surface prior to the a master source identified with holes, scribe
next lay-up. During lay-up of details, damage lines, trim lines or any other feature of the
will be the result of employees using knives or part that requires duplicating to other tools.
other sharp objects during the trimming of the The master model is the physical representa-
composite material. If proper care is not tion of the design or a point of reference to
taken, the employee will not only cut the which all support tooling, both for fabrication
material but also cut into the tooling surface. and inspection, would be indexed. Because
While not as detrimental to a metallic tool, this surface will provide the reference pattern
damage of this kind may be catastrophic to a for all subsequent operations beyond initial
tool fabricated from a composite material. The fabrication, such as assembly fixtures index-
cut will allow a breach in the vacuum ing a variety of details from different
integrity in addition to allowing resin to pen- locations, extreme care must always be taken
etrate beyond the surface of the tool. Also, in protection of the master model. Master
when laminates are removed from tooling models may be fabricated from a variety of
after completion of the cure cycle, damage materials. Common materials include plaster,
occurs when personnel use sharp equipment machined urethane or epoxy board stock,
to force the completed detail from the tool. monolithic graphite or most ferrous and non-
The greatest care must be given when ferrous metals. Each material offers distinct
attempting to remove the detail, to prevent advantages and disadvantages. To determine
inadvertent damage if the detail fails to which material is the most feasible, the entire
cleanly release from the tool surface. Damage, tooling family philosophy must be reviewed.
not only to the tool, but also to the detail may Master models are generally stored indefi-
result. To prevent this damage from occur- nitely so that they may be referred to over the
ring, proper steps must be taken. Employees life cycle of the manufactured parts. In cases
must be indoctrinated in the proper tech- where cost and/or time schedules are impor-
niques of tool maintenance and lay-up tant, temporary models are produced and
procedures and must be provided with then destroyed once they have been used.
acceptable tooling aids to assist in the safe However, because of the hygroscopic nature
removal of cured details from the tool surface. of plaster, care must always be taken to pro-
Soft wood or plastic wedges must replace tect the master model from the environment
hammers and hard-faced chisels for detail to maintain accuracy. Adequate storage con-
removal and tool surface preparation. Tools tainers, allowing for complete protection,
must be designed with adequate laminate must be utilized throughout the life
thickness to prevent damage to the tool if expectancy of the model.
564 Toolingfor composites
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
laser jet directly from the flat pattern generated steel blade, the plaster is 'faired' or swept flush
by the data. Section cuts taken at specific sta- between the templates to form a smooth accu-
tion lines from two-dimensionalblueprints can rate surface. Because of the propensity of
be used to saw out a template. Except for the plaster to absorb moisture, it should be sealed
NC machining method, deburring is generally after the surfacehas had adequate time to cure.
required to remove spurs or sharp edges from Commercially available lacquers can be used
the templates prior to use. Holes are drilled to seal the surface and provide a suitable pro-
into the templates for threaded rod spacers and tection within the shop environment.
screen support rods. For larger models, air pas-
sages are cut into the bottom of the template to
25.3.3 FOLLOW BOARD METHOD
allow for even curing of the plaster. Once suffi-
cient templates have been prepared, bluing is A method widely used when a constant cross
applied to a flat ridged steel table and scribed section is to be built is the follow board. A flat
with an awl to denote the location of each tem- surfaceis required with an accurate side surface
plate. Flatness of the table is critical and should to act as a guide rail. A template of the contour
be within 0.127 mm (0.005 in). Tooling balls is prepared from a rigid 3 mm (0.125 in) mini-
which indicate the x, y and z direction are mum sheet of aluminum or steel and attached
sometimes placed on the table corners as refer- to a wooden guide support. Plaster is mixed
ence points for the system. Tooling balls can and built up on the surface to within 3mm
vary in size but a common size is 12.7mm (0.125 in) of the final contour. Partial drying is
(0.5 in) diameter on a 6.35 mm (0.250 in) diam- recommended before the final plaster mix is
eter x 12.7mm (0.5in) long pin. The pins, each applied. This will prevent shrinking and crack-
with a 'ball' on top are placed into location ing of the plaster surface which would affect
holes and optically sighted relative to the posi- accuracy. Using the template and guide sup-
tion of the each ball location. Location can also port, the plaster contour is formed by pushing
be treated relative to a position on the master the template evenly over the surface (Fig. 25.2).
such as a station line. Each template is attached
90" to the base table with angles and held to FOUOW
BOARD
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
FOLLOW BOARD METHOD
place. Plaster is mixed with hemp and placed FOR PRODUCING PLASTER MASTER
against the screen to approximately 9.5 mm Fig. 25.2 Follow board method for producing plas-
(0.375 in) below the template surface.A second ter master.
layer without hemp is added to this surface to
approximately 12.7 mm (0.5 in) A sawtooth
25.3.4 SWEEP METHOD
scraper is used to build a striated surface and
allowed to dry. A final mix is made with the A third method called a sweep is best utilized
fine grade of plaster and using a flat spring when a symmetrical surface s;ch as a cone or
566 Toolingfor composites
hemispherical shape is involved. As with the operation significantly. The system, known as
follow board method, a flat surface from which Automated Tool Manufacture for Composite
a frame can be constructed of the shape to be Structures (ATMCS),is an expert system with
produced is required. For large shapes, inter- macros which dramatically speeds up the tool
mittent templates should be placed within the design process. ATMCS takes the composite
framework to allow support for the sweep and detail surface model into either IBM Catia or
provide adequate support for the sweep to fair EDS Unigraphics I1 and creates the tool
against. The sweep itself is usually made from required around the part model.
sheet metal 3 mm (0.125 in) minimum thick- The system, acting through a series of
ness and supported by a wooden guide or inquiries made to the tool designer, selects the
other mechanical guides that can ride the sur- optimal configuration, material, manufactur-
face of the flat surface table. Smaller shapes, of ing process and design. The design is then
course, do not require this extent of rigging. created around the part model, with signifi-
Plaster can be reinforced with saturated hemp cant savings in time. Although the system was
fibers, mixed into the slurry and applied to developed initially for the aircraft industry
form rough shapes and to form strengthening and is presently used for basic open-faced lay-
ribs on the back surfaces of casts. All master up molds, it could be expanded for many
models fabricated from plaster require, in different types of tools and processes such as
addition to sealing with commercial grade lac- resin transfer molding and injection molding
quer, suitable storage containers if the model is in other industries.
required to be stored for any period of time
outside the shop environment.
25.4 COMPOSITE TOOLS
tooling holes. Tools can be made directly is always a good idea at a minimum of 6.2 kPa
from a NC machined master model or from a (25 in Hg). A loss of 500 Pa (2 in Hg) within 5
plastic faced plaster splash taken from a mas- min with the pump nonoperating is acceptable.
ter model not capable of elevated Apply masking tape around the tool periphery
temperatures and pressures. The choice of for later application of the sealant tape. It is
glass or carbon fiber/epoxy for the mold is absolutely necessary, regardless of prior his-
generally governed by the complexity and tory of the master surface, that it can be
CTE of the part to be fabricated. Lay-up released with a suitable hard wax or other
molds must be capable of maintaining a vac- release agent. The prepreg manufacturer may
uum tight environment while being subjected recommend a specific release agent for his
to high temperatures and pressures. prepreg system and it is advisable to follow
those instructions due to the possibilities of
chemical reaction occurring between the resin
25.4.2 PREPREG METHOD
system of the tool and the release agent used
There are a considerable number of prepregs (Table 25.2). After the cleaning and releasing
available as epoxy 'B' staged glass or carbon processes have been completed, release coated
reinforced cloth. Prepregs can be obtained in tooling pins should be placed into the holes of
rolls or as precut squares or rectangles. The the master. These are generally index and
weave style can vary depending on the locating holes that have bushings and are used
amount of drape to be encountered but gener- to position or align one tool to another, or to a
ally plain or satin weaves are readily available. production part. Bushings can be installed dur-
The resins are tailored for tack, out time and ing lay-up of the tool or potted in after final
glass transition temperatures at a minimum cure of the tool.
and are around 40% by volume of the prepreg. In general, a face or gel coat layer is not
(Tooling prepreg manufacturers have very used by most manufacturers today. The reason
detailed procedures that they recommend for is associated with the difference in CTE of a
their specific system. These comments are not neat resin on the face and the CTE of the
meant to supersede the recommendation of a underlying reinforced prepreg which over the
manufacturer, but rather to place emphasis on life span of a tool can cause cracking and craz-
important steps that should not be overlooked ing of the face and subsequent loss of vacuum
for tool fabrication.) integrity. If a gel coat is used it should be of
Within the last several years, an innovation minimum thickness to minimize these effects
for tooling prepregs is the capability for low over time.
temperature curing 61°C (145°F) in an auto- A lightweight (style 7781) cloth is the first
clave, followed by a free standing post cure at layer applied to prevent mark through to the
177°C (350°F) after removal of the tool from surface from heavier cloth. Carefully lay each
the master. This has allowed the use of plastic ply onto the surface and work out wrinkles or
faced plaster and urethane based tooling air bubbles and maintain the warp direction of
boards for direct lay-up of composite tools. each ply in the 0" direction. An overlap
Monolithic graphite with a low CTE and capa- between the plies should be 3-6 mm
bility to withstand 315°C (600°F) under (0.125-0.250 in). Some manufacturers recom-
autoclave pressures can be a good choice. mend a debulking step at this point to ensure
The first step prior to prepreg application on no air entrapment at the interface and a
the master surface is to ensure that the prepreg smooth surface on the tool. Debulking is
and the master surface are absolutely clean and accomplished by application of a peel ply net
free of debris and that the surface is smooth to the edge of the laminate and working out
and without pin holes. A quick vacuum check wrinkles and air bubbles. A resin dam (sealant
568 Toolingfor composites
tape) can be placed around the perimeter to permit a higher resin content on the tool sur-
prevent resin flow (Fig. 25.3). Next, lay-up one face. Over this layer, one ply of polyester
ply of Teflon@beyond the resin d a m and attach breather cloth or 7500 style glass cloth is
to the resin dam. Using the manufacturer’s applied. A nylon vacuum bag is placed over
recommendation, holes should be placed into the entire stack and a vacuum of at least
the Teflon ply to allow for resin bleed. Pre-per- 625mm (25 inHg) is applied for at least one
forated film can be obtained for this purpose hour. Removal of the bag, breather, separator
and provides greater control over the size a n d film and peel ply should be done very carefully
spacing of the holes. If only one lightweight to avoid lift up or shifting of the prepreg lay-
ply has been applied, no holes are required to ers. The orientation for each additional ply
Composite tools 569
Vacuum Line
Vacuum Vacuum Bag Sealant
,,Breather
Tdl Laminate \
Release Film
Fig. 25.3 Laminate pre-bleed stackup.
should be such that a balanced system is main- after every 4-5 plies. Final build up of the lam-
tained to minimize stress build up in the inate should be at least 0.013 mm (0.375 in) or
laminate. Prepreg manufacturers will clearly whatever is recommended by the prepreg
stipulate the lay-up sequence.After the second manufacturer. Final vacuum bagging is per-
or third ply has been laid down, knurled bush- formed in the same manner as for debulking
ings should be placed onto the tooling pins with a layer of peel ply, perforated Teflon,
and pressed down to seat them. Subsequent polyester breather and vacuum bag. Prepreg
plies will be placed over the bushings to inte- manufacturer will provide a detailed heat up
grated them into the laminate. After the rate and cure temperature for their system and
seventh or eighth ply, the pins can be removed this should be carefully followed. Most sys-
so that later plies can cover the bushing com- tems can be initially cured at up to 63°C
pletely to prevent vacuum leaks. In some (145°F) and 586-689 kPa (85-100 psi) of pres-
instances a pad or build up of plies over the sure for 14 h.
bushing is recommended. An alternate After the autoclave cycle, carefully remove
method is to pot the bushings into the lami- the bag and films from the laminate to avoid
nate after the final cure. To do this a tapered lift up from the master surface. Attachment of
wax or rubber plug should be placed over the the egg crate structure (support or back-up
pin to allow space for the potting compound structure, Fig. 25.4) to the laminate is very
after the final cure. Each ply should be care- important to minimize any potential residual
fully worked into corners and radii making stresses built into the laminate or stresses from
sure all entrapped air is removed. Wrinkles the egg crate itself. Leave the laminate on the
should also be carefully worked out before master surface and attach board structure of
another ply is placed over it. If a persistent the same material to the surface of the lami-
wrinkle or air bubble can not be rolled out, nate. If the laminate is glass/epoxy, the egg
then carefully slit the pockets with a sharp crate material can be made from glass/epoxy
knife and work it down into the surface. In the or aluminum honeycomb sandwiched
excess area of the tool, thermocouples can be between glass. The point is to avoid stresses
strategically located between the plies for caused by the difference in CTE between the
recording during the autoclave run. As a rule egg crate and laminate by using similar mate-
of thumb, debulking should be performed rials.
570 Toolingfor composites
The egg crate should be cut to the contour of oven cure at 177°C (350°F) (Le. metal or mono-
the laminate with a standoff of 3.17mm lithic graphite) the post cure can be performed
(0.125 in). This prevents hot spots during pro- without removal of the tool from the master.
duction part curing and also mark off into the However, if the master material will not toler-
tool laminate. The egg crate should be con- ate this temperature, careful removal of the
structed so that it will lie flat on the surface. tool from the master must be done prior to the
The intersections of the board stock are held post cure.
together with cloth and resin with at least Separation of the tool from the master
three strips per junction. To ensure minimal should be done carefully to avoid damage to
stress to the laminate from the egg crate struc- the master or the tool itself. Tooling pins
ture, it is advisable to remove the structure should be removed prior to separation. Tools
from the laminate and cure the strips holding with severe contours may require plastic
the structure together at 177°C (350°F). wedges to be inserted around the tool periph-
After curing, the structure can be placed ery until it releases. Once the tool is separated,
back onto the laminate and 'tied' into the lam- the surface should be inspected for pinholes or
inate with at least three strips of cloth and resin roughness. Pinholes can be filled with resin
around the periphery of the egg crate. Shims and the roughness can be smoothed out with a
can be used to provide for the standoff. If the fine grit sandpaper. Edges of the tool can be
type of master used for the lay-up permits an 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 FEP, bleeder and the vacuum bag. Depending
ply wrinkle in order to work it down. Bushings on the resin system and the tooling aid mater-
should be placed over the tooling pins at this ial used, a precure is recommended and
point and worked into the resin to seat them. A should be supplied by the manufacturer.
heavier cloth such as 7587 glass or 2548 carbon Fabricate an egg crate structure using 9.25 mm
can be used for the remaining plies. Since the (0.375 in) thick board stock of similar material
cloth was precut into squares or rectangles and to the laminate to avoid stresses caused by the
the warp direction was maintained, each ply difference in CTE between the egg crate and
should be placed at 45" to the previous ply. laminate. If the laminate is glass/epoxy, the
Overlaps of 6.35 mm (0.250 in) between plies egg crate material can be made from
should be maintained but a seam should never glass /epoxy or aluminum honeycomb sand-
be placed over a seam from a previous ply. wiched between a glass laminate. The egg
After each ply, add additional resin to cover the crate should be cut to the contour of the lami-
surface. Place the next ply and work the resin nate with a standoff of 3.17 mm (0.125 in). The
up through it by pressing the cloth with the standoff prevents heat differences or hot spots
brush. If there is not sufficient resin to com- on the tool surface during production part cur-
pletely wet out or saturate the ply, additional ing and also prevents mark off from the back
resin should be used. Saturation of the cloth up structure pressing upward into the tool
with resin on a table separate from the lay-up surface laminate. The egg crate should be con-
surface and then transferring the saturated ply structed so that it will lie flat on a surface. The
to the tool can cause air entrapment and bridg- intersections of the board stock are held
ing of the ply. After the fourth ply, or prior to together with cloth and resin with at least
the resin curing, apply a peel ply to the surface three strips per junction. To ensure minimal
for a compaction cycle. The peel ply when stress to the laminate from the egg crate struc-
removed before other operations will eliminate ture, it is advisable to remove the structure
the need for sanding the surface prior to bond- from the laminate and cure the strips holding
ing. This is followed by a Teflon film with the structure together at 177°C (350°F). This
perforations every 250-300 mm (10-12 in). will allow the tool surface to be tied into a sta-
Cover this with a heavy glass or bleeder cloth to bilized support structure and minimize
bleed off excess resin during compaction. warpage during subsequent cure cycles.
Finally, place a nylon vacuum bag over the sur- After the support structure is cured, the
face using sealant tape to attach to the surface structure can be placed back onto the laminate
and apply a vacuum of at least 6.2 kPa and attached or 'tied' to the tool laminate with
(25inHg). Hold this vacuum for 10-12h or at least three strips of cloth and resin around
overnight or until the peel ply can be removed the periphery of the egg crate. Shims can be
without disturbing the laminate layers. used to provide for the standoff to prevent
Following this cycle, the bag and peel ply can warpage. If the type of master used for the lay-
be removed along with the tooling pins and up permits an oven cure at 177°C (350°F), then
lamination can commence as previously the post cure can be performed without
described. Debulking should be performed removal of the tool from the master. However,
after every 6 plies or before the resin begins to if the master material will not tolerate this tem-
cure. Final laminate thickness should be 9.5 mm perature, careful removal of the tool from the
(0.375in). It is probably a good idea to build up master must be made prior to the post cure.
the bushed hole area with additional plies to Allow the tool to stand at ambient temperature
ensure vacuum integrity. for a minimum of 24 h prior to post cure.
After the final ply has been applied, the After the final 177°C (350°F) post cure,
compaction step is repeated with the peel ply, 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) trim and routing operations are always con-
or thicker may be used as a transfer medium ducted at ambient temperatures, CTE is not
by relocating the position of the holes to the considered in the design of this type of tooling.
surface of the Mylar and then using the Mylar Procedures for laminating the room tempera-
as a temporary master surface while fabricat- ture cured system are similar to those for drill
ing the fixture. Prior to fabrication, it must be fixtures. Periodic debulking is not required
determined if the fixture is to mount on the and the tool is not required to maintain any
outside surface of the part (OML) or the inter- vacuum requirements. Thickness can vary
nal surface of the part (IML). Since master depending on final use but is usually about
models normally represent the OML surface, 9.5 mm (0.375 in). If the tool is to be used for
most support tooling such as drill and trim fix- routing, a set back or offset will have to be
tures may be fabricated directly off this determined as defined by the type of routing
surface. Occasionally the surface required will equipment used. This set back must be identi-
be a specific distance above or below the sur- fied on the surface of the tool to alert
face of the master model. If the surface is personnel to which equipment is acceptable
above, tooling sheet wax at the specific dimen- for use with the tool. Failure to use the correct
sion required must be placed on the master set back will result in an under trimmed or
surface prior to fabrication of the tooling aid. over trimmed condition. A witness or verifica-
Sheet wax is commercially available in numer- tion line is usually scribed on trim fixtures as a
ous thickness to accommodate most reference to which edges may be checked for
requirements. If the surface required lies damage. This allows shop personnel to
inside the master model surface, a 'splash' quickly verify the accuracy of the trim fixture
consisting of plaster and hemp reinforcement with minimal inspection equipment. With drill
must first be pulled from the master surface fixture tooling, a determination must be made
and then the splash surface can be waxed to as to what surface the trim fixture is applied. If
the specific dimension inside the master sur- the tool is to represent the same surface of the
face. Tool pins are placed in the tooling aid. master model, then the tool may be directly
After the face coat and two layers of glass have taken from that surface. However, if the sur-
been applied, the drill bushing is seated onto face required is internal or external to the
the surface with additional lamination over master, appropriate steps including plaster
the bushing to provide an integral lock to the splashes or waxing must be completed to
tool. Template thickness can vary depending obtain the correct surface.
on use, but 9.5 mm (0.375 in) in thickness is
typical.
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
Bibliography 575
from the master model to produce a core pot- lighten the template to assist in handling.
ting template. Core may then be accurately Lightening holes can be placed by removal of
potted, laminated and then drilled after curing sections of the template not serving a specific
by referencing the location from the potting function. However, as material is removed to
template. Similar templates may be produced reduce weight, stiffeners must be added to
to locate individual details or other assemblies prevent warpage that may affect dimensional
that have to be located during detail construc- stability.
tion. Slits or eyebrows are cut into the laminate
to locate the edge of the production part ply
BIBLIOGRAPHY
and color coded and identified accordingly.
All templates are fabricated from room tem- Mallik, P.K., Fiber Reinforced Composites, New York
perature glass/epoxy cured systems and are Marcel Dekker, 1968.
designed to be light in weight with a thickness Fiberite Manufacturing Procedures, Toolrite Tooling
Materials System.
of 3.1-3.8 mm (0.125-0.150 in). United States Gypsum, Tooling Techniques.
Because some templates may be quite large, Morena, J.J., Advanced Composite Mold Making, New
provisions must be made where possible to York: Van Nostrand Reinhold.
26
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 Fig. 26.1 Schematic of the prepreg lay-up used in
effects which could ultimately lead to the rejec- autoclave cure (Springer, 1986).
tion of the part. A comprehensive discussion of
consolidation in composites would include lay-up used in autoclave cure. In a traditional
many complex phenomena. Simultaneously, lay-up process, prepregs with different fiber
there is heat, momentum and mass transfer, orientation and architecture are placed in cer-
accompanied by the chemical curing reaction tain order forming a near-net-shape composite
of the resin and the deformation and motion of structure. During the lay-up operation,
fibers. whether it is done manually or using a robot,
Consolidation techniques have been used in the trapping of air pockets within the structure
the fabrication of both thermoset and thermo- is unavoidable. Thus a consolidation step after
plastic composite parts, but are more crucial the lay-up operation is necessary.Prepregs are
steps in thermoset composite processing. The usually provided with relatively low fiber vol-
traditional composite manufacturing process ume fraction. With the consolidation step, the
for aerospaceindustry products usually starts fiber volume fraction of the composite product
with the B-stage impregnated prepregs con- can be increased and excessive resin can be
sisting of fiber preforms and staged resin removed.
matrix. Usually the resin content is relatively The basic mechanisms involved in a consol-
high. In order to achieve the required compos- idation process are the fiber deformation and
ite material properties which are dominated resin flow, which are coupled with thermal
by the fibers, consolidation is used as an effects and the resin cure reaction. A similar
important processing step. consolidation process can also be seen in soil
Figure 26.1 shows a setup of the prepreg mechanics such as the settlement of a founda-
tion. However, the deformation behavior of
fibrous materials is substantially different
Handbook of Composites. Edited by S.T. Peters.Published from that of granular structures and resin flow
in 1998by O1apman & Hall, London. ISBN 0412 540207 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
Efforts were made to describe the d a l d t ver- When the permeability and the resin viscos-
sus a data with a modified Arrhenius type ity are known, with the imposed applied
equation. The proposed empirical equations pressure condition, the rate of the outgoing
are resin flow can be calculated using the Darcy
equation. In general, flow may be multi-direc-
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 be solved. In practice, resin flow in one partic-
ular direction may be dominant, and the
da/dt = K3 (1- a ) (26.5) analysis can be handled as 1-D permeable
flow.
a > 0.3
where 26.2.2 FIBER DEFORMATION
K , = A, exp (-AE,/RT) The main contribution from Gutowski's model
is the description of fiber deformation behav-
K2 = A, exp (-AE,/RT) ior. Instead of treating fibers as separate layers,
a network concept is introduced. In other
K, = A, exp (-AE,/RT) words, fiber-to-fiber contact is assumed within
a fiber assembly, even in the case of aligned
A,, A, and A, are the pre-exponential factors,
fiber bundles. Thus a fiber filament span
AE,, AE, and AE, are the activation energies, R
between the neighboring contact points
is the universal gas constant, and T is the
becomes a small bending beam. During a con-
absolute temperature. The constants in the
solidation process when fibers are pushed
expression are found as:
closer, more and more fiber-to-fiber contacts
B = 0.47 take place, and the span length reduces. Thus
the bending stiffness of these small fiber
A, = 2.101 x lo9 min-' beams increases rapidly, resulting in nonlinear
elastic deformation response. The nonlinear
A, = - 2 . 0 1 4 ~ l O ~ r n i n - ~ elastic response of a fiber assembly under a
compressive load has been also studied in the
A, = 1.960 x lo5 min-l textile field, and an empirical formula was
proposed (van Wyk, 1946).
AE, = 8.07 x lo4J mol-' A proposed fiber deformation model for
aligned fiber bundles considers the deforma-
AE, = 7.78 x 104 J mol-' tion status variable, the fiber volume fraction
V f ,as a function of the consolidation pressure
AE, = 5.66 x lo4J mol-' (Gutowski, 1985).The expression is
L Resin Flow
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
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
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.
600
- PR,Theory Example problem 3: Bleeder ply molding
two models show significant different results. Specifically, a selected cure cycle must
On the other hand, the numerical schemes of ensure that:
the two models are different. Springer’s model
the temperature inside the material does
requires only the solutions of a series algebraic not exceed a preset value at any time during
equations, while in Gutowski’s model nonlin-
the cure;
ear partial differential equations have to be
2. at the end of the cure the resin content is
solved. A comparison study has been pre- uniform and has the desired value;
sented by Smith and Poursartip (1993). 3. the material is cured uniformly and com-
pletely;
26.3 CURE CONTROL 4. the cured composite has the lowest possible
void content;
Fiber reinforced thermosetting resin compos-
5. the cured composite has the desired ther-
ites manufactured in autoclaves are made by
mal and mechanical properties;
forming the uncured fiber-resin mixture into
6. the curing is achieved in the shortest time.
the desired shape and then curing the mater-
ial. Curing requires the application of heat and Figure 26.10 shows schematically the overall
pressure. Heat is used to facilitate and control cure process model structure. In an early study,
the chemical reactions of the resin, and pres- Loos and Springer (1983a)proposed a thermo-
sure is used to consolidate the composite, chemical model. Heat transfer from the
squeeze out the excess resin, and minimize the environment to the composite material deter-
void content. A cure cycle usually means the mines the temperature distribution, the degree
magnitude, duration, and profile of the tem- of cure of the resin, and the resin viscosity
perature and pressure applied during a curing within the composite structure. The tempera-
process. Selection of the cure cycle directly ture inside the composite can be calculated
affects the quality of the finished composite using the law of conservation of energy. By
product, such as fiber content, fiber distribu- neglecting the energy transfer by convection,
tion, and void percentage. the energy equation can be expressed as:
Viscosity b Flow
/
Reaction kinetics
Fig. 26.10 Schematic of overall cure process model (Dave et al., 1990).
Cure control 587
(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)
)$(:I
a =
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
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
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
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 In thermal expansion molding, two basic
process is done with a vacuum bagging sys- methods are employed: the trapped or fixed-
tem or with an autoclave. With the tool still on volume rubber method and the
the model, the support structure, either a solid variable-volume rubber method. Figure 26.16
laminate or an ’egg-crate’ panel is attached to shows the setup for both methods. The fixed-
the tool by means of locally applied fabrics, volume method exploits the large difference
room-temperature curing, and high-tempera- between the coefficient of thermal expansion
ture resistant resins. Once the support of the elastomer and that of metals. The elas-
structure is cured to the laminate shell, it is tomer is confined within a closed metal tool
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 Rubber tool sized to fill
the cavih, in the pan
throughout the aerospace industry to produce
parts that are structurally reliable, repro-
ducible, and dimensionally accurate.
,Pan
Teflon separator film Breather cloth
/ Vacuum bag
.--- Floating-plate
pressure control
-
pan 30 excess pressure is vented
by forcing the floating plate
to the bag.
‘PFP master
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
REFERENCES
Clays, Geotechnique, 1967,17,261-273.
Batch, G.L. and Macosko, C.W., A Model for Two- Gutowski, T.G., A Resin Flow /Fiber Deformation
Stage Fiber Deformation in Composite Model for Composites, S A M P E Quarterly, 1985,
Processing, Proc. 20th Intern. SAMPE Tech. 16(4),58-64.
Conf., September 1988, pp. 641-650. Gutowski, T.G., Morigaki, T. and Cai, Z., The
Bhi, S.T., Hansen, R.S., Wilson, B.A., Calius, E.P., Consolidation of Laminate Composites, J.
and Springer, G.S., Degree of Cure and Viscosity Composite Mater., 1987,21, 172-188.
of Hercules HBRF-55 Resin, Proc. 32nd Intern. Gutowski, T.G., Cai, Z., Bauer, S., Boucher, D.,
SAMPE Symp. Exhib., Vol. 32., 1987, pp. Kingery, J. and Wineman, S., Consolidation
1114-1118. Experiments for Laminate Composites, J.
Biot, M.A., General Theory of Three-Dimensional Composite Mater., 1987,21,650-669.
Consolidation, J. Appl. Pkys., 1941,12, 155-164. Gutowski, T.G. and Cai, Z., The Consolidation of
Biot, M.A., Theory of Elasticity and Consolidation Composites, in The Manufacturing Science of
for a Porous Anisotropic Solid, J. Appl. Phys., Composites, Proc. Manufacturing International
1955,26(2), 182-185. 88, Vol. IV,(ed T.G. Gutowski), 1988, pp.13-25.
Biot, M.A. , General Solutions of the Equations of Halpin, J.C., Kardos, J.L. and Dudukovic, M.P.,
Elasticity and Consolidation for a Porous Processing Science: An Approach for Prepreg
Material, J. Appl. Meck., 1956, March, 91-96. Composite Systems, Pure Appl. Chem., 1983,55(5).
Borstell, H. and Turner, K.T., Tooling for Autoclave Harmon, B.D., Graphite-Epoxy Tooling, in
Molding, in Engineered Materials Handbook, Vol. Engineered Materials Handbook, Vol. 1: Composites,
1: Composites, ASM International, 1987, pp. ASM International, 1987, pp.586-589.
578-581. Kardos, J.L., Dudukovic, M.P., McKague, E.L. and
Cai, Z . and Gutowski, T.G., Fiber Distribution and Lehman, M.W., Void Formation and Transport
Resin Flow in the Molding Process, Proc. 7th During Composite Laminate Processing: An
Int. Conf. Composite Mater. (ICCM-7), 1989, 1, Initial Model Framework, in Composite
76-82. Materials: Quality Assurance and Processing,
Connor, M., Gibson, A.G., Toll, S. and Manson, ASTM STP 797, (ed C.E. Browning), 1983, pp.
J.A.E., A Consolidation Model for Powder 96-109.
References 595
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;
Mechanical drilling of composite materials 597
cutting speeds range from 244 surface Depth of cut will vary depending on the
m/min (800 surface ft/min) to 762 surface thickness of the part and the amount of mate-
m/min (2500 surface ft/min) with PCD end rial to be removed.
mills;
when cutting parallel to the fiber direction,
27.3.1 ADVANTAGES
the wear ratio on the cutting tool increases
compared with cutting perpendicularly to Computer numerical controlled lathes (CNC)
the fiber direction; can be used to machine simple to very complex
surface finish remains below 20Ra [arith- rotational parts. CNC machining produces
metical average roughness (see IS0 R488)] accurate parts at a high production rate.
when cutting with PCD end mills and the
flank wear is approximately 0.127 mm
27.3.2 DISADVANTAGES
(0.005in);
0 the surface finish deteriorates above 150 Ra Delamination can also occur on a lathe (Fig.
when cutting with a carbide end mill and the 27.1), therefore the part may require a finish
flank wear has reached 0.127 mm (0.005in); cut moving from the largest diameter to the
0 roughing feedrates range from smaller diameter. Graphite chips are a serious
0.23 mm/rev (0.007 in/rev) to 0.38 mm/rev problem. The spinning chuck creates a fan
(0.012 in/rev) and finish feedrates range effect on the graphite particles. The exhaust
from 0.076 mm/rev (0.002 in/rev) to system must be adequate to control the
0.13 mm/rev (0.005 in/rev); graphite chips. Also, the machine ways and
0 the depth of cuts should range from one the ball screws on the machine must have
quarter to one half of the diameter of the sealed protection to minimize wear. The com-
end mill cutter. Depth of cut will vary puter control requires protection from the
depending on the rigidity of machine ways, graphite chip particles.
spindle and workholding devices.
The disadvantages associated with milling 27.4 MECHANICAL DRILLING OF
of composites include controlling the graphite COMPOSITE MATERIALS
chips (dust particles), confining them to a small
area and having an adequate collection system. Drilling holes in composites can cause failures
A second problem is controlling the outer lay- that are different from those encountered
ers of the composite so that the fibers will shear when drilling metals. Delamination, fracture,
instead of lifting up under the force of the cut- break-out and separation are some of the most
ting action and leaving extended fibers beyond common failures. Delamination (surface and
the cut surface. Also when cutting perpendicu- internal) is the major concern during drilling
lar to the lay of composite fibers, edge composite laminates as it reduces the struc-
break-out can occur. This can be controlled by tural integrity, results in poor assembly
designing a backup structure in the tooling. tolerance, adds a potential for long term per-
formance deterioration and may occur at both
the entrance and exit plane. Delamination can
27.3 CONVENTIONAL TURNING
be overcome by finding optimal thrust force
The turning of graphite composite is utilized (minimum force above which delamination is
to produce round surfaces that need to mate initiated). Figure 27.2 shows push out delami-
with either metal of graphite parts. The cutting nation at exit because at a certain point
speeds can be over 305 m/min (1000 ft/min) if loading exceeds the interlaminar bond
the part can be held securely and PCD tool strength and delamination occurs. Figure 27.3
inserts are utilized. shows peel-up delamination at entrance
598 Composite machining
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)
-
[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 (CFRP) and glass fiber-epoxy (GFRP) lami-
quality. Tool life is normally determined by the nates using HSS and carbide tipped drills
extent of delamination and fiber break out. For made the following observations. Both chisel
machining graphite composites with or with- edge and flank wear increased on the carbide
out aluminum backing, PCD tooling is drill with a higher ratio of wear between 200
suggested with the same speeds and feeds and 400 holes (test sample 400 holes). The tool
used for machining graphite composites with- wear was greater in the CFRP laminates due to
out any backing. the abrasive nature of carbon fibers. Flank
For machining graphite composites with wear is more pronounced in GFRP when the
titanium backing, it is not recommended that feed was increased and the same effect is
the same drill be used for both the titanium noted when speed is increased. The HSS drills
and graphite sections. Initially a hole should lasted for ten holes in the graphite and twenty
be drilled up to the titanium layer with a holes in the glass.
hydraulic depth sensing device at high speeds
and feed. A second drill with lower speed and
27.4.1 DFULL GEOMETRY
feed for machining titanium should be used.
Finally finish reaming operation and counter- Drill point geometries influence the torque
sinking should be performed for assuring hole requirements. Lip relief and rake angles are
quality. determined by the application. The dagger
A study carried out on carbon fiber-epoxy drill is ideal to machine graphite composites
600 Composite machining
Table 27.3 Typical through-cutting traverse rates (in mm/s) with AWJs for different composites3
Table 27.4 Surface waviness and corresponding cutting traverse rates (in mm/s) for some composite
materials3
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;
where the traverse rate is uniform. Surface fin- 0 no thermal stresses;
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;
finishing operations. 0 optimal range of parameters available to pre-
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.
Ultrasonic machining 605
\
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
(3.94 in) because of the limitation on the size of Sonotrode (tool) material
the tool. Some of the variables that influence
Tools with diamond tips have good material
USM for close tolerances are as follows:
removal characteristics and very low wear but
are difficult to machine. Table 27.7 shows accu-
Abrasive type and size racy results of using a non-rotating steel
sonotrode.
Abrasives contained in the slurry do the actual
machining so they must be selected on the
basis of the workpiece material and the surface Ultrasonic vibrations
quality needed. As in the case of AWJ, larger The ideal condition would be the amplitude of
abrasive grains give higher material removal ultrasonic vibration to be equal to the grain
rates and rougher surfaces. The grain diameter mean diameter. If the amplitude is too small
cannot be larger than amplitude of the the abrasive cannot enter the machining gap, if
sonotrode as this would inhibit the injection of too large it causes the grains to be incorrectly
the grains to the machining gap. Common projected. A mixture of both the types of abra-
types of abrasive used are A1,0, oxide, Sic, BC sive may be used and a suitable amplitude
and diamond. selected to determine which size grain enters
Table 27.5 shows recommended abrasive the machining gap.
for various materials. The grain diameter
affects surface roughness, overcut and
Surface area
machining rates. When high removal rates are
necessary with no high surface quality This factor influences removal rates and tool
required, 180-280 mesh abrasive do the job. wear. With a small diameter, higher feed rate
For finer surface finish 320-600 mesh abrasive is obtained but also higher tool wear is
is recommended. Table 27.6 shows surface noticed. This can be overcome by using a dia-
roughnesses for different workpiece materials. mond tool or with a closed loop force sensitive
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.
systems have been supported by DoD and 28.3.1 KEY FEATURES OF MECHANICALLY
NASA4r6.Numerous papers have been pre-
~~
FASTENED JOINTS
sented Over the years in a series Of Figure 28.1 represents a generic single fastener
DoD/NASA/FAA 'Onferences On Fibrous
joint, while Fig. 28.2 depicts a multiple fas-
Composites in Structural De~ign~,'~-'~. Many of tener configuration. Many of the most
the design principles which have been devel- important features of joints are illus-
'ped to take into account the trated in the single fastener case s h o r n in Fig.
characteristics of bolted composite structures 28.1. Key dimensions are D, the fastener diam-
have been described4,6, 13. eter, t, the thickness of the joint structural
It is not possible within the scope Of this elements, e, the edge distance (distance from
discussion to describe all the details and the fastener center to the edge of the
Processes that are necessary for achieving the upper plate) and W, the width of the part of
design of specific joints. The objective is rather the upper plate to the left of the fastener.
to give the reader Some insight into the Similar featups apply to the lower plate ele-
factors that control the behavior of mechani- ment. Note that the Same load, p, is passed
fastened joints in structures' successively through various sections of the
The behavior of mechanically fastened joint, including the bearing section in front of
joints is governed by types Of information: the fastener of area Dt which is in compres-
(l)the features that the behavior Of the sion, the b o shearout sections of total area 2et
joint around individual fasteners and; (2) the which are loaded in primarily in shear, the net
behavior of multiple arrays of fasteners. The section,(w - D)t which is in tension, the
behavior of individual fasteners can be consid- gross section wt which is also in tension.
ered in terms of a generic rectangular element The average stresses associated with these
surrounding each fastener (Fig. 28.1), whose sections are:
length and width are represented as ratios
wi& respect to the fastener diameter. The average bearing stress, ab= P / D t ;
effects of the geometry of this element together average shearout stress, a,, = P/2et;
with effects of the reinforcement arrangement average net section stress, aN= P/(W - D)t;
used in the laminate for the element determine average gross section stress, aG= P / Wt.
the structural conditions under which the ele- (28.1)
ment will fail. Once the characteristics of the
rectangular element are selected, its deforma- LOAD PATH
tion characteristics can be combined with
those of other rectangular elements making up
the joint to obtain the performance of the joint P
t
Axit!
tit h
Lateral
Pitch
w
eff
* Lateral Pitch
There is obviously a competition for space The behavior of this approximation empha-
between the bearing section and the net sec- sizes the tradeoff between the effect of the
tion. Increasing the fastener diameter, D, to bearing section and the net section on the peak
lower abhas to decrease (W - D)t, the net sec- net section stress. A similar functional fit to the
tion, thereby increasing uN, and vice versa. curve of KNt (the stress concentration based on
Furthermore, if D / W is much less than 1, the a,) against D / W was given for isotropic plates
case is similar to that of a fastener in an infi- by Hart-Smith9, based on photoelasticity
nitely wide plate; in such a case all the peak results reported in the literature; when stated
stresses become a constant multiplier of the in terms of Kgt, the Hart-Smith approximation
bearing stress ab, which becomes large for leads to
D/W<<l. If D is large enough to fill most of
the available width, the net section becomes
K;t (bolt loaded hole) = W/D + 2/(1- D/W)
small, oNbecomes large, and the peak net sec- - 1.5/ (1+ D / W ) (28.4)
tion and shear stresses become proportional to
He also gave an expression for KNt for open,
uNfor this case. As seen in Fig. 28.4, is large
unloaded holes (i.e. with no load transfer
for small D / W as well as for D / W approach-
between the fastener and plate) in isotropic
ing 1, leading to a minimum around D / W =
plates; when the stress concentration is
0.59J2. The quantity 0.89ub/uG + 1.8 uN/uG
expressed as a ratio with respect to ac rather
which is plotted in Fig. 28.4 gives a reasonable
than uN the Hart-Smith open hole expression
approximation to the curve of KGt against
reduces to:
D / W, so that the use of eqn (28.1) to express ob
and uNin terms of D / W, shows: Kgt (open hole) = 2/(1- D / W )
Kgt 0.89W/D + 1.8/(1 - D/W) (28.3) + (1 - D/W)* (28.5)
\
Y
4 --
3 -- elastic measurements)
01 I
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
-
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
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
-
l€NSlON FAIUIIL BO11 PULLING lHlOUGn U M I W T E
and reinforcement, failure may take the form PEICfNTAGf W-DEGIEE PLIES
of shearout or net tension rather than bearing
failure; bearing strength only identifies the BEARING STRESS CONTOURS 6 5 1 )
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 WLT DIUETER = 0.25 IN.
discussed in Section 28.3.6, in which e/ W (usu- (10RQUED WLW
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" O M Z O 3 D ~ S O ~ M ~ W l W
RKfNlAGE f4S-DEGltE PLIES
and 90" directions with respect to the load
axis, implying that other orientations are not
encountered; in addition, the 45" reinforce- Fig. 28.12 'Carpet' plot of maximum bearing stress
vs. percentage of reinforcement in key directions4.
ment is arranged symmetrically as double
plies of k45" reinforcement. The notation com-
monly used to describe the stacking sequence the reinforcement arrangement in the vicinity
is condensed to reflect percentages of plies in of the joint.
the three customary directions, 25/50/25 rep-
resenting 25% 0", 50% 45", and 25% 90", or 28.3.4
quasi-isotropic, reinforcement, for example.
The effects of reinforcement percentages on Single fastener joints cannot generally achieve
maximum achieved bearing stress are shown anything close to the strength of the laminate
in Fig. 28.12, a three-parameter 'carpet plot' being loaded and are not usually encountered
which is used to show the effect of percentage in structural joints. Single fastener coupons
of reinforcement in the 0", 90" and 4 5 " direc- do, however, serve as building blocks for
tions on maximum achieved bearing stress for design of multi-fastener joints (Fig. 28.2) since
a fixed joint geometry. The contours of con- stress analysis and strength test results on sin-
stant bearing strength indicate that maximum gle fastener geometries provide data which
joint strength is achieved within a broad translate directly to multi-fastener arrays in
plateau lying between 3040% 0" and 1040% structures. There are two principal features
+45" reinforcement. To avoid low strength that affect multi-fastener arrays; that of bear-
against shearout failure, it is generally agreed ing-bypass load is illustrated in Fig. 28.13. The
that a minimum number of 90" plies, at least bypass load, Pb , can be considered as a load
lo%, should be included in the laminate. added at the d o a d e d (right) end of the upper
Laminates reinforced in fewer than three element in the single fastener joint in Fig. 28.1.
directions, i.e. 0/90° and k45" reinforcement, In the case of a multi-fastener array (Figs. 28.2,
should be avoided if possible, since they 28.14), Pbpfor a given fastener is equivalent to
respond ductiley with excessively low yield the sum of the loads developed by the fasten-
strengths. These recommendations may be dif- ers lying to the right of (i.e. those lying in the
ficult to follow if considerations other than direction of the load from) the one under con-
maximum joint structural performance govern sideration. For each fastener, the load P, in
620 Mechanical fastening and adhesive bonding
- -
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'
ce)
radial pressure distribution should be avoided,
-
BEARING
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-
Fig. 28.16 Contact angles for pure bearing load and
pure bypass load. 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-
contact region varies with load and is smaller tion; bearing failures cannot.
than that of exact-fit fasteners. Crews and Naik and CrewsIs described test methods
Naik8 treated the case of 1.2% clearance, i.e. a for joint strength under combined bearing-
hole diameter 1.2% greater than the fastener bypass loading, with compressive as well as
diameter, for which contact between the fas- tensile bypass loads. Typical results are given
tener and hole occurs from about -60" to +60° in Fig. 28.17 for a 1.2% clearance fit fastener in
for typical loads.) a quasi-isotropic carbon epoxy laminate.
For intermediate bearing/bypass ratios, the Failure modes here are designated 'TRB' ('ten-
contact region is a mix of the two situations. sion reacted bearing', i.e. bearing failure with
Oplinger12gave the variation of the radial pres- tension bypass loading), 'TRC' (bearing 'fail-
sure distributions for exact fit fasteners, for ure with compression bypass loading), 'NT'
joints in tension, which showed how the con- (net section tension), 'NC' (net section com-
tact region is modified as the bearing/bypass pression) and 'OSC' or 'offset compression'
ratio varies, while Naik and Crewss treated which refers to the failure mode illustrated in
cases of both exact and clearance fits for both Fig. 28.18 for compression bypass load.
tension and compression loaded joints; in addi- Although the load distribution for the five-
tion, Madenci7 gave comparable results for fastener joint shown in Fig. 28.12 is
cases of shear loaded joints. A number of represented as having the same P, for each fas-
efforts have treated the contact problem for tener, this condition cannot be achieved for
pure bearing by assuming a radial pressure joints in general. As shown in Fig. 28.1913,
distribution which varies around the hole as there is usually considerable variation of fas-
the cosine of the angle with respect to the load tener loads along the joint. In a two-fastener
axis; in addition, for combined bearing and joint such as that shown in Fig. 28.20, the
bypass loading (following industry practice) upper and lower plate elements ('U' and 'L')
Hart-Smith9 and others have, as a matter of have to stretch equally under load if there are
expediency, superposed the peak stresses pre- no fastener deflection effects (no fastener tilt-
dicted for pure bearing and pure bypass (i.e. ing or bending).
the values of Kt: predicted by eqns (28.4) and
622 Mechanical fastening and adhesive bonding
Bypass stress, S Wa
nP'
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.
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.
I'
-
E
, -
CONFIGURATION A
O m 1 INAN.
element thickness and local bearing load pre- 28.3.5 FASTENER EFFECTS
dominates here. Note that configuration D, the Joint strengths for local areas (Fig. 28.13)
strongest, uses a combination of variable fas- around individual fasteners are affected by a
tener diameter and element tapering to number of parameters associated with the fas-
achieve a maximum thickness of the outer ele- teners. Some of these include: whether the
ments which is greater than that in joint is in single or double shear (Fig. 28.21);
configuration C, to obtain maximum joint the use of countersunk (flush head) compared
strength. Thus, judicious use of element taper- with protruding head fasteners (Fig. 28.22);
ing and variation of fastener diameters as well effects of fastener diameter; effects of fastener
as other joint parameters can improve joint clamping; fastener clearance effects, and effect
performance. With untapered joints, the maxi- of fastener deflections on fastener load distrib-
mum benefit of additional rows of fasteners is ution. Bearing strengths are significantly
not much more than 20% greater than that for affected by the use of single compared with
single row joints. Joint tapering will provide
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 ~
-
COMPRESSION JOINT w-
pressures) that can be calculated in terms of Complications, such as the way in which the
the pitch of the fastener threads from machine fastener head and nut/washer combination
design formulas. Bolt tensions for a given bears on the surfaces of the plate element will
torque level are notoriously variable because influence the outcome of such calculations and
of friction effects in the bolt threads, but spec- must be taken into account. In addition, the
ified torque levels which have been through-thickness distribution of bearing
determined empirically probably represent pressure between the fastener and the sur-
minimum clamping levels necessary to insure rounding the plate element should be
maximum bearing strengths that can be included in the calculations. The method of
achieved when variations in service condi- Harris, qalvo and Hoosonz3which treats the
tions are taken into account. Steps should be bore of the fastener hole as an elastic founda-
taken to avoid loss of clamping pressure due tion for the beam used to model the fastener
to through-the-thickness viscoelastic deforma- has been applied6for such calculations.
tion of the laminatez1”at elevated temperature
and humidity.
28.3.6 TEST METHODS
Fastener clearances are typically on the
order of 0.075 mm (0.003 in) or less for typical Joint strength tests are needed to establish cer-
0.635 mm (0.25 in) aircraft fasteners. Analytical tain key parameters of the joint as inputs to
studies have shown that bearing stresses design analyses. Such data as failure stresses
increase significantly for such relatively small for pure bearing load as obtained from single
clearances since the angle of contract decreases fastener coupons, and open hole coupon
rapidly as the clearance increases. Clearances strengths for both tension and compression
also have a significant effect on the fastener loading, are needed to establish joint perfor-
load distribution since the last in a series of mance for pure bearing and bypass loads.
fasteners cannot take up load until all the Intermediate combinations of bearing and
clearances have been taken up. bypass load must also be considered to pro-
In addition to the effect of clearances on fas- vide empirical curves for dealing with the
tener load distribution, effects of fastener general situation. Because of differences in the
bending deflections must be taken into way the fastener contacts the surrounding
account in load distribution calculations such plate materials, bearing tests have to be con-
as those provided by the A4EJ, SASCJ and ducted to treat both single and double lap
SAMCJ codes described above. In the case of (single and double shear) configurations. In
the two-fastener joint shown in Fig. 28.20, single lap joints in particular, tests are needed
bending and rotational deflections of the fas- to establish the effect of fastener rotation and
teners will modify the load distribution bending deflection. Fastener deflections must
described in the discussion of that figure for be determined in tests of the type just
zero fastener deflection. For E,t,>>E,t,, in Fig. described for providing fastener response data
28.20 for example, fastener deflections will in connection with predictions of load distrib-
allow some load to be transferred to the sec- ution in multifastener joints. In addition,
ond fastener, as opposed to the case of no fastener head pull-through strength tests have
fastener deflections discussed earlier which to be performed to allow for joint configura-
led to Pf2= 0. Fastener deflection effects can be tions in which overall bending takes place, in
inferred from bolt bearing tests which provide which case out-of-plane forces between the
for deflection measurements. Alternatively, fastener and joint plates tend to be sigruficant.
analytical approaches based on beam models The details of test methods for mechanically
for the fastener which include both bending fastened joints are described by Shyprykevichz4
and shear deformations have been used13. and in Mn-HDBK-1725.
Adhesive joints 627
28.4 ADHESIVE JOINTS the adhesive is never the weak link;(3) recog-
nition that the ductility of aerospace adhesives
28.4.1 INTRODUCTION is beneficial in reducing stress peaks in the
adhesive; (4) careful use of such factors as
Adhesive joints are capable of high structural adherend tapering to reduce or eliminate peel
efficiency and constitute a resource for struc- stresses from the joint; (5) recognition of slow
tural weight saving because of the potential cyclic loading, corresponding to such phenom-
for elimination of stress concentrations which ena as cabin pressurization in aircraft, as a
cannot be achieved with mechanically fas- major factor controlling durability of adhesive
tened joints. Unfortunately, because of a lack joints, and the need to avoid the worst effects
of reliable inspection methods and a require- of this type of loading by providing sufficient
ment for close dimensional tolerances in overlap length to ensure that some of the adhe-
fabrication, aircraft designers have generally sive is so lightly loaded that creep cannot occur
avoided bonded construction in primary there, under the most severe extremes of
structure. Some notable exceptions include: humidity and temperature for which the com-
bonded step lap joints used in attachments for ponent is to be used.
the F-14 and F-15 horizontal stabilizers as well Much of the discussion to follow will retain
as the F-18 wing root fitting, and a majority of the analysis philosophy of Hart-Smith, since it
the airframe components of the Lear Fan and is considered to represent a major contribution
the Beech Starship. to practical bonded joint design in both com-
While a number of issues related to adhe- posite and metallic structures. On the other
sive joint design were considered in the earlier hand, some modifications are introduced here.
literaturezG3, much of the methodology cur- For example, the revisions of the
rently used in the design and analysis of Goland-Reissner single lap joint analysis36
adhesive joints in composite structures is have been re-revised according to the
based on the approaches evolved by L.J. Hart- approach presented in Refs. 53,54.
Smith in a series of NASA/Langley-sponsored Certain issues which are specific to compos-
contracts of the early 1 9 7 0 as~ well
~ ~as~from ite adherends but were not dealt with in the
the Air Force’s Primary Adhesively Bonded Hart-Smith efforts will be addressed. The most
Structures Technology (PABST) programw3 of important of these is the effect of transverse
the mid-1970s. The most recent such work shear deformations in organic composite
developed three computer codes for bonded adherends.
and bolted joints, designated ‘A4EG’, ’A4EI’
and ’A4EKW under Air Force Contract . The
28.4.2 SUMMARY OF JOINT DESIGN
results of these efforts have also appeared in a
CONSIDERATIONS
number of open literature publi~ations~’-~. In
addition, such approaches found application
28.4.2.1 Effects of adherend thickness:
in some of the efforts taking place under the
adherend failures versus bond failures
NASA Advanced Composite Energy Efficient
Aircraft (ACEE) program of the early to mid- Figure 28.25 shows a series of typical bonded
198Os5O,51. joint configurations. Adhesive joints in general
Some of the key principles on which these are characterized by high stress concentrations
efforts were based include: (1)the use of simple in the adhesive layer. These originate, in the
one-dimensionalstress analyses of generic com- case of shear stresses, because of unequal axial
posite joints wherever possible; ( 2 ) the need to straining of the adherends, and in the case of
select the joint design so as to ensure failure in peel stresses, because of eccentricity in the
the adherend rather than the adhesive, so that load path. Considerable ductility is associated
628 Mechanical fastening and adhesive bonding
types in Figs. 28.25 and 28.26 corresponds to a Scarfjoints with unbalanced stiffnessesbetween
specific range of adherend thicknesses and the adherends do not achieve the uniform shear
therefore of load capacity, and as the need for stress condition of those with balanced
greater load capacity arises, it is preferable to adherends, and are somewhat less structurally
change the joint configuration to one of higher efficient because of rapid buildup of load near
efficiency rather than to increasing the the thin end of the thicker adherend.
adherend thickness indefinitely. Step lap joints (Fig. 28.25(h)) represent a
practical solution to the challenge of bonding
thick members. This type of joint provides
28.4.2.2 Joint geometry effects
manufacturing convenience by accommodat-
Single and double lap joints with uniformly ing the layered structure of composite
thick adherends (Fig. 28.25(b), (e) and ( f ) ) are laminates. In addition, high loads can be trans-
the least efficient joint type and are suitable ferred if sufficiently many short steps of
primarily for thin structures with low running sufficiently small ’rise’ (i.e. thickness incre-
loads (load per unit width, i.e. stress times ele- ment) in each step are used, while maintaining
ment thickness). Of these, single lap joints are sufficient overall length of the joint.
the least capable because the eccentricity of
this type of geometry generates significant
28.4.2.3 Effects of adherend stiffness
bending of the adherends that magnifies the
unbalance
peel stresses. Peel stresses are also present in
the case of symmetric double lap and double All types of joint geometry are adversely
strap joints, and become a limiting factor on affected by unequal adherend stiffnesses,
joint performance when the adherends are rel- where stiffness is defined as axial or in-plane
atively thick. shear modulus times adherend thickness.
Tapering of the adherends (Figs. 28.25(d) Where possible, the stiffnesses should be kept
and (g)) can be used to eliminate peel stresses approximately equal. For example, for step lap
in areas of the joint where the peel stresses are and scarf joints between quasi-isotropic car-
tensile, which is the case of primary concern. bon epoxy (Young’s modulus = 55 GPa = 8 x
For joints between adherends of identical stiff- lo6 lb/in2) and titanium (Young’s modulus =
ness, scarf joints (Fig. 28.25(i))are theoretically 110 GPa = 16 x lo6 lb/in2) ideally, the ratio of
the most efficient, having the potential for the maximum thickness (the thickness just
complete elimination of stress concentrations. beyond the end of the joint) of the composite
(In practice, some minimum thickness corre- adherend to that of the titanium should be
sponding to one or two ply thicknesses must 110/55 = 2.0.
be incorporated at the thin end of the scarfed
adherend leading to the occurrence of stress
28.4.2.4 Effects of ductile adhesive
concentrations in these areas.) In theory, any
response
desirable load capability can be achieved in
the scarf joint by making the joint long enough Adhesive ductility is an important factor in
and thick enough. However, practical scarf minimizing the adverse effects of shear and
joints may be less durable because of a ten- peel stress peaks in the bond layer. If peel
dency toward creep failure associated with a stresses can be eliminated from consideration
uniform distribution of shear stress along the by such approaches as adherend tapering,
length of the joint unless care is taken to avoid strain energy to failure of the adhesive in shear
letting the adhesive be stressed into the non- has been shown by Ha~?-Smith~~ to be the key
linear range. As a result, scarf joints tend to be parameter controlling joint strength; thus the
used only for repairs of very thin structures. 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
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:
I I
[a RIGID KkU
f-
--f
T-
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:
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
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')
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 In the absence of thermal effects ( Tth = 0) and
and AT is the temperature change. assuming that Bi 1 Bo, the maximum value of
Note that is related to the resultants (axial the shear stresses occurs at the right end of the
adherend stress times thickness) at the ends of joint as noted earlier (Fig. 28.31). With thermal
the joint as shown in Fig. 28.36. The shear effects present, the situation is complicated by
stresses are then given 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)
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
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)
- I --
E
wL"
DI PLACEMENTS
U/.IS(X - L M ]
l o ~ x < l + l o ;=
w w,sinh[
sinh[Ulfl8t]
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-
+ -tu
---
t
+ tb x ; W, = -(1 - k) (28.22) wise set to 1 corresponding to very long outer
2 2 L 2
adherend lengths. A plot of k against the
The Goland and Reissner (GR) expression for adherend loading stress is is given in Fig. 28.40
the parameter k has been re-examined by for two different values of adherend thickness
Hart-Smith%and more recently by Oplinger", corresponding to bond thickness-to-adherend
based on the discussion in Ref. 74, the thickness ratios (p, in eqn (28.23b)) of 0.5 and
Goland-Reissner expression appears to pro- 0.1. This plot suggests that k is fairly constant at
vide adequate accuracy unless the adherends a value of about 0.25 for a wide range of
are excessively thin,not more that one or two applied stress values once the initial drop has
times the bond layer thickness, in which case occurred. The effect of bond-to-adherend thick-
the expressions given in Refs. 73, 74 and pro- ness ratio is not particularly great and can
vide corrections for bond layer thickness 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
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)
Figure 28.41 gives a comparison of the maxi- stresses vary essentially in proportion to the
mum bond stresses as functions of the loading load even in the single lap joint, as just dis-
stress ax for two different adherend thick- cussed. The stresses are plotted in this figure
nesses in a joint with a bond layer thickness of as a function of adherend thickness with the
0.01. It is interesting to note that the peel and adherend axial modulus as a parameter. The
shear stresses take on quite similar values. trend toward higher bond stresses and there-
Since the maximum peel stress varies approx- fore a greater tendency toward bond failure
imately as y i according to eqn (28.27) (the with increasing adherend thickness which was
contribution of U being relatively minor), the discussed in Section 28.4.2 is clearly borne out
relationship for ys given in eqn (28.26) sug- in these curves. Note also that reduction of the
gests that the peel stresses should be expected adherend modulus tends to aggravate the
to vary as (t/tb)1/2, while the same variation is bond stresses. In addition it is apparent that
seen from eqn (28.27) for the maximum shear there is considerable separation between the
stresses since p also contains (t/t,)'/* as a fac- peel and shear stresses in the case of the dou-
tor. Thus both stresses should vary with the ble lap joint, the peel stresses for the latter case
thickness ratio by the same factor. The fact that being smaller. This reflects the fact that the
they are numerically close together for all peel stresses vary linearly as yd defined in eqn
stresses is partly due to the effect of other (28.18b) and therefore vary as (t/tb)1/4 rather
parameters that enter into eqns (28.27) and than as (t/tb)l/*as in the single lap case. Thus,
(28.28) and partly due to the fact that k does peel stresses for double lap joints are not as
not vary much with load for axgreater than 5. much of a factor in joint failure as they are in
A slight nonlinearity can be observed in the single lap joints, although they are still large
curves of Fig. 28.41 for the lower loading enough relative to the shear stresses that they
stresses. can not be ignored.
Figure 28.42 gives a comparison of maxi- Failure characteristics of single and double
mum bond stresses in single and double lap lap joints will be discussed below. If the
joints for a fixed value of the loading stress ax. adherends are thin enough, failure in double
For loading stresses above this value the bond lap joints should be in the form of adherend
&=looOO, Gb=150,%=SO0
'4 I M.02; (52, g=10
12
4
E "
si3
lo
/
0 10 20 -
=* - 30 40
Fig. 28.41 Maximum bond stresses in single lap joint, bond thickness = 0.01.
644 Mechanical fastening and adhesive bonding
'
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 +
Fig. 28.42 Maximum bond stresses in single and double lap joints, fixed vx = 10.
axial (tensile or compressive) failure. For sin- on single lap joint performance is quite long
gle lap joints, adherend bending stresses are range. Figure 28.43 shows that for a joint with
significant at the ends of the overlap as indi- an adherend thickness of 2.54 mm (0.1 in) the
cated in Fig. 28.39; using standard beam bond stresses do not reduce to their minimum
formulas, the maximum axial stress for com- values until the overlap length reaches a value
bined bending and stretching (the latter stress in the range of 10-12.7 cm (4-5 in), for a load-
corresponding to the single lap joint in tension ing stress of 69 MPa (10 ksi). Double lap joints
loading) for the bending deflection given in also require some minimum length before
eqn (28.22) can be expressed as stresses settle out as a function of overlap
- length, but in this case the stresses reach mini-
QJrnax
= OX3(1+ t,/t)k (28.29) mum values with respect to overlap length for
The maximum adherend axial stress is lengths on the order of 5 to 10 adherend thick-
largest for adherends which are particularly nesses, in the present case amounting to
thin with respect to the bond thickness; these 1.3-2.5 cm (0.5-1 in).
will be prone to brittle bending failures for
composite adherends or to yielding associated
28.4.3.4.2 Effects of adherend tapering
with bending for metal adherends. Hart-Smith
discusses difficulties with the use of standard In this section we will consider joints with
single lap shear test specimens50.The problem adherend thicknesses which vary along the
is that adherent bending failures are likely to joint length. These include the configurations
occur with such specimens rather than bond shown in Figs. 28.44 and 28.45, namely, double
failures and test results obtained in such cases strap joints with tapered outer adherends and
tend to be irrelevant and misleading. scarf joints as well as step lap joints. As dis-
One additional characteristic difference cussed in Section 28.4.2.2, tapering the outer
between single and double lap joints should adherends of strap joints as in Fig. 28.44(a) is
be discussed. The effect of lateral deflections 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
I am i nat e meta 1
I
I
Triangular Elewnt
Fig. 28.45 Generic step lap joint.
take advantage of the layered structure of the tapered double strap joints, scarf joints and
composite adherend. The average slope of the step lap joints. The overall approach is to aim
region represented by the line through the for a highly efficient joint which reduces the
steps in Fig. 28.45 tends to control the average effects of shear and peel stress concentrations
shear stresses developed in the bond. Within at the ends of the joint. Ideally we would like
each horizontal section, equivalent to the tread to achieve the joint strength provided by the 'P
of a staircase, the behavior is analogous to a over A' concept obtained with the case dis-
joint with constant adherend thickness, and cussed in Section 28.4.3.2 for perfectly rigid
the differential equation given in eqn (28.10) adherends (Fig. 28.27), in which increasing the
(Section 28.4.3.2)applies locally when tu and tL joint length indefinitely brings the shear stress
are adjusted to match the local situation. An in the bond down to any required level regard-
expression similar to eqn (28.12), i.e. for thejth less of the magnitude of load being supported
step, 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
PB
+- 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 the maximum shear stresses within each gives some shear stress predictions for joints
step, and the overall solution is a chain of such with uniform adherend thickness for compari-
expressions with allowance for continuity of son with the tapered cases which are
the shear strain and resultants, Tuj and TLjat considered in Fig. 28.48.
the points where neighboring steps join. In Figure 28.46 defines the notation used in
each step of the joint the shear stresses will Fig. 28.45 in terms of 'fully tapered' outer
have a distribution similar to that of Fig. 28.36, adherends (Fig. 28.46(a)), partially tapered
the size of the peaks being governed primarily adherends in which the taper extends only
by the length of the step through the parame- part of the length of the joint (Fig. 28.46@))and
ter P.Z./t.The aspect ratio for the step, Zj/t,
can fully tapered adherends with an 'initial rise',
11
in prmciple be kept small enough to almost i.e. in which the thin end of the adherend does
completely avoid any peaking by using a large not come to zero thickness. (The term '% initial
number of steps and keeping the length of rise' implies that the rise is expressed as a per-
each one small. In practice, the number of centage of the maximum adherend thickness.)
steps is governed by the number of plies in the The three cases considered in Fig. 28.48 can
laminate. In addition, if the joint is used to be compared with the case for uniform
connect a composite adherend to a metal com- adherends with equal upper and lower
ponent, machining tolerance requirements adherends modulus (E, = EL)in Fig. 28.47. For
and cost considerations for the metal part the situation of no initial rise, two cases are
enter into the selection of the number of steps. considered in Fig 28.48, the case of 50% taper
The following discussion will address the and that of full taper. There is an appreciable
specific benefits of adherend tapering in 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.
5 T
(A) Shear stresb - - Double Strap Tapered Adherends
joints are arranged in a symmetric double lap the scarf joint is the effect of adherend stiffness
configuration which avoids bending effects. unbalance ( E , # Ei; ’0’ and ‘i’ refer to the outer
Figure 28.49 represents a balanced stiffness and inner adherends as in Fig. 28.36). The
design for dissimilar materials, by achieving a results given in Fig. 28.50 represent the effect
continuous thickness change over the length of varying degrees of stiffness unbalance. The
of the joint. The most important parameter for 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-
0.2, 0.4 form adherend case. However, it is clear that a
TI, E.16 ffii QI graphite epoxy stiffness unbalance will increase the shear
E.8 msi
stress peak and weaken the joint. For the equal
Fig. 28.49 Stiffness-balanced scarf joint configura- stiffness case the shear stress is constant and
tion. equal to the average stress at all points.
Adhesive joints 649
EU = 8,000 tu = n = .2 EL I EU = 4
G b = l 6 0 Eb-600 t b = O . O l
-
Sigma x = 10
2
If there is no reason why the joint cannot be might be lost if performance in hot wet envi-
configured as in Fig. 28.49 for dissimilar mate- ronments is required.
rials so as to take advantage of the benefits of Step lap joints798oare treated in Figs. 28.51
the balanced stiffness case, then in principle, to 28.53. Figure 28.51 shows a generic joint
the scarf joint provides a near ideal solution to configuration that is introduced to illustrate
achieving as much load capacity as is required some of the effects of design parameters on
in any situation without overstressing the stresses in the joint. The results presented in
bond layer. However, the dimensions of the Figs. 28.52 and 28.53 were generated for this
joint may grow too large to be practical for discussion using a linear elastic response
high joint load. In addition, an extremely good model for the adhesive; in practice, consider-
fit, for example, to tolerances on the order of able strength capability of the adhesive is
the bond thickness over large lengths, has to unused if elastic response of the adhesive is
be maintained to ensure that the joint can assumed; Fig. 28.54 taken from the discussion
maintain uniform load capacity over its by Hart-Smithsois an example of joint design
length. Thermal stresses will also be a factor in using elastic-plastic response for the adhesive.
various combinations of dissimilar materials The elastic adhesive model used in Figs. 28.52
which will prevent the ideal form of behavior and 28.53 is adequate for illustrate some of the
from being achieved. In terms of the Hart- controlling parameters on joint design. These
Smith approach to avoiding creep failure results are based on the classical Volkersen-
under slow cyclic loading, the balanced scarf type analysis with provision for resultant and
joint is at a disadvantage in not providing a shear strain continuity at the interfaces
shear stress minimum. For this situation the between neighboring steps, as discussed pre-
allowed load would have to be limited to pre- viously. The 5-step design in Fig. 28.52 and the
vent environmental conditions corresponding 10-step design in Fig. 28.53 were chosen with
to hot wet exposures; thus the advantage of the following characteristics:
the scarf joint in eliminating stress peaks
650 Mechanical fastening and adhesive bonding
I I / / V I
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
( A ) FM78 NON P O R O U S
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-
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
geometries ( H a r t - S ~ n i t h ~These
~ ~ ) . have sub- double lap joint with equal adherend stiff-
sequently been incorporated in the 'A4Ex' nesses (i.e. Eo = Ei; to = fi/2). Figure 28.57(a)
series of computer programs- mentioned gives the distribution of upper adherend axial
previously. stress resultant while Fig. 28.57@) gives the
Figure 28.57 (see notation of Fig. 28.36) shear stress distribution in the bond layer. The
shows an example of the use of the bilinear linear portions at the ends of the resultant dis-
stressstrain curve approximation, in this case tribution in Fig. 28.57(a)correspond to the ends
for predicting the stresses in a symmetrical of the shear stress distribution in Fig. 28.57@)
0
0 0.6 1 1.I 2
K
le
0.5 --
o i I
0 0.c z 1.Q 2
Fig. 28.57 Stress distributions in double lap joint - ductile adhesive response.
Adhesive joints 655
where the shear stress is a constant because of then eqns (28.36a, b) give the same value. The
the plateau in the bilinear representation of the factor (2GbOymax/zp- 1)1/2in eqn (28.36b)acts as
stress-strain curve, in agreement with the equi- a load enhancement factor and represents the
librium relation given in eqn (28.6). Following increase of joint load capacity due to ductile
the analysis developed by Hart-Smith, the adhesive response over the maximum load
lengths of the plastic zones designated in Fig. allowed by elastic response of the adhesive.
28.57(b) as Ip are given by Note that eqn (28.36b) can be rearranged to
express 5x)ma,in terms of the maximum strain
lp = (aX/2zp- l/pbd)to;p,, = [2Gbflto/EotbI’/*
energy of the adhesive:
(28.35)
Here p,, (subscript ’bd’ denoting balanced
where ye = zp/Gb, (28.37)
double lap) is equivalent to p given in eqn
(28.14) when the latter is specified for the case then eqn (28.3613)can be written:
of equal-stiffness adherends, while 5, is the 2
-
nominal loading stress at either end of the = p’(2Gb()SE) (28.38)
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- lent bilinear stress-strain law was shown in
ing any meaning. Thus if /33,/2 < zp, no plastic Ref. 35 to give the same joint load capacity as
zone is present and the behavior of the joint the solution for the problem using the actual
can be considered to be purely elastic. The stress-strain curve of the adhesive. The conve-
maximum value of 5, for this case can be nience of the bilinear stress-strain description
expressed by inverting the shear stress expres- is in the simplicity of the solutions it allows;
sion in eqn (28.17) with oth= 0, for the case of once the length of the plastic zone at each end
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- apply for the elastic zone as were given in eqns
sponds to ductile response of the adhesive (the (28.9) and (28.10) for the resultant and shear
plateau of the bilinear stress-strain curve), the stress distributions, together with linear resul-
Hart-Smith analysis35provides the required tant and constant shear stress distributions in
expression for 0, The two cases are summa- the plastic zones.
rized as follows: The most obvious effect of ductility in the
adhesive behavior is the reduction of peak
< zp (elastic response):
pbdSX/2
shear stresses. In addition, there is a beneficial
effect on reduction of peel stresses. For the
‘x)max = 2zp/pbd E (28.36a)
double lap joint considered in Fig. 28.57, the
maximum peel stresses denoted by ob),ax
PbdCx/22 zp (ductile response):
which occur at the ends of the joint, are given39
by:
(28.36b)
(
y = 3- i’” ;
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
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 Equation 28.43 for the joint overlap length is
extremes, i.e. hot wet conditions. The Hart- the heart of the Hart-Smith approach to dura-
Smith approach focuses primarily on creep bility of bonded joints for cases where
failure associated with slow cyclic loading (i.e. adherend failure is ensured over bond failure
one cycle in several minutes to an hour) under for static loading and in which peel stresses are
hot wet conditions, this corresponds, for eliminated from the joint design. This type of
example, to cyclic pressurization of aircraft requirement has been used in several contexts.
fuselages. In the PABST program4143,18 test For example60,it becomes part of the require-
specimens used for characterizing adhesives ment for acceptable void volume in the bond
(so-called 'thick adherend' specimens) which layer, since in t h s case the voids, acting essen-
are designed to produce essentially uniform tially as gaps in the bond layer, reduce the
shear stress along the bond were tested at high effective length of the overlap. The criterion
cycling rates (30 Hz) and were able to sustain has to be modified numerically for joints other
more than 10 million loading cycles without than symmetric double lap joints with equal
Adhesive joints 659
stiffness adherends and uniform thickness. For suggest the need for consideration of crack
more sophisticatedjoint configurations such as growth phenomena in bonded composite
step lap joints, the A4EI computer code pro- joints. Indeed, a major part of the technical
vides for a step length requirement equivalent effort that has been conducted on the subject
to that of eqn (28.43) for simple double lap of durability of adhesive joints6”” has been
joints. based on the application of fracture mechanics
In addition to creep failures under hot-wet based concepts. The issue of whether or not a
conditions, the joint may fail due to cracking fracture mechanics approach is valid needs
in the bond layer. Johnson and Mall7*pre- further examination.Apparently, no crack-like
sented the data in Fig. 28.60 which shows the failures occurred in the PABST program,
effect of adherend taper angle on development which was a metal bonding program, even
of cracks at ends of test specimens consisting when brittle adhesives were examined at low
of composite plates with bonded composite temperatures. The amount of effort which has
doublers, at lo6 cycles of fatigue loading; here been expended by a number of respected
the open symbols represent the highest load workers on development of energy release
levels at which cracks fail to appear while the rate calculations for bonded joints certainly
solid symbols are for slightly higher loads at suggests that there is some justification for
which cracks just begin to appear. It is noted that approach, and the results obtained by
that even for outer adherend taper angles as Johnson and Mall appear to substantiate their
low as 10” (left-most experimental points in need for composite joints in particular.
Fig. 28.60) for which peel stresses are essen-
tially nonexistent for static loading, crack
28.4.5 MECHANICAL BEHAVIOR OF
initiation was observed when the alternating
COMPOSITE ADHERENDS
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
28.4.5.1 Joint failure characteristics
is of interest to establish the occurrence of
bond cracking at shorter cycling times, say less Typical failure modes in structural joints are
than 3 x lo5 cycles corresponding to expected illustrated in Fig. 28.61 which are indicative of
lifetimes of aircraft. Effects of cycling rate and adherend rather than bond failures. In the case
environmental exposure are also of interest. of single lap joints (Fig. 28.61(a))bending fail-
Nevertheless, the data presented in Ref. 65 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,
FM-XII MBOND while for composite adherends the bending
D NO MBOND
failures are brittle in nature. In the case of dou-
APPLIED ble lap joints, peel stresses build up for thicker
CYCLIC PREDlClED
adherends causing the types of interlaminar
S I A E S S , IM
~ 5 MPa
,
,,.*
-- failures in the adherends illustrated in Fig.
28.61(b).
0 M
TAPER ANGLE. 0.
60
deg
Po 28.4.5.2 Thermal stress effects
Thermal stresses are a concern in joints with
Fig. 28.60 Crack development in bonds of tapered adherends having dissimilar thermal expan-
composite doublers at lo6loading cycles7*. sion coefficients. Figure 28.62 illustrates the
660 Mechanical fastening and adhesive bonding
A. c
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 loading stress as 69 MPa (10 ksi). Similar
consisting of an aluminum inner adherend effects occur with the peel stresses, although
and a 0/90° carbon epoxy outer adherend. The the peel stresses due to thermal mismatch
stresses due to thermal mismatch between the alone have the same sign at both ends of the
aluminum and composite arise if the cure tem- joint; with a composite outer adherend the
perature of the bond is substantially different thermally induced peel stresses are negative,
from the temperature at which the joint is which is beneficial to joint performance.
used. The case considered here represents a Peak peel and shear stresses obtained from
121°C (250°F) cure temperature for the adhe- these relationships for various combinations
sive and a room temperature application, a of metal and composite adherends whose
temperature difference of -79°C (-175"F), properties are given in Tables 28.2 and 28.3 are
which (see Tables 28.2 and 28.3) would result in shown in Table 28.4. For joints with an alu-
a strain difference of 0.002 between the alu- minum inner adherend, the difference in
minum and composite if no bond were present. thermal expansion between the adherends is
(The material combination considered here, relatively large, giving considerably higher
aluminum and carbon epoxy, represents the thermal stresses for the most part. In addition,
greatest extreme in terms of thermal mismatch carbon epoxy has a particularly low thermal
between materials normally encountered in expansion, which tends to produce higher
joints in composite structures.) Thermal thermal stresses with carbon epoxy adherends
stresses in bond layers of double lap joints can in combination with metals than do other
be determined from the expressions given in composites. Note that boron epoxy in combi-
eqns (28.14-28.20). (These calculations are all nation with titanium gives particularly small
based on an assumed elastic response of the thermal stresses because of similarity of the
adhesive.) thermal expansion coefficients shown in
Hart-Smith3"39 provides corrections for Tables 28.2 and 28.3 for these materials. As
ductile response in the presence of thermal
Table 28.3 Generic metal properties (MIL-HDBK-5
effects. Figure 28.62 illustrates how the ther- 1983)
mal stresses combine with the stresses due to
structural load to determine the actual stress Ti6-Al4-4V 1025 2014
distribution in the adhesive. The thermal Steel Aluminum
stresses in themselves develop an appreciable
Young's 110.3 206.9 69.0
fraction of the ultimate stress in the adhesive, modulus,
and although they oppose the stresses due to GPa
structural loading at the left end, they add at
the right end and give a total shear stress that Poisson 0.3 0.3 0.3
ratio
is somewhat beyond the yield stress of typical
adhesives, even with as small a structural 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)
Table 28.4 Bond layer thermal stress in double lap joints (0/90 composite outer adhered, metal inner
adherend)
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)
(28.15-20) for stresses in the bond layer are 3. Oplinger, D.W. and Gandhi, K.R., Analytical
modified by the resulting alteration of p. The studies of structural performance in mechani-
correction given here amounts to treating 1/ 3 cally fastened fiber-reinforced plates. In Proc.
A r m y Solid Mechanics Conf. 1974, Army
the thickness of each adherend as an extension
Materials and Mechanics Research Center
of the bond layer, and assigning the shear stiff- Manuscript Report AMMRC MS 74-8 (1974).
ness of the adherend for that part of the 4. Garbo, S.P., Ogonowski, J.M. and Reiling, H.E.,
effective bond layer. The factor 1/3 corre- Jr, Effect of variances and manufacturing tolerances
sponds to a linear distribution of shear stress on the design strength and life of mechanically fas-
through the adherend thicknesses, which is tened composite joints. v2 Air Force Wright
consistent with the assumption that the axial Aeronautical Laboratories Report AFWAL-TR-
81-3041 (1981).
deformations are approximately uniform
5. Hyer, M.W. and Klang, E.C., Contact stresses in
through the adherend thickness. pin-loaded orthotropic plates, Virginia Tech Center
As an example, consider joint with a 0/90 for Composite Materials and Structures Report
carbon epoxy outer adherend joined to an alu- CCMS-84-02 (1984).
minum inner adherend, with adherend 6. Ramkumar, R.L., Saether, E.S. and Appa, K.,
thicknesses of 2.53 mm (0.1 in) and 5.06 mm Strength analysis of laminated and metallic plates
(0.2 in), respectively, and a 0.253 mm (0.01 in) bolted together by many fasteners, Air Force Flight
Dynamics Laboratory Report AFWAL-TR-86-
bond thickness. Assume a shear modulus of 3034 (1986).
the bond layer of 1.06 GPa (150 ksi) and trans- 7. Madenci, E. and Illeri, L., Analytical determina-
verse shear moduli of 4.82 GPa (700 ksi) for the tion of contact stresses in mechanically fastened
composite adherend and 26.5 GPa (3800 ksi) composite laminates with finite boundaries.
for the aluminum. A value of 1.839 is then Intern. J. Solids Sfructures 30, pp. 2469-2484
obtained for Ksh, and the value of p and the (1993).
maximum shear and peel stresses which 8. Crews, J.H. and Naik, R.A., Combined bearing
and bypass loading on a graphite/epoxy lami-
depend on it are reduced by a factor of (Ksh)1/2 nate. Composite Structures, 6, pp. 2148 (1986).
or 1.36 for this case. The shear and peel 9. Hart-Smith, L.J., Mechanically-fastened joints
stresses are therefore approximately 30% for advanced composites - phenomenological
lower than the values predicted with the considerations and simple analyses. In Fibrous
unmodified bond shear modulus. This type of Composites in Structural Design. New York:
correction can be shown to give relatively Plenum Press (1980)pp. 543-574.
good predictions of the adhesive stresses in 10. Petersen, R.L., Stress Concentration Factors. New
York: John Wiley and Sons (1974)p. 135.
comparison with finite element analyses. In 11. Lenoe, E., Oplinger, D.W. and Burke, J,J.,
addition, the departure of Ksh given in eqn Fibrous Composites in Structural Design. In
(28.44) from 1 gives a good indication of the Proc. 4 f h Con& Fibrous Composites in Structural
range of joint parameters for which adherend Design, New York: Plenum Press (1980).
shear deformations are important. 12. Oplinger, D.W., On the Structural Behavior of
Mechanically Fastened Joints in Composite
Structures. In Fibrous Composites in Structural
REFERENCES Design, New York Plenum Press (1980) pp.
575-602.
1. Waszczak, J.P. and Cruse, T.A., A synthesis proce- 13. Nelson, W.D., Bunin, B.L. and Hart-Smith, L.J.,
dure of mechanically fastened joints in advanced Critical Joints in Large Composite Aircraft
materialsJ Air Force Structure. In pyoc. 6th Con$ Fibrous Composites in
Laboratory Report AFML-TR-73-145 (1973). Structural Design, Army Materials and
2. Oplinger, D.W. and Gandhi, K.R., Stresses in Mechanics Research Center Report
mechanically fastened orthotropic laminates. In AMMRC MS 83-2 (1983), pp. u-2to II-38.
Proc. Zst Con5 Fibrous Composites in Flight Vehicle 14. whitney, J.M. and Nuismer, R., stress fracture
Design, Air Force Flight Dynamics Laboratory criteria for composites containing
Report AFFDL-TR-74-103 (1974).
664 Mechanical fastening and adhesive bonding
Air Force Flight Dynamics Laboratory Report Critical joints in large composite aircraft struc-
AFFDL-1R-76-141 (1976). ture. In Proc. 6th Conf. Fibrous Composites in
42. Shannon, R. W. et al., Primary adhesively bonded Structural Design, Army Materials and
structure technology (PABST): General Material Mechanics Research Center Manuscript Report
Property Data, Air Force Flight Dynamics AMMRC MS 83-8 (1983).
Laboratory Report AFFDL-TR-77-101 (1977). 53. Oplinger, D.W., A layered beam theory for single
43. Land, K.L., Lennert, F.B. et a/., Prima ry adhesively lap joints, US Army Materials Technology
bonded structure technology (PABST): Tooling, Laboratory Report MTL TR 91-23 (1991).
Fabrication and Quality Assurance Report, USAF 54. Oplinger, D.W., Effects of adherend deflections
Technical Report AFFDL-TR-79.3154 (October, on single lap joints. Int. J. Solids Structures, 31
1979). (18), pp. 2565-2587 (1994).
44. Hart-Smith, L.J., Adhesive bond stresses and 55. Hart-Smith, L.J., Adhesively bonded joints in
strains at discontinuities and cracks in bonded fibrous composite structures, Douglas Aircraft
structures. Trans. J. Engng Mater. Tech., 100, pp. Paper 7740. Presented to the Intern. Symp.
128-144 (1978). Joining and Repair of Fibre-Reinforced Plastics,
45. Hart-Smith, L.J., Differences between adhesive Imperial College, London (1986).
behavior in test coupons and structural joints, 56. Hart-Smith, L.J., Induced peel stresses in adhesive-
Douglas Aircraft Company Paper 7066. bonded joints, Douglas Aircraft Company,
Presented to ASTM Adhesives Committee D- 14 Technical Report MDC-J9422A, August 1982.
Meeting, Phoenix, Arizona, 1981. (see also USAF Report AFWAL TR-82-4172,
46. Hart-Smith, L.J., Design methodology for bonded- (1982).)
bolted composite joints, Douglas Aircraft 57. Hart-Smith, L.J., Brown, D. and Wong, S.,
Company, USAF Contract Report AfWAL-TR- Surface preparations for ensuring that the glue will
81-3154, Vol I and I1 (February 1982). stick in bonded composite structures, 10th
47. Thrall, E.W., Jr., Failures in adhesively bonded DoD/NASA/FAA Conf. Fibrous Composites in
Structures, AGARD-NATO Lecture Series No. Structural Design, Hilton Head Is, SC (1993).
102, ‘Bonded Joints and Preparation for 58. Hart-Smith, L.J., Ochsner, W. and Radeckv, R.
Bonding’, Oslo, Norway and The Hague, L., Surface preparation of fibrous composites
Netherlands, April 1979 and Dayton, Ohio, for adhesive bonding or painting. Douglas
October 1979. Service Magazine, 1, pp. 12-22 (first quarter
48. Hart-Smith, L.J., Further developments in the 1984).
design and analysis of adhesive-bonded structural 59. Hart-Smith, L.J., Ochsner, W. and Radecky, R.
joints, Douglas Aircraft Company Paper 6922. L., Surface preparation of fibrous composites
Presented at the ASTM Symp. Joining of for adhesive bonding or painting. Canadair
Composite Materials, Minneapolis, MN, April Service News, 2, pp. 2-8 (1985).
1980. 60. Hart-Smith, L.J., Effects of adhesive layer edge
49. Hart-Smith, L.J., Adhesive bonding of aircraft pri- thickness on strength of adhesive-bonded joints,
mary structures, Douglas Aircraft Company Quarterly Progress Report No. 3, Air Force
Paper 6979. Presented to SAE Aerospace Contract F33615-80-C-5092 (1981).
Congress and Exposition, Los Angeles, 61. Hart-Smith, L.J., Effects of flaws and porosity on
California, October 1980. strength of adhesive-bonded joints, Quarterly
50. Hart-Smith L.J., Stress analysis: a continuum Progress Report No. 5, Air Force Contract
analysis approach. In Developments in Adhesives F33615-80-C-SO92 (1981).
- 2 (ed. A. J. Kinloch), London: Applied Science 62. Frazier, T.B. and Lajoie, A.D., Durability of adhe-
Publishers, pp. 1-44(1981). sive joints, Air Force Materials Laboratory
51. Hart-Smith, L.J. and Bunin, B.L., Selection of Report AFML TR-74-26, Bell Helicopter
taper angles for doublers, splices and thickness Company (1974).
transition in fibrous composite structures. In 63. Becker, E.B. et al., Viscoelastic stress analysis
Proc. 6th Conf. Fibrous Composites in Structural including moisture difision for adhesively bonded
Design, Army Materials and Mechanics joints, Air Force Materials Laboratory Report
Research Center Manuscript Report AMMRC AFWAL-TR-84-4057 (1984).
MS 83-8 (1983). 64. Jurf, R. and Vinson, J., Efects of moisture on the
52. Nelson, W.D., Bunin, B.L. and Hart-Smith, L.J., static and viscoelastic shear properties of adhesive
666 Mechanical fastening and adhesive bonding
joints, Dept. of Mechanical and Aerospace 73. Tsai, M.Y. and Morton, J., On numerical and
Engineering Report MAE TR 257, University of analytical solutions to the single lap joint.
Delaware (1984). Intern. J. Solids and Structures (1994).
65. Mostovoy, S., Ripling, E.J. and Bersch, C.F., 74. Benson, N.K., Influence of stress distribution on
Fracture toughness of adhesive joints. J. strength of bonded joints. In Adhesion,
Adhesion, 3, pp. 125-144. (1971). Fundamentals and Practice, New York: Gordon
66. DeVries, K.L., Williams, M.L. and Chang, M.D., and Breach, (1969), pp. 191-205.
Adhesive fracture of a lap shear joint. 75. Adams, R.D. and Wake, W.C., Structural
Experimental Mechanics, 14, pp. 89-97 (1966). Adhesive Joints in Engineering, Amsterdam:
67. Trantina, G.G., Fracture mechanics approach to Elsevier Applied Science Publishers (1984).
adhesive joints, University of Illinois Dept. of 76. Kuenzi, E. and Stevens, G., Determination of
Theoretical and Applied Mechanics Report mechanical properties of adhesives for use in the
T&AM 350, Contract N00019-71-0323 (1971). design of bonded joints, Forest Products
68. Trantina, G.G., Combined mode crack extension in Laboratory Note FPL-011 (1963).
adhesive joints, University of Illinois Dept. of 77. Snedon, I., The distribution of stress in adhesive
Theoretical and Applied Mechanics Report joints. In Adhesion, (ed. D.D. Eeley), Ch. 9,
T&AM 350, Contract N00019-71-C-0323 (1971). Oxford: Oxford University Press (1962).
69. Keer, L.M., Stress analysis of bond layers. Trans. 78. Carpenter, W., Goland and Reissner were cor-
ASME J. Appl. Mech. E., 41, pp. 79-83 (1974). rect. J. Strain Analysis, 24(3), pp. 185-187 (1989).
70. Knauss, J.F., Fatigue life prediction of bonded pri- 79. Hart-Smith, L.J., Further developments in the
mary joints, NASA Contractor Report design and analysis of adhesive-bonded struc-
NASACR-159049 (1979). tural joints. In Joining of Composite Materials,
71. Wang, S.S. and Yau, J.F., Analysis of interface American Society for Testing of Materials
cracks in adhesively bonded lap shear joints, NASA Special Technical Publication ASTM STP 749
Contractor Report NASA-CR- 165438 (1981). (1981).
72. Johnson, W.S. and Mall, S., A fracture mechanics 80. Hart-Smith, L.J., In Fiber Composite Analysis and
approach for designing adhesively bonded Design, Federal Aviation Administration
joints. In Delaminafion and Debonding of Technical Center Report DOT/FAA/CT-88/18,
Materials, ASTM Special Technical Publication Vol. 2, Ch. 3 (1988).
STP 876, American Society for Testing and 81. DoD/NASA Advanced Composites Design
Materials, pp. 189-199 (1985). 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
retrospect, such a demonstration was neces- ing resins or adhesives. They create a weak
sary as a public relations exercise to convince interface, with failure occurring at only a frac-
the decision makers to apply the technology, tion of the strength that would have been
where appropriate, on the primary structure developed by grit-blasting. However, the
of large aircraft. Nevertheless, the technology resulting weak bonds cannot be detected by
did not die. The combination of phosphoric conventional ultrasonic nondestructive
acid anodizing for aluminum alloys, a pheno- inspection. Also, most bonded composite
lic-based corrosion-inhibiting primer and structures are so thin that they will not fall
adhesives formulated to resist the absorption apart even if the bond has as little as one-tenth
of water has since been applied very exten- of the strength of a properly processed bond.
sively on the primary structures (wings, Consequently, little has been done about the
fuselages, and tails) of Cessna and SAAB air- problem, in the mistaken belief that doing so
craft with excellent results. would incur an unnecessary expense.
The composites bonding industry could be On the contrary, even if local bond failures
described today as being in the same state that can be tolerated structurally, once they become
metal bonding was in 25 years ago, but with detectable in service they cause expensive
one big difference. The need to properly pre- inspection programs and possibly rework, not
pare the surfaces of composite laminates prior necessarily to add to the strength of the parts,
to bonding is acknowledged only by those but to prevent the flaws from being detected
who have suffered a major problem from hav- and repaired again on subsequent inspections.
ing failed to do so on some previous occasion. Failing to ensure that the glue sticks properly
Ironically, there are many researchers and pro- in the first place is definitely a false economy.
duction engineers worldwide who are aware The delay in solving the corresponding prob-
of the problems and their causes. However, lems on bonded metal structure gave the
there is no highly visible activity like the technology such a bad name in the USA that it
PABST program to draw attention to the was the direct cause of the extensive use of riv-
issues. This chapter cannot be expected to eted structure when bonding would have been
solve these problems, but it is hoped that it lighter, less expensive, and more durable, with
will raise the level of awareness of the subject better than a twentyfold reduction in the inci-
and that its content will help achieve better dence of fatigue cracks and a dramatic
bonded composite structures by providing improvement in damage tolerance. Lest the
standards for inspecting the surfaces before same preference for mechanical fastening
bonding, rather than creating the impossible rather than bonding continue to be followed
situation of trying to detect weak bonds after for thin composite structures, it should be
bonding. What is needed is a method that will noted that the typical fasteners cost about a
ensure a reliable bond every time, using pro- hundred times as much as the simple rivets
cedures to which all manufacturers of used with aluminum structures. Worse, the
composite structures will be willing to adhere. minimum diameter of the specialty fasteners
The first part of this challenge has already for composites is 50% larger than the diameter
been accomplished: light grit-blasting or thor- of comparable rivets. Conventional aluminum
ough mechanical abrasion has been shown to rivets are not used for carbon composite struc-
work. Unfortunately, more often than not, tures because of concern about galvanic
films of adhesive are applied to the surfaces corrosion, between the rivets and the carbon
left by the removal of a peel ply without any fibers, so composite structures that could have
surface treatment. Most, and possibly all, peel been bonded must be locally reinforced to be
plies are known not to create a suitable surface mechanically fastened instead, adding to both
for bonding, at least when used with laminat- the cost and weight.
Historical background 669
There are, then, very great incentives for aerospace industry. It seems significant that,
reliable processing of adhesive bonds in com- today, some factories prohibit the use of bond-
posite structures. There is also no hstory of ing directly to a composite surface created by
properly processed composite bonds failing in the mere removal of a peel ply and that the
service. (This is also true of metal bonding. All automotive racing industry has experienced
in-service failures are the result of environ- the same kind of premature failures with peel-
mental attack, at load levels far too low to ply treatments that the aerospace industry has
have initiated mechanical failure of the bonds. suffered. If what may be called the peel-ply
Testing during the PABST program of coupons bonded joints were twice as strong as they
cut from retired aircraft stored at Davis- actually are, there would be little concern.
Monthan, Arizona, showed that there was no Conversely, if they were only half as strong,
structural deterioration after 20 years.) the problem would have been more widely
There are others that call for improvements recognized long ago and far more done about
in surface preparation for bonding of compos- it. The real problem with peel-ply bonded
ites. Robert Schliekelmann, the famous pioneer joints is that, while quite unreliable in the eyes
of Redux bonding at Fokker, was sufficiently of those closest to the subject, they usually
concerned about the failure to recognize the have sufficient strength to pass ultrasonic
need for proper surface treatment of compos- inspections (because there are no gaps) and are
ites as well as metals to make a plea’ for more sufficiently strong some of the time that the
attention to this issue. Almost a decade ago, joints do not fail prior to delivery of the com-
Douglas engineers prepared an article on the ponent. This makes it difficult to present a
subject2to help the airlines until the repair man- convincing case to non-technically minded
uals could be updated. The article was judged participants in the industry that there is a real
to be of sufficient importance to be reprinted in problem. One non-failure tends to be inter-
the Canadair house journal3.Every experiment preted as complete success.
had to be repeated to create new photographs This chapter cannot possibly provide all the
and every phenomenon was duplicated, answers on the subject of surface preparations
thereby verifying that the problems discussed for composite bonding. It took a $20 million
in the original article really existed. A similar 5 year program to solve the corresponding
concern was expressed in England, where problems for metal bonding. It should also be
Parker and Waghom4 reported on a far more acknowledged that the concerns expressed
comprehensive test program on the effects of here are based exclusively on consistently bad
surface preparation on adhesive bond strength experiences with 180°C (350°F) cured epoxy
for carbon-epoxy laminates. They also con- composites. (The problem may be associated
cluded that ‘composite surfaces must be with the curing of the laminate and the peel
abraded to achieve strong adhesive-bonded ply as much as with the adhesive.) It may also
joints.’ Pocius and Wentz advocated the use of be significant that most, if not all, of these
Scotchbrite pads with embedded abrasive par- problems were associated with nylon peel
ticles as an effective and reliable technique for plies, whose use with a 180°C (350°F) cured-
achieving good composite bonds5. A recent laminate is believed by some polymer
research program6 addressed both thermoset chemists to be undesirable, because the nylon
and thermoplastic composites. Reference 6 also may break down and transfer a thin film of
cites other English research. The problems still low-molecular weight material to the compos-
exist, on both sides of the Atlantic Ocean. ite surface. Photographic evidence of this
A more recent article on this subject7,voiced phenomenon is included here. Such a surface
concerns because of the reintroduction of infe- would be very difficult for an epoxy adhesive
rior techniques throughout much of the 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 peel plies. Not one in-service delamination has
about the use of nylon at 120°C (250"F), but occurred in those composite structures pre-
some adhesion failures of glued joints have pared for bonding by the grit-blast technique.
occurred with those materials also. The domi- It is hoped that this chapter will inspire
nant factor may be the low surface energy those who believe that their structural adhe-
level of the composite cured against a slick sive bonds are both strong and reliable to
peel ply, or one contaminated by a release assess composite surfaces prior to bonding. (A
agent to ensure that it can be removed easily request for information from a major US aero-
without fracturing (damaging) the composite space manufacturer about a peel ply different
laminate. from those used at Douglas resulted in their
It is certain that the criteria by which manu- switching to another peel ply. Microscopic
facturers evaluate their peel plies are precisely examination of the surface to be bonded made
the opposite of those that someone else trying it clear to them that one of their problems
to promote adhesion in a bonded joint would could be tied directly to the choice of a new
follow. Some peel plies are even coated with peel ply. Once alerted, they checked all related
release agents to ensure that they can be procedures and even changed one of their old
removed easily without damaging the basic and trusted peel plies once its true capabilities
laminate. Silicone transfer has been observed had been exposed.)
with some peel plies supposedly totally free of This chapter concentrates exclusively on the
contamination. What is needed to create a issue of surface preparation. Obviously, one
bondable surface is a tear ply that will remove must also follow correct thermal and pressure
a small amount of surface resin over the entire profiles during cure to achieve a properly
area to be bonded. However, peel plies known cross-linked adhesive that has a chance to flow
to be capable of achieving this are almost and wet the surface to which it is to be
invariably shunned because they are so hard bonded. Prebond moisture, in both laminates
to peel off, because they break and inevitably and adhesives, is also known to be a major
lead to local contamination as the process is cause of weak bonds. These and other impor-
restarted, or because there is concern that the tant issues are discussed in References 7 and 8.
interior of the laminate will be damaged. This does not imply that they are any less
It cannot be asserted on purely technical important.
grounds that there are no circumstances under We now present electron-micrographs of
which some peel plies will produce an ade- glue that failed to stick to the composite, com-
quate surface for adhesive bonding. It stands posite surfaces to which the adhesive did not
to reason that some users of this approach stick, similar surfaces to which the glue will
have been spared the problems Douglas and not stick, surfaces to which adhesive is known
others have encountered, or the products to have stuck in the past, and surfaces to
would have all been removed from the mar- which it is hoped it will stick. The effectiveness
ketplace. However, it is likely that still others of light grit-blasting as a reliable surface treat-
have also suffered, but are unaware of the ment has already been established. It was used
cause of their problems. Nevertheless, the on all bonded joints of the Lear Fan all-com-
argument against peel plies is irrefutable on posite aircraft9, creating bonds stronger than
economic grounds. The cost of investigating the surrounding structure even when half the
weak bonds has been far, far greater than overlapping area was disbanded because of
would have been incurred if Douglas had inappropriate solid-rubber tooling used for
insisted that all suppliers and subcontractors the fuselage skin splices. The bond to the grit-
lightly grit-blast or thoroughly hand-sand blasted surface was so strong, where the
composite surfaces following removal of 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. 29.9 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).
I
Fig. 29.17 Same sample at higher magnification
Fig. 29.15 Peel-ply imprint on epoxy surface to (mag x750).
which the glue will not adhere (mag X38).
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
I 1
--- -1
removal of a tear ply that adhered to the the production level in over 20 years. Because
matrix as tenaciously as conventional peel the metal-bond problem was resolved so
plies refuse to adhere. This, in turn, raises quickly, very few panels were involved. There
questions about the feasibility of tear plies as a were no in-service failures because every
surface-preparation technique since the lami- affected panel was identified before delivery
nate is damaged far more than by light and reinforced by rivets.
grit-blasting, as a comparison between Figs. Peel-ply ’surface preparation’ for bonding
29.10 and 29.27 will attest. of composites has not been as thoroughly
explained. There have been many instances of
such weak bonds not being detected until they
29.5 COMMENTARY
had split apart in service, even though there is
In the mid-l980s, a major effort was aimed at no reason to believe that the bonds wore out
the resolution of a problem associated with under mechanical loads. The observed modes
adhesive bonding of aluminum alloy struc- of failure are consistent with a manufacturing
tures. In that case, as in the problem discussed problem. There is little doubt that gentle grit-
here, the glue failed to stick and interfacial fail- blasting is the most reliable method of
ures resulted. However, there remains a very preparing thermoset composite surfaces for
great difference between the two cases. In the bonding. Sanding can work only on fairly fine-
earlier case, every factor associated with the weave cloths in composite laminates.
weak bonds that passed all ultrasonic inspec- Otherwise, it is not possible to sand to the bot-
tions was identified in a matter of weeks. The tom of all depressions left by the peel ply
conditions had been replicated in a laboratory without also sanding significantly into the
and the investigation closed within a few structural fibers. A few other manufacturers
months. Significantly, there were no loose have used tear plies, which leave a completely
ends and the problem has not recurred. The fractured resin surface, rather than the more
primary cause of the problem was condensate commonly used easily removed peel plies dis-
on adhesive film that had been removed from cussed here. More use should be made of tear
storage before it had thawed out. plies. However, if a tear ply were used on a
However, there was a second factor lightweight honeycomb or foam sandwich
involved as well. The first violation of proper panel, there is a good chance that the core
processing procedures would not cause a would fail instead.
defective bond unless the moisture was There can also be no doubt that when prob-
trapped at the interface between the details. lems have occurred as a result of bonding
This condition happened consistently with directly to the surface left by removal of a peel
one kind of bonding tool, while similar parts ply, or one with totally inadequate sanding,
made concurrently on a different kind of tool they are widespread and serious. These prob-
showed no such problems. The second kind of lems have been experienced at many places.
tool permitted complete ventilation of any Yet, if they happened as repeatedly as the
trapped volatiles as well as of any generated defects caused by the combination of the two
during the cure. There were no large area factors cited above, one would have expected
defective bonds. Both tools produced local such a backlash against the procedure that
bond defects where a tool or the parts were out every unreliable peel ply would have been
of contour. These problems were eliminated withdrawn from the marketplace, preventing
by correcting the tools and by better straight- any recurrence of the problems. That has not
ening of the stiffeners. This problem was happened so, presumably some organizations
resolved very quickly, whereas the present are able to bond successfully to composite
problem with peel plies has not been solved at 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 for bonding has been found to be extremely
process successfully has no reason to investi- reliable in service. While one needs to buy
gate why he is successful, so the differences appropriate equipment, the cost of doing so is
between his techniques and those that lead to a small fraction of the typical cost of even one
trouble have remained unidentified. composite detail. With the right equipment,
It seems that there is something else training of technicians is straightforward.
involved as well possibly prebond moisture or There can be no valid argument in favor of
something associated with venting during the not mastering the art of grit-blasting. While
cure or possibly the breakdown and transfer of there may be choices for the surface prepara-
nylon peel plies cured at too high a tempera- tion during initial fabrication, peel plies
ture or the transfer of a release agent on some cannot possibly be stripped off a second time
peel plies. Weak interfacial bonds between the to create a new 'clean' surface during repairs.
adhesive layer and both composite adherends It may be that some manufacturers make
should never have been strong enough to rip a successful bonds to peel-ply composite sur-
properly cured adhesive back and forth from faces already. It may also be possible that
one interface to the other in the manner that is coupling agents may be found to enable others
so evident in Fig. 29.8. And, more significantly, to do the same. However, it is undeniably true
attempts to replicate the weak bonds in the that, for at least two decades, some manufac-
laboratory have been inconclusive and, at turers of composite components who have
times, inconsistent. This merely reinforces the relied on peel plies alone as surface prepara-
assumption that the problem is not yet fully tion for bonding have created weak bonds that
understood without, in any degree, diminish- have fallen apart in service. The cost of unan-
ing the conviction that the problem is serious ticipated repairs and investigations has greatly
and needs to be resolved. exceeded any expected initial cost savings.
It would be helpful if there were a reliable Given the widespread nature of these prob-
a peel-dominated quality-control test for com- lems, it is appropriate to recommend that the
posite surface preparation that was use of peel-ply surface preparation alone be
equivalent to the wedge-crack test used for discontinued unless it can be shown that its
metal bonding. Unfortunately, the experi- use never results in interfacial failures
ments performed to date have been between the composite and adhesive layers. It
bedevilled with extraneous influences that are is quite clear, from experience, that the cost of
not yet understood but have a much greater even one in-service bond separation exceeds
effect on the strength of the coupon than the by far the savings derived during an entire
variations in surface treatment. Neverless the production run by not thoroughly abrading
goal remains. the surface.
Scanning electron microscope images,
such as those presented here, show easily dis-
29.6 CONCLUSIONS
tinguishable differences between the matt
As acknowledged above, more technical infor- rough surface created by mechanical abrasion
mation needs to be uncovered about adhesive and the microscopically smooth furrows
bonding to fiber-polymer composite surfaces associated with peel-ply removal alone. It is
created by simply removing a peel ply. The not difficult to ensure that the surface prepa-
weak bonds associated with this technique are ration is adequate for bonding or painting
a financial burden that is both serious and easy before the bond has been made. Conversely, it
to avoid. is extremely difficult to detect a weak bond
The use of low-pressure grit-blasting as the nondestructively once the error has been
final step in the preparation of these surfaces made.
References 685
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.
0 0
Shear test
(30.3)
1
E =-a,
E,
Laminated plate theory 689
Defining the plane stress stiffness matrix [QJ = laminate, x, y, s and 1,2,6 are interchangeable.
[SI-', another form of eqn (30.3) is 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.
where rn = cos 8, n = sin 8. A summary of some with the [Q] matrix, the S12(and SJ, terms
other useful transformation relations is given reflect the deformation in the direction per-
in Section 30.7. It is clear from these relations pendicular to the direction of loading, and are
that when 8 = 0, then Q,, = Q,, = 0, which commonly referred to as the ‘component due
means shear and extension are uncoupled, i.e. to Poisson’s effect’ (implying the major
shear loading only causes shear deformation, Poisson’s ratio). The S,, and S2, (and S,, and
and extensional loading causes extensional S62)terms reflect the amount of shear deforma-
deformation with Poisson’s effect but no shear tion under extensional loading, and are
deformation. commonly referred to as ’coupling terms’.
Using the off-axis plane stress stiffness coef- Unlike the off-axis unidirectional ply shown in
ficients, the constitutive relations of eqns (30.4) Fig. 30.4@), the 0-degree unidirectional ply
and (30.3) can be generalized to a ply of any shown in Fig. 30.4(a) does not exhibit any
orientation: 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
and inversely 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
For example, a physical interpretation is unstretched. In practical terms, the plies in the
shown in Fig. 30.4. In general, the terms on the laminate are assumed to be completely
diagonal (S,,, S,, S,) reflect the amount of bonded to each other, allowing no interlami-
deformation in the direction of loading. As nar shear. Some other assumptions are that the
Fig. 30.4 Extensional loading of (a) a unidirectionalply and (b) an off-axis ply and their associated off-axis
stiffness matrix.
Laminated plate theory 691
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;;
2' 1 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 where, as before, m = cos 8, n = sin 8. One step
to simplify the analysis even further. If the further, the on-axis ply stresses can be obtained
laminate is symmetric about the midplane so by multiplying the on-axis ply strains by the
that the B coefficients are identically zero, then ply stiffness matrix [Q] as shown in eqn (30.6).
the in-plane (described by N, [A], E ) and bend- The laminate engineering constants, which
ing problems (described by M I [D], IC)become have meaning with symmetric laminates only,
uncoupled. In this case, it is much easier to are calculated from the compliance matrix and
invert two 3 x 3 stiffness matrices to get the are useful for comparison to the properties of
compliance matrices (see also Section 30.7 for other materials, such as metals
the explicit terms to invert a matrix)
[a] = [AI-’
I
‘EP ‘11 ‘12 ‘16 ‘IN, ’
= a12 aZ a26 N2 (30.17) [a*] = [a]h (30.21)
E;
\E: ‘16 ‘26 ‘66. tN6 ,
The summation process can be used to deter- X' = transverse tensile strength,
mine the effective laminate expansion Y = longitudinal compressive strength,
coefficients. Y' = transverse compressive strength,
The hygrothermal load, sometimes called S = shear strength. (30.24)
non-mechanical load, can be computed by
The maximum ply strain values can be inter-
multiplying the laminate stiffness by the
preted by dividing the above strengths by the
hygrothermal strain (i.e. laminate thermal
appropriate ply stiffness coefficient.
expansion coefficients multiplied by the
change in temperature). The stress induced by cx* = max longitudinal tensile strain,
moisture absorption can be accounted for sim- E ~ ' *= max longitudinal compressive strength,
ilarly by using PAC in place of aAT. Thus, the E * = max transverse tensile strength,
non-mechanical loading in the laminate can be Eyf* =
Y
max transverse compressive strength,
expressed as 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.
The mechanical and non-mechanical loads, N Early laminate failure theories fail to
and W , can be added together to determine account for Poisson's effects and interaction
the total load experienced by the laminate. between loads in orthogonal directions (a
complex load condition). For example, the
major weakness of both the maximum stress
30.4 FAILURE CRITERIA
and the maximum strain failure criteria are
The ultimate objective in any structural design their inability to couple stress, or strain, com-
is to create a structure able to withstand ponents in determining the ultimate failure of
deflections or loads without failing. The initial a ply. It is important to understand that the
concern is to remain below a prescribed deflec- longitudinal tensile failure of a ply is affected
tion as part of stiffness criteria. Once these not only by the longitudinal load, but also by
criteria are satisfied, the focus shifts to a the magnitude of applied transverse loads. As
strength criterion, such that applied stress a result, stress interaction criteria are widely
must not exceed laminate strength. used throughout the industry to determine ply
Composite materials normally possess dif- failure in a laminate.
ferent strengths when loaded in either tension
or compression. The following represent the
minimum number of strength properties nec- 30.4.1 QUADRATIC FAILURE CRITERION
essary to characterize a unidirectional or fabric
Tsai developed a two-dimensional stress inter-
ply. They are determined using material
action failure criterion and predicted the
coupon tests, previously outlined in Fig. 30.2.
strength of an orthotropic ply subjected to
X = longitudinal tensile strength, combined stresses or strains. This analysis
696 Laminate design
takes into account the effects of other stress before failure occurs);
components on the strength in any one direc- R < l failure has already occurred (i.e. occurs
tion. Tsai postulated a criterion in stress space prematurely at some point below the
consisting of the sum of linear and quadratic applied stress or strain) and the applied
scalar products as follows: stress or strain level can not be attained
(e.g. if R = 0.5, then only half the
F ‘1DOI
1
+ Ftp1I 1 i, j = x, y, s (30.26)
applied stress can be sustained).
or, in expanded form,
Equation (30.28) is substituted into eqn (30.26)
and the solution of this quadratic equation can
be obtained.
+ ( F p x + Fyuy)I1
[ F I , ~ l ~ ~+][F,u,]
R‘ R -1 = 0 (30.29)
Note that Fxs = Fys= F, = 0, and the six strength
parameters are interpreted from the ply i, j = x, y, s
strength values (reviewed in Section 30.8):
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
1
F = - root is used), respectively.
s
2
Failure envelopes can be plotted to show
laminate strength for any combination of
1 1 1 1
F = -- - F = -- - (30.27) loads. Instead of the stress space representa-
x x y Y Y’ tion, however, the examination of failure
The stress interaction term, Fx,*, can have a envelopes in strain space is a useful alterna-
value of -1 I Fx; < 1although is recommended tive. The representation of failure envelopes in
to be -1/2. When F,; = -1/2, the quadratic fail- strain space is preferred because strain is usu-
ure criterion is a general case of the von Mises ally specified in laminated plate theory. Strain,
criterion (Section 30.8.2). unlike stress, is at most a linear function of the
Instead of simply evaluating the failure cri- thickness. Furthermore, failure envelopes are
terion to determine if the laminate failed, it is fixed in strain space, and are independent of
useful to consider a nondimensional ratio to other plies with different angles which may
provide a perspective of the significance of the exist in a laminate. Thus, they can be regarded
applied stress relative to material strength. as material properties. Another additional
Tsai defines the strength ratio, R, such that advantage of strain space is that the axes are
dimensionless.
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- the laminate. Composite materials are not
dency for forward swept wings to diverge at merely a light-weight substitute for heavy-
increasing speeds was counteracted by this weight metals. Structural performances which
laminate design: the increase in lift creates a are not possible with metals are easily achiev-
decrease in angle of attack, as the laminate able. Examples of such unique properties
twists in the direction opposing the forces. include Poisson’s ratios greater than unity or
It is conceivable that in the future the even negative, bending-twisting coupling, and
graphite golf shafts currently gaining in popu- zero or negative coefficients of thermal expan-
larity could be tailored to the individual golfer. sion (CTE). The problems and examples below
The same coupling principle could be applied. illustrate the engineering constants of angle-
A golfer’s tendency to consistently slice the ply and related laminates. Examples of large
ball might allow the designer to customize a and negative Poisson’s ratios and examples of
golf shaft which not only bends, but also bend-twist coupling are also given.
twists slightly under the bending load of the
bad swing.
30.5.2 UNUSUAL POISSON’S RATIOS
Personal computer software based on a com-
30.5.1 UMQUE BEHAVIOR
puter spreadsheet allows rapid sensitivity
The most unique features of composite materi- studies and parametric analysis of the behav-
als are the highly direction-dependent ior of laminates. Laminated plate theory with
properties. Highly coupled deformation and micromechanics is programmed into ’Mic-
load-carrying capability can be designed into Mac/In-Plane’2. A companion charting tool,
Fig. 30.8 Top view of the Grumman X-29 aircraft with wings that twist under flexure to counteract the
detrimental aerodynamic effects.@ NASA)
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
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
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
22.50
15.00
7.50
0.00
15 30 45 60 75 15 30 45 60 75
Ply Angle, 8 (degrees) Ply Angle, 8 (degrees)
(4 (b)
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 laminate exhibits a very large Poisson's ratio
shear modulus, E , is a maximum, of course, of 1.32, when compared with that of an
for the [*45] laminate. isotropic material (0.3). Besides the unique
Figure 30.10(b) shows the engineering con- Poisson's ratio behavior, it is also important to
stants for laminates with 50% 0" plies and 50% examine the values of the other coupling coef-
angle-plies. With the exception of the trans- ficients.
verse modulus, the results are similar to those
for the angle-ply laminate shown in Fig. EXAMPLE
30.9(b).When the ply angle is 90", the values
for the engineering constants in Figs. 30.10(a) Table 30.2 considers the resulting deforma-
and 30.10(b)are the same. tions on coupon specimens under load, and
Figures 30.11(a) and 30.11(b)show the engi- Fig. 30.12 indicates the relative magnitude of
neering constants for some unusual laminates. deformation due to large and negative
When the ply angle, 8, is 15", Fig. 30.11(a) Poisson's ratios.
shows an off-axisunidirectional laminate and
Fig. 30.11(b)shows an angle-ply. For all other 30.5.3 STIFFNESS AND COUPLING
ply angles, the laminates are unbalanced.
From Fig. 30.11(a),it can be observed that the It is useful to look at the A, B, D stiffness matri-
[15/60Is laminate exhibits an extremely large ces of some simple laminates. For ease of
negative Poisson's ratio of -0.32, meaning the comparison, the stiffness matrices can be nor-
laminate will expand in the transverse direc- malized to have units of [force/length2]by
tion under longitudinal tension loading and defining
compress in the transverse direction under [A*]= [ A ] / h , [B*] = 2[B]/h2,
longitudinal compressive loading. From Fig.
30.11(b), it can be observed that the [-15/30Is
Laminate design 701
,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
0.00 0 0.00 0
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,
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 B* matrix with nonzero terms. The first and
two 90" plies can be combined into four differ- fourth laminates are balanced and so the A*16
ent laminates. From Table 30.3 it can be and A*26coefficients are zero. For the second
observed that while the A* matrix remains and third laminates which differ by the sign of
unchanged through varied ply stacking the off-axis plies, the stiffness behavior differs
sequences, large differences arise in the B* and only in that the A*16,A*26,D*,6 and D*26coeffi-
D*matrices. cients are of opposite signs.
From Table 30.4 it can be observed that only Table 30.5 displays different quasi-isotropic
the fourth laminate is unsymmetric and has a laminates. Note that the normalized A* matrix
Table 30.3 Normalized stiffness coefficients for four IM6/epoxy laminates, in units of Msi
- 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
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
SOLUTION
1 L
(i) Compute the laminate stiffness matrix and -
+@ = a , 6 ~ l R
invert to get the compliance matrix: R
I
62.563 -26.647 -64.893
[a*] = -26.647 563.836 -224.518
-64.893 -224.518 495.374
@ = -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
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 --
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.
706 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
Peliminary desian
Detailed desian
Member sizing - laminate design
Material specs
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- ~~~~~~~~
of an aircraft component are shown in Tables The data required to support preliminary
31.1 and 31.2 respectively. The component design investigations include stiffness, den-
selected for this example is a vertical stabilizer. sity, strengths, fatigue characteristics, data at
The design requirements define maximum tol- elevated and low temperature, forms in which
erable deflections, imposed loads, a weight the material is available and associated mater-
goal, production rate, cost goal, service life ial prices. In addition, some experience with
and operating temperature extremes. In real- the material in the fabrication process selected
ity, the set of preliminary design requirements is required to support decisions concerning
would be much larger including, perhaps, production rates and costs. Generally, reliable
maintenance and inspection characteristics, published data can be used for preliminary
descriptions of qualification tests, center of design. Only when no data is available is it
gravity characteristics, and numerous others. necessary to generate data in this phase of the
design.
712 Design of structure with composites
The sequence of decisions in this design materials incur increased engineering develop-
case would typically be to make a preliminary ment, testing, and increased raw material costs,
decision on a manufacturing technique, fol- data from previous applications is quite valu-
lowed by selection of one or more materials able in performing cost trades and making
based on cost and availability. Once this has preliminary design decisions.
been done, the component is 'sized' for stiff- Table 31.3 suggests the ever-increasing
ness, strength and service life in each scope of structural applications for reinforced
candidate material. Material properties and composites. The requirements identified in
strengths are used for these calculations. this table are as diverse and varied as the
Material selection may depend on weight components. The result of the wide range of
minimization or life cycle cost minimization requirements imposed upon composite mate-
or a combination of the two criteria. rials, compounded by the ingenuity of
The result of this process is a material selec- material developers, has led to an over-
tion and a preliminary design. This 'design' whelming array of constituent materials.
possesses enough detail to support confidence Many of these materials are very specific sys-
that (1)the material selection is justified, and tems with a narrow range of applications.
(2) that the design concept is feasible in this Some materials are suited to numerous uses.
material. The set of mechanical properties and This multiplicity of materials and features has
strengths was, by no means, a complete or final produced a plethora of design data. In order
set of design values, but rather contains those to make material comparisons and selections
characteristics needed to support preliminary on a rational basis, the designer needs to
design calculations. These values are generally establish a clear set of requirements for the
the 'best available' from material supplier data, material. These requirements are sometimes
literature publications, data from other projects captured in a document which governs mate-
and data from material specifications. rial procurement. The aerospace industry
While the dominant design goal of aerospace typically refers to these documents as mater-
designers is usually to reduce weight, the dri- ial specifications.
ving requirements vary widely from one The situation in which the structural
product to another. Table 31.3 provides a syn- designer usually finds himself at the initiation
opsis of the diversity of these requirements of a design includes a broad and usually
across defense and commercial industries. This incomplete set of requirements and a moun-
table indicates that requirements are numerous tain of literature on a vast array of materials. A
and, therefore, the derived design objectives are design checklist, such as that contained in
diverse and numerous. Payoffs are achieved in Table 31.4, may be of some help in getting
the form of weight savings or greater service started in this situation. This checklist offers a
life. Sometimes, as in the case of carbon-carbon systematic approach to determining what
rocket nozzles, the use of composite materials information is needed at each step and sug-
results in a new level of performance which is gests which design team members need to be
difficult to quantify due to a lack of economic involved at various points in the process.
alternatives. Table 31.3 shows a very large The structural design team will employ a
range in quantified payoffs. Each of these prod- process which resembles this one in order to
ucts reflect a history of successive applications develop a preliminary design which specifies
and successive generations of the same applica- configuration, materials, manufacturing
tion. With each successive development effort, process, and establishes a basis of confidence
the industry has become better at understand- to proceed with final design. This basis com-
ing and defining requirements, material prises having answers or a plan to develop
characteristics, and payoffs. Since composite answers to all key questions.
Design process 713
c
a,
Y
a
8
.3
4
3
714 Design of structure with coinposites
Figure 31.2 shows the makeup of a typical preliminary design. The primary assumption
design team. For designs with composite mate- made in this section is that the materials of
rials, the team may be larger than design teams construction are laminated composites with
using other engineering materials. The focus of continuous fiber reinforcement. These materi-
the team is the individual with design responsi- als are typical of structural applications.
bility. Essential members are representatives of
manufacturing, tooling, and materials procure-
31.3.1 MATERIALS
ment. Others might include materials
suppliers, and specialists in testing and analy- The subject of material design data, and the
sis. In some product development activities, the closely related subjects of material characteri-
team includes subcontract managers or mater- zation and specifications, assume greater
ial procurement specialists who interact both importance for composites than for conven-
with other team members and with other com- tional materials. There are several primary
panies who also need to be considered as team reasons for this: lack of a single, comprehen-
members. More important than the list itself, is sive design database or source; greater
the early and continued involvement of all variability in measured values from one mate-
members. Interaction among these team mem- rial to another and from one lot of the same
bers produces the design. As shown in Fig. 31.1, material to another; differences between pre-
preliminary design begins with requirements dicted and measured component performance
definition and produces a design complete to introduced by variables associated with
the point of materials identification, fabrication 'workmanship' in the manufacture of the part.
approaches, size and shape, and preliminary The most basic reason, however, is the simple
lay-ups and joint designs. The development of fact that the engineering development process
this information requires the constant input encompasses design of both the material and
and review of all key team members. the structure. For these reasons, the designer
One feature of the design team which is of composite structure needs to focus more
unusual is the inclusion of the material sup- attention, and usually more resources, on the
plier in the design team. There are several subject of materials, than his counterpart
reasons for doing this. Sometimes, existing using only conventional materials.
materials do not 'fit the bill'. In these instances, Material data is required in order to make
further material development or modification key design decisions, first in the preliminary
may become part of the design process. The design phase and later in detailed design. The
material specification can be looked at as a type and extent of the data depends on the
blueprint for the material supplier to use in application, but, typically, data on the stiff-
design of the desired material. It is important nesses, strengths, and densities of candidate
to recognize the material supplier as a member materials is needed.
of the design team so that his inputs and Figure 31.3 shows relative ranges of specific
development efforts can be integrated into the tensile modulus for composites with various
design. Otherwise, some beneficial options fiber reinforcements. Specific modulus is a
may be excluded, both in terms of existing term which refers to the ratio of composite
materials and near term material development modulus to composite density. Specificmodu-
efforts which may be of value to the project. 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
31.3 PRELIMINARY DESIGN
ranges of material costs for these same families
The discussions which follow concern the por- of materials. Both of these figures were con-
tion of the design process characterized as 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
I
I ,
I
I
EGLASS ARAMID T300 M I-M
FIEF! FlBER GRAPHITE GRAPHKE GRAPHITE
FER
Material
Fig. 31.3 Specific tensile modulus of various composite materials.
properties available from each specific mater- materials is usually made on the basis of per-
ial. These ranges are the result of including formance. Figure 31.4 considers only material
different forms of the material and the entire cost, which in some applications, is the major
range of laminate values, including quasi- portion of product cost. In other applications,
isotropic values on one end and unidirectional material cost is completely overwhelmed by
values on the other. manufacturing costs or other life-cycle costs.
Figure 31.4 suggests some general conclu- Material cost is typically about 30% of compo-
sions. First, there are three more or less distinct nent cost in aircraft parts, less than 10% in
regions of composites. The first group is glass- satellite components, and generally higher than
reinforced composites. The second is 30% in most commercial applications. It is
intermediate modulus graphite and aramid therefore critical that product cost analysis
fiber-reinforced composites. The third group include all important cost contributors.
includes high and ultra high modulus graphite Generally, ’you get what you pay for’ or,
fiber composites. Each of these types is suitable more precisely, ’you must pay for what you
for a distinct range of applications. A compari- need.’ However, the range of properties and
son of where the common metals fall on this costs within a family of materials is an indica-
figure provides a pretty good explanation of tion of the latitude which a structural designer
why aramid and graphite have replaced metals has when employing reinforced composites.
in applications where the market can ’pay for The upper end of each range of specific
performance’. Glass has replaced metals in modulus in Fig. 31.3 is established by values
those applications where some performance for a unidirectional laminate. While this is one
can be sacrificed for lower cost, increased envi- equitable basis for comparing reinforced mate-
ronmental resistance or longer life. rials to each other, it is not a good basis to use
The second conclusion suggested by Fig 31.4 for design calculations because so many
is that there is extensive overlap in the price of requirements drive the design towards multi-
aramid and intermediate modulus graphite directional reinforcement. Foremost among
fiber composites. Selection from this group of 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
one direction. Figure 31.5 shows the relation- forced composite materials. This table shows
ship of tensile modulus in x and y directions mechanical properties and strengths for four
and inplane shear modulus (xy) for a varying fiber-reinforced materials. These material
lay-up angle, 13.The same type of relationship properties and strengths are the basic data
exists for strengths and thermal expansion from which laminate values are calculated. As
coefficients. A design which maximizes modu- explained in Chapter 30, lamination theory
lus in one direction at the same time simply uses layer values to determine engi-
minimizes modulus in the direction transverse neering constants and to estimate strengths for
to this and minimizes inplane shear modulus any desired laminate. Materials testing is
as well. Strength in the transverse direction therefore conducted primarily at the layer
and inplane shear strength will be low in mag- level. Laminate test coupons are employed to
nitude also. These low properties and confirm predictions and 'workmanship'. The
strengths in the 'secondary directions' will exceptions to this statement are strengths
severely limit the ability of the laminate to which are laminate-specific, such as bearing
resist load and deformation in these direc- strength and interlaminar shear strength.
tions. Highly directional laminates are However, these are values which are impor-
therefore not appropriate for structures which tant to only specific regions of the component,
act as plates or shells, and for beams with sig- and generally do not enter into material selec-
nificant secondary loads. Highly directional tion decisions.
laminates also present severe design con- For preliminary design, laminate values are
straints in joint regions where loads are typically predicted from available ply-level
multi-directional in nature. values. Design calculations and trades are con-
Multi-directional reinforcement offers a ducted with these predicted laminate values.
more robust design because strengths and Later, in detailed design, predictions are con-
properties are dominated by fiber properties firmed with selective tests of design laminates.
in all inplane directions. Furthermore, lami-
nates with multi-directional reinforcement
Carpet plots
offer more desirable cure characteristics and
usually avoid high levels of residual stress, The infinite number of combinations of ply
internal damage or warpage in thin parts, thickness, ply angle and material reinforce-
induced by cooldown from cure temperatures. ment is both a curse and a blessing in
Successful instances of unidirectionally rein- preliminary design. Once the design require-
forced parts are nearly non-existent. ments have been identified and quantified, the
Table 31.5 provides a typical list of materials question of how to meet these requirements
data required for structural design in rein- with any given material presents itself. An
extremely useful tool in addressing this ques- forcement in each of three specified directions.
tion is the simple carpet plot. This graphical While 0, 45 and 90" plies are most commonly
representation provides a way to present the used, the three angles can be any selected val-
entire range of properties, or strengths, avail- ues. Another common combination is
able from a particular family of laminates. 0/30/60. Typically, values are calculated using
Figure 31.6 shows a carpet plot of tensile mod- a difference of 10%between successive points,
ulus for laminates comprised of layers of which requires about 1000 data points per set
T300-epoxy with orientations of 0,45 and 90". of curves. For this reason, creation of carpet
The plot contains all possible proportions of plots is done with the aid of computers.
the three directions, and is read as the legend Development of carpet plots of strength
indicates. This type of plot treats laminates as values is less straightforward. The primary
homogeneous combinations of various per- complication is the definition of failure of the
centages of layers. Carpet plots do not laminate. An extensive discussion of laminate
recognize lay-up sequence. Generally, this pre- failure modes is contained in Chapter 30.
sents no limitation, but for laminates Calculation of laminate strength involves con-
composed of very few plies, or laminates sideration of progressive failure of each layer
employing significantly unbalanced stacking and construction of strength envelopes for
sequences, the assumption can lead to incor- combined states of loading. Construction of a
rect strengths. carpet plot requires an approximation of ply
Carpet plots of material properties are con- strength which is adequate for preliminary
structed directly from a table of values for trade studies and initial member sizing. The
many specific laminates. Values of moduli, recommended approach is to define laminate
Poisson ratios, and expansion coefficients are strength as the product of allowable fiber
calculated from lamination theory for a series strain and the laminate modulus in the appro-
of laminates with varying percentages of rein- priate direction. This calculation assumes that
140
120
-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
0 1 I
0 10 20 30 40 50 60 70 80 90 100
PERCENTAGE4M)EGREE LAYERS
the laminate contains fibers oriented in at least 427 MPa and 15.5 GPa, respectively. If this set
two directions, and further ignores the Poisson of properties were not suitable, the three carpet
effect in the calculation of strength. While this plots would be used to iterate to an optimum
approximation tends to overpredict strength, set of values and an accompanying laminate.
it has proven to be suitable for preliminary The use of carpet plots can greatly facilitate
laminate selection in strength critical struc- the laminate selection process in the early
ture. Using this definition of strength, carpet stages of design. It should be noted that these
plots can be directly constructed from allow- plots are simply visual representations of the
able tensile and compressive strain values, results of lamination theory calculations, using
and predicted modulus values. ply level input values. Carpet plots of all
Carpet plots provide a quick method for inplane material properties: elastic moduli,
selecting a candidate laminate for the prelimi- Poisson ratios, thermal expansion coefficients
nary design process. For example, let us and moisture expansion coefficients can be
assume that design calculations indicate that a developed from the appropriate equations.
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. Design values
One is a laminate comprised of about 55% Appropriate values for properties and
0" layers, 35% 45" layers and 10%90" layers. If strengths are required in both of the primary
tensile strength and inplane shear stiffness design phases - preliminary and detailed. For
were important to the design, it would be nec- preliminary design, values are typically
essary to consider the values associated with acquired from existing sources. These can
the selected laminate. Related carpet plots pro- include data published or provided by mater-
vide ranges of tensile strength (Fig. 31.7) and ial suppliers in the form of brochures, design
shear modulus (Fig. 31.8). These are about 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
40 T
t
I
0 0 0 0 0 0 0 0 0
7 01 r n d In (D b 00 : g
F
PERCENTAGE&DEGREE LAYERS
professional society proceedings or publica- Test methods also tend to vary from one lab-
tions, data from textbooks such as this one, or oratory to another. In general, it is best to be
data developed on previous projects within wary of specimens other than the standard
the organization. An abbreviated list of ones. Standard coupons and test methods are
sources of preliminary design data is pre- defined by the American Society for Testing
sented at the end of this chapter. and Materials (ASTM), and other organiza-
As might be expected, this available data tions such as Suppliers of Advanced
comes in various forms, so comparison of data Composite Materials Association (SACMA).
from different sources may require some judg- The primary value of employing standard
ment and mathematical manipulation. Fiber coupons and tests is the confidence established
volume fraction usually varies from one with time and existing databases. While each
source to another. The data is sometimes nor- standard coupon may possess some shortcom-
malized to a 'standard' value, typically about ing, it does offer consistency and a basis of
60%. This normalization process is rarely comparison with existing data.
explained in the literature, but most often con- Fiber volume and coupon configuration are
sists of simply multiplying measured values only two variants present among published
by the ratio of 0.60 to whatever fiber volume data. Others include the resin system, material
was measured. The values most frequently form, and method of fabricating panels from
normalized include tensile and compressive which specimens are taken. These variants
modulus, and tensile and compressive underscore the reasons why existing data can
strength. The validity of normalizing compres- be useful for preliminary design, but almost
sive strength is debatable because always needs to be augmented or replaced by
compression strength of reinforced composites data specific to the design application for final
is dependent, to some extent, on the matrix. design. Two different approaches are
The validity of normalizing values other than employed in the development of design val-
the four mentioned above is dubious. ues. The first of these is to buy existing
722 Design of structure with composites
commercial grade composite material, charac- displacement and rotation at both ends, and
terize it, and design to those values. The loaded by a uniform load along the entire
second is to include the material supplier in the length, I, as shown in Fig. 31.9. Design require-
process by jointly developing a specification to ments are summarized below:
which the delivered material must comply.
While the second approach may increase mate- w = 2.0 nVmm
rial costs, it guarantees the suitability of the A
material and usually results in the use of S h
higher or more specific design values.
I = 1500 mm
A material specification typically defines 4
acceptable values of all critical characteristicsof
the material to be purchased. The specification
may be a simple one page document speclfylng Fig. 31.9 Example: trade study of beam with a uni-
reinforcement, resin system, and limiting val- form load.
ues of fiber volume, or a multiple page
document including minimum values of mod-
1. Maximum beam weight is not to exceed
ulus, strengths, cure characteristics, and other
5.0 kg or 3.33 g/mm excluding end fittings.
items. Material procurement cost will tend to
2. Maximum beam deflection (at midspan)
follow the number and stringency of the criteria
must be less than 2.5 mm under the load
specified, since the material supplier will need
shown in Fig. 31.9.
more quality assurance activity before delivery
3. Maximum stresses in the beam must not
and may need to perform additional material
exceed allowables, including a factor of
development.The more demanding a specifica-
safety of 2.0.
tion becomes, the greater the need to identify
4. The cross section of the beam must be
and work with one (or more) material suppliers
closed and rectangular as shown.
in its development. One reason for this is sim-
ply to ensure the development of a specification Four materials will be considered for this
which can be met by at least one supplier. A application: aluminum (7075 alloy), E-
good specification needs to recognize the nor- glass/ epoxy composite, T300 graphite / epoxy
mal variation in material characteristics from composite, and M60J graphite/epoxy compos-
one manufactured lot of material to another. ite. Formulas for deflection, maximum
Data illustrating this lot-to-lot variation will be compressive stress, and beam weight, in
shown and discussed in a later section of this pounds per inch, are presented below:
chapter.
Deflection: d = (w14/384EI)
where €I = (Ebth2)/2
31.3.2 DESIGN EXAMPLE
Max. stress: f, = M c / I
Key aspects of the preliminary design process f, = ( M / W
have been described in this chapter. An exam- = (wL2/4hbt)
ple, consisting of the design of a composite
Weight: W = v(2h+2b)t < 3.33 g/mm
beam, is included here to illustrate the
methodology typically employed in prelimi- One additional constraint must be introduced to
nary design, and to provide a demonstration the design. Buckling of one side of the rectangu-
of a trade study performed for the purpose of lar section is governed by elastic moduli and by
material selection. the width-to-thickness ratio of that side. The
The structural element selected is a beam of crippling strength of a side can be sigruficantly
constant cross section, fixed against lower than the laminate compressive strength or
Detailed design 723
inplane shear strength. In order to prevent com- However, the cost of a beam fabricated in T300-
pressive or shear buckling of the sides and epoxy may still exceed the cost of an aluminum
flanges, a rule of thumb is to limit the side beam, despite the fact that less T300 material is
dimension, h, to no more than twenty times the required. The next calculation might be to esti-
thickness, and to limit the flange dimension, b, mate the fabricated costs, including materials,
to no more than fifteen times the thickness. of the T300 and aluminum designs, to ascertain
Using these relations, h and b are eliminated the cost differential. A final comparison can be
from the equations and replaced by multiples of made between T300 and M60J fiber reinforced
t. The three equations are then solved by itera- beams. As presented in Table 31.6, the addi-
tion for each of the four materials using tional weight savings associated with an M60J
properties and strengths shown in Table 31.6. beam is relatively small. The cost differential is
The summary table presents a comparison of going to be substantial because M60J prepreg is
the calculated design thicknesses and corre- over $200 per kilogram while T300 prepreg is
sponding beam weights for each of the four about $20 per kilogram. Only a substantial
candidate materials. The deflection requirement payoff in increased component life or overall
proved to be the dominant requirement for all system performance would justify the selection
four materials, i.e. the thickness required to sat- of M60J over T300.
isfy the deflection requirement was greater, in In a real design situation, the trade would
each case, than that required to limit imposed probably be more complex. Perhaps, the load
stresses to acceptable values. The estimated pre- would be a cyclic load or an intermittent load,
liminary design weight of each design is less leading to consideration of fatigue allowables.
than 5 kg, as required. Or, perhaps the natural frequency of the beam
Several conclusions can be drawn from this is another important design consideration in
comparison. First, the aluminum and E-glass the structural system. The trade methodology
designs are comparable on a weight basis due remains the same, but additional characteris-
to the fact that the lower density of fiberglass tics would need to be considered.
offsets its lower stiffness. End fittings have
been ignored, along with numerous other
31.4 DETAILED DESIGN
details, in this preliminary study, but it is
worth noting that the additional weight intro- Many of the activities which constitute
duced by metallic end fittings would probably detailed design are extensions or iterations of
cause the E-glass detailed design to be heavier activities already performed in preliminary
than the aluminum design. The T3OO/epoxy design. However, a few topics require special
design offers a significant weight savings over attention. This section will focus on three areas
aluminum and E-glass, deriving primarily specifically. These include a discussion of the
from its higher modulus-to-density ratio. development and use of material design data,
the approach to joining and the development measurement of this property, and the
of joining details, and the construction of expected variation in this characteristic.
drawings. Differences in design values and measured
strengths are larger. However, preliminary
design values are all exceeded by average mea-
31.4.1 USE OF MATERIAL DESIGN DATA
sured values, confirming the fact that strength
The first of these three areas is an extension of critical regions are conservatively designed.
the discussion of material data introduced in There are some differences in values mea-
the section on preliminary design. The point sured from one lot of material to another. The
was made in that section that material data kind and amount of variation is described in
relies heavily on ply-level values. A typical set more detail in Figs. 31.10 and 31.11. Specified
of mechanical material data is shown in Table 'acceptance values' are shown on each figure
31.7. The material of interest is T50 graphite for reference. In this case, these acceptance val-
fiber in an epoxy resin system. The material ues are lower than those used for preliminary
was ordered in significant quantity to an aero- design. The figures also show results of tests
space specification and was manufactured in conducted by the material supplier and by the
ten lots. Table 31.7 is subdivided into material receiving company. Differences in these results
properties and strength values. The values provide some insight into the influence of test
shown as 'measured' are average for all speci- methods, facilities, and personnel. The first
mens from all ten lots of material. The table figure compares tensile modulus and the sec-
also includes preliminary design values for the ond tensile strength. Figure 31.10 indicates
sake of comparison. that, while values are different from lot to lot,
This comparison shows excellent agreement all lots exceed the specification value for ten-
between measured and preliminary design sile modulus and are therefore acceptable. The
material properties. The largest differences are measured ply-level data confirms the design
in coefficient of thermal expansion (CTE) val- values of tensile modulus. The measured val-
ues, and these are on the order of 20-25%. This ues for tensile strength exhibit larger
is excellent agreement considering the difficul- variations, but are also higher than the speci-
ties and uncertainties associated with the fied value. Once again, all measured values
Table 31.7 Mechanical design values for T50/epoxy tape: preliminary and measured layer properties and
strengths
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 database for establishing preliminary design
acceptable. values for the next application.
This data is typical of aerospace applica- Table 31.8 contains a further comparison of
tions. The types and amounts of data will, of predicted and measured laminate values for
course, depend on the specific application. T50-epoxy tape, developed in the same appli-
The major difference between this data and cation. The values in this table correspond to
preliminary design data is that the data sup- specific design laminates. Three sets of values
porting final design will be specific to the are shown for each of the design laminates -
material form, resin system, and fiber volume the first developed from preliminary design
selected. Final design data is an extension of layer values, the second from measured layer
data available for preliminary design. It will values, and the third directly from tests per-
generally focus on ply level values since this is formed on laminate coupons. Using measured
the most cost-effective way to obtain data for layer properties produces a better correspon-
all of the laminates which will be employed in dence between predictions and measurements,
final design of the part or assembly. These val- but not an exact overlay. The primary differ-
ues now become an important part of the 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
by handling and fabrication that simply are allowables, and so provides maximum lever-
not accounted for by theory. These differences age in terms of applying testing resources to
are larger for strengths than for properties, development of design confidence.
and account for the knockdown factors nor- A less extensive series of laminate tests
mally used in developing material design may be required in addition to the unidirec-
strengths. tional coupon testing. The purpose of these
One final point to be made concerning these tests would be to provide some selective con-
comparisons is that differences exist, but are firmation of key design properties and
not typically an inhibitor to designing with strengths for comparison with values pre-
composites. These variations must be recog- dicted from measured layer values. In
nized in the design process, and can be addition, some very specific strength charac-
handled with statistically-derived knockdown teristics, such as bearing strength, are specific
factors, and conservative but realistic design to laminates, and cannot be reliably predicted
approaches. Key design values can also be from layer values. If this allowable is critical
controlled through development of intelligent to the design, tests of specific design lami-
material specifications. In most designs, the nates may be necessary.
usual variations are easy to accommodate. The
important point is that they need to be quanti-
31.4.2 JOINING
fied and included in the design process.
This leads to a discussion of the role of test- Joining of composites normally presents some
ing in the development of design allowables. It challenges and tends to influence the configu-
was previously pointed out that normally little ration of the part. The two recognized
or no testing is performed in support of pre- methods for joining composite structure to
liminary design. In fact, the only testing which other composite or to metallic parts are adhe-
is essential is that performed to determine crit- sive bonding and mechanical fastening. The
ical values which are just not available. advantages and disadvantages of each method
In the process of detailed design, however, will be discussed, followed by some guide-
the picture changes. Once a material is lines for selection between the two. The
selected and a design acquires some maturity, discussion is not an exhaustive one by any
the values critical to establishing sufficient means, but is intended to highlight key con-
confidence in the final design can be identified siderations which determine joint designs and
and addressed through test. The emphasis is provide some initial direction to the designer.
usually placed upon layer level coupons for Numerous factors need to be considered in
two reasons. The first is that the information the selection process. Figure 31.12 offers a list
obtained from unidirectional, standard of the most common requirements. It should
coupons is the most direct information avail- be kept in mind that some of these 'require-
able about the material. Failure modes are ments' may become design variables in the
predictable and repeatable, and results can be course of the process. Geometry of the mem-
directly converted to allowables. An addi- bers being joined, for instance, could be
tional benefit deriving from the use of altered locally to facilitate joint design.
unidirectional coupons is that direct compar- Reliability potentially includes an array of
isons to other materials and different lots of requirements, one of which is the implications
the same material can easily be made. of joint failure on system performance. Is it
The second reason for allocating the major- catastrophic or benign? Is it easily detectable
ity of testing resources to ply-level testing is prior to failure or insidious?
that this data can be used for prediction of a Determination of this list of requirements
wide range of laminate properties and will lead directly to the formulation of key
728 Design of structure with composites
How important
i
,
is weight?
How critical
is cost?
Reliability
t Service life
Implications of
fai Iure
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
Local reinforcement
As in metal structures, local reinforcement is
,
w
(1 .O)
Scale: 118
generally required where any hole or cutout is See view B view
placed in a structural part. Analogous to metal 0.10 (reference). .- .K-
, _ f ~ . 2(reference)
~
_f I
parts, reinforcement can be bonded or fas- I
drawing are unique. There are countless varia- table defining the material: fiber reinforce-
tions on the format of a drawing, so the ment, resin system, material form, resin
discussion will be more or less limited to the content, material source or sources, and sur-
content, with a specific format shown only for face treatments. The second is to invoke a
the purpose of providing an example. document, such as a specification, which
A drawing detailing a composite part needs defines the material required. If the second
to specify geometry, materials, sources of approach is used, it may still be a good idea to
those materials, ply sequence for each unique provide a brief identification of the material
laminate, details of transition regions, process- on the face of the drawing to facilitate inter-
ing definition, post fabrication instructions for pretation by analysts, tool designers,
drilling, sawing, etc. and any inspection manufacturing and inspection personnel.
requirements. Other details, such as individ- Table 31.10 shows an example of material
ual ply patterns, may be necessary for a description employing both methods.
specific part, but this list is suggested as one of Specifying a fabric requires the designer to be
general applicability. familiar with all of the variable characteristics
Dimensions are defined in the same manner of the material form - weave style, surface
as for metal parts with the exception of thick- treatment, and end count. This is necessary
nesses. Thickness is really defined by laminate because fabrics are available in numerous
sequence meaning that the part will be as thick weave styles, with various surface treatments,
as the cured laminate dictates. A thickness and can be woven with any of several differ-
dimension is normally shown as a reference ent size yarns.
dimension and provided for tooling design. It Each unique laminate in the part requires
should be recognized that specifymg a thick- definition sufficient to allow a fabricator to lay-
ness as a fixed dimension demands up the part. Figure 31.15 presents a typical
compliance to that dimension. Unless manu- example of the usage of a ply sequence table on
facturing ‘tool try’ units have been fabricated the face of a drawing. The figure identifies the
to determine cured laminate thickness with surface that ply number 1 is placed upon and
the particular manufacturing process speci- then details the ply stacking sequence to be fol-
fied, there is no guarantee that the thickness lowed. It is desirable, but not always practical,
can be achieved with the number of plies and that the first ply shown in the table be the first
resin content specified. ply physically laid up on the tool. The ply table
Dimensional tolerances are generally deter- contains a column identifying the material of
mined by tooling design and the amount of each ply since sometimes a single laminate
material shrinkage. Experience with the contains plies of different materials.
process and material is the only reliable guide Areas of transition are handled as shown
in setting tolerances. in Fig. 31.16. The two adjacent regions of
Material definition can be accomplished in ‘constant’ thickness are defined by appropri-
two ways. The first is to create a note or a ate tables as shown. The tables, however,
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 tests
Engineering Material
development Procurement Material acceptance tests
Tool tries
In-process inspection
F)
fabrication
Trim
Bonding
Drilling holes
Sawing
Witness panels
Dimensional verification
Non-destructive inspection
acceptance
Proof test / acoustic
emissions
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
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
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, $3
”P
Fig. 32.3 External and internal forces and moments.
fa = 1h
0
Fadt + Pa + 9, +ma + 0,) + 9(7, - u p )
0 equation (32.1) excludes the terms corre-
sponding to inertia, body and surface
forces;
(112) 0 in nonlinear terms of eqn (32.1), N, = N :,
N,= Np”, Nap= N u t where N,O, Np”, Nap”are
the stress resultants that correspond to
membrane prebuckling state of the struc-
ture;
0 constitutive equations (32.2) should exclude
terms W and Mr.
General equationsfor composite structures 741
f
K = K4Ks5-K4; (32.6)
where (mn = 11,12,13,23,22,33; r = 0, 1,2)
-
_
l
r +_l 1kAtA(t;+ )-
i=l
::;t (32.7)
(32.8)
. ,
Constitutive equations, (32.2), include also
temperature terms
N,' = J:)
h,
K mn = -a (2)
h2 mn Fig. 32.9 Rib parameters.
ii
As a first approximation a system of densely A, = cjEjsin4pj
arranged equivalent ribs can be also treated as j=1
a system of continuous layers as depicted in n
Fig. 32.8. For the layers, simulating the rib ele- A,, = A,, = cjEisin2pjcos2pj
ments in Fig. 32.9, the non-zero inplane 1=1
stiffness coefficients are
A:) = E-d
d
A, = Ill
j=1
c.G.cos’pj
n
rn
A,, = cjGjs’n2p,
A$) = 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
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
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
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'
f(
where Fig. 32.14 Normal and shear stress resultants acting
in a thin-walled beam.
S = $Bds
where
D
] (32.14)
ez = e; + c z k z d z
SX(s) =
I
By ds
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: c2(D,, + 2033)
52 =
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
c = ITdY
w(x,y) = wp [1 -f2(X)IP2(y) (32.19)
The following are used: 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
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- p, z) is reduced to the following set of equa-
linear problems are required. tions in terms of radial displacement of the
basic surface ut, deflection w,and rotation of
32.5.3 NONSYMMETRICALLY LAMINATED the normal to the basic surface 6 , i.e.
PLATES ?ut’”’ + ~ Y ~ U +~ (7
“ ’ - np2 - n2)Yur” + (1 - np2
= 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
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
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
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
17 I=[."."
BllD,
+{(l +=)I BP22
where
1
; =(y) 2
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
Table 33.1 Definition of lamina properties and equations used to calculate material properties
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
graphite fibers, but have a higher density and upon the type of analyses being performed or
lower modulus. Since the lamina properties the analysis code being used. If a strength or
are assumed to be used as preliminary design failure analysis is performed, then the follow-
and analysis parameters, the effects of temper- ing strength allowables may be required; q,
ature, environment and fatigue are not o,,-q,-0,and T,,. Tables 33.2 and 33.3 include
considered. However these conditions must be these elastic and strength properties, which
considered during the final design develop- were compiled from various sources, such as
ment. military standards, material supplier data and
published literature. References are included
for each property so that the engineer may
33.3.1 TWO-DIMENSIONAL (2-D) LAMINA
directly consult a particular reference if further
PROPERTIES
information is required. These references are
The elastic lamina properties required for a listed in Tables 33.4 and 33.5.
composite 2-D analysis are typically E,, E,, G,,, The lamina properties for glass, polyethyl-
and vI2. The specific properties may depend ene and aramid fibers are listed in Table 33.2.
Lamina allowables 761
Polyethylene and aramid fibers are more com- these properties are difficult to test and data is
monly known by their trade names as Spectra not always readily available. The 3-D lamina
and Kevlar. Kevlar 29 and 49 are included for properties listed in Tables 33.2 and 33.3 are
aramid properties. The polyethylene fibers estimated based on 2-D properties. The fol-
include Spectra 900 and 1000. E-glass and S- lowing section describes the methods for
glass (trade names) are included for glass calculating lamina properties in the 3-direc-
fibers. Table 33.3 lists lamina properties for tion when data is not available.
standard, intermediate and high modulus
graphite fibers. Data for non-USA produced
33.3.3 ESTIMATING LAMINA PROPERTIES
fibers is not included.
WHEN DATA IS NOT AVAILABLE
The type of material system is also indi-
cated in Tables 33.2 and 33.3. Design Lamina properties through-the-thickness (3-
allowables for a prepreg material system ver- direction) are often not readily available,
sus a wet filament wound system may result although they may be required to perform an
in different properties. It is important to con- analysis. When data is not available, these
sider the processing method when selecting properties can be determined by assuming
the properties to be used in a design. One pro- that the lamina is transversely isotropic. For a
cessing method may result in a lower moduli transversely isotropic lamina, the properties in
or strength than another. The effects of differ- the 2- and 3-directions are assumed to be the
ent processing methods on design allowables same. Thus the following equations may be
is discussed in further detail at the end of this used to determine elastic properties in the 3-
chapter. direction':
The majority of the 2-D properties is based
E, = E,
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) G*, = G12
thick). Properties based on thin specimens r
L3
may not represent those for thick composites
G23 = 2(1 + vz3)
(typically greater than 6.35 mm (0.25 in) thick).
The exact definition of a thick composite is not
consistent within the composites community. '13 = '12
Thick composite structures may have proper- The transverse Poisson's ratio, v23, can be
ties lower than those of thin composites, so the determined from the following relationship2:
engineer may need to perform additional test-
ing for certain applications.
to assume that the fiber and matrix are and lower void content than a wet filament
isotropic, although certain fibers are consid- wound part. This can affect properties such as
ered to be anisotropic. The fiber or resin shear the elastic modulus (E,) or tensile strength (uJ.
modulus can be calculated by: It is important that the engineer understand
E the limitations of the selected processing
G=----'--
2(1 + v) method and adjust the design allowables
accordingly. Processing parameters which can
The following equations may be used to esti- affect the lamina allowables are fiber volume
mate strength properties in the 3-direction. fraction and void content. Design allowables
should be modified if the process used to
u3= u2
determine the lamina properties deviates from
the intended process for the final composite
-a3= -u2
part; this ensures that unrealistic properties
The equations listed above should be consid- are not being used to design the part.
ered a starting point for estimating 3-D lamina There are numerous fabrication methods
properties when actual test data is not avail- applicable for composites. The methods which
able. The values may need to be verified by will be discussed are those that apply to con-
testing as the design progresses. tinuous fiber reinforcement. These include
filament winding, hand lay-up and resin
transfer molding (RTh4). The method of cure
33.4 LAMINATE ALLOWABLES
can also affect the lamina properties. For
Laminate elastic properties and strengths can example, one part can be filament wound with
be determined by testing or by using a lami- prepreg tow and another can be hand layed up
nated plate code. During the initial design with prepreg tape. These parts have different
phase, laminate allowables are typically deter- fabrication methods, but they may be cured in
mined by using a laminated plate code. This is the same manner; in an autoclave with vac-
especially true if the composite lay-up devi- uum and pressure. It is very likely that these
ates from a 'standard' lay-up, such as a two parts would have similar properties and
quasi-isotropic laminate ([90, +45, 4 5 , OIJ. require no adjustment of lamina properties.
There is typically more test data available for a However, if the filament wound part was wet
quasi-isotropic lay-up than any other lay-ups. wound and cured in an oven without vacuum
Laminate testing is often performed after com- or pressure, then the lamina properties would
pletion of the initial design, material selection need to be adjusted if they were based on
and composite lay-up has been decided. properties derived from testing using prepreg
Laminate testing would be performed to con- tape. A wet filament wound part typically has
firm predictions and processing effects. a lower fiber volume fraction and higher void
content. Thus in determining if lamina proper-
ties need to be modified, the engineer must
33.5 EFFECTS OF PROCESSING
VARIABILITIES ON DESIGN ALLOWABLES
consider the complete method of processing,
including the raw material and cure method,
The actual fabrication method used to build a not just the automated or manual process
composite structure can have an impact on the which is being used to fabricate the part.
design allowables. Some processing methods In general, if a part is wet filament wound,
can result in a higher fiber volume fraction it will possess a lower fiber volume fraction
and lower void content than others. For exam- and a higher void content than a hand-layed
ple, an autoclave cured part using prepreg up part using prepreg tape and cured in an
tape will typically have a higher fiber volume autoclave. Wet filament wound parts cured in
References 763
Table 33.2 Lamina properties for glass, aramid and polyethylene fibers in epoxy matrices
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
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
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)
'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)
02
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
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)
Table 33.3 continued Lamina properties for graphite fibers in epoxy matrices
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
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)
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
1
'3 = '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
Lamina property references 773
Table 33.4 References for lamina properties of glass, aramid and polyethylene fibers in epoxy matrices
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
02
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
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
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
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 34
Yu.M. Tarnopol’skii and VI L. Kulakov
34.1 STRUCTURAL HIERARCHY OF FIBROUS The test results are used to calculate the
COMPOSITES properties of materials with more complex
configurations of fiber arrangement and of
Fibrous composites are inhomogeneous mate-
hybrids, i.e. materials with different reinforce-
rials with multiple levels of structural scale.
ments in the same lay-up.
The three levels of structural scale can be
For multilayered composites, the largest
arranged in a hierarchy. The characteristic
structural scale is the thickness of the lami-
dimensions for the three levels are: fiber diam-
nated plate that is equal to the sum of stacked
eter, lamina thickness and plate thickness. The
laminae and interleaves. The theory of lami-
most appropriate test methods and structural
nated plates allows one to determine the
analysis techniques are different for each level
properties of the plate using the properties of
in the hierarchy. Test objectives and associated
the monolayers and their stacking sequence. If
problems are also different for each level.
the monolayers are part of a structural ele-
The smallest scale is the diameter of the
ment, then the highest level of scale is the
reinforcing fiber. The properties of the rein-
characteristic size of the object. The dimen-
forcing fiber and polymer matrix and their
sions of structural elements typically exceed
interaction are studied in the field of microme-
chanics. the thickness of the plate by several times. The
The second level scale is the thickness of the properties of components are measured by tra-
unidirectional lamina. Macromechanics ditional mechanical and physical test
describes the properties of a monolayer under methods’.
loading at an angle to the fiber direction. A The results of the analyses or tests at the
monolayer is defined as a flat or curved ele- first level are used as input for the analyses at
ment of material composed of a polymeric the second level. The same relationship holds
matrix and reinforcement of the same type and for the second and third levels. Upon convert-
orientation throughout the layer. It is the basic ing each scale to a continuum at the next
structural element of laminated and fibrous higher scale, it is important that for each level
composites. The characterization of monolay- under consideration the number of elements
ers by mechanical test methods is given be sufficient, e.g. through the width and thick-
particular emphasis in this chapter since test- ness of the lamina or through the thickness of
ing of anisotropic materials is a relatively the plate, so the transition from a discrete
novel and seldom studied field of mechanics. 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.
Handbook of Composites. Edited by S.T. Peters. Published
in 1998 by Chapman & Hall, London. ISBN 0 412 54020 7
Problems of composite testing 779
etc.) must be sufficiently large to support this of fiber waviness can cause the measured val-
approximation43r6. ues of longitudinal modulus of elasticity and
Once the general test method has been strength to be considerably lower than those of
selected, the details of the loading and the materials with ideally straight fibers. Fiber
sample geometry must be selected. For fibrous waviness also influences on the coefficient of
composites, the principal difficulties lie in the thermal expansion in the fiber direction. The
generation of a uniform stress field in a repre- modulus of elasticity perpendicular to the
sentative volume of material, i.e. the fiber direction and the in-plane shear modulus
elimination of end and edge effects. This is dif- are not significantly affected by fiber wavi-
ficult even for the most simple types of tests. ness.
The difficulties increase with increasing All of the aforementioned unique testing
degree of anisotropy, i.e. materials reinforced requirements apply to composites of a fibrous
by high-modulus or high-strength fibers and laminated structure. Additional difficul-
(boron, carbon and organic fibers). ties arise when spatially reinforced composites
End effects are primarily influenced by the are tested because the transverse strength and
method of fastening and loading of the speci- stiffness are derived from a rigid framework
men, the length of the grip section, and the rather than from a compliant matrix.
fiber orientation. The region involved in end
effects extends in the direction of the greatest
34.2.4 SUMMARY TABLES
stiffness of the material and increases with the
anisotropy of the material. The most common methods of testing com-
Edge effects are primarily influenced by the posites in tension, compression, torsion and
size and shape of the specimen, the fiber ori- bending are described in Tables 34.1-34.5 . The
entation and the angle of specimen cutting. If high performance test fixtures designed
strength anisotropy is present, improper load- specifically for composite testing, their
ing and fastening can lead to changes in the description and recommended applications
failure mode and the resulting strength value. are given in Reference 7.
A most important considerationis the selec-
tion of the specimen width. The width must be
34.3 TEST SPECIMENS
large enough to avoid the effect of cut fibers at
free edges which is important for specimens of The important relationships between fabrica-
off -angle, angle-ply and cross-ply materials. tion methods, test methods and required
Edge effects are manifested as interlaminar specimen shapes are shown in Fig. 34.1.
stresses at the free edges of the specimen, the Specimens for mechanical testing are classified
direction and magnitudes of which depend on as flat specimens (bars and plates), rings (com-
the fiber lay-up. plete and segments) and tube@.
Material quality also causes unique require- The specimens and test methods in Fig. 34.1
ments for testing composites. Quality cannot are used to characterize the monolayer. Flat
be ignored during testing because the material monolayers can be characterized with speci-
and structure are formed simultaneously. In mens that have a different fiber lay-ups but the
addition, composites are extremely sensitive same general, flat, long, narrow shape. To ade-
to mechanical and thermal history. Structural quately characterize wound monolayers, it is
imperfections, in particular porosity, waviness necessary to use both rings and tubes. Ring
and misalignment of fibers, require special specimens of a unidirectional fiber lay-up are
attention. The presence of porosity affects the used to assess characteristics in the fiber direc-
measurement of polymer matrix dominated tion. Tubular specimens with a 90" wind angle
properties, e.g. shear strength. Small amounts 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)).
Tension and compression 787
The greatest technical challenge in tension forces acting on the specimen ends (Table 34.1,
testing of composites, especially unidirec- Method (c)),it is impossible to achieve a suffi-
tional composites, is the reliable transmission ciently uniform stress distribution over the
of tensile forces from the grips to the speci- faces of the specimen. As a result, premature
men. This is generally performed through the local failure of the specimen occurs. When the
use of friction forces. Tabs bonded to the spec- loading is achieved by shear forces acting on
imen improve the efficiency of load the sides of the specimen as specified by
transmission considerably. The tabs should be ASTM D3410 (Method (d)), the stress distrib-
made of a material that has a much lower ution in the specimen is also non-uniform,
modulus of elasticity and a higher total elon- especially when flat wedge grips are used.
gation than the respective characteristics of the The best method is a combination of the two
specimen material. Tabs have been made of methods in which normal forces are applied
fiberglass reinforced composites, aluminum at the ends and shear forces are applied along
and wood veneers. The thickness of tabs the faces of the specimen grip section
should be between 1.5t and 4t, where t is the (Method (e)).
specimen thickness. The tabs must have a In compression testing of unidirectional
large enough area that the ultimate shear load composites in the fiber direction, three basic
capacity of the bond between the tabs and the modes of failure are observed: buckling of the
specimen is greater than the breaking load of reinforcing fibers, transverse cracking of the
the specimen gage section. matrix, and shearing of reinforcing fibers at a
The mode of failure in tension depends on 45" angle without local buckling of the rein-
the relationship between the external load forcement. Transverse cracking is caused by
and the reinforcing fibers and on the type of differences in the Poisson's ratios of the mate-
reinforcement lay-up. When unidirectional rial components and by a non-uniform
composites are loaded in the reinforcement transverse strain distribution along the speci-
direction, they fail by breakage of the rein- men length. Materials reinforced at an angle to
forcing fibers. This is accompanied by the specimen's longitudinal axis fail in shear
transverse cracks, longitudinal shear cracks without crumpling at the end faces because all
and delamination of the polymer matrix. of the shear load is taken up by the matrix. The
Increasing the angle between the load and the aforementioned basic modes of failure can be
reinforcing fibers causes the mode of failure accompanied by a series of other phenomena:
to change gradually from shear and splitting inelastic and non-linear deformation of the
of the polymer matrix parallel to the fiber reinforcing fibers and matrix, delamination,
direction to pure transverse tensile cracking surface peeling, overall buckling and crushing
of the polymer matrix. The failure mode of of the end faces. Failures with different combi-
composites with a balanced angle-ply rein- nations of these phenomena can make the
forcement depends on the angle of the fiber determination of the failure mode very diffi-
lay-up. cult.
In compression testing, great care must be
taken to ensure stability of the specimen, espe-
34.4.2 COMPRESSION TESTING OF FLAT
cially in the gage section. Buckling of the
SPECIMENS
specimen side face is not always detectable
The main problem in compression testing of and will cause erroneous strain measure-
flat specimens is the selection of a loading ments. Special test fixtures are used to prevent
method that ensures compressive failure. overall buckling of the specimen.
When the loading is achieved by normal
788 Mechanical tests
specimen and to a certain extent it prevents gage section where the state of stress is the
buckling of the specimen. The external pressure most uniform. However, edge effects have
may also be applied by mechanical devices considerable influence on the shear strength.
such as multiple cam. Therefore, it is better to bond the specimen to
The primary difficulty in compression test- the rail links than to use mechanical fasteners.
ing of rings by external pressure is the The stress distribution is not affected by the
selection of a relative thickness, t / R , to reduce loading direction, i.e. along the diagonal or
secondary loading effects. Depending on the parallel to the sides of specimen gage section.
relative thickness of specimen, t / R , and the Measuring the shear properties by tensile
degree of anisotropy of the material E,/G,, loading of an anisotropic strip is distinguished
three different failure modes have been by its apparent simplicity (Table 34.1, Method
observed. Thin-walled rings fail by buckling, (f)). The strip can have one of several different
thick-walled rings fail by biaxial compression, fiber lay-ups. This method is not used to deter-
and optimum thickness rings fail by circum- mine in-plane shear strength because it yields
ferential compression. Analysis of the test data low values. A state of pure shear is not assured
must consider the radial as well as circumfer- even with a +45" lay-up.
ential stresses. A similar test method involves tensile load-
Delamination of the inner layers of the ring ing of a strip of a unidirectional material cut at
makes it difficult to correctly calculate the an angle, 8, to the reinforcing fibers. The opti-
compressive strength. This delamination is mum angle is the one for which the relative
often noisy. The occurrence of this failure shear strain y 1 2 / ~is
x maximized and the shear
mechanism also depends on the relative thick- stress rI2reaches its critical value. This angle
ness of the ring. Delamination of helical depends on the anisotropy of the elastic and
windings can lead to unwinding of the speci- strength properties of the material tested. For
men. Hoop wound rings can fail by advanced composites, the optimum angle is 10
layer-by-layer delamination. 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,
34.5 SHEAR
the strain gage angle, and the direction of
loading. In order to ensure that the stress state
34.5.1 IN-PLANE SHEAR
is uniform, relatively narrow strips, L/w = 14
Shear properties, especially shear strengths, to 16, are used.
are difficult to measure. The simple and eco- The in-plane shear modulus is often mea-
nomical rail shear test is often used for this sured by twisting a square plate with four
purpose (Table 34.3, Methods (a) and (b)).The point loading (Method (c)). The wide accep-
extent of edge effects and the uniformity of the tance of this method may be attributed to the
shear stress distribution over the specimen simplicity of its calculations. However, the
width depends on the length-to-width ratio of experiments should be performed with utmost
the specimen gage section L/w and on the care. This method is only applicable for small
relation of elastic constants G,/E of the mate- deflections, wp < O.lt, on plates made of mate-
rial. Edge effects are negligible tor L/w > 10. rials which are uniform in thickness and
Edge effects cannot be eliminated for materials orthotropic along the specimen axes. Test
with v, = vyxG -1. Thus, this method cannot be results for several different materials have
used for such materials. The elastic constants shown that the P-wp relationship remains lin-
obtained by the rail shear test are less sensitive ear up to wp/t z 1. However, in practice, the
to the relative ratio, L/w, since the measure- deflection, w should be limited to 0.5t to pre-
P'
ments are taken in the center of the specimen vent instability. Only the initial linear section
790 Mechanical tests
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
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
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’.
Definitions and issues 795
question of the relationship of material ’how strong is this composite structure’, even
strength to structural strength. In general, the if the array of material strengths are known
strength of (fiber reinforced) composite mate- (shown in Fig. 35.2). Hence, there is a need to
rials is represented by an array of values that develop understandings and representations
reflect the anisotropic nature of the materials of the critical damage and failure modes that
(Fig. 35.2). For planar materials, at least the control the performance of engineering com-
tensile strength and compressive strength in ponents. This technology is currently
the fiber direction and transverse to the fibers incomplete, but discussions of those topics
and the in-plane shear strength are required will follow.
for a complete answer to the question of ’how A second fundamental concept is
strong is this material’. However, as an array, microstructural architecture. As shown in Fig.
those values do not directly show ’how strong 35.3(a), many fibrous composite components
is a composite structure’. Several possible are made in layered or laminated form, with the
answers to that question are typically given. fibers in different layers having different direc-
One may use a ’failure criterion’ that compares tions; in some cases the plies are made from
all of the point stress components with all of different materials to form a ’hybrid’ compos-
the material strength components (such as the ite. In addition, the fibers may not be straight,
Tsai-Hill or Tsai-Wu riter ria)^ in some collec- but may be woven, braided, or arranged in
tive form based on concepts such as critical mats of various types (Fig. 35.3(b),(c)). These
energy, critical shear resistance, etc. The salient details have a major influence on the durability
point to be made is that the complexity of and damage tolerance of the materials. In fact,
(inhomogeneous) composite materials and most composite material systems are ‘designed’
their array of anisotropic material strengths to be ’fiber dominated’, to take advantage of
give rise to the development of a correspond- light, strong and stiff (but brittle) fiber materials
ing array of damage and failure modes in that are available. Typically, the fibers, their
these materials that must be understood and geometry and their arrangement are important
correctly modeled to answer the question of parts of the question.
f 1 Strength tensor:
Composite *
IL-kr
Fig. 35.2 Schematic illustration of ’principal strength’ directions in a unidirectional continuous fiber com-
posite laminate.
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 0 Remaining strength and life models are
degradation of intrinsic strength and stiffness. developed and predictions are made for
For metals, the material stiffness and strength each independent failure mode (such as
are generally constant during the life of the fiber failure in tension or micro-buckling in
engineering component. This may not be true compression, etc.).
for composites. Stiffness changes of the order 0 Mechanics representations of the state of
of 10-20% may be caused by micro-cracking, stress and state of material are constructed
for example. Since many structures are stiff- on the basis of a 'representative volume' of
ness designs, this mode of degradation must the material that is typical of the distributed
be considered. In addition, the intrinsic mate- damage state that controls the remaining
rial strengths (indicated in Fig. 35.2) may also stiffness and strength of the composite. A
be degraded, especially by such things as typical representative volume of material is
physical or chemical aging. This behavior a controlling ply in a laminate, but may be a
must also be part of the supporting predictive micro-buckling ligament, a small group of
technology developed for these materials. fibers, etc.
Nondestructive methods of tracking such 0 Various methods are used to characterize
degradation are under development, but this and monitor the rate of strength degrada-
remains as a challenge currently. tion in composites. A typical parameter
Methodologies for the assessment and pre- which is useful for that purpose is stiffness
diction of durability and damage tolerance of change; however, that parameter is not
composite materials typically involve the fol- appropriate in some cases.
lowing features: 0 Micromechanics (mechanics analysis at the
Damage modes and failure modes 797
"'r! 'r!-.e-
I
rt
.1!
.I: I
Strain
35.3 DAMAGE DRIVERS AND DAMAGE by local discontinuitiesin stress state, typically
'RESISTANCE' caused by neighboring plies or ply groups
(bonded together) that would have very dif-
In the previous section, a number of damage ferent strain states if they were not bonded.
and failure modes that occur in composite Hence, the orientation of the plies in a lami-
materials, and ultimately control durability nate and the stacking sequence of those plies
and damage tolerance, were identified. Many are controlling players in the development of
of these modes are related to the manner in the interlaminar stresses that drive delamina-
which the composites were put together. This tion. This problem has been exhaustively
raises the basic question of 'can one design studied, and methods of reducing interlami-
composite materials to be durable and damage nar stresses have been widely d i s c ~ s s e d ' ~ - ~ ~ ,
tolerant?' Most of the rest of this discussion but because of the inhomogeneous and often
will address this question. anisotropic nature of composites, interlaminar
Some general concepts will be followed by stresses generally cannot be eliminated in lam-
some micro-mechanics methods of quantifymg inated systems, so mechkical methods are
answers. Microcracking is likely to be the most widely used to control that tendency. The most
pervasive damage mode in typical composites, successful of these is weaving, i.e. to use
especially under long-term loading, and most woven fiber architectures to reduce the
especially under cyclic loading. Even though anisotropy of a given ply, and therefore, to
most matrix materials are chosen because they reduce the 'disagreement' between the
offer some level of ductility, in most composite response of any two or more plies. Woven
systems the matrix is highly constrained so materials are now widely used, especially for
that cracks develop due to local constraint, this reason. A second approach is to 'stitch' the
local stress concentrations, and local defects composite in the region of non-uniform stress,
that grow rapidly under what is generally a typically near an edge of the laminate.
'plane strain' condition. Hence, matrix tough- Stitching simply 'clamps' the edge of the mate-
ness, in the general sense, is the key to the rial to prevent it from separating; the internal
reduction of matrix cracking. Increasing the stresses are still present. Stitching has a some-
strain to failure of the matrix material is a pri- what smaller number of proponents, but is a
mary objective, and increasing the plane-strain successful method as well. Finally, three-
fracture toughness of the matrix is a compan- dimensional reinforcement, such as mats or
ion objective. There is a richly developed braids, also serve the purpose of providing
science and technology associated with matrix constraint to the delamination drivers. These
toughening; some starting points are listed in methods are not as widely used at this time,
Wilkinson et al.24and Hedrick et al?5. largely because of the difficulty associated
A second damage mode identified earlier is with manufacturing.
delamination. This problem is a strong combi- A less obvious influence on durability and
nation of structural and material concerns. The damage tolerance is the bonding between the
material concerns are essentially the same as fiber and matrix. The nature of this influence
those discussed for matrix cracking, with one has only come to light in recent years. Some of
important exception. Matrix toughness does the mechanics models needed for this discus-
not translate directly into interlaminar tough- sion will be developed in the next section; only
ness. Hence, resistance to delamination cannot a few general points will be made here. First,
be controlled entirely with material property the properties of composite materials are
increases. The structural part of the problem determined not only by the properties of the
does, however, present opportunities. It was constituents, but they are also greatly influ-
mentioned before that delamination is driven enced by the manner in which the constituents
802 Durability and damage tolerance of fibrous composite systems
interact. This critical interaction is, of course, strain to failure by as much as a factor of
controlled by the bonding between the con- In general, although design rules are
stituents, between the fibers and matrix in our not yet fixed, design of the interphase region is
case. Typically, this bonding is ‘controlled’ by a new and important opportunity for the
a fiber coating or ’sizing’. However, it is now enhancement of the durability and damage
known that such things as notched fatigue tolerance of composite system^^^^*.
behavior can be improved by as much as two The final subject in this section is ’failure
orders of magnitude by carefully ’designed’ criteria’; which are used to describe remaining
’interphase’ regions between the fibers and the strength. In general, failure criteria are chosen
matrixz6.There are at least two basic concepts on the basis of the known failure mode. If fiber
operating in these effects. First, if one can fracture controls strength, then a suitable crite-
toughen the composite by toughening the rion may be just the stress in the fiber direction
interphase between the fibers and matrix, the divided by the strength in that direction. If
composite is likely to be more durable, as dis- matrix behavior is controlling, a shear stress or
cussed above. Second, the interphase region combined stress criterion may be appropriate.
can greatly influence the local stress state, and Figure 35.12 shows a comparison between
reduce the driving force for fiber-matrix strength ‘envelopes’predicted by two popular
debonding. An illustration of that is shown in criteria. It is important to note that the inputs
Fig. 35.11. If one considers the strength of a to the failure function will, in general, change
composite under loads applied perpendicular as a function of time and loading history. The
to the fiber direction, then it is clear that the general form of any failure criterion will usu-
fiber causes a local stress concentration,in pro- ally be some function of the ratios of stress in
portion to the difference between its principal material directions to strength in
properties and those of the matrix. However, if those directions, as mentioned earlier. Under
a coating around the fiber is introduced, this long-term conditions which induce damage,
local concentration can be greatly reduced. In the local stress changes as damage causes
fact, for a ’rigid’ fiber, compared to the matrix, redistribution, and the principal values of
it is not surprising that a compliant coating on material strength change, due to such things
the fiber will increase the transverse composite as constituent degradation or micro-damage.
strength by as much as a factor of two, and the Hence, to calculate damage tolerance by using
Interphase region
Criterion:
I -
Maximum stress -
Applied
Stress (ksi)
0 90
Angle of Loading (deg)
Composite
Fig. 35.12 Allowable uniaxial loading as a function
Fig. 35.11 Schematic diagram of the geometry of of angle of loading relative to the fiber direction in
the interphase region in a fibrous composite, sub- a unidirectional lamina, estimated from a maxi-
iected to loading.
” transverse to the fibers. 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.
Estimation of remaining strength and life 805
of the explicit time, cycles, and environmental sile fiber failure, and it is assumed that some
dependence that leads to phenomenological fatigue behavior of unidirectional material
behavior such as creep, creep rupture, fatigue, under uniaxial stress in the fiber direction has
and aging into the calculation of remaining been measured, a 1-D SN relationship can be
strength. From thermodynamic principles, the derived, of the form:
F, = 1 - lyl(l
following expression can be derived:
- Fa),( n d( $)
N)1-1 (35.2)
s,
S"
= A + B (log N)p (35.3)
State of State of I I
life N, N2
Fig. 35.15 Schematic flow diagram of the manner in which the MRLife simulation scheme calculates
remaining strength and life.
806 Durability and damage tolerance offibrous composite systems
Remaining I
Strength
-
Cycles Cycles
Fig. 35.16 Calculated remaining strength predic- Fig. 35.18 Assumed degradation of fiber strength
tions for (a)0" lamina degradation alone; (b) added for the sample laminate.
effect of matrix cracking; (c) added effect of fiber
degradation (e.g.by oxidation).
cycles, according to the rate shown in Fig. Fig. 35.18. Then the strength model, eqn (35.1),
35.17 (from cracking rates that must be correctly integrates that micro-change into the
measured or estimated). With this internal global calculation, and eqn (35.2) shows the
stress redistribution, only, added to eqn (35.2), damage tolerance to be curve (c) in Fig. 35.16
the damage tolerance changes to curve (b) in for that situation. Hence this 'micro-kinetic'
Fig. 35.16. Of course, if creep occurs in the approach has the capability to estimate
matrix (perhaps because of increased durability and damage tolerance for very
temperature), in which case the local fiber complex situations involving combinations of
stress will increase again as a function of many time and cycle dependent phenomena
cycles to change the form shown in Fig. 35.17. in composite systems, using a mechanistic
Finally, suppose creep rupture is occurring, approach.
driven, for example, by oxidation of the fibers An example follows. Using the methods
that is reducing the diameter of the fibers, D, described above, the rate of matrix cracking
in eqn (35.1), in the manner shown in 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
Fiber- Stress increase due
35.19 shows an example of the predicted and
Direction observed life for several load levels of a quasi-
Stress isotropic laminate made from such material
40 ' 1
I
Cycles
4
5x10 9.999~10
4
I
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
Fig. 35.17 Assumed increase in stress in the 0" ply using the MRLife performance simulation
due to matrix cracking. 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.
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
18. Ishida, H. (ed.), Controlled Interphases in 30. Jayaraman, K., Gao, Z . and Reifsnider, K.L., The
Composite Materials, New York: Elsevier, 1990. interphase in unidirectional fiber reinforced
19. Warren, R. (ed.), Ceramic Matrix Composites, epoxies: effect on local stress fields. J. Comp.
New York: Chapman and Hall, 1992. Tech. Res., 1994,16(1):21-31.
20. Reifsnider, K.L. (ed.), Fatigue of Composite 31. Jayaraman, K., Reifsnider, K.L. and Swain, R.E.,
Materials, London: Elsevier Science Publishers, Elastic and thermal effects in the interphase:
1991. Part 11. comments on modeling studies. J. Comp.
21. Jamison, R.D., Fiber fracture in composite lami- Tech. Res., 1993,15(1):14-22.
nates. In Proc. lntl. Con$ on Composite Materials 32. Jayaraman, K., Reifsnider, K.L. and Swain, R.E.,
VI, 1987, no. 3, pp. 185-199. Elastic and thermal effects in the interphase:
22. Jamison, R.D., Schulte, K., Reifsnider, K.L. and Part I. comments on characterization methods.
Stinchcomb, W.W., Characterization and analy- J. Comp. Tech. Res., 1993,15(1):3-13.
sis of damage mechanisms in tension-tension 33. Gao, Z . and Reifsnider, K.L., Micromechanics of
fatigue of Graphite/Epoxy Laminates. In Efects Tensile Strength in Composite Systems. Fourth
of Defects in Composite Materials, ASTM STP 836, Volume, ASTM STP 2256, (eds W. W. Stinchcomb
American Society For Testing and Materials, and N. E. Ashbaugh), Philadelphia, PA:
Philadelphia, PA, 1984, pp. 21-55. American Society for Testing and Materials,
23. Tiwari, A., The Development of an Interpretive 1993, pp. 453-470.
Methodology for the Application of Real-Time 34. Xu, Y. and Reifsnider, K.L., Micromechanical
Acousto-Ultrasonic NDE Techniques for modeling of composite compressive strength. J.
Monitoring Damage in Ceramic Composites Under Comp. Mater., 1993, 27(6):572-587.
Dynamic Loads. PhD Dissertation. Blacksburg, 35. Reifsnider, K. L. and Gao, Z., Micromechanical
Virginia: Virginia Polytechnic Institute and concepts for the estimation of property evolu-
State University, 1993. tion and remaining life. In Proc. Intern. Con5
24. Wilkinson, S.P., Liptak, S.C., Lesko, J.J., Dillard, Spacecraft Structures and Mechanical Testing,
D.A., Morton, J., McGrath, J.E. and Ward, T.C., Noordwijk, the Netherlands, 1991, pp. 653-657.
Toughened bismaleimides and their carbon 36. Curtin, W.A., Theory of mechanical properties
fiber composites for fiber-matrix interphase of ceramic-matrix composites. J. Amer. Ceram.
Studies. In Proc. 6th Japan-U.S. Conf Composite SOC.,1991, 74(11),2837-2845.
Materials, 1992. 37. Reifsnider, K.L., Performance simulation of
25. Hedrick, J., Patel, N.M. and McGrath, J.E., polymer-based composite systems. In Durability
Toughening of epoxy resin networks with func- of Polymer-Based Composite Systems for Structural
tionalized engineering thermoplastics. In ACS Applications, (eds A.H. Cardon and G.
Advances in Chemistry Series, no. 233, Verchery), New York: Elsevier Applied Science,
Toughened Plastics I: Science and Engineering, (eds. 1991, pp. 3-26.
C.K. Riew and A.J. Kinloch), 1993, pp. 293-304. 38. Reifsnider, K.L. and Stinchcomb, W.W., A criti-
26. Swain, R.E., Reifsnider, K.L., Jayaraman, K. and cal element model of the residual strength and
El-Zein, M., Interface/interphase concepts in life of fatigue-loaded composites coupons. In
composite material systems. J. Thermoplastic Composite Materials: Fatigue and Fracture, ASTM
Comp. Mater., 1990, 3, 13-23. STP 907, (ed. H.T. Hahn), Philadelphia, PA:
27. Case, S.W., Micromechanics of Strength-Related American Society for Testing and Materials,
Phenomena in Composite Materials. MS Thesis. 1986, pp. 298-313.
Blacksburg, Virginia: Virginia Polytechnic 39. Reifsnider, K.L., Use of mechanistic life predic-
Institute and State University, 1993. tion methods for the design of damage tolerant
28. Carman, G.P., Eskandari, S. and Case, S.W., composite material systems. In ASTM STP 2257,
Analytical investigation of fiber coating effects (eds M.R. Mitchell and 0. Buck), Philadelphia,
on shear and compression strength, symposium PA: American Society for Testing and Materials,
on durability and damage tolerance, ASME 1992, pp. 205-223.
WAM, (in press), 1994. 40. Reifsnider, K.L., Evolution concepts for
29. Jayaraman, K. and Reifsnider, K.L., The inter- microstructure property interactions in compos-
phase in unidirectional fiber-reinforcedepoxies: ite systems. In Proc. IUTAM Conf.
effect of residual thermal stresses. Comp. Sci. Microstructure-Property Interactions in Composite
Tech., 1993,47, 119-129. Materials. Aalborg, Denmark, 1994.
ENVIRONMENTAL EFFECTS ON COMPOSITES 36
Ann F. Whitaker, Miria M . Finckenor, H a r y W. Dursch,
R.C. Tennyson and Philip R. Young
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
-
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.
Environments and efecfs 815
I; ‘I
..-
c
-.
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)
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
Protective coatings 819
.
.- -
b
Development of Facilities, Quality Control Springer, George S., Sanders, Barbara A. and Tung,
Procedures, and Testing Techniques for Randy W. 1981. Environmental Effects on Glass
Irradiation of Spacecraft Composite Materials. Fiber Reinforced Polyester and Vinylester
Report for Contract NAS1-16854. Composites. In Environmental Effects on
Fried, N. 1969. Marine Applications. In Handbook of Composites Materials, pp. 126-144. Westport, CT
Fiberglass and Advanced Plastics Composites, (ed. Technomic Publishing.
George Lubin) pp. 747-783. New York: Van Spry, William J. 1987. Sports and Recreational
Nostrand Reinhold. Equipment. In Engineered Materials Handbook,
Graner, William R. 1982. Marine Applications. In Vol. 1, (ed. Theodore J. Reinhart et al.) pp.
Handbook of Composites, (ed. George Lubin) pp. 845-847. Metals Park, Ohio: ASM International.
514-529. New York: Van Nostrand Reinhold. Staunton, R. 1982. Environmental Effects on
Kamenetzky, R.R. and Whitaker, A.F. 1992. Composites. In Handbook of Composites, (ed.
Performance of Thermal Control Tape in the George Lubin) pp. 514-529. New York: Van
Protection of Composite Materials to Space Nostrand Reinhold.
Environmental Exposure. NASA TM-103582. Sullivan, Lawrence J. and Ghaffarian, Reza. 1988.
Kessler, D.J., Reynolds, R.C. and Anz-Meador, P.D. Microcracking Behavior of Thermally Cycled
1989. Orbital Debris Environment for Spacecraft High Temperature Laminates. Paper read at
Designed to Operate in Low Earth Orbit. NASA 33th Intern. SAMPE Symp. Exhib., March 7-10,
TM-100471. 1988, Anaheim, CA.
Levine, Arlene, (ed.). 1991. LDEF-69 Months in Tennyson, R.C. 1991. Composite materials in space
Space: First Post-Retrieval Symposium. NASA - results from the LDEF satellite. Canadian
CP-3134. Aeronautics and Space J. 37(3):120-1 33.
Levine, Arlene, (ed.). 1992. LDEF-69 Months in Vette, J.I., Lucero, A.B., Wright, J.A., King, J.H. and
Space: Second Post-Retrieval Symposium. Lavine, J.P. 1967. Models of the Trapped
NASA CP-3194. Radiation Environment. NASA SP-3024.
Lisagor, W. Barry. 1979. Mechanical Property Whitaker, A.F. 1991. Coatings Could Protect
Degradation of Graphite/Polyimide Composites Composites from Hostile Space Environment.
After Exposure to Moisture or Shuttle Orbiter Advanced Materials and Processes 139(4).
Fluids. In Graphite/Polyimide Composites, (ed. H. Whitaker, A.F. and Young, L.E. 1991. An Overview
Benson Dexter and John G. Davis, Jr.) of the First Results on the Solar Array Materials
pp.273-287. NASA CP-2079. Passive LDEF Experiment (SAMPLE), A0171.
Piellisch, Richard. 1991. New solar arrays mean Paper read at First LDEF Post-Retrieval
new materials. Aerospace America 29(5):20-23. Symposium, June 2-8,1991, Orlando, FL.
Pilpel, Edward D. 1982. Expanded Design Analysis Whitaker, A.F. 1991. Preliminary Assessment of
of the Use of Composites in Determining Snow LEO Effects on LDEF Experiment A0171
Ski Characteristics. In Materials Overview for Composite Material Surfaces. Paper read at
2982, SOC.Advanc. Mater. Proc. Engng, pp. LDEF Materials Workshop, Nov. 19-22,1991, at
616-627. Langley VA.
Schonberg, W. 1990. Hypervelocity Impact Testing Young, Philip R., Slemp, Wayne S., Witte, Jr.,
of Non-metallic Materials. 17th Cong. Intern. William G. and Shen, James Y. 1991.
Council of the Aeronaut. Sci., Sept. 9-14, 1990, Characterization of Selected LDEF Polymer
at Stockholm, Sweden, paper ICAS-90-1.7.3. Matrix Resin Composite Materials. Paper read
Sigur, W.A. and Gray, C.R. 1990. Composite at 36th International SAMPE Symposium and
Applications on the External Tank. Final Report Exhibition, April 15-18,1991, at San Diego, CA.
from Martin Marietta Manned Space Systems,
NASA Contract NAS8-33708.
SAFETY AND HEALTH ISSUES 37
Jennifer A. Heth
K = Minimal hazard
Low exposure
High toxicity
0 9- AM 6
nw
Extreme exposure
X = Elevated hazard
Low toxicity
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
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.
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.
Periodic exposure assessments should be con- or a new process is to be used. After any new
ducted taking into consideration routes of process or modification of an old one, good
exposure associated with composite use (Table work practice is to ensure that existing con-
37.1). Monitoring should be routine, and on trols to prevent exposure are implemented
demand whenever unusual odors are noticed, and effective.
visible contamination is heavier than normal, Two potential exposures posed by composite
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 controls are defined as ’methods of controlling
could result in irritation leading to dermatitis employee exposures by job rotation, work
or sensitization, and inhalation of particulates assignment, or time periods away from the haz-
from operations such as cutting, grinding and ard’. These controls may be implemented when
finishing. Both concerns can be eliminated or e n p e e r i n g controls cannot reduce the exposure
minimized with implementation of proper to permissible levels (Fig. 37.6). Administrative
gloves/clothing, good ventilation and process controls also encompass ’other work rules’, such
conditions, and effective training. as company policies (Table 37.2).
One example of a process hazard in the
composites industry, controllable through
37.3.1 ADMINISTRATIVE CONTROLS
engineering and administrative rules, is an
In the National Safety Council’s Fundamentals out-of-control exothermic reaction. This is an
of Industrial Hygiene (3rd Edn), administrative unintentional runaway chemical reaction of a
Table 37.2 Workplace tools to prevent exposures
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-
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
Moisturizing creams 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
pigments or solvents. Components of the any product containing additives with known
resin system may be supplied individually or potential health effects. Reference to the
and formulated by the user, supplied as ‘Part MSDS will advise you of hazardous materials.
A and Part B’ and blended before use, or sup- Some commonly used additives are listed in
plied mixed as a ’one-pack’ system. Table 37.7.
be chemically coated or stiff enough to cause believed to be 3.5 pm or less. Anything larger
irritation by penetrating the skin or tissues of than that will be removed from the body via
the nose, throat or bronchi. Little has been nose and throat functions. If the fibers are res-
studied and is known about cured materials pirable, the toxic effects may vary
being ground, drilled, milled, cut or sanded. significantly. There are low risk fibers (irritants
Should fragments of fibers be small enough to such as fiberglass) and there are significant
be respirable, there is concern that a general or risk fibers that can result in asbestosis or can-
fibrous dust hazard to the lungs can occur. cer (such as asbestos fibers). Therefore, each
Therefore, precautions should be used to min- fiber should be assessed on its own toxicolog-
imize exposure. ical properties.
Knowledge of the fiber used should include:
length, diameter, aspect ratio and fragmenta-
37.5.3 SOLVENTS
tion propensity. Knowledge of fiber
parameters, along with how the composite will Solvents are used in many aspects of compos-
be handled, is critical to protect from exposure. ites manufacturing, from resin formulation to
Fiber diameter size for respirability is clean-up activities. There are several groups of
836 Safety and health issues
solvents, ketones and chlorinated, which have enforcement’ safety philosophy to control haz-
dominated the industry. Known health effects ards. This encompasses all the workplace tools
of major solvents are outlined in Table 37.10. and techniques discussed.
With increased concern for safety, health Safety, encompassing health, should be
and environmental impacts of solvents in the treated as a value. It is not a priority to be
workplace, the use of solvents is decreasing raised or lowered with business cycles or man-
and exposures are being minimized. When agement changes. It should be a constant
choosing a solvent, make certain that regula- philosophy exhibited each day (Fig. 37.8). If it
tory investigation is done to avoid is a value in the composites industry, then the
unnecessary rework. It is possible that a sol- technology of composite materials can
vent of choice may become obsolete due to develop naturally, without unnecessary hin-
emission regulations or toxicity concerns. drances impeding growth.
that substantial subsurface damage can result disadvantages as manual tapping with the
with little or no surface detectable condition. additional disadvantage of increased cost.
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
uncured composite materials. These materials surface loading on the ultrasonic probeI8.This
have at times found their way into a compos- can be seen as a phase, amplitude, or resonant
ite laminate and are cured in place. Some of frequency shift in the ultrasonic element. This
the plastic materials are particularly problem- method is particularly useful in complex
atic in that they may bond into the laminate bonded structures where access limitations
and go undetected by the through-transmis- restrict the use of ultrasonic through-transmis-
sion inspection. Fortunately, however, most of sion testing and the complex internal
these materials offer a reflected signal strength reflections make pulse-echo signals difficult
sufficient to be detected by pulse-echo ultra- or impossible to interpret.
sonics.
38.4.5 ULTRASONIC CORRELATION
38.4.3 ULTRASONIC POLAR BACKSCATTER
Ultrasonic correlation offers a novel approach
This inspection approach makes use of slightly to the ultrasonic inspection of highly attenua-
angled ultrasonic beams to detect flaws in tive materials19. It has proven effective in the
composite materials. The angle orientation fre- evaluation of some of these materials where
quently allows one to associate flaws with a conventional pulsed ultrasonic systems have
particular ply orientation. The method is par- experienced difficulties in penetrating the
ticularly useful for characterizing matrix material. The correlation approach achieves
cracking within the composite plies. It is also this increased sensitivity using a continuous
sensitive to linear voids or porosity. It has been wave, cross-correlation technique which
successfully used"j to characterize the various enhances the sensitivity of the test but sacrifices
levels of damage in impacted laminates. The inspection speed. A block diagram of a continu-
approach has also been used to measure direc- ous wave correlator is shown in Fig. 38.5.
tional velocity variations and elastic properties The principal advantage of the correlator is
in composite^'^. From these measurements, the that it provides substantial enhancements in
anisotropic elastic properties can be calcu- the signal-to-noise (S/N) ratio of the ultra-
lated. At the current time, this inspection sonic signals. This S/N enhancement is
method remains primarily a laboratory tool. achieved through a modification of the time
The angulating mechanism would be some- scale required to produce an A-scan trace.
what difficult to manipulate and control in the Since the correlator uses continuous genera-
field and the inspection times can get long, tion and accumulation of the ultrasonic
since multiple scans at a variety of orientations signals, the maximum possible efficiency of
are required. Further, the composite designs data accumulation can occur. The S / N
currently in use have not required the detailed enhancement allows the correlator to produce
level of inspection provided by this method. usable A-scan traces where conventional
pulsed ultrasonic systems are unable to pro-
duce a recognizable pattern.
38.4.4 ULTRASONIC RESONANCE
For example, the correlator has been used to
This one-sided ultrasonic inspection method characterize polytetrafluoroethylene (PTFE,
detects laminar discontinuities within com- Teflon@),a material very difficult to penetrate
posites or bonded structures by setting up a with conventional ultrasonic techniques. The
continuous ultrasonic wave within the mater- results have been obtained by measuring
ial and sensing the mechanical stiffness, or ultrasonic velocity as the temperature of the
impedance of the material. A delamination or PTFE sample changed. Figure 38.6 shows a
disbond reduces the surface normal stiffness velocity versus. temperature profile with an
of the material and this, in turn, reduces the excellent indication of a change in the slope of
844 Nondestructive evaluation methods for composites
7
Transmit
Test
Noise Specimen
I I
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
X-radiology 845
are today. While carbon fibers are not gener- typically possess the resolution of X-ray films,
ally imaged by X-rays, boron and silicon the use of very small X-ray sources and geo-
carbide fibers are typically deposited on a metric magnification techniques have
tungsten filament and this filament can be permitted the recovery of much of this sensi-
imaged in X-radiographs. This allows one to tivity. Figure 38.7 shows a magnified image of
detect fiber fractures and determine fiber ori- a honeycomb core area. This 'bee's eye view'
entations and placements, so long as the of the honeycomb core reveals the onset of
number of plies does not get too large. damage in the cell wall. In practice, one must
X-radiography is particularly useful for the find a suitable compromise between spatial
detection of honeycomb core defects in resolution and area of coverage. The cost
bonded sandwich assemblies. The low density advantages of this approach have made it very
and thin composite skins usually provide min- attractive. Many military aircraft maintenance
imal interference for the X-rays to image the facilities either have or are acquiring real-time
honeycomb core materials. Core defects such X-ray inspection equipment.
as blown core, crushed core, condensed core,
fatigued, corroded or cut core and foaming
38.5.1 X-RAY BACKSCATTER IMAGING
adhesive voids can be detected by radi-
ographic methods. It is also frequently Conventional radiographic inspection tech-
possible to detect water intrusion into the hon- niques rely on the attenuation of a beam of
eycomb core using X-ray methods. penetrating radiation to form an image of a
Significant progress has been made in part. At low X-ray photon energies typically
recent years in the use of non-film electronic used with composites, a large portion of that
imaging systems for X-rays. These systems attenuation is due to Compton scattering. This
allow the real time viewing of X-ray images suggests the use of scattered radiation to ana-
and can drastically reduce the demand for X- lyze the inspection object. One approach
ray film. While video imaging systems do not utilizing a novel, X-ray backscatter camera
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- For composites, tomography offers similar
spective. A typical radiograph is a advantages. The tomographic image shown in
two-dimensional projection of a three-dimen- Fig. 38.10 shows variations in density across
sional object. The tomographic result retains the width of the composite material.
the three-dimensional nature of the image. A
computed tomography image of a tree, for 38.5.3 NEUTRON RADIOGRAPHY
example, would appear similar to the visual
image if one sawed through the tree at one X-rays are attenuated as a function of the den-
location. The tomographic image would show sity of the material through which they pass. If
the differing density of summer and winter X-ray attenuation is plotted as a function of
growth and the presence of knots, voids, etc. increasing atomic weight of the attenuating
848 Nondestructive evaluation methods for composites
I
ap
Fig. 38.10 Computed tomogram of graphite silica
composite tube.
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
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.
Laser shearography/holography 851
formed by the superposition of two wave- benches and elaborate vibration isolation sys-
fronts, an object beam and a reference beam, tems, however, the vibration problems of
on a suitable recording material, such as pho- working in a production environment (much
tographic film.When properly illuminated by less an in-service environment) were not satis-
the reference beam, an observer looking factorily solved. The holographic inspection
through the developed hologram sees a virtual approach is sensitive to very small amounts of
image of the original object. When the real relative motion in the part surface. Typically a
object undergoes a small displacement over part is tested by taking an image of the part at
part of the surface, due to stressing by thermal rest, then stressing the part surface, either with
or mechanical means, a variation in the rela- a small amount of heat or a mild vacuum. This
tive phase of the wavefronts will be produced light stressing causes the area of the surface
and a fringe pattern can be observed. Laser over the flaw to deform slightly more than the
illuminationprovides the spatial and temporal surrounding material. Displacements as small
coherence in the light beam to permit the as one-quarter wavelength of the laser light
observation of the fringe pattern, a technique being used cause a fringe to appear in the
called holographic interferomeW7.An exam- interference pattern. Unfortunately, unwanted
ple of a holographic interferometry inspection test object motion of an equally small ampli-
of a composite tube to reveal impact damage is tude will also cause fringes. The development
shown in Fig. 38.15. of phase locked loop holographic systems has
Laser interferometric holography tech- gone a long way to eliminate the problems
niques were evaluated for composites testing associated with low frequency vibration.
in the 1960s. In fact, several composites and Holographic inspection systems which use
bonded assembly testing systems were con- video imaging systems and 'develop-in-place'
structed. In spite of the use of massive optical reference holograms are currently being used.
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.
References 855
22. Bryant, L.E. and McIntire, P. (eds.), 33. Cohen, J., Elements of thermography for nonde-
Radiography and Radiation Testing, structive testing, NBS Technical Note 1177,
Nondestructive Testing Handbook, Vol. 3, National Institute of Standards and Technology,
Radiography and Radiation Testing, Amer. SOC. Washington, D.C., (1983).
Nondestr. Testing, Columbus, OH, 1985. 34. Jones, T. and Berger, H., Thermographic detec-
23. ASTM E-1441, Standard Guide for Computed tion of impact damage in graphite-epoxy
Tomography (CT) Imaging, Amer. SOC.Testing composites, Materials Evaluation, 1992, 50,
Materials, Philadelphia, PA, 1993. 1446-1453.
24. ASTM E-1570, Standard Practice for Computed 35. Jones, T.S., Berger, H. and Weaver, E., Large area
Tomographic (CT) Examination, Amer. SOC. thermographic inspection of GRP composite
Testing Materials, Philadelphia, PA, 1993. marine vessel hulls, Therrnosense XV: Intern.
25. Antal, J.J., Dance, W.E., Moravec, J.D. and Conf. Thermal Sensing and Imaging Diagnostic
Carollo, S.F., Experience with an on-off mobile Applications, (Lee R. Allen, ed.), SPIE Vol. 1933,
neutron radiography system, Proc. Second World pp. 197-206.
Conf. Neutron Radiog., (eds. J.P. Barton, G. Famy, 36. Jones, T.S. and Lindgren, E.A., Thermographic
J.L. Person and H. Rottger), Dordrecht: D Reidel inspection of marine composite structures,
Publishing Co. 1987,407414. Thermosense XVI: Intern. Conf. Thermal Sensing
26. Cluzeau, S. and Le Tourneur, P., Stationary and Imaging Diagnostic Applications, (John R.
DIANE equipment: description and perfor- Snell, ed.), SPIE Vol. 2245, pp. 173-175, (1994).
mance of the thermal neutron source, Nuclear 37. Vest, C.M., Holographic Inteferomety, New York:
Instruments and Methods in Physics Research B, John Wiley, 1979.
1994,89,428431. 38. Hung, Y.Y., Shearography: a new optical
27. Miller, R.K. and McIntire, P., (eds), method for strain measurement and nonde-
Nondestructive Testing Handbook, Vol. 5, Acoustic structive testing, Optical Engineering, 1982,21(3),
Emission Testing, Amer. SOC.Nondestructive 391-395.
Testing, Columbus, OH, 1987. 39. Newman, J.W., Shearographic inspection of air-
28. Sundaresan, M.J., Henneke, E.G. and Brosey, craft structure, Materials Evaluation, 1991, 49(9),
W.D., Acousto-ultrasonic investigation of fila- 1106-1109.
ment-wound spherical pressure vessels, 40. Urabe, K. and Yomoda, S., Non-destructive test-
Materials Evaluation, 1991,49,601-606,612. ing method of fiber orientation and fiber
29. Huber, R.D. and Green, R.E., Noncontact content in FRP using microwave, Prog. Sci.
acousto-ultrasonics using laser generation and Engng of Composites, Fourth International
laser interferometric detection, Materials Conference on Composite Materials, Tokyo,
Evaluation, 1991,49, 613-618. 1982.
30. McMaster, R.C., McIntire, I? and Meister, M.L., 41. Bakhtiari, S., Ganchev, S. and Zoughi, R.,
(eds), Nondestructive Testing Handbook, Vol. 4, Microwave swept-frequency optimization for
Electromagnetic Testing, Amer. SOC.Nondestr. accurate thickness or dielectric property moni-
Testing, Columbus, OH, 1986. toring of conductor-backed composites,
31. Mahoon, A., Automated eddy current testing of Materials Evaluation, 1993, 51(6), 740-743,748.
composites, Proc. 20th Intern. SAMPE Tech. 42. Gray, S., Ganchev, S., Qaddoumi, N.,
Conf., Vol. 20, pp. 517-523, SAMPE, Covina, CA, Beauregard, G., Radford, D. and Zoughi, R.,
1988. Porosity level estimation in polymer composites
32. Wolfe, W.L. and Zissis, G.J., The Infrared using microwaves, Materials Evaluation, 1995,
Handbook, Office of Naval Research, Dept. of the 53(3), 404408.
Navy, Washington, D.C., 1985.
REPAIR ASPECTS OF COMPOSITE AND 39
ADHESIVELY BONDED AIRCRAFT STRUCTURES
Anton L. Seidl
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
ailerons, wing and stabilizer tips, nose domes, from the backside, with the additional benefit
and nacelle cowling. When exposed to hot of causing only minimal disruption to the
gases over long periods, polymeric resin aerodynamic surface. Figure 39.1 illustrates
binders, irrespective of chemistry, can become this principle.
completely destroyed through a process some- If the backside is inaccessible, the damage
times described as thermo-oxidation. This must be repaired from the aerodynamic skin
condition may be found on all types of com- side, inevitably enlarging the repair surface
posites, including those with inorganic and making the repair more difficult to per-
matrices, such as metal matrix composites. form. With only one side accessible, the
Preventive maintenance may consist of the question of how best to apply vacuum pressure
application of heat-resistant, ablative or intu- is always problematic and requires consider-
mescent coatings. Extensive redesign of the able operator skills. (Applying vacuum
detail may be necessary, using metals or, if a pressure for a bonded repair is an art form that
fiber composite is to be used, choosing a poly- must be learned as any other.) As an alternative
imide or similar high temperature resistant to field repairs, panels are often removed from
resin system. the affected structure and routed to a repair
facility specially equipped to effect the appro-
priate restorations. It should be noted that the
39.4 DAMAGE REMOVAL TECHNIQUES
damages affecting the aerodynamic skin sur-
face normally require 'flush' repairs to
39.4.1 PLANNING THE REPAIR 'THINK
preserve the original contour, particularly in
BEFORE CUTTING'
zones of the aircraft defined as aerodynami-
After determining the full extent of the damage, cally critical. Except for small damages, the
the repair technician must consider a range of tooling and skill levels required to effect proper
possible approaches, based on such considera- repairs do not exist at field stations.
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- REPAIR PLIES-/ -FILLER
cian's experience and intuitive problem-solving
abilities are of paramount importance.
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
Typical repairs 865
and a vacuum of approximately 67 kPa (20 the structure. Wet lay-ups normally involve
inHg) is applied. The panel is then heated the use of the same type of fabric used in the
slowly to approximately 74°C (165°F) and original construction, in conjunction with a
allowed to remain at temperature for a mini- laminating resin capable of room temperature
mum of one hour. cure under vacuum pressure. The quality of
the repair is generally enhanced by applying
moderate heat (100°C max) by means of heat-
Evacuation of fluids from core with face
ing blankets, heat lamps or hot air.
sheets intact (‘through-the-facesheet’)
evacuation
Heating blankets
First, all protective coatings and moisture bar-
rier plies must be removed from the areas to be Heating blankets used in conjunction with
evacuated. Then the gelcoat of the outermost vacuum pressure repairs should have an out-
ply should be abraded to expose the fibers. put (watt density) of no less than 7750 W/m2
(Fibers inadvertently damaged during this (5 W/in’). To facilitate draping over curved
process require subsequent repair.) Next, sev- surfaces, heating blankets with silicone rub-
eral layers of breather fabric are applied and ber-embedded elements are preferred over
the assembly envelope-bagged. Then a vac- mineral fiber-insulated pads, because of their
uum of 34-40 kPa (10-12 in Hg) is applied and inherent flexibility. Stiffer pads should only be
the panel heated very slowly (5°C per minute used on flat surfaces.
maximum heating rate) to approximately 75°C
(165°F) and maintained at that temperature
Heat lamps
and vacuum pressure for a minimum of 24 h.
After this initial drying cycle, the temperature Heat lamps that are used either as the primary
should be increased to 107°C (225°F) and heat source, or as a means of augmenting other
maintained for an additional four hours. heat sources, should be 250-300 W tungsten or
quartz tube, explosion-proof types. When
using heat lamps as the primary source, the
Handling of dried details - inspection and
effective heat input is controlled by the stand-
storage
off distance, as shown in Fig. 39.3. To avoid
After drying, details should be re-examined overheating any portion of the assembly being
and, if satisfactory, stored in a clean, dry envi- repaired, thermocouples should be placed at
ronment until the appropriate repair actions several locations to monitor the temperature
can be taken. 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-
39.6 TYPICAL REPAIRS
perature within specified limits.
39.6.1 WET LAY-UP REPAIRS AT AMBIENT OR
ELEVATED TEMPERATURES Hot air blowers
So-called ’wet lay-up’ repairs are the most fre- Hot air blowers similar to hair dryers are often
quently recommended because they require used to accelerate resin cure; they may also be
only the most basic in terms of equipment, used for reticulation of unsupported film
tooling, and repair materials. On the other adhesives. Such devices are typically designed
hand, they are also the most limited in terms with 1000-2000 W heater elements and fan
of size and applicability because such repairs drive motors.
do not restore the full, pre-damage strength of
866 Repair aspects of composife and adhesively bonded aircraft structures
6. Apply perforated release film, breather/ 9.Oil-free solvents and clean cheesecloth
bleeder fabric, thermocouples, and vacuum wipers.
bag. Apply vacuum and check bag for 10. Heat lamps and/or blankets, hot air gun.
leaks. 11. Thermocouples and temperature monitor-
7. Cure laminate under 67-81 kPa ing equipment.
(20-24 in Hg) vacuum pressure, while 12. Compressed air and vacuum source capa-
observing the appropriate time/ tempera- ble of being regulated.
ture relationship specified for the repair 13. Environmental conditions: Work should be
resin. Maintain vacuum pressure through- done indoors, under conditions of moder-
out the cure cycle. ate temperatures (ambient) and low
8. Remove bagging materials. relative humidity (40-65%).
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
Voids and porosities in vacuum-pressure cured as panel edge close-out in preference over
laminates and bondlines metal stampings.
Major disadvantages of ’vacuum-pressure-
only’ cures are a reduction in the compaction 39.6.6 SURFACE PREPARATION FOR NON-
of the laminate and the inevitable formation of METALLIC SUBSTRATES
porosities in the laminate and/or adhesive
bondline. The finished repair yields, as a rule Abrasion and cutting of plies
of thumb, approximately only 80% of the Taper-sanding is the preferred method of creat-
strength of an autoclave-cured part in terms of ing a scarf joint at the substrate/repair
shear and flexural properties. The problem of interface, especially if the substrate material is
compacting thick laminates may be overcome made from a woven fabric. Repairs in unidi-
to some extent by hot debulking each ply, or a rectional tape laminates often use step joints,
stack of several plies of a laminate, under vac- with each repair ply butted against the original
uum pressure before the final cure. This ply. Instead of sanding, the splice joint is then
method is labor-intensive but useful; it draws prepared by cutting each ply carefully with a
off entrapped gasses, improves resin flow, sharp instrument such as an ’Exacto’ knife. It is
fiber wet-out and therefore overall laminate common to use a lap of 13-19 mm (0.5-0.75in)
quality. per ply, although there is lack of agreement
with respect to the optimum lap distance or the
Prepregs co-cured with film adhesives stacking sequence of fabric plies, i.e. whether
the smallest or the largest ply should be placed
Repair technicians often use a compatible film first. Some authorities calculate the overlap as
adhesive together with a prepreg when mak- a function of materials thickness (e.g. L = 187‘)
ing a repair. A layer of film adhesive is whereas others recommend a straightforward
especially desirable as a bond ply over honey- 13 mm (0.5 in) overlap per fabric ply and a
comb core because it enhances the honeycomb 25 mm (1in) overlap per tape ply in the zero
peel strength by providing a deeper glue fillet degree orientation3,11-13.
than would be achieved with prepreg alone.
There is, however, beside the added cost, a
slight weight gain that must be considered Use of peel plies
when repairing a weight and/or balance criti- Multi-stage processes using precured lami-
cal part. nates often use peel ply fabrics which, upon
removal, yield a surface that requires no fur-
ther cleaning or abrading. Chapter 29
Prepregs applied over metal substrates
contains some important observations about
Prepregs applied over metallic substrates peel piles.
always require the use of a layer of film adhe-
sive between the metal and the non-metal. The
Grit blasting
metallic substrate also requires the normal
surface preparations applicable for metal Grit blasting followed by solvent wiping is
bonding, by one of the methods described in sometimes used to prepare non-metallic sub-
Section 39.6.8. Prepregs are often used to pro- strates for subsequent bonding and
vide debris protection in damage-prone areas laminating operations. Plastic media with a
of thin-skinned sandwich panels, notably Mohs hardness of 3.0-3.5 (US Plastic and
wing flaps and other panelling in line with the Chemical Corporation’s Polyextra and
landing gear. Occasionally, prepregs are used Polyplus granulated plastics, sieve size 30/40,
Typical repairs 871
propelled at a low incident angle (15-30") and Cleaning, deoxidizing, anodizing, bonding primer
at moderate nozzle pressure (25-30 psig) have application /cure
been demonstrated to remove coatings effec-
tively without damage to fibers, and to leave For optimum joint strength and bond durabil-
surface conditions of high quality5. ity, all metal surfaces that are to be adhesively
joined require the following essential steps: (1)
degreasing; (2) alkaline cleaning; (3) deoxidiz-
39.6.7 BASIC REPAIR JOINT PREPARATION ing; (4) low voltage anodizing in chromic or
Whatever the specific surface preparation phosphoric acid; (5) application, and (6) pre-
method, the focus must be on producing a baking of a bonding primer. For other than
smooth, contamination-free, activated bond complete rebuilds, which imply complete tear-
surface capable of promoting adhesion and, down of the bonded elements, stripping of all
after the cure, capable of transferring the struc- adhesive residues, and full reprocessing of
details through solution tanks, tank etch-
tural loads across the joint with minimal
ing/anodizing and primer prebaking are often
disruption of the load path and minimal stress
omitted at the expense of repair quality and
build-up. Stress risers of any kind, abrupt
longevity. Comparable values of various pre-
changes in thickness, brittle adhesives, the
bond surface treatments are shown in Fig.
wrong scarf angle, poor detail fit-up, preloads,
39.4.
etc. should be avoided.
Non-tank anodizing
39.6.8 REPAIR OF METAL BONDMENTS
A process known as PANTA (Phosphoric Acid
Honeycomb panels with metal face sheets Non-Tank Anodizing) exists but requires
extensive preparatory work, equipment and
Because thin-skinned honeycomb sandwich
special skills, and has therefore not been fully
panels are the most easily damaged, structures
accepted by the industry at the present time.
of this type are most often in need of repair.
Parts processed in this manner have been
Several kinds of repair activity are considered
demonstrated to be almost equivalent to tank-
typical by the industry:
processed parts in terms of bond strength and
1. minor repairs consisting of the application d~rability'~.
of cold or hot bonded metal patches;
2. partial skin and/or core replacement with
Surface preparation for in situ non-autoclave
or without the benefit of autoclave pres-
repairs
sure;
3. rebuild or remanufacture (considered depot Typically, the repair patches or partial
level repair). replacement skins are cleaned, acid etched,
anodized, primed and prebaked. Structure
not amenable to tank solution processing, i.e.
Aluminum surface preparations
the lap joint areas of the structure being
The quality of the repair is directly related to repaired, is typically prepared with an acid
the quality of the surface to which the adhe- paste, followed by a deionized water rinse,
sive is applied. Poorly or inadequately air drying, and spray application of a bond-
prepared bonding surfaces are the primary ing primer without, however, the benefit of
reason why bonded repairs fail. 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
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
Fig. 39.4 Effect of various aluminium surface treatments on repair bond strength and durability.
omitted, at some sacrifice in terms of bond primers, have been demonstrated to produce
strength and durabilityI5. joints of considerable durability and should be
encouraged in preference over abrasion with
aluminum oxide paper only.
Abrasive cleaning of lap joints
For reasons of expediency, many repairs are
Application of bonding pressure
effected under conditions considered marginal.
One common practice is to abrade the joint
Vacuum bagging and bondline thickness control
area with aluminum oxide paper, followed by
solvent wiping and the application of the adhe- For non-autoclave repairs, the most common
sive. Repairs of t h s type, whether the adhesive method of applying bonding pressure is by
selected be a paste or a film, are rarely of long means of a vacuum bag. Film adhesives used
duration and should be considered ’interim’ for repair are normally scrim-supported and
repairs only. On the other hand surface prepa- thus provide bondline thickness control. (A
rations using three-dimensional abrasives such listing of representative film adhesives avail-
as Scotchbrite@,a product of the 3M Company, able with supporting scrims is provided in
in conjunction with high quality bonding Table 39.2. This listing is for reference only and
Typical repairs 873
not an endorsement for any given product.) line porosities that inevitably result in lowered
When using paste adhesives, scrim cloth is bond strength, which must be taken into
normally inserted between the adherends to account during the repair design. In an effort to
prevent adhesive squeeze-out and resin star- overcome these negative effects, a unique bag-
vation in the bondline. ging method called 'double-bagging' was
developed a number of years ago. This method
provides for an inner, 'low vacuum' bag 34 kPa
Bondline porosities resultingfiom vacuum
(under 10 in Hg) for expelling volatiles, and an
pressure
outer, 'high vacuum' bag 81-98 kPa (24-29
The repair technician must be aware that not in Hg) to provide the equivalent of 4147KPa
all film adhesives are equally suitable for bond- (12-14 psig) bonding pressure on the assembly.
ing under vacuum pressure; indeed, most The intent of this method is to minimize the
products are formulated for positive (i.e. auto- effect of full vacuum pressure on the resin dur-
clave) pressure applications. After curing ing cure by isolating the laminate within a
under vacuum, some adhesives exhibit bond- separate diaphragm.
874 Repair aspects of composite and adhesively bonded aircraft structures
colder portions to reach the appropriate cure alarms may prevent part damage during
temperature. Occasionally, heat lamps or other the cure cycle.
auxiliary means must be employed in conjunc- 3. Heat sinks may drain away heat energy
tion with heating blankets to provide required for resin cure, leaving residual
additional heat inputs at critical locations to uncured materials of unacceptable struc-
make sure the resins are fully cured. It is tural value. Hot bonding should not be
imperative that thermocouples be used at as carried out during adverse atmospheric
many locations as necessary to monitor the conditions or while the aircraft is cold-
cure cycle and to ensure the repair meets spec- soaked.
ification requirements when completed. 4. Improper heat-up rate control may cause
resin flow and gel anomalies resulting in a
product of marginal quality. Heat-up rates
Specific risks associated with heat
must be monitored or appropriate control
The principal risks associated with repair devices used.
activities on structures that require the use of 5. Foaming adhesives may generate exother-
thermosetting resins and adhesives are: mic reactions resulting in irreversible
damage. This hazard can be avoided by
1. Water or residual moisture in any portion of
minimizing the width of splice gaps to be
the assembly may vaporize and cause addi-
filled through careful sizing and fit-up of
tional damage such as ply separation, core
details prior to and during lay-up. Non-
node bond separation, or skin-to-core bond
metallic core details should be joined by
failure (see Section 39.5).
crush splicing rather than by adhesive
2. Overheat conditions may develop under a
foams to reduce the amount of reactive
heating blanket, causing irreversible dam-
polymers present in the panel during the
age, occasionally a fire. Constant
cure cycle.
monitoring or the incorporation of overheat
876 Repair aspects of composite and adhesively bonded aircraff structures
'
0 15' 30' 45 goo
5052 100% 80% 76% 19% 2%
*O fI I I
\
0
8'.
1
-- - - _
O0 15O 30° 450 900
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
0.45 kg (1lb) of composite materials used in flakes and molded into test panels. Mechanical
aircraft, ship or missile manufacture, and physical properties were found to be 80%
0.90 kg (2 lb) of material ends up in landfills. of that obtained with virgin prepreg. Work
The average ratio is 1.3 to 1. This waste was then begun to use material directly from
includes both material generated by the mate- the shredder, to avoid cutting the high tensile
rial supplier and material generated by the strength material into 50 mm (2 in) flakes.
end item manufacturer. In time, composite Early indications are that approximately the
scrap produced at repair facilities will add to same strengths can be obtained with the ran-
this total. Approximately $1billion of all types domly oriented material. Preliminary analysis
of raw prepreg is wasted annually and $25 indicates that most epoxies can be comingled
million is spent on its disposal, according to and coprocessed.
information prepared for the Naval Industrial Niche markets are being sought for uses of
Resources Support Activity (Broudy, 1993). the reclaimed prepreg, based on the 80%
Another concern is with the legal status of strength obtained and the comparatively lim-
prepreg waste: is it considered hazardous? ited amount of carbon/epoxy produced in the
Both state and federal regulations must be US, estimated to be 5.5 x lo6kg (2.5 million lb)
considered. California, for one, has require- annually. Markets are sought which would
ments for cured and uncured waste and its provide highest profitability for the manufac-
disposal. Other state requirements may vary turer; sporting goods and medical prosthesis
for both material forms. devices are possibilities.
The objective of the CECMT program is to
develop a plan for reclamation of
40.4 REUSE TECHNOLOGIES
carbon/epoxy prepreg scrap and demonstrate
the recyclability of the material, based on a Cured thermoset composites undergo the fol-
survey of users which revealed that carbon/ lowing steps in preparation for reuse. Cutting
epoxy is the major prepreg contributing to the complete items ( e g boats) into small pieces
waste stream. This scrap or waste material is suitable for handling for shredding is the first
sometimes referred to as 'offal'. The aerospace step in the process. Items 1.35-1.80 m2
industry generates 60-80% of the prepreg (15-20 ft2).in size or scrap (cured or uncured)
offal, with 50% of the total in broad goods may go directly to shredding. Shredding
form. The most widely used epoxide is reduces the material to sizes suitable for the
tetraglycidylmethylenedianaline (TGMDA) next step, whether it be particle preparation
cured with diaminodiphenylsulfone (DDS). (grinding, milling, granulating) or pyrolysis.
Other accomplishments of the program, as Shredding will not be necessary for pyrolysis
reported by Lause (1993) of GLCC, are as fol- if the item can be accommodated in the pyrol-
lows. A low speed, high torque shredder was ysis furnace. Classification of the shredded
found to be best for cutting high tensile and material or of the resulting particles will be
high shear strength carbon fibers. Other cut- required if more than one product is desired
ting blades evaluated were guillotine, carbide, (eg. glass fiber and powder). Shredding for
slitter and shear types. A low torque machine most experimental work provides chips (or
did not give a clean cut. The shredder employs piecesj50 mm x 400 mm ( 2 in x 8 in) to 50 mm
two cutting blades, rotating inwards or x 50 mm ( 2 in x 2 in); granulation gives 9 mm
counter to one another, powered by a 30 hp (3/8 in) and smaller particles; and grinding or
motor. Shredder input was the scrap prepreg milling a powder, suitable for filler, of 50 pm
collected from Gerber cutters, i.e. random size or less. Size of particles and powder is deter-
and shape. The offal was cut into 50 mm (2 in) mined by screen size.
886 Reuse and disposal
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- carried out experiments in cooperation with
age of ester bonds, giving phthalic acid in Michimae using a batch type external heating
good yield and soluble carboxyl-containing pyrolysis furnace (Kitamura, 1993). The sys-
oligomers of potential utility were isolated. tem was conducted for scrapped reinforced
Recovered oligomers for acid curing of plastic (RP) ship material. When material is
epoxy resin systems have been explored with heated for about 10 min, gas is produced and
encouraging results. Smooth transparent films more gas can be collected as the temperature
perhaps suitable for coatings have been rises. The amount of gas which can be col-
obtained. The use of recovered oligomer as lected reaches a peak at 275°C (527°F).The gas
saturated acid in the ex novo synthesis of UP produced is either water cooled or run
resins has also shown promise. 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
40.4.3 PYROLYSIS
common for RP used in ships. The residue is
Pyrolysis is the controlled thermal degrada- fiberglass and carbon, i.e. 40 wt YO and 12
tion of an organic material into one or more wt YO, respectively.
recoverable substances through the applica- The Japan Marine Recreation Association
tion of heat in an oxygen-free environment. under the Ministry of Transport and Sasakawa
Pyrolysis should not be confused with inciner- Foundation has been developing a mobile
ation, which is the total oxidation of all the pyrolysis/incineration system for RP ships
organic materials. Pyrolysis has been used for since 1990. It is economically advantageous for
years to reduce plastic and rubber wastes, par- large structures like RP ships to be treated as
ticularly the stockpiles of used tires. they are without pre-processing. The mobile
Pyrolyzing SMC in the USA, however, is rela- pyrolysis/incineration system comprises two
tively new. trailers, each of which has a body 7 m (23 ft)
Primary emphasis to date has been applied long, and 2.6 m (8.6 ft) wide, holding a
to scrap materials in the manufacturing destructive distillation furnace and a rotary
process. Ultimately, recycling of parts at the kiln, respectively. The system first pyrolyzes
end of their application life cycle must be an RP ship into pieces less than 6 m (20 ft) in
addressed if elimination of all SMC from land- length under a temperature condition of about
fill is to be achieved. 400°C (750°F). After shredding into small
Pyrolysis has a major advantage in that it is pieces, removing metals and moving to the
well suited to handling contaminated scrap, second trailer on which a kiln is loaded, the
i.e. SMC which contains paint, adhesives, fas- residue is then incinerated in the rotary kiln. A
teners or is mixed with other materials. pilot plant on land has been constructed and
The SMC Automotive Alliance of the SPI tested and mobile pyrolysis/incineration sys-
Composites Institute (1991), a group of mater- tem trailers will be completed in 1993.
ial suppliers and molders, has worked on
pyrolysis of SMC auto scrap. In its early
40.4.4 CHEMICAL DEGRADATION
stages, the main problem was shredding and
feeding materials into the pyrolysis equip- Under the proper conditions, the chemical
ment. A discrete chip with minimum polyester reactions that are utilized to produce ther-
breakup is needed to make the process cost moset and thermoplastic polymers can be
effective. By-product utilization is the other reversed to regenerate the various monomers
factor which will influence the feasibility of involved. Among these are the 'chem-olysis'
the process for SMC waste disposal. processes: hydrolysis, glycolysis, methanoly-
In Japan, The Ship Research Institute (SRI) sis, aminolysis, as well as polyurethane (PUR)
Properties and products of recycled materials 889
foam and reaction injection molding (RIM) ical solvent which is blended both in the waste
depolymerization, saponification, refinery paste and waste resin, to keep them in a
cracking, and thermal 'unzipping' of poly- pumpable state, Premix has used the waste to
olefins. fuel cement kilns (Butler, 1991). This waste
Since these approaches take the organic will be used to fire the kiln and then the ash
polymers back to more basic chemical build- from the firing is put into the cement. This
ing blocks, they have the potential advantage process also eliminates the need to landfill the
of yielding known chemical streams that can ash. Some bathtub manufacturers in Japan use
be converted, using existing purification and special incinerators to recover the steam for
polymerization technology, to new polymer boilers from the waste. However, in this case,
with properties equivalent to the virgin poly- secondary treatment equipment is necessary
mer. The depolymerization processes will also to prevent air pollution.
free up the glass reinforcement used in the
composite. In the polyester field, chemical
40.4.7 DISPOSAL/RECYCLING MODELS FOR
degradation is being utilized primarily for
REUSE TECHNOLOGIES
polyethylene terephthalate (PET).Inasmuch as
this thermoplastic is primarily used without A disposal/recycling model for composite
reinforcement, e.g. bottles and film packaging, waste material has been developed by Vital
no detailed attention will be given here. Visions Corp. to help evaluate practical and
Typical products obtained in chemical degra- cost effective disposal or recovery methods
dation or depolymerization are dimethyl (Wood, 1991). The State of Minnesota has
terephthalate (DMT) and ethylene glycol (EG). funded a study for development of an eco-
Pyrolysis, another form of chemical degrada- nomic model to determine if collection of fiber
tion, has been discussed previously; it is a reinforced plastic scrap from processors can
practical recycling process for unsaturated produce profitable products, either materials
polyester (SMC). or end-use goods (McDermott, 1992).
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)
Table 40.3 Properties of BMC reinforced with recycled glass reinforced SMC
and Plowgian, 1993). Table 40.4 shows that Treatment Council) of the Japan Reinforced
strength can be maintained and there is a Plastics Society, as the final step in a complete
reduction in density. The latter implies a lower recycling evaluation beginning with cutting
weight for a given car part, an added benefit up and shredding large RP parts, obtained
for the auto recycling evaluation underway. physical and mechanical property data for
In Japan, the RTC (RP Recycling and 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.
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
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 to 30% recycled content. The recycled PUR
(PUR) COMPOSITES must be ground into a fine powder before
reprocessing to obtain the Class-A surface.
While the major activity in thermosets has been
with unsaturated polyesters (SMC and BMC),
property data have also been reported on recy-
40.5.3 RECYCLED THERMOPLASTIC
cled glass reinforced PF, Table 40.9 (Olson, COMPOSITES
1992)and PUR, Table 40.10 (Graham, Jutte and
Shipp, 1993). Work to recycle reinforced PUR Glass-filled polypropylene (PP) has received
will increase as structural reaction injection the most attention, perhaps because of its
molding (SRIM) finds more use in structural potential for automotive use. Owens-Corning
applications and PUR presumably continues to studied the effects of repeated recycling by
be the resin most used. Krauss-Maffei granulation of the PP and injection molding
(Germany)has a new RIM system that can pro- (Graham, Jutte and Shipp, 1993). Table 40.11
duce exterior auto body panels with a Class-A shows a loss in properties caused by polymer
surface from reinforced PUR that includes up 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.
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 40.12 Propertics of polybond modified 30% recyclcd glass reinforced polypropylene
solid by-product (essentially glass fiber and pyrolyzed SMC can be recycled successfully
filler). In one test by the SMC Automotive into general purpose and Class A automotive
Alliance, the resulting composition was gas SMC, at up to 30% of the calcium carbonate
14%, oil, 14% and inert solid 72%. The gas gen- filler loading with no adverse effects on pro-
erated was sufficientto fuel the pyrolysis unit, cessing or physical properties (Rusch, 1993).
making it self-sustaining. The energy content The pyrolysis experiments performed by
was close to natural gas. The solid by-products Michimae in Japan on scrapped RP ship mate-
can be processed into fillers for SMC, BMC or rial gave the yields in Table 40.17. The pyro-oil
thermoplastics. When milled into a filler, the which was recovered had a strong acid content
Properties and products of recycled materials 897
Table 40.15 Properties of recycled neat NBC RIM Table 40.16 Properties of recycled NBC SRIM part
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)
2 wt YO of municipal solid waste. The joint lished infrastructure for recycling could head
effort targets the plastics portion of the fluff. off severe government restrictions on plastics
The recovery of plastics from shredder residue use.
is hampered by frequent contamination from As with durables in general, aids for recy-
paint, other plastics, metals, and adhesives. cling vehicles include design for easy
Thus another goal of the effort is to develop separation and collection, parts consolidation
better methods to purify scrapped plastics. to simplify separation, material identification
The Department of Energy’s Argonne on parts, restriction of plastic parts to recy-
National Laboratory has developed a process clable resins, and avoidance of paints, coatings
to separate plastics and other recyclable mate- and heat sensitive additives. Automakers
rials from the ’fluff’ of shredded automobiles. worldwide have agreed on an identification
The process utilizes a fluidized bed process code for all plastic parts heavier than
and yields PUR, fines, iron oxide and mixed 100 g (3.5 oz). Ford Motor Company has
plastics. issued guidelines on design for for recyclabil-
Germany appears to be moving away from ity (Miller, 1993)
its rules forbidding incineration of many kinds Germany has been a leader in design for
of waste. The Environment Ministry report- reuse. Porsche, on assignment from the
edly will introduce legislation that would Automotive Engineering Research
allow incineration of composites and certain Association, investigated designs for medium-
plastics if recycling proves too expensive priced autos in which plastic parts could be
(Protzman, 1993). readily dismantled and recycled. The best
designs for meeting these objectives were
those in which combinations of easily disman-
40.7 DESIGN FOR REUSE
tled parts were manufactured from a single
recyclable resin. An example of such a combi-
40.7.1 AUTOMOBILES
nation is a PP bumper system with a PP
An obvious approach to assist in the economic sheath, an expanded PP core and glass-mat-
success of recycling of multi-material parts is to reinforced PP beam (Nir, Miltz and Ram,
design the item originally for ease of disassem- 1993).Many reclamation projects focus on the
bly. Of particular interest are automobiles and bumper system. Bumpers are collected in pilot
white goods (e.g. refrigerators). The major auto programs, ground into particles and blended
makers of the US Council for Automotive with virgin resins. Use of a single recyclable
Research (USCAR), through their Vehicle resin has been practiced by Peugeot, Ope1 (sin-
Recycling Partnership, are studying ways to gle resin bumpers) and BMW (body panels).
enhance compatibility and dismantling of plas- The use of one resin in different forms, as
tic parts (Wigotsky, 1993). Some bumper parts described above, is also under development
now need only four bolts instead of twelve. by Reko and DSM in auto dashboards.
Potential amendments to the US Resource In Landshut, Germany, BMW has a facility
Conservation and Recovery Act, passed in capable of dismantling 25 cars a day. Eighty
1976, may specifically name automobile solid percent of the parts in the BMWs low end ‘3
waste. Federal regulations could possibly series’ can be reutilized in some form. Plastic
require certain car design features, if only by bumpers are turned into interior wall panels.
excluding certain materials. The VRP is work- Seat covers and PU foam are used as sound-
ing to establish a strong infrastructure for deadening material for the floor in the ’3
recycling plastic parts, starting with things series’. BMW also has three dismantling plants
that are easy to get at, such as fender liners, fan in the USA (New York City, Los Angeles and
shrouds and radiator supports. A well-estab- Orlando) (Protzman, 1993).
Applications and markets 901
binder, usually polyester, filled with up to 85% 40.9 LEGAL AND ENVIRONMENTAL
by volume of recycled composite scrap ASPECTS
(Darrah, 1993). One application encapsulates The major federal waste legislation in the USA
the scrap-resin mixture between two FRP addressing solid waste issues is the Resource
skins. The resulting panel has passed the full Conservation and Recovery Act of 1976. It
scale fire test for exterior panel systems. requires the Environmental Protection Agency
Work in Japan has been done to develop a (EPA) to set guidelines for government pro-
gypsum filled with milled composite ther- curement of recycled products and it
moset scrap and a mortar with milled mandates Federal agencies and contractors to
composite scrap, both with mechanical prop- implement affirmative procurement programs.
erties suitable for construction (Kitamura, Most states and many local governments have
1993). established programs to procure recycled
materials. The 1976 Act was reauthorised in
40.8.3 ELECTRICAL PARTS 1988 and continues in effect (Donnelly, 1993).
An industry concern is that the federal reg-
In Germany, two parts made with new SMC ulations might venture into the areas of car
formulations containing 10-15% by weight design, if only by excluding, within certain
fiber rich recyclate are already in production time periods, certain materials and design
or approved for production. These are an elec- approaches.
trical distribution cabinet and a cable In the meantime, Senator Baucus (D-MT),
distribution base (Schaefer and Plowgian, Chairman of the Senate Environment-Public
1993). Strength and modulus can be main- Works Committee, unveiled in April, 1993, a
tained with a reduction in density. four-part blueprint for recycling to be part of a
recycling bill to be introduced later. Two parts
concern composites: the Federal Government
40.8.4 OTHER APPLICATIONS
should take the lead in procuring goods made
Peninsula Copper Industries has identified an from recycled materials and second, manufac-
application for small chips of printed circuit turers should be responsible for their products
board in an epoxy/coal tar base (Hanson, when they become waste.
1991). This composite is used as a cushion In Germany, increasing concern for the
material between rails and the steel approach environment has led to proposed laws for the
plates at railroad crossings. Initial tests indi- reuse of post consumer and post industrial
cate that this composite is an effective waste. Legislation for recycling of consumer
replacement for rubber-based materials goods packaging was enacted in 1992, setting
presently used. Several parts from SMC, made minimums for collection and recycling
from recycled SMC, have gone into production through 1995. Now proposed is the German
or are approved for production in Germany. Refuse Act for Car Recycling, with its priority
These include sinks, seats and chairs. for material recycling (Schaefer and Plowgian,
In the thermoplastic field, a commercial 1993).
application for ‘Nyrim’ nylon block copoly- Other proposed legislation would levy a tax
mer-based SRIM is a manhole cover (Reitz, on new cars to pay for their eventual
1992). It utilizes a 3.545% fiber reinforcement disposal. Another proposal by Germany’s
package. The recycled SRIM composite Environmental Minister would make automo-
yielded properties comparable to virgin injec- bile manufacturers responsible for the final
tion molded impact-modified nylon. disposal of their cars. Still another stipulated
that by 1993, plastics in new cars produced in
Organizations active in composites recycling 903
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
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.)
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.)
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.
Current applications 911
Another suspension application demon- by the 'lost-core' process in which a low tem-
strating the durability and load carrying perature melting alloy such as tin-bismuth is
capability of composites is wheels. The com- used as a form to mold the hollow sections.
mercial introduction of polymer composite The core is then melted away from the cured
wheels was on the 1989 Shelby CSX modified part in a subsequent operation. An alternative
version of the Dodge Shadow. Developed by is to 'weld' two thermoplastic pieces to form
the Motor Wheel Corporation, the Fiberide@ the manifold. To reduce cost, some fuel
wheel uses a combination of structural SMC intakes are being integrated with the air
and XMC. These materials provided a mix- intake manifold.
ture of chopped random and oriented Injection molded phenolic compounds are
continuous E-glass in a vinyl ester resin. At used in many engine and transmission appli-
reduced weight, the composite wheel out- cations because of dimensional stability and
performed both steel and aluminum wheels creep resistance at higher temperatures.
in fatigue. The development of polymer com- Current applications include pulleys, torque
posites that retained acceptable lug nut converter reactors, thrust washers, water out-
torque after wheel heating caused by extreme lets, valve covers, radiator end caps, motor
braking conditions was a technical advance commutators and fuel rails (Fig. 41.6).
that made this application possible. While the performance advantages of com-
A front suspension stabilizer link was posite drive shafts and propeller shafts (lower
introduced on the 1994 Ford Taurus and weight, better NVH, increased durability) has
Mercury Sable. Made from a glass fiber rein- been established, cost remains a barrier to
forced copolymer polyacetal, this was the their wide spread use. A composite drive shaft
first use of a structural thermoplastic com- has an economic advantage, however, when it
posites in such an application in North replaces two-piece metal shafts. The most suc-
America. This durable part does not require cessful designs have used glass and/or carbon
painting and reportedly provides a 42% fiber composite overwrapped on an alu-
weight reduction and 33% cost reduction minum tube using pultrusion or filament
over the replaced steel part. winding processes.
have been commercialized. Pultruded glass (300 miles per hour), may offer an opportunity
fiber reinforced thermoplastic composite pan- for composites because of the need to mini-
els are used to construct a 'Secured Modular mize weight. Weight reduction is especially
Automotive Rail Transport' (SMART) for important for magnetic levitation (MAGLEV)
Union Pacific Railroad. Each three-tier struc- systems where the vehicle is suspended above
ture serves as a 'car rack' to protect eighteen the guideway to provide friction free move-
automobiles from damage and theft during ment.
transport to the dealer. The use of composites
also significantly reduces the maintenance cost
41.4.5 MILITARY APPLICATIONS
of the car rack.
Composite hopper car covers protect grain Limited applications of composites are found
and other dry materials that need protection in combat and non-combat ground vehicles in
from moisture. The covers, which range from the US military, but if current development
9-15 m (3040 ft) in length, are fabricated by a programs are successful, much greater use of
hand lay-up process. Two prototype composites should result. Modern warfare
glass/polyester filament wound railroad cars requires rapidly deployable, survivable vehi-
termed the 'Glasshopper' have been in service cle systems. Thus, weight reduction in all
since 1981 without failure. Produced in a joint vehicles, including armored vehicles, is desir-
venture by ACF Industries, Cargill and able. In addition to weight savings,
Southern Pacific, the corrosion resistant, light- composites can potentially offer increased
weight composite car can carry a greater durability, improved signature management!
payload, but is significantly more expensive better personnel protection and lower produc-
than a steel hopper car. tion cost.
The goal of an ongoing Army project, the
Composite Armored Vehicle Advanced
41.4.4 MASS TRANSIT APPLICATIONS
Technology Demonstrator (CAV ATD), is to
Buses and passenger rail systems offer many establish the feasibility of using polymer com-
more opportunities for the application of com- posites in the primary structure of a 20 tonne
posites than are presently in service. Some (22 ton) combat vehicle to achieve a 33%
cosmetic and semi-structural applications weight saving over a traditional metal vehicle.
have been successfully implemented, but few Composites are also being considered for com-
examples of structural components are found. bat vehicle armor - used either alone or in
The durability of polymer composites has conjunction with ceramics and/or metals - to
lead to extensive use in seats for buses, sub- provide significant weight savings over cur-
ways, people movers and trains. Composite rent materials. The High Mobility
sandwich panels with glass fiber-phenolic Multi-purpose Wheeled Vehicle (HMMWV),
skins over aramid or aluminum honeycomb which is currently in production, utilizes an
are used in walls, ceilings and floors of many integrated hood/fender assembly molded
European mass transit cars. These rigid panels from SMC. In upgraded versions, composite
are very lightweight and the use of phenolic armor is attached to the HMMWV.
resins allows attainment of fire/emission stan- Phenolic spa11 liners containing Kevlar or
dards. The end caps of transit cars are often S-2 Glass@fibers are used in the M113A3
molded composites. Pultruded exterior panels Armored Personnel Carrier and Bradley
are being substituted for aluminum on buses Fighting Vehicle to provide troop protection.
to reduce weight and decrease assembly cost. Longer service life and chemical protection
The development of high speed rail sys- were the motivation for the incorporation of
tems, which attain speeds up to 480km/h 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
Woven roving are the most common fabrics Nguyen, 1992).Their use is limited because of
due to their low cost. They are available in a cost and also because they cannot bear much
variety of weights and weave patterns, but a load in compression.
800 g/m2 (24 oz/yd2) plain weave is probably
the most frequently used. In small boat con-
42.2.3 CORES
struction, the fabric is usually mat-backed, in
which a chopped strand mat has been stitched Linear PVC foam is used extensively in boat
or powder bound to one side of the fabric. hulls, at a density of 80 kg/m3 (5 lb/ft3). The
Woven yarn, also called textile fabric or resilience of the material allows hull deforma-
cloth, is more expensive and therefore used tion during impact with no skin/core
infrequently. These materials are finer in tex- debonding, skin damage or core shear failures.
ture than woven rovings and are used as Crosslinked PVC foam is used in decks, bulk-
surfacing plys, particularly in tooling. heads and cabins because it has better
Knitted glass fabrics are becoming more structural properties and will not creep at the
common. The rovings are stitched together, higher topside service temperatures. It is
which keeps the strands relatively parallel (no available in a wide range of densities, but is
crimp as in weaves) and stabilizes the fabric usually used at 80 and 100 kg/m3 (288 and
against distortion during handling. The orien- 3601b/yd3). Both types of PVC foam are
tations of the separate layers and the number closed cell, absorb very little water and are
of separate layers, which compose knitted fab- moderately priced.
rics can be varied, although a 2-ply 0/90 is End grain balsa, also widely used as the
most common. Knitted fabrics are currently core in boat sandwich structures, is inexpen-
available up to 2500 g/m2 (72 oz/yd2). sive and has excellent structural properties.
Chopped strand mat is most commonly Under some circumstances, however, balsa
used where a resin-rich layer is desired, such as can rot. If skin/core debonding occurs and
between the core and fabric in sandwich struc- water is allowed to penetrate this interface, the
tures. Usually the first ply next to the gel coat wood will eventually degrade. It has been
is a layer of mat, which reduces print-through shown, however, that balsa will provide a long
of the reinforcement as well as providing addi- marine service life with proper maintenance
tional protection from water permeation. (Baltek Corporation, 1986).
S-2 glass is about six times the cost of E- Composite core is also available. The mate-
glass, so it is rarely used in marine structural rial is made in two forms, either sinusoidal
applications. S-2 made in the G filament is nested-wave, or in a closed cell configuration
sized for epoxy and when made with the K where planar webs alternate with sinusoidal
filament is sized for polyesters and vinyl webs (Plunkett et aI., 1992).This type of core is
esters. essentially a collection of sine wave stiffeners
Carbon fiber is also rarely used because of fused to skins with a laminating resin. It
cost. America’s Cup racing sailboats use car- appears to have great potential for marine and
bon throughout the boat and some racing civil engineering structures and has in fact
powerboats use carbon as well. Carbon has an been used to make about 200 prototypes,
additional problem in that it can corrode met- including deckhouses, storage tanks, build-
als in contact with it in the presence of water ings and parabolic solar energy concentrators.
(Tucker, Brown and Russell, 1990; Aylor and
Murray, 1992). 42.2.4 SKIN/CORE BONDING
Polymeric fibers, namely Kevlar and
Spectra, are sometimes used in marine appli- A good bond between skin and core is critical
cations where weight is critical (Sloan and to the performance of sandwich structures. In
918 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
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
\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
Fig. 42.4 Propulsion shaft fairwater. (Courtesy of B.F. Goodrich Aerospace, Engineered Polymer Products
Business Group, Jacksonville,FL.)
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
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
(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.
References 929
Greene, E. 1990. Use of Fiberglass Reinforced Kelly, J.J. 1993. Thick Composites Technology
Plastics in the Marine Industry. Ship Structure Development Program.
Committee Report SSC 360. Kramers, S.D. Engineering for the Americas Cup.
Hepburn, LCDR R.D., Magliulo, G. and Wright, Proc. 1993 Intern. SAMPE Conf., Philadelphia,
T.W. 1991. The US Navy's New Coastal PA, 25-28 Oct 1993.
Minehunter (MHC): Design, Material and Korczynski, J.F. 1993. Development of Composite
Construction Facilities. Naval Engineers J., May Heat Exchangers For Seawater Applications.
1991. Proc. 1993 Intern. SAMPE Conf., Philadelphia,
Hitco 1986. Hitco Technical Report 20-04.16, Rev.C. PA, 25-28 Oct 1993.
Hoffman, P. and Kelly, J.J. 1992. Manufacture of Leon, G.F. and Coffenberry, B. 1992. Proposed
Advanced Composite Submarine Structures Fabrication Process for Thick Composite
(MACSS).Proc. 37th Intern. S A M P E Symp. Submarine Structures. Proc. 37th Intern. S A M P E
Huss, J. Rowland. 1990. Structural Response of Symp.
Marine Sandwich Panels to Uniform Pressure Lewit, S. 1990. Use of Polyester Mat as a Bedding
Loading. Naval Engineers Thesis, Massachusetts Material for Cross-linked PVC Foam Cored
Institute of Technology, Cambridge, MA. Production Laminates. Proc. 3rd Intern. Conj on
Interlux 1993. Technical Bulletin 900B Marine Applications of Composite Materials,
Jacquemet, R. and LaGrange, A. 1988. Aging of Florida Institute of Technology, Melborne, F1.
Laminated Polyester/Glass and Evolution of Little, BJ., Ray, R., Wagner, P., Lewandowski, Z.,
Their Mechanical Characteristics in Marine Lee, W.C., Characklis, W.G., Mansfield, F. 1991.
Media. Composites, 4:4046. Biofouling, 3:45.
Johannsen, T.J., 1990. Correct Core Installation, Little, B.J. and Wagner, P. 1986.J. Adhesion 20:187.
Bonding Techniques and a Repair Case History Marino, R., Rockett, T., Rose, V. 1985. Blistering of
of a 56 ft Sailboat and a 47 ft Sportfishing Yacht. Glass Reinforced Plastic Marine Materials: A
Paper read at the Atlantic Marine Surveyors Review. NOAA/Seagrant Technical Report 88,
Conference on Newest Developments in Marine Advisory Service, Narragansett, RI.
Boatbuilding and Repairing, 9-10 October 1990, Miriyala, S.K., Tucker, W.C., Brown, R. and Rockett,
Annapolis, MD. T.J. 1993. The Mechanism of Galvanic Blistering
Jones, J.M., Walsh, M., Mansfield, F.B. 1991. in Carbon Fiber Composites. Proc. ICCM/9
Microbial Electrochemical Studies of Coated Madrid, Spain V.5 pp. 546-553.
Steel Exposed to Mixed Microbial NRaD 1992. Naval Command, Control and Ocean
Communities. Corrosion 91, Paper 108, NACE. Surveillance Center Technical Document 2348,
Jones, J.M., Vasanth, K.L., Conrad, T.K., Little, B., San Diego, CA 95152-5000.
Ray, R. 1992a. Corrosion Resistance of Several NSWC, Carderock Division. 1993. Low Cost, High
Conductive Caulks and Sealants From Marine Quality Composite Ship Structures Technology
Field Tests and Laboratory Studies With Mixed Demonstrated. Research Release, David Taylor
Communities Containing Sulfate Reducing Model Basin, Bethesda, Maryland, 20084-5000,
Bacteria. Intern. Symp. on Microbiologically May 1993.
Influenced Corrosion (MIC) Testing ASTM. Owens Corning Fiberglas 1991. 5-2 Glass Armour.
Jones, J., Walsh, M., Little, B., Ray, R., Mansfield, F. Case History. Landing Helicopter Deck (LHD)
1992b. ESEM/EDS Studies of Coated 4140 Steel Deckhouse Armor Application, Owens Corning
Exposed to Marine, Mixed Microbial Fiberglas Corp., Pub. No. 15-ASP-16157-A., Jan
Communities Including SRB. 8th Intern. Congr 1991.
on Marine Corrosion and Fouling, Taranto, Italy. Pfund, 8. 1992. Light-Curing Resins. Professional
Juska, T., Mayes, J.S. and Seemann, W. 1993. Boatbuilder Magazine, No. 18, August/
Mechanical Properties and Impact Damage September 1992.
Resistance of Composites Fabricated by Low Pfund, B. 1993. Pre-preg Reinforcements.
Cost, Vacuum Assisted, Resin Transfer Molding. Professional Boatbuilder Magazine, No. 24,
Naval Surface Warfare Center, Carderock August/September 1993.
Division, SSM-64-93/ 04. Plunkett, J.D., Cohen, R., Kunz, B.P. and Kunz, J.
Juska, T. 1993. An Evaluation of Low Temperature 1992. Light-weight, Volume-Produced
Curing Prepregs. Naval Surface Warfare Center, Industrial Honeycomb Composites For Marine
Carderock Division, SSM-64-93/07. Structural Applications. MTS '92 Con& Proc.,
930 Marine applications
Marine Technology Society, Washington, D.C., Suitt, D. and Girona, F. 1993. Development of a
October 19-21. Standard Family of Composite Material
Reichard, R.P. 1992. Pressure Testing of FRP Centrifugal Pumps for Naval Surface Ships.
Sandwich Panels. M A C M ‘92 Conf. Proc., Naval Engineers J., May 1993.
Composites Education Association, Inc., March Tucker, W.C., Brown, R and Russell, L. 1990.
22-24,1992. Corrosion Between a Graphite/Polymer
Russell, M. 1992. Inspection and Repair Manual for Composite and Metals. J. Composite Materials
Fiber Reinforced Plastic Boats and Craft. 24:92.
NAVSEA Technical Manual T9008-B4-MAN- Tucker, W.C. 1991. Degradation of
010. Graphite/Polymer Composites in Seawater. J.
Seemann, W. 1990. US Patent Number 4 902 215. Energy Resources Technol. Trans. ASME 113 4:264-
Sloan, F. and Nguyen, H. 1992. Applications of 268.
Extended-Chain Polyethylene Fibers in the Tucker, W.C., Little, B.J., Ray, R., Wagner, P. 1993.
Marine Composites Industry. MACM ’92 Con$ Microbial Degradation of Fiber Reinforced
Proc., Composites Education Association, Inc., Polymer Composites. Proc. ICCM/9, Madrid,
March 22-24,1992. Spain, V.5, p. 554
Smith, C.S. 1990. Design of Marine Structures in Wilhelmi, G.F. 1988. Composites for Ship
Composite Materials, London and New York Machinery Applications. Presented at the
Elsevier Applied Science. SNAME Spring Meeting, 10 June 1988,
Stachiw, J.D. and Frame, B. 1988. Pittsburgh, PA.
Graphite-Fiber-Reinforced Plastic Pressure Wilhelmi, G.F., Appleman, W.M. and Loo, T.C. 1986.
Hull Mod 2 for the Advanced Unmanned Composite Shafting for Naval Propulsion
Search System Vehicle. Naval Ocean Systems Systems. Naval Engineers J., July 1988.
Center Technical Report 1245. Venus-Gusmer 1989.6th Edition Catalog.
COMMERCIAL AND INDUSTRIAL 43
APPLICATIONS OF COMPOSITES
Stewart N.Loud
fiber and resin products, and increasingly to industry to be counter productive to even use
hybrids of several materials. As a result, the term ‘advanced composites’ anymore.
advanced and hybrid fiber reinforced prod-
ucts are now moving into the application 43.4 APPLICATIONS REVIEW
sectors formerly dominated by metals and
even glass fiber products. Also, the focus on Following is an alphabetical review of applica-
’defense conversion’ has resulted in retarget- tion segments of this market or of unique and
ing of some governmental budgets to support emerging material systems used broadly in
defense contractor conversion to civil applica- related industrial applications. Representative
tions. Many of these applications reside in the organizations are cited as examples of the
commercial and industrial market sectors, the types of companies and institutions active in
focus of this chapter. these market sectors so that the reader can
A vast diversification of composites has research further into the applications of inter-
occurred in this sector. From the 1960s and est. Applications believed at this time to offer
1970s with many electrical, electronic, appli- the opportunity for significant growth are pre-
ance and business equipment applications, sented in the most depth. Some applications
the business has grown into pressure vessels, covered also fit into other market sectors, but
laptop computers, centrifuges, flywheels, fuel their technology is unique or they are indus-
cells, railroad car components, drive shafts, trial components sold into the other markets,
fuel pumps, loom components, musical so they are described here. Throughout the
instruments, oil and gas riser pipe, power chapter, tables highlight many applications by
lighting and distribution poles, industrial major market sector, some long established
process rolls, advanced wind turbines and and many in the emerging growth stage, to
much more. The processes used here have stimulate the reader’s thinking on other poten-
remained fairly constant: pultrusion, filament tial applications that might benefit from
winding, compression molding, injection applying composites. Those applications in
molding and hand lay-up, but the use of resin the tables that tend toward more usage of the
transfer molding has increased dramatically highest performance materials are listed with
for many of these applications. Materials an asterisk (*).
applications that were almost exclusively
fiberglass and polyester, thermoplastics, or
43.4.1 ANTENNAS
low-temperature curing epoxies have evolved
into much more vinyl ester usage and Telescoping composite tubes are used to form
migrated to the use of more high-performance a lightweight antenna support intended for
fibers such as KevlaP and Twaron@aramids, military use and the ultimate in portability.
Spectra@high-molecular weight polyethylene The tubes must be exceptionally light, so the
(HMWPE), and many types and forms of the producer used woven Spectra UHMWPE fiber
carbon fibers. Ceramic matrix composites in epoxy resin. They are fabricated using a
(CMCs)and metal matrix composites (MMCs) conventional roll-wrap process similar to that
are of increasing interest and are sometimes used to produce composite fishing rods. The
competing with polymer-based fiber compos- total weight is only 1.8-2.2 kg (4-5 lb) includ-
ites (PMCs), for example in automotive drive ing 11 nested tubes that collapse to only 711
shafts. Even carbon fiber reinforced carbon mm (28 in) for portability but can easily be
matrix materials (C-C) are moving from the extended and locked to form a support pole
aerospace sector into commercial use. The use 6.7 mm (22 ft) long.
of ’advanced’ materials has now matured Resin transfer molding is increasingly dis-
enough that it is considered by many in the 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
43.4.2 BRIDGES
adhesively/mechanically bonded to the
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
station in the heat of a fire fight. The bottles Larger flywheels also show promise for
must store air for long periods at 31 MPa stationary energy storage and peak power
(4500 psig). shaving applications, and the business
opportunity for such systems could be enor-
mous. Federal technology centers, such as the
43.4.12 FLYWHEEL MECHANICALBATTERY
Lawrence Livermore and Oak Ridge National
SYSTEMS Laboratories, now are part of teaming
US Flywheel Systems, Inc. (Camarillo, CA), arrangements to enhance flywheel technol-
Calstart (Burbank, CA), American Flywheel ogy transfer from defense and other
Systems (Seattle, WA) and others all hope to government programs to the private sector.
supply kinetic energy storage flywheel sys- The rims of the rotating wheels in these sys-
tems (now often called mechanical storage tems are filament wound using advanced fiber
batteries) for future electrical vehicles in composites, including E glass, S-2 glass,
California and elsewhere (Fig. 43.3). Flywheel Kevlar and carbon fibers. At speeds attainable
batteries have an estimated 5-10 times the by composite wheels, metal flywheels disinte-
watt hours per pound storage capacity of con- grate. Use of this system is a good example of
ventional lead acid batteries. They are technology transfer from aerospace to the
impervious to temperature variations, may be civilian sector.
drained repeatedly of stored energy without An electric car with a flywheel storage sys-
cyclic degradation, can be recharged in as little tem on board (and perhaps with regenerative
as a few minutes, should last 3040 years with- braking through the flywheels) could
out requiring replacement or maintenance, approach zero emissions and is expected to
and create no toxic waste problems. Mileage meet the much tighter California air quality
range in an electric car (such as GMs Impact) standards set for early next century. California,
could reach a projected 482-640 km (300400 New York and Massachusetts, have mandated
miles) or more according to some developers, that 2% of cars sold in those states in 1998
as opposed to a practical range of only 95-128 must be zero emission vehicles; the percent-
km (60-80 miles) for today’s electric cars using ages increase to 5% in 2001 and 10% in 2003.
conventional battery systems. 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’
Fig. 43.3 Flywheel battery components. (Courtesy launched by President Clinton in September
of American Flywheel Systems.) 1993.
Applications review 939
43.4.13 FUEL TANKS FOR NATURAL GAS Chrysler and many city transit bus operators
VEHICLES (NGV) such as Tacoma, Sacramento, Salt Lake City,
Reading, Binghamton and other Northeast
Lincoln Composites (Lincoln, NE) and ED0 and Canadian cities. Recent failures of CNG
Corp. (Canada) introduced certified 'all-com- tanks during refueling (reportedly caused by
posite' compressed natural gas (CNG) exposure to unexpected acid solutions) appear
pressure vessels under the 1993 US to have been solved with an installation
ANSI/AGA standard called NGV2 for ultra- redesign and protective coatings. Additional
light, nonmetallic natural gas vehicle fuel interest comes from utilities such as Southern
tanks. The availability of these certified plas- California Gas & Electric and Columbia Gas
tic-lined, composite-overwrapped fuel tanks is companies.
expected to accelerate the usage of advanced Carbon fiber priced today at about $5-6/kg
composites into this potentially large alter- ($ll-l3/lb) for high-strength 12K fiber is
nate-fuel marketplace for composites. Besides about twice as expensive as S-2 glass fiber and
weight savings of up to 70% (compared with much higher than E glass but appears eco-
steel, aluminum, or metal-lined NGV tanks) nomically competitive for this market. One of
and greater durability, the new tanks offer the above supplier companies did a cost and
increased fuel capacity, extending driving weight analysis to decide how much of a pre-
range. mium would have to be paid if
The weight savings are achieved through higher-strength fibers were used rather than E
use of a hybrid composite, for example using a glass. Using E-glass/epoxy overwrap, the
30 msi modulus T650/35 carbon fiber from weight would be about 45 kg (100 lb). S-2 glass
Amoco Performance Products (Alpharetta, reduces the weight to 36-38 kg (80-85 lb), and
GA) or a Toray T700S/12K carbon fiber. a 12K carbon fiber/epoxy overwrap reduces
Hybridized with the carbon fiber might be an the weight to 18-20 kg ( 4 0 4 3 lb). Using fiber
E-glass fiber roving from Owens-Corning, costs of $2.20, 11-13.00 and 26.50/kg ($1, $5-6
PPG, or Vetrotex Certainteed to reinforce an and $12/lb) respectively, the estimated fiber
epoxy resin formulation. The composite is fila- cost per NGV pressure vessel is $64 for E glass,
ment wound over a thermoplastic liner of $300-315 for 5-2 glass, and $285-310 for car-
high-density polyethylene (HDPE). In the bon fiber. Combining the various cost
hybrid, carbon fiber provides an extremely components brings the heaviest (E glass) tank
high strength-to-weight ratio, with the ability cost to $380-400, S-2 tank to $700-720, and the
to withstand many pressure cycles along with carbon fiber tank to $600-620. Thus, to save
superior fatigue characteristics, while the about 27.2 kg (60 lb) by switching from E glass
fiberglass enhances toughness. HDPE liners to carbon fiber reinforcement, the cost pre-
are lighter weight than steel or aluminum and mium is about $220, or $3.6-3.7 per pound
more resistant than both to the highly corro- saved. Auto designers in the past have sug-
sive elements sometimes found in natural gas gested that a $2 premium per pound saved
supplies around the USA. A minimum 15-year was acceptable, but they might be willing to
life expectancy is set for the NGV2 tanks; after pay more now in view of the environmental
that they are to be discarded. benefits gained by burning cleaner fuel.
Other pressure vessel programs are under- The combined production of mid-size
way at Comdyne I, Compositek (Kaiser),Fiber pickup trucks in the USA by Chrysler, Ford
Dynamics, Amalga and Structural and General Motors is reported to be more
Composites. Large customers for the older than 600 000 per year. If only 10% are built
fiberglass/epoxy overwrapped aluminum with natural gas as the fuel and there are two
NGV fuel tanks include General Motors and 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 American Laminators (Drain, OR) and the
pounds of materials required. Transit buses Wood Science & Technology Institute
may be an even larger market. (Corvalis, OR) have developed a superior line
of glued-laminated (glulam) wood beam
Table 43.4 Transportation system equipment products based on Douglas fir and compos-
ites. Because these beams are a hybrid
Seats/frames material system, they marry the light weight
Monorail cars and high strength of aramid/carbon fiber
Mobile storage modules - CNG* composites with the already light weight,
CNG/NGV fuel tanks* high strength nature of wood to make a prod-
Rail freight car doors uct that can compete favorably with steel,
Rail car knuckles
Hydrogen storage tanks*
concrete, and other wood beams. Of special
Intermodal containers note is that these new composite/wood
Maglev train guideways* beams for buildings or bridges outperform
High-speed train brakes* conventional wood beam products and usu-
Concept/show car chassis* ally can be offered at a purchase price or first
Electric vehicle frames/chassis* cost of about 2545% less than conventional
Racing car brakes and clutches* glulam beams!
Solar-powered racing vehicles*
Highway reflecting markers
Dead weight design load is reduced by
Airport approach light towers 40-60°/0 for large structures and long spans.
Airport ticket counter tops For structures where deflection is a major con-
Drive shafts - pickup trucks* sideration in design, the patented technology
Aircraft escape slide inflation bottles* takes advantage of the high modulus of Akzo
Ship propulsion shafts* Nobel Fortafil carbon fiber with 33 msi modu-
Cablecar cabins and support arms* lus and 550 ksi tensile to more than double the
Shipboard crane components
design capacity in compression versus typical
unreinforced glulam products. Where
increased tensile performance is required,
43.4.14 GLULAM BEAMS
Akzo Nobel Fibers’ Twaron or DuPont’s
Composites are leading to revolutionary wood Kevlar 49 aramid yarn is used. Some of these
beams for bridges; laminated beams benefit beams can be massive; e.g. typically 24 m long
dramatically from use of carbon and aramid x 1200 mm deep x 254 mm wide (80 ft x 4 ft x
fibers and cost less. Wood structural building 10 in) to much larger. The fibers reinforce pul-
materials have required only the highest qual- truded plates that are adhesively laminated
ity wood to achieve necessary performance during the standard beam forming and bond-
levels. Wood (’the original composite’) has a ing.
high strength-to-weight ratio; however, highly Many structures (100 as of this writing) are
engineered components such as beams have already in place using the new composite glu-
had to allow for the inherent variability of lams, in California, Oregon, Wisconsin and
wood and wood types. The best woods have Hokkaido, Japan. More structures now are in
come from ’old growth’ forests that today are the design stages (ca. 100) including large
in decline or are in designated wilderness domed structures with over 164 m (500 ft) clear
areas. Logging practices and environmental spans, for Japan, USA and European clients.
considerations (remember the spotted owl?) Estimates by various participants suggest that
have removed ’old growth’ as a source and the global opportunity for this
have driven producers to consider new tech- composite/wood beam technology is in the
nologies. billions of dollars. In the USA, the conventional
Applications review 941
glulam market is over $1.2 billion/year and is TGV car designer and builder, must decide
supplied by 147beam manufacturers. Potential whether the weight savings, lack of fade and
requirements in the 45 million kg (100 million projected longer life (as with similar C-C air-
lb) range for just the high strength carbon and craft brakes systems) justify a change in the
aramid fibers are seen about the year 2000. One steel brakes now in service. With plans to
observer close to the project said that 'this has build similar high-speed rail systems in Texas
to make a big splash in composites and could and other parts of the USA, there is growing
be the biggest new composites application in interest in the results of the tests. Several com-
20 years!' panies in Japan have similar interest in using
C-C brakes on proposed advanced bullet
trains, which also might reach speeds of 350
43.4.15 HIGH-PRESSURE TUBING AND
km/h. Later magnetic levitation (maglev)
BATTERY CASINGS
trains which will approach 500 km/h may be
Amalga Composites filament winds carbon assessed for use of these ultra-high-perfor-
fiber/epoxy over battery casings for Johnson mance brakes.
Controls. The Inconel liner has a carbon
fiber/epoxy overwrap which is under 0.34
43.4.17 HYDROGEN FUEL STORAGE
MPa (50 psi) stress when discharged and 5.86
MPa (850 psi) when fully charged. These bat- Hydrogen storage tanks may offer potential
teries are designed to be buried in the desert to for filament-wound pressure vessels, but it
power instruments during the night and they will be several years before this can possibly
are recharged during the day. Amalga also occur. Syracuse University received a grant
makes vessels for high-pressure applications, from the Department of Energy to prove a
including a filament wound carbon novel approach to hydrogen storage. The
fiber/epoxy-overwrapped steel tank to with- hydrogen would be stored in a filament-
stand 3.41 MPa (500psi) for use as an wound tank in which activated carbon
emergency backup pressure cell for the F-22 granules are closely packed. After being
fighter. Other interesting high-pressure prod- cooled in a liquid nitrogen heat exchanger to
ucts are carbon fiber/epoxy-reinforced the desired storage temperature, the hydro-
metallic cylinders that achieve 41-83 MPa gen is passed through the activated carbon
(6000-12 000 psi) of pressure capability. Lower where some is adsorbed. It is then stored at
pressure pneumatic tubes are being made by low temperature (150K) and relatively low
Amalga for service at 1.7 MPa (250 psi), and pressure 5.51 MPa (800 psig) before being
these usually are reinforced with a fiber- released via slight heating of the granular
glass/epoxy overwrap. carbon while opening a valve for controlled
release into the nearby hydrogen-oxygen fuel
cell. A design engineer predicts that a car
43.4.16 HIGH-SPEED TRAIN BRAKES -
powered by an electric motor energized with
CARBON-CARBON
a hydrogen-oxygen fuel cell will be able to
Carbone Industrie in France has been testing outperform a similar vehicle powered by a
carbon-carbon brakes on the French TGV gasoline engine. Since hydrogen as a fuel
Atlantique line. Two similar but slightly differ- requires a massive change to the fueling
ent applications are being tested; for the drive infrastructure, the timing for this market sec-
wheels and for the bogey. The C-C brakes tor is hard to predict. If such an infrastructure
must qualify on cars being stopped from is installed, there will likely emerge many
300-350 km/h (to 215 mph) before they can be more composites applications such as large
considered for regular service. Alsthom, the tanks and pipelines.
942 Commercial and industrial applications of conqposites
43.4.20 MAGLEV TRAIN GUIDEWAYS km ($10 million per mile) for a dual track
Magnetic levitation or maglev train system con- guideway. Their design includes a concrete
cept definition contracts are funded by the box beam for the guideway with the bottom
DOT-Federal Railway Administration under of the vehicle ’wrapped’ around the beam for
the $151 billion Intermodal Surface safety. The guideway might use a hybrid of
Transportation Act which was passed in 1991 fiberglass and carbon fiber rebar rather than
and included $750 million to be used specifi- steel rebar reinforcement. Foster-Miller is
cally to complete the design and construction of focused on high-performance, low-cost guide-
a USA demonstration maglev line about 32 km ways. Most of their current emphasis is on
(20 mile) long. The German Transrapid maglev using high-strength FRP post-tensioning
system design is planned for the 20km (13 members (both transverse and longitudinal)
mile) demonstration system to be built in in the upper areas of the guideway. West
Orlando, FL. USA and Canadian companies Virginia University is working on a DOT-FRA
competing for future maglev system contracts contract titled: ’Assessment of Maglev
include Northrop Grumman, Foster-Miller, Guideway Systems’. Imbedded fiber optic
Magneplane, Boeing, Bombardier and systems may be used to monitor entire guide-
Morrison-Knudsen (the latter three are propos- way systems and to detect potential trouble
ing the most extensive use of composites on the spots such as joints. West Virginia University
‘rolling’ stock, perhaps including the outer data show that if FRP rebar or tendons are
skins of the maglev cars plus the interiors). used, the load-carrying capacity is about
On the maglev vehicles, General Electric is twice that achieved with steel. Although the
developing shielded superconducting mag- initial cost might be five times greater, the
nets and their coil design, shielding, motors, weight reduction can be 80%, so on a perfor-
levitation and carbon fiber/epoxy cryostats. mance-per-pound basis, FRP would be lower
To employ the latest methods of producing in installed cost than steel rebar reinforced
low-cost composite train vehicle structures concrete. WVU also is looking at more
advanced composite materials, including car-
and to keep costs down, carbon fiber will be
bon fiber and hybrids. Another option is to
used selectively, with high-performance fiber-
use an aramid fiber tendon, and candidates
glass the main reinforcement for sandwich
include Teijin’s Technora, Akzo Nobel Fiber’s
panels, possible low-FST (fire, smoke toxicity)
Twaron and Du Pont’s Kevlar.
materials for the vehicle interiors.
Regarding the guideway, they favor a U-
shaped configuration and either reinforced 43.4.21 MEDICAL, HEALTH AND SAFETY
concrete throughout or with a composite
PRODUCTS (SEE CHAPTER 44)
grille at the center of each guideway beam. To
reinforce the concrete, they recommend using BioMechanical Materials Corp. (Camarillo,
post-tensioned FRP tendons in the magnetic CA) and Composiflex (Erie, PA) are among
field and closest to the path of the cars and those selling carbon fiber/acrylic and carbon
more conventional steel rebar prestressing in fiber/urethane sheet stock to orthotic equip-
the lower regions of the supporting columns, ment distributors. They in turn sell this
well away from the high magnetic field to material to hundreds of small local laboratories
avoid raising the maglev drag coefficient sig- that fabricate components tailored by ortho-
nificantly. Magneplane International predicts tists for each patient, including such items as
that the guideway will be the dominant cost arch supports, knee braces and custom sports
component, so it has first design priority. braces. BioMechanical Materials among others
Their target is not to exceed $6.2 million per also sells large quantities of composite sheet
944 Commercia2 and industrial app2ications of composites
and fabricated parts to sports shoe manufac- older heavy tungsten studs to impact (rather
turers, such as Brooks and L.A. Gear, for than scrape) the road surface. A Duralcan
enhancing performance and the marketability MMC with 15 v/o alumina in 6061 aluminum
of the top-end shoes. Hexcel supplies a unique is being substituted to limit road damage
hybrid E-glass and carbon fiber fabric rein- because of its lower weight. MMC wire is
forced epoxy 'chip' for arch supports in Reebok being shipped at the rate of 'several tons per
sports shoes. For electrical hazard protection, month' for this application. Another interest-
Composiflex produces a hybrid composite of ing wire application is for flame spraying
fiberglass/carbon fiber/epoxy to fabricate where the MMC adds to service life; alumina-
lightweight toe plates for safety boots and reinforced aluminum wire is sprayed onto
puncture-resistant insoles, replacing the tradi- steel as an antiskid surface in marine environ-
tional steel inserts. This company gets its name ments such as ships, piers and oil platforms.
from their product with multiple plies of ori- Previously, pure aluminum was flame sprayed
ented fiber composite which can control onto a steel surface before painting, serving as
bending to certain directions. a corrosion barrier.
Among the many other applications in
Table 43.6 Medical products work or which have been tested to date are the
following: extruded truck frame channels [C-
MRI scanner cryogenic tubes* channels of about 304 x 76 x 7620 mm (12 x 3 x
X-ray tables* 25 in)], motorcycle drive sprockets, a propor-
Underwater therapy treadmill
tional valve for a truck lift gate, compressor
Wheelchairs*
Orthotics - shoe arch, neck & knee braces* piston-ring inserts, sporting goods such as golf
Prostheses - artificial limbs* clubs and brake components for standard and
External fixaters - orthopaedics* high-speed rail cars. Other promising applica-
Rehabilitation baths tions are automobile brake rotors (initial
Medical centrifuges* orders are now being used for early produc-
Hip implants* tion at this time) to reduce weight by replacing
Heart valves*
Dental/prosthetic cements
cast iron. Further component applications
X-ray file cassettes* likely to emerge include pickup truck drive
Medical sensors* shafts, engine cylinder liners, automotive sus-
Walking canes* pension arms, aircraft camera mounts,
Artificial ligaments* electrical housings, and pistons for automotive
engines, piston inserts that reduce the energy
required for high-speed reciprocating motion
43.4.22 METAL-MATRIX COMPOSITES (MMCS)
in large gas compressors, and tubing and forks
Duralcan USA (Novi, MI) markets low-cost for high-performance racing and mountain
MMCs reinforced with alumina or silicon car- bicycles.
bide particulate reinforcement. One of their Recyclability is a major market issue for
most successful applications is the use of rein- high-tonnage applications of many materials,
forced aluminum wire for tire studs. Finland especially now in Europe. Duralcan claims
and Sweden (and many USA states) banned that their MMCs have a potential advantage
the older steel-jacketed tungsten carbide studs over many other materials, including poly-
from all-weather/snow tires due to road wear. mer-matrix composites, since MMCs can be
Many people assumed that studs degrade recycled as a composite material or easily
highways prematurely because they wear reclaimed into high-quality aluminum by
away road surface. The real culprit is centrifu- melting and removing the reinforcing parti-
gal force acting on the studs that causes the 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 various sizes for reinforcing the necks of gui-
EMI/RFI Shielding. DSM Engineering tars or banjos, plus for making bridge blanks,
Plastics, Inc. (Evansville, IN) and others report fingerboard underlays, stiffening braces and
a noticeable trend toward using higher-tem- other components requiring extra strength,
perature glass-filled thermoplastics for stiffness and/or creep resistance. Other instru-
components used in the electronics industry, ments now offered in carbon fiber and other
mainly for connectors. Currently, the liquid composite materials, all claiming better tone
crystal polymers (mainly Vectra from Hoechst and clarity, are violins and bows, bases, drums
Celanese and Xydar from Amoco) are widely and sticks, sousaphones/tubas (an old applica-
used for electronics applications. Having been tion in FRP), harps, pianos and more.
part of the Akzo organization for several years
(and before that, Fiberfil), they have worked
closely with Akzo Nobel Fortafil Fibers Table 43.7 Consumer products
(Rockwood, TN) to develop special grades of
Camera tripods*
chopped and milled carbon fibers with suit-
SCUBA tanks*
able finishes. Other suppliers include Toho Banjos*
Carbon Fibers and Hexel. Heavy-tow fiber Sousaphones/ tubas
(50K filament count and greater) made from Harps*
commercial-grade PAN precursor is well Pianos
suited to making lower-cost chopped fiber. Umbrellas*
Usage of carbon fiber has been going up every Attache/brief cases*
Cassette tape/CD player cases*
year and has reportedly passed annual con- Exercise equipment*
sumption of 2.25 million kg (5 million lb) per Art work bracing systems*
year that would translate into compound vol- Guitars*
umes five to ten times that. Violins and bows*
Bases*
Camera cases*
43.4.25 MUSICAL INSTRUMENTS Eyeglass frames*
Kaman Aerospace (Bloomfield, CT) offers the Caskets
Binocular /monocular bodies*
Ovation Instruments guitar. The top of the Running shoe arches*
Ovation series is called the Adamas and its Audio earphones*
excellent tone is attributed to the use of a com- Drums and sticks*
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
43.4.26 OIL AND GAS APPLICATIONS
veneer. Fiberglass composites are also used for
other Adamas components, including the Conoco, Inc. (Ponca City, OK), Shell (Houston,
bowl. These are mostly handmade guitars so TX) and others are involved in oil and gas
annual production is small. A producer of clas- exploration to production depths typically to
sical guitars is Kuau Technology (Maui, 619-928 m (2000-3000 ft) and to even more than
Hawaii) with carbon fiber/epoxy and the RTM 4 km (15 000 ft). Conoco is the first company
process is their preference. The Luthier’s with one of the new tension-leg platforms
Mercantile (Healdsburg, CA) catalog for (TLP) in use. Shell is building such a platform
stringed musical instrument producers gener- and planning several more in partnership with
ates 99% of their business via mail order. They Exxon and British Petroleum. The oil industry
offer carbon fiber/epoxy bar and sheet stock in has a ’steel and concrete bias’ which is the result
Applications review 947
of many years of experience, relatively low ini- closely with IFP and Aerospatiale Space &
tial cost, ample supply, current design codes, Strategic Systems are Lincoln Composites
etc. However, new materials are the major tech- (Lincoln, NE and teamed with Aarding BV in
nology thrust needed in offshore structures The Netherlands) plus Coflexip & Services,
because the industry is forced to spend too Inc. (Paris). Coflexip is reportedly the leading
much money fighting corrosion of steel. producer of sub-sea pipelines and risers to
Current offshore structural applications of transport oil and gas products at offshore pro-
composites include low-pressure pipe, grat- duction facilities. The initial product of the
ings, handrails, equipment covers or Lincoln-French joint venture was a composite
enclosures and ladders. Future application TLP riser pipe that connects well-heads to
development is likely to focus on FRP for tethered floating platforms. Risers provide a
high-pressure piping, pressure vessels, accom- casing to protect the well bore and to carry the
modation modules and blast walls. FRP oil to the surface. Tethers will be 244.5mm
products (mainly E-glass reinforced) provide (9.60 in) diameter tubes, with a wall thickness
installation savings ranging from 10-70%, of about 13.5mm (0.53 in) and 12-17m
improved life-cycle costs, enhanced safety, (40-55 ft) long.
30-70% weight savings and environmental
advantages, according to studies by Conoco. It
is expected that a variety of composite materi- Table 43.8 Oil and gas exploration
als will be used for offshore structures, with
Tension leg platform tethers*
carbon fiber, aramid and fiberglass reinforce-
Fire shields - drilling rigs
ments, thermosets and thermoplastic matrix Drilling tubes*
resins and some hybrids. Sucker rods/slides
The Institute Franfais du Petrole supported Oil well logging probes*
development of advanced composite tubes Tribological bushings, seals, ' 0 rings*
developed by Aerospatiale for risers on off- Drilling motor shaft
shore stationary drilling platforms and tension Drill casing
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). Longer-term commercial application growth
Internal working pressures are in the 34-103 in this sector for advanced composites should
MPa (5000-15 000 psi) range, tensile loads to include moorings and tendons, drilling and
90 000 kg (100 tons) will be accommodated by production risers, drill pipe and tubing and
a special high-strength threaded steel alloy some pressure vessels. With platform construc-
coupling, and the design life can be as high as tion costs exceeding $1.5 billion per unit, there
20 years. Typical drilling risers will be up to 10 could be a substantial dollar potential for the
times the height of the Eiffel Tower [up to 3000 various composite applications. One producer
m (9800 ft)] and weigh over 2.2 x lo6 kg (2500 estimates the current usage of steel to be as high
tons). Syntactic foams control buoyancy and as 1.5-1.8 x lo9kg (1.7-2.0 million tons) used for
reduce the effects of sea loads from waves, oil- and gas-well downhole tubulars. Much of
currents and storms. The case for composites that could be displaced by composites (at one
is clear, as weight savings could exceed fifth the weight) because of their advantages in
544 000 kg (600 tons). A 900 kg (one ton) high specific strength, fatigue resistance, corro-
reduction in the offshore superstructure or the sion resistance, lighter weight, low coefficient
risers results in a savings of 272 kg (3 tons) of of thermal expansion and reduced installation
displacement load on the platform. Working cost (due to lighter weight)
948 Commercial and industrial applications of composites
by Hardcore Composites (New Castle, DE), reportedly buy most of their carbon
Seemann Fiberglass (Hanrahan, LA), and TPI fiber/epoxy rolls from Lincoln Composites.
(Warren, RI). Shafts from about 2-10 m (6-33 ft) long are
Composite auto hauler composite cars with fabricated using hybrid carbon fiber and fiber-
all-pultruded components of fiberglass/poly- glass in epoxy which are about one-fifth the
ester have been developed by W. Brandt weight, operate at faster speeds and use less
Goldsworthy & Assocs. (Torrance, CA) along energy than the conventional steel rolls.
with Alcoa Composites and Stoughton Fiberite (Wilmington, DE), Epoch Industries
Composites (Brodhead, WI) for the Union (Garland, TX), Addax (Lincoln, NE), and
Pacific. Many other freight car development Quality Composite, Inc. (Sandy, UT) are
programs are under way at Trinity Industries among others that fabricate such products.
and elsewhere. Corrosion resistance and light Amalga Composites, Inc. (Milwaukee, WI) is a
weight are the two primary benefits of com- more recent entry into the filament winding of
posites that are sparking this interest. carbon fiber/epoxy tubes for the industrial
rolls used in paper and plastic film converting
machinery and reportedly is a major supplier
43.4.31 RAILWAYS AND TUNNELS
to American Roller (Bannockburn, IL). They
Besides pultruded and filament wound com- use Grafil’s 33 msi carbon fiber but leave the
posite cableways, ducts and piping, there is a finishing and coating operations to American
vast array of associated molded parts for Roller. According to ARC, there are many
trackside, station equipment and furniture. potential applications for composite rolls.
Development of fiberglass reinforced pheno- These include replacing the steel rolls com-
lic-matrix composites, with their superior FST monly used in winder core, winder shaft, idler,
properties, has become an important contribu- layon and dancer/ transducer positions to
tor to the increasing acceptance of composites manufacture film, flexible packaging, foils,
for interior components. European countries magnetic audio and video tape and photo-
now virtually mandate using phenolic resin and pressure-sensitive papers on printing
composites for underground railcar and sta- presses, laminators, coaters and blown film
tion components. Some of ICI’s Modar lines. However, selecting the right composite
acrylic-modified polyester and also the less for each of these positions is not quite as sim-
flammable phenolic-based composites were ple as ordering an off-the-shelf product. ARC
used in the Channel Tunnel, mainly for electri- technical and marketing people make a special
cal cable tray. The market for composites in point of explaining why each composite roll
railways and tunnels could double during the should be customized to the end-user’s spe-
next few years due mainly to the greater atten- cific application and operating parameters,
tion being paid to safety, including improved especially because of the many types of com-
fire, smoke, and toxicity performance (reduced posite materials and structural designs
FST). available on the market today.
Another filament wound tube fabricator for
this application is SpyroTech Corp. (Lincoln,
43.4.32 ROLLS AND AIR SHAFTS
NE). Also, TPI (Warren, RI, and formerly
Industrial rolls and expanding air shafts used called Tillotson Pearson) has been using fila-
inside cardboard core tubes on winders to take ment winding to make fiberglass/epoxy and
up paper, films and foils will be major growth carbon fiber/epoxy tubes for paper mill rolls.
applications in the industrial composites sec- It is noteworthy that Mitsubishi Rayon in
tor. Tidland Corp. is said to be the world’s Japan is one of the largest suppliers of such
leading supplier of core shafts of all types and rolls in the world. These suppliers market the
Applications review 951
-
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- while other blade manufacturers had to fold
ment wound composite tubes are to be used when the market started to collapse several
for the high-speed rotors but most of the tech- years ago.
nology details remain proprietary to Urenco. Sandia National Laboratories (of
At this writing, Louisiana Energy Services Albuquerque, NM) developed advanced wind
continues with the approval process for the turbine technology using the vertical axis
required environmental impact report in sup- approach and signed a technology agreement
port of their license application. They hope to with Flo-Wind Corp. (Pleasanton, CA). Flo-
start construction soon, and have the new Wind has used extruded aluminum blades but
plant in full operation in the late 1990s. plans use of composite blades. Flo-Wind cur-
Similar composite centrifuge rotors are rently operates 'over 500' such turbines with
believed to be standard design for European aluminum blades currently in operation on
and Japanese uranium enrichment work. two California windfarms, likely candidates
for retrofit with composite blades. Glasforms
(San Jose, CA ) is one of their prime suppliers
43.4.37 VALVES
for composite parts.
Dresser Valve & Controls Division, Nil-Cor Competition continues to develop overseas.
Operations, (Alliance, Ohio), sells several Japan's Tomen Corp. has joined with
types of composite valves to the chemical American and British firms to build several
industry. Over 100 000 Nil-Cor advanced com- large wind power farms in Wales and
posite valves are currently in service at over Cornwall, UK, operated by a company called
100 USA paper mills. Their current valve prod- British Wind Farms, based in London.
uct line includes fiberglass and carbon fiber Included in their plans was the construction of
reinforced PPS, polysulfone and vinyl ester in 300 windmills with a total generating capacity
several sizes and types. Fiberglass reinforce- of 77 000 kW. Many European countries are
ment and Dow Chemical's Derakane 470 vinyl making sizable commitments to increased use
ester resin (among others) are used in ball and of windpower, including Denmark, Germany,
butterfly valves for the chemical industry. Holland and Spain.
The National Renewable Energy
Laboratory, a unit of the Department of
43.4.38 WIND TURBINE BLADES
Energy (formerly called the Solar Energy
TPI, Inc. located their composite wind turbine Research Institute), is in Golden, CO. They are
blade production in Portsmouth, RI. TPI interested in all types of alternate energy sys-
makes fiberglass/vinyl ester blades regularly tems, including battery-operated vehicles,
for large operators of wind energy farms in the engines that can use different types of fuels,
USA. The size of the individual generating including hybrids and biofuels. NREL spon-
units has gradually increased from the 50 and sored an effort called the 'Advanced Wind
100 kW sizes with 8 m (27 ft) composite blades Turbine Next Generation Preliminary Design
that were most common several years ago to Project', with the goal of bringing wind power
the larger 300-kW units that are now in generation costs down from the current 7-84
demand. Each of the three new size blades is to below the P 5 4 per kwh with coal genera-
17 m (56 ft) long and uses a sizable quantity of tion. Wind generators must be made of
material. Production rates have reached as materials likely to last at least 30 years, so the
high as 5000-6000 blades per year. Among the additional cost of using carbon or aramid
critical aspects of making large windmill fibers to reduce rotor blade weight and/or
blades is the need for proper balance. This is improve performance might be amortized
one reason that the TPI product has succeeded 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.
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
glass-reinforced polymeric composites and include strength, creep stiffness, and fatigue
other reinforced resins are composites while characteristics. For example, for anchoring a
metal alloys are not. Interest in the former sys- metallic hip prosthesis a high modulus
tems was associated with the need to replace crosslinked, filled methacylate 'grouting' or
or augment biological tissues which are com- bone cement is usually sought. For cementless
posites in their own rights. For instance bone, hip prostheses, carbon-fiber reinforced high
skin and blood vessels are typical natural com- performance thermoplastic polymers, such as
posites. In both natural and man-made poly(ether-ether ketone), PEEK, or aromatic
composites (or composite biomaterials) the poly sulfones (PS) are being explored.
strength and modulus of the matrix are depen- Cartilage is a low-load bearing, natural
dent on the shape, stiffness and orientation of composite and its synthetic substitutes can be
the reinforcing materials as well as their adhe- made of reinforced elastomers. Elastomeric
sion to the matrix. High modulus fibers tissues such as skin and blood vessels are
uniaxially oriented in a low modulus matrix made primarily of collagen and other biopoly-
can produce stiff solid composites with maxi- mers which impart compliance and elasticity.
mum strength and modulus along the fiber Synthetic substitutes of these tissues are far
direction as in carbon fiber-reinforced epoxy from being perfected. However, a key consid-
resins. Complex high density natural compos- eration is the use of an elastomeric polymer or
ites include cortical bones, dentin, cartilage as design to provide inherent or engineering
well as wood. Should air be a distinct phase of elasticity, respectively.
the composite, a foam is produced, as in syn- Bioceramics and particularly hydroxyap-
thetic sponges or lung tissues and cancellous atite (HA) have been used or proposed for use
bone (Park and Lakes, 1992). in many orthopedic and dental applications
Early application of hard or dense synthetic (Heimke, 1989, 1990). However, the mechani-
composites as biomaterials includes the use of cal properties of HA were not sufficient for
reinforced acrylics as dental fillings. The com- demanding load bearing applications, such as
posite resins consist of a polymer matrix such fracture fixation or spinal fusion, and this led
as crosslinked methacrylate resin and a stiff, to its limited use in this area (Bostman et al.,
inorganic filler including barium glass or silica. 1989). To address this issue, Knowles and
The methacrylate resin can be based primarily Bonfield (1993) developed a glass-reinforced
on the glycidyl methacrylate derivations of HA with enhanced mechanical properties.
bisphenol A. The choice of such components is Utilizing glasses of the types xNa,O-(l-x)
consistent with the repair site, i.e. dentin, P,O, and xCaO-(l-x) P,O, (where x = 0.2, 0.3
which in turn is a composite, made primarily and 0.5), a systematic study was conducted on
of collagen and microscopic inorganic crystals the effect of increasing network-modifying
of an apatite of calcium and phosphate. In gen- oxides in the glasses on the mechanical prop-
eral, the primary tissue of the teeth such as erties of composites containing 2.5 and 5 wt Yo
dentin is denoted as mineralized tissue where filler. The results indicate that HA reinforced
the primary function is load-bearing. A closely with CaO-P,O, glass at about 2.5 wt Yo is of
related tissue to dentin, both positionally and significant benefit to both the stabilization of
functionally is bone, which is a complex min- HA and production of high flexural bend
eralized collagen. The composition and strength composites. This is illustrated in Fig.
orientation of the bone components as load- 44.1. for three types of CaO-P,O, glasses
bearing composites vary in different bones. where that mole ratio CaO/P,O, was 20/80,
Thus, in designing synthetic devices for repair- 30/70 and 50/50 for composites designated as
ing bone, one has to take into account the C,P, C,P and C,P, respectively.
properties of the hard tissue in question. These
Orthopedic implant applications 959
-
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
Two FRP material systems are primarily Two classes of FRP composite fracture fixa-
being considered for femoral component tion devices have been primarily considered:
development: carbon fiber-reinforced polysul- nonabsorbable and fully absorbable. Compliant
fone (CF/PSF), and carbon fiber-reinforced nonabsorbable plates and nails have been
polyether etherketones (CF/PEEK) (Davidson, investigated as a means of avoiding stress
1987; Skinner, 1988). Several studies have shielding associated with the use of stiff metal-
addressed the effect of the biologic environ- lic components (Woo et al., 1976).
ment upon the mechanical material properties Unfortunately, clinical results have indicated
of these two composite materials with mixed that, in high load bearing applications such as
results. CF/PEEK has been demonstrated to be the tibia, compliant fracture fixation plates
very durable in physiologic saline environ- allow excessive motion at the fracture site caus-
ments when PEEK was APC2 grade (ICI, ing unacceptable levels of pain upon weight
Tempe, AZ) (Strait et al., 1991; D’Ariano et al., bearing (Tayton et al., 1982; Tayton and Bradley
1994;Zhang et al., 1994),while 380 grade PEEK 1983). This presents a ’Catch-22’ situation in
(IC1 Films Inc., Wilmington, DE) has been which compliant bone plates may only be able
found to be sensitive to hydrolytic degradation to be utilized in very low load bearing applica-
of the fiber/matrix interface (Meyer and tions, however, without high load bearing,
Latour, 1993). CF/PSF strength has been stress shielding is not a serious concern and
reported in separate studies to be both very compliant plates are then no longer needed.
stable (Overland et al., 1993) and significantly Whde the advantages of nonabsorbable com-
degraded by exposure to physiologic saline posite fracture fixation devices are therefore
and exudate environments (Strait et al., 1991; questionable, fully absorbable composite frac-
Latour and Black, 1992,1993).Biocompatibility ture fixation devices offer significant potential
studies of both CF/PSF and CF/PEEK com- advantages over currently used metallic
posite materials have suggested that, in bulk devices. These materials have the potential to
form, these materials should provide accept- be developed into components with sufficient
able biocompatibility for use in femoral initial stiffness and strength for load bearing
component applications (Wen et al., 1990). fixation, which are then slowly degraded and
However, the generation of wear debris from absorbed by the body following healing such
implant/bone abrasion, and subsequent that implant retrieval is unnecessary.
potential inflammatory reactions, is an impor- Two types of fully bioabsorbable compos-
tant concern. ites have been investigated: (1) polymer fiber
reinforced polymer, and (2) ceramic reinforced
polymer. Bioabsorbable polymeric materials
44.3.2 FRACTURE FIXATION DEVICES
for both fiber and/or matrix which have been
FRP composite material devices are being widely investigated are polyglycolic acid
developed for the replacement of metallic (PGA), polylactic acid (PLA), polydioxanone
plates, screws, pins, and nails for fracture fixa- (PDS) (Tormala et al., 1991; Bostman et al.,
tion. In contrast to joint replacement, these 1991), poly-e-caprolactone (PCL) (in’t Veld,
applications require only temporary implants. 1993), and polyhydroxybutyrate (PHB)
The ideal fracture fixation device would be (Knowles et al., 1992). More recently, bioab-
sufficiently rigid initially to provide adequate sorbable polycarbonates and ’pseudo’-
fracture stabilization, then gradually decrease polyamino acids have also been developed as
in stiffness over time to transfer stress to bone well (Pulapura and Kohn, 1992). Types of
after fracture union to avoid stress shielding, ceramic fibers which have been investigated
and then eventually disappear to eliminate the are phosphate glasses and calcium phosphate
need for retrieval surgery. 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
Composites for soft tissues 963
joint replacement (Wright et al., 1988). This, 44.4 COMPOSITES FOR SOFT TISSUES
however, proved to be a very poor choice of Composite biomaterials have been mostly
reinforcement. Wear resistance studies with associated with their use in conjunction with
this material provided mixed reports ranging
hard tissues. However, composites for repair-
from significantly decreased to significantly
ing or replacing soft tissues can potentially
increased wear rates (McKellop et al., 1981), become quite important due to the growing
while fatigue resistance was found to be actu-
interest in vascular and skin grafts, as well as
ally decreased by an order of magnitude
bioartifical organs. Simple devices such as
compared to the unreinforced UHMWPE
sutures for soft tissue repair have been
(Connelly et al., 1984). This behavior can be patented in composite forms. For instance,
explained by the very brittle nature of carbon composite silk sutures with compliant copoly-
fiber and the very low interfacial bond ester matrix have been described as having
strength between the fiber and matrix (Meyer lower tissue reactivity, and higher strength
and Latour, 1991). This combination leads to retention in the biologic environment as com-
rapid crack initiation and propagation and pared with wax-coated silk sutures (Shalaby,
third body wear during articulation via fiber Stephenson and Schaap, 1984). Composite,
fragment release. This incident in the history woven vascular prosthesis with absorbable
of implant design provides a clear example of [10/90 poly(^-lactide-coglycolide)] and non-
the complexities of composite materials absorbable (polyethylene terephthalate)
behavior, and demonstrates the fact that fiber segments, were made and used as model sys-
reinforcement of a polymer does not necessar- tems for studying the derivation of neointima
ily improve mechanical performance. in vascular grafts (Greisler et al., 1988).
Although carbon fiber was not a good Composite artificial blood vessels were pre-
choice for the reinforcement of UHMWPE, as pared by injecting water-soluble chitosan
the old saying goes, ‘the baby should not be derivatives (e.g. hydroxypropylchitosan) and
thrown out with the bath water’. Potential heparin into a microporous polytetrafluo-
improvement of wear, creep, and fatigue resis- roethylene tube followed by freeze-drying
tance of UHMWPE may still be achieved using (Yamamura et al., 1992).What may be consid-
other types of reinforcement. In particular, a ered as a bioartificial vascular graft is the one
reinforcement is required which has properties prepared by endothelial cell seeding of a
of high strength, high strain to failure, high woven synthetic graft using filtration tech-
bond strength to UHMWPE, high wear resis- nique (Idezuki, 1993). Thus, canine venous
tance, and which is as biocompatible as endothelial cells which were seeded onto a
UHMWPE in both bulk and particulate form. low porosity vascular prosthesis were
While UHMWPE is the most commonly allowed to grow around the fibers in early
used polymer for articulation, other composite periods. They then formed a monolayer on
systems have been investigated such as carbon the internal surface of the tube at later periods
fiber reinforced triacine resin and polymer in vitro. Properties of polyester fiber blends
fiber reinforced elastomeric composites were evaluated as totally (Greisler, et al.,
(Harms, 1984; Sutphin et al., 1993). Despite the 1988a) or partially (Yu and Chu, 1993)
failure of CF/UHMWPE articulation compo- absorbable vascular grafts.
nents, the reinforcement of polymeric Melt-blended absorbable polymers made of
articulation surfaces is still an active area of lactide and glycolide having the proper chem-
research for the development of improved ical composition to provide controlled
prostheses. 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.
REFERENCES
Daniels, A.U., Chang, M.K.O. and Adriano, K.P.
Andriano, K.P., Daniels, A.U. and Heller, J. 1992. 1990, Mechanical properties of biodegradable
Biocompatibility and mechanical properties of a polymers and composites proposed for internal
totally absorbable composite materials for fixation of bone. J. Appl. Biomater. 1: 57-78.
orthopaedic fixation devices. J. Appl. Biomat. 3: DAriano, M.D., Latour, R.A. Jr., Kennedy, J.M.,
197-206. Schutte, H.D. Jr. and Friedman, R.J. 1994 Long
Andriano, K.P., Daniels, A.U. and Heller, J. 1992. term shear strength durability of CF/PEEK
Mechanical Properties of Composites Reinforced composite in physiologic saline. Trans. SOC.
with Suvface-ModifiedAbsorbable Calcium-Sodium- Biomat., 17, 184.
Methaphosphate Microfibers. Proc. 4th World Davidson, J.A.. 1987. The challenge and opportu-
Biomat. Congr., Berlin, Germany. nity for composites in structural orthopaedic
Andriano, K.P., Daniels, A.U. and Heller, J. 1991. applications. J. Composites Techn. Res., 9(4):
Biocompatability and mechanical properties of 151-161.
totally absorbable composite material for Engh, C.A. and Bobyn, J.D. 1988. The influence of
implant use. Trans. SOC.Biomater. 14: 10. stem size and extent of porous coatings on
Andriano, K.P., Daniels, A.U., Smutz, W.P. and femoral bone resorption after primary cement-
Wyatt, R.W.B. 1993. Preliminary biocompatibil- less hip arthroplasty. Clin. Orthop. 231: 7-28.
ity screening of several biodegradable Fishbane, B.M. and Pond Sr., R.B. 1977. Stainless
phosphate fiber reinforced polymer. J. Appl. steel fiber reinforcement of poly-
Biomater. 4(1): 1-12. methymethacrylate. Clin. Orthop. Rel. Res. 128:
Black, Jonathan. 1992. Biological Performance of 194-199.
Materials. Fundamentals of Biocompatibility. New Gillett, N., Brown, S.A., Dubleton, J.H. and Pool,
York: Marcel Dekker Inc. R.P. 1985. Biomaterials 6 113.
Bobyn, J.D., Mortimer, E.S., Glassman, A.H., Engh, Goldring, S.R., Clark, C.R. and Wright, T.M. 1993.
C.A., Miller, J.E. and Brooks, C.E. 1992. The problem in total joint arthroplasty: Aseptic
Producing and avoiding stress shielding. loosening. J. Bone Joint Surg. 75A: 799-801.
Laboratory and clinical observations of nonce- Greisler, HI!,Dennis, J. W., Endean, E.D., Ellinger,
mented total hip arthroplasty. Clin. Orthop. 274: J., Buttle, K.F. and Kim, D.U. 1988 (a).
79-96. Derivation of neointima in vascular grafts:
Bostman, O.M. 1991. Current concepts review. Circulation 78 (3 pt. 2) 1-6-12.
Absorbable implant for the fixation of fractures. Greisler, H.P., Endean, E.D., Klosak, J.J., Ellinger, J.,
J. Bone Joint Surg. 73-A: 148-153. Dennis, J.W., Buttle, K. and Kim, D.U., 1988 (b)
Bostman, O., Hirvensalo, E., Vainionpaa, H., Polyglactin 910/polydioxanone bicomponent
Makela, A., Vihtonen, K., Tormala, P. and totally absorbable vascular prosthes. J. Vasc.
Rokkanen, P. 1989.Ankle fractures treated using Surg. 7: 697-705.
biodegradable internal fixation. Clin. Orthop. Harms J., Mittelmeier H., and Mausle, E. 1984.
238: 195-203. Results of animal studies on the use of carbon
Buckley C.A., Lautenschlager E.P. and Gilbert J.L. fiber-reinforced plastic protheses. In The
1991. High strength PMMA fibers for use in a Cementless Fixation of Hip Endoprostheses. (ed. E.
self-reinforced acrylic cement: Fiber tensile Morscher), pp. 249-251. New York: Springer-
properties and Composite toughness. Trans. SOC. VerIag.
Biomat. 14: 45. Heimke, G. 1989. (Ed.) Bioceramics Vol. 1, Ishiyaku
Callaghan, J.J. 1990. Total hip arthroplasty. Clinical Euro-America, Japan.
perspective. C h . Orthop. 276: 3340. Heimke, G. 1990. (Ed.) Bioceramics, Vol. 2, Cologne,
References 965
Topoleski, L.D.T., Ducheyne, P. and Cuckler, J.M. Woo, S. L.-Y., Akeson, W.H., Coutts, R.D.,
1992. The fracture toughness of titanium-fiber- Rutherford, L., Doty, D., Jemmott, G.F. and
reinforced bone cement. J. Biomed. Muter. Res. 26: Amiel, D. 1976. A comparison of cortical bone
1599-1617. atrophy secondary to fixation with plates with
Tonio, A.J. and Folmer, R.C.H. 1987. The clinical use large differences in bending stiffness. J. Bone
of plastic plates for osteosynthesis in human Joint Surg. 58-A: 190-195.
fractures. Clin. Muter. 2: 275-279. Wright, T.M. and Trent, P.S. 1979. Mechanical prop-
Tormala, P., Vasenius, J., Laiho, J., Pohjonen, T. and erties of aramid fibre-reinforced acrylic bone
Rokkanen, P. 1991. Ultra-high-strength cement, J. Muter Sci. Letts. 14: 503-505.
absorbable self-reinforced polyglycolide (SR- Wright, T.M., h a c , C.M., Faris, P.M. and Bansal,
PGA) composite rods for internal fixation of M.. 1988. Analysis of surface damage in
bone fractures: In vitro and in vivo study. J. retrieved carbon fiber-reinforced and plain
Biomed. Muter. Res. 25: 1-22. polyethylene tibial components from posterior
Vainionpaa, S., Kilpikar, J., Laiho, J. Helevitro, P., stabilized total knee replacements. J. Bone Joint
Rokkanen, P. and Tormala, P. 1987. Strength and Surg. 70-A: 1312-1319.
strength retention in-vivo of absorbable, self- Yamamura, K., Sakurai, T., Kizawa, H. and Harada,
reinforced polyglycolide (PGA). Biomuteriuls. 8: H. 1992. Jap. Pat. Appl. 92-58845; Chem. Abstr.
46-47. 119(24):2565852.
Wagner, H.D. and Cohn, D. 1989. Use of high-per- Yu, T.J. and Chu, C.C. 1993. Bicomponent vascular
formance polyethylene fibres as a reinforcing grafts consisting of synthetic absorbable fibers.
phase in poly(methylmethacry1ate) bone J. Biomed. Muter. Res. 2 7 1329-1339.
cement. Biomuteriuls. 10: 139-141. Zhang, G., Latour, R.A. Jr., Kennedy, J.M., Schutte,
Wen, L.M., Merritt, K., Brown, S.A., Moet, A. and H.D. Jr. and Friedman, R.J. 1994. Long term
Steffee, A.D. 1990. In vitro biocompatibility of compressive strength durability of carbon fiber
polyetheretherketone and polysulfone compos- reinforced PEEK composite in physiologic
ites. J. Biomed. Mater. Res. 24: 207-215. saline. Trans. SOC.Biomuteriuls, 17: 160.
SCIENTIFIC APPLICATIONS OF COMPOSITES 45
Vicki P. McConnell
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 Coronograph Spectrometer (UVCS), designed
toughness than either epoxies or BMIs. Lastly, as an occulted telescope to focus on solar
HST’s high-resolution spectrograph optical winds (McConnell, 1993~).As with HST, opti-
bench was manufactured by Hercules cal mechanisms require accurate and
Aerospace Co. (Magna, UT) to specifications repeatable positioning, so UVCS’s design cen-
from Ball Aerospace Systems Group (Boulder, tralized upon a three-segment carbon
CO). Carbon fiber/epoxy offers CTE equal to fiber/epoxy structure. Ball Aerospace Systems
quartz and maintains 2 m (6.5 ft) of optical sur- Group and COI built the seven-sided truss of
faces to within 0.0254 mm (0.001 in). flat panels that result in cylindrical shape.
Launched in December 1995, the Solar and Some 80 separate stability requirements had to
Heliospheric Observatory (SOHO) was be met, along with strict mass requirements
designed to be pointed directly at the Sun to (the structure weighs 21.7 kg (48 lb) but sup-
study the interactions between the Sun and ports 91.6 kg (202 lb) of instrumentation), and
Earth’s environment. The largest moving the ability to survive launch loads of 18G.
instrument aboard SOHO is the Ultraviolet High-modulus pitch-based carbon fiber /epoxy
970 Scientific applications of composites
prepreg met weight, mass and optical stabil- to the central cylinder, large curved and coni-
ity parameters with no outgassing or cal shell structure, mirror support sleeves, and
microcracking. Especially thin prepreg solar array panels. Eastman Kodak built the
(0.063 mm (0.0025 in) cured ply thickness) 2643 long optical bench that forms the main
also enhanced the thermal conductivity of the structural element, with carbon fiber skins
fiber, an added stability factor (Kilpatrick, over honeycomb core.
1992).
LDEF composite specimen testbed
AXAF orbiting observatory Proof positive of the hostile effects of space
Slated for launch from the Space Shuttle in startled cosmonauts on the Mir space station
August 1998, the Advanced X-Ray in 1992 when they found not a shred
Astrophysics Facility spacecraft will bridge remained of the Soviet flag after a year in
the gap between the two Great Observatories orbit on the station's exterior. Further proof
currently in orbit: Hubble Space Telescope and comes in data retrieved from NASA's Long
Compton Gamma Ray Observatory. Duration Exposure Facility (or LDEF), a 12-
TRW (Redondo Beach, CA) is prime con- sided circular spacecraft launched into low
tractor for AXAF and the spacecraft will Earth orbit (LEO) from the Challenger shuttle
contain four sets of unique cylindrical, grazing in April 1984 and retrieved in 1990 (Fig. 45.2).
incidence mirrors. These are mounted concen- By 1993, postflight analysis of the 86 experi-
trically in a nested array. Carbon fiber/epoxy ment trays containing more than 10 000
is used in equipment compartments attached different material specimens has been carried
out by a team of international scientists. (Fig. 45.3). Atomic oxygen is identified as the
Research on LDEF's composites specimens most detrimental factor to polymer-matrix
has provided a benchmark for next-genera- composites, especially on uncoated surfaces
tion space materials, such as those that make (George, 1992). Erosion has been observed to
their way onto the international space station 0.127 mm (0.005in) (about one ply of laminate)
(Stein, 1993). on leading edge components made from car-
The six-year duration of LDEF's exposure bon fiber with epoxy, polyimide and
to the LEO space environment provided the polysulfone matrices.
longest term flight data ever retrieved for Micrometeroid damage was not cata-
analysis at that time. Post-retrieval sympo- strophic on any LDEF specimens, but can
siums have shared analytical conclusions, compromise surfaces and lead to substrate
and NASA selected M/Vision software from erosion (Blair, 1992) (Fig. 45.4).Another con-
PDA Engineering (Costa Mesa, CA) as one clusion drawn based on post-flight analysis
format for the sizeable LDEF Materials was that predicting erosion rates and formu-
Database which contained research informa- lating material with enhanced A 0 resistance
tion on about 35% of the LDEF materials by should key on fiber resistance as the dominant
the end of 1994. factor. A prediction model for A 0 erosion
An important conclusion drawn from LDEF yield in polymer materials has been developed
specimen analysis is that environmental (Tennyson, 1993), based on the repeatable
effects are dependent upon the location of atomic composition of the polymer.
composite hardware on a spacecraft - leading An LDEF follow-on spacecraft, the
or trailing edge, shielded or unshielded from European Retrievable Carrier (EURECA) was
degradation factors (only metal matrix com- retrieved by the shuttle Endeavor in June, 1993
posites with aluminum matrices showed no after 11 months in a 370 km (230 mile) orbit.
location-dependent degradation; magnesium- EURECA's mission focused on materials and
matrix composites oxidized on sample edges) fluids in low microgravity and LEO exposure
Fig. 45.3 LDEF orientation in orbit. (Reprinted with permission of Bland A. Stein, NASA Langley Research
Center.)
972 Scientific applications of composites
(cryogenic to 2760°C (5000°F)). R&D efforts necting rods and other engine parts. Thin-
resulted in innovative materials science gauge titanium aluminide foil has been tested
among five composite categories (Mcconnell, in heart valve assemblies and pacemaker cases.
1990), with more than 2000 airframe and Adaptation of computational fluid dynamics
scramjet propulsion components, structure, (CFD) - the study of high-speed laminar air
and systems built (Table 45.1). flow developed to maximize NASP's body con-
Until October 1994, NASP represented the figuration - has proven useful in analyzing
hypersonic flagship program of the USA. At aircraft and automotive aerodynamics, as well
that time, the initial program goals transitioned as blood flow in artificial hearts. Dr. Steve
into the hypersonic system technology pro- Charles of the Center for Retina Vitreous
gram (HYSTP), funded jointly by the US Air Surgery (Memphis, TN) began work with the
Force and NASA and which will focus on Rockwell Science Center (Thousand Oaks, CA)
development of hypersonic scramjet propul- in February 1992 to apply NASP-developed
sion. Yet resulting scientific R&D from the CFD to modeling fluid flow inside the eye. CFD
NASA program generated considerable tech- will help analyze the role played by rapid eye
nology transfer to a broad range of commercial motion (up to 600"/s) in retinal detachment,
applications, including oilfield pipe, auto and possibly enhance the precision of surgical
engines and hip joint implants. One of the tita- procedures. Dr. Charles performs some 15 000
nium MMCs developed did not exist before the vitreous retinal surgeries annually and ulti-
NASP program and is 100 times more resistant mately expects to use CFD to design a new
to corrosion than standard aircraft titanium. suite of surgical tools, 'applying hard science
An aluminum/beryllium alloy tested in NASP rather than guesswork to the entire tool set'.
heat exchanger prototypes has since found
application in computer actuator arms, provid- 45.2.3 DELTA CLIPPER EXPEFUMENTAL
ing a 20% increase in data access speed. Big LAUNCH VEHICLE (DC-X SSTO)
Three automakers have studied NASP-devel-
oped titanium MMCs and alloys to cut weight Under a $60 million contract from the Ballistic
by 50% in valves, piston rings, cam shafts, con- Missile Defense Organization, McDonnell
Douglas Aerospace (Huntington Beach, CA) -73°C (-100"F), the aeroshell incorporated
developed its Delta Clipper experimental pro- built-in longitudinal longerons to handle
totype (DC-X) to prove the practicality, engine/truss, parachute deployment and
reliability, operatability and cost efficiency of a landing gear loads.
reusable single-stage-to-orbit (SSTO) flight Glass fiber/epoxy was used in the 762 mm
vehicle. Comparative figures suggest that (2.5 ft) tall nose cone since it required signal
reusable rockets like a full-scale DC-X could transparency for antennae. McDonnell
reduce commercial/military payload delivery Douglas decided that carbon fiber/epoxy
costs to under $500/lb - an attractive alterna- skins over syntactic foam in the DC-X base
tive to the $10 OOO/lb for the Space Shuttle heat shield provided the best material system
(1993 figures). for meeting weight, price, and scheduling
The one-third scale DC-X prototype had demands. The shield (about 396 mm (13 ft) on
completed five suborbital flight tests before a side) featured a unique 'super circle' sec-
being grounded by an on-board explosion that tional design, joined with titanium fasteners.
damaged the composite aeroshell. Despite this Both the prime and subcontractor worked to
accident, DC-X landed safely and the shell the philosophy of building real structures to
was repairable. Data collected in the first flight collect and prove data before moving on to
test series formed the advanced technology more expensive program goals, something of a
backbone for an upgraded DC-XA vehicle, first in such R&D efforts.
developed jointly by McDonnell Douglas The durability of composite aeroshell mate-
(now the Boeing Co.) and NASA (with some rials and overall system design was proven in
$43 million in NASA funding) in 1995. The the June 1994 explosion; according to the pro-
DCX-A was renamed the Clipper Graham in gram director, the 1220by 4570 mm (4 by 15 ft)
1996, and completed several milestone flights vertical tear would probably have demolished
that year: altitude of 10 300 ft with 550 ft lat- other launch vehicles. McDonnell Douglas
eral movement, and a second flight 26 hours developed and fabricated a robust carbon
after the first to demonstrate rapid turn- fiber/epoxy liquid hydrogen tank for DCX-A
around. in 1996,8 ft in diameter and 16 ft tall, but 33%
Rapid prototyping played an essential role lighter than previous aluminium alloy tanks.
in the cost effectiveness of building the DC-X
prototype, including construction of compos-
45.2.4 GROUND-BASED SCIENTIFIC
ite aeroshell, nose cone, and base heat shield
INSTRUMENTS
components (McConnell, 1993~). The aeroshell
and nose cones were fabricated by Scaled
Wind tunnel blade
Composites (Mojave, CA); five aerodynamic
composite flaps on the carbon fiber/epoxy While CFD places air-flow analysis within the
aeroshell provided the ability to ascend nose domain of computer mathematics, there is
first and return to Earth for a 'tail sitter' land- nothing quite like proving an aerodynamic
ing. Composites accommodated the program's concept in a wind tunnel. At NASA's Ames
ambitious scheduling with rapid aeroshell Research Center (Moffett Field, CA), different-
construction (nine months) and by allowing sized wind tunnels can accommodate small
continuing modifications without huge cost models of experimental structures and shapes
overruns. Lay-up of woven fabric composite as well as full-scale vehicles (such as tractor
skins over foam core resulted in aeroshell wall trailers and an F/A-18 aircraft). Compressors
thickness range of 12.7-38.1 mm (0.5-1.5 in). generate high-speed air flow with rotating
Besides enduring external temperatures to blades, usually constructed of aluminum or
149°C (300°F) and internal temperatures to 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 posite prototype support post tubes were fab-
design was based on a dual ring of 10 000 elec- ricated to test various designs to balance
tromagnets accelerating needle-thin proton multiple performance parameters with cost
beams at 20 trillion eV cryogenic temperature constraints (Sondericker 1991; Nicol 1992,
and ultrahigh vacuum. After a decade of work 1993; Hiller, 1991, 1992, 1993). Material and
and investment of $2 billion, however, process systems examined included continu-
Congress cancelled the program. While much ous carbon fiber/epoxy laminates,
was made in the national press about the injection-molded chopped glass fiber/PEI,
wasted effort (and the huge hole in the and RTMd glass fiber/bismaleimide.
ground), SSC composites research has yielded Machine-woven near-net shape preforms were
unprecedented results that were directly also considered, along with RTMd phenolic
applicable to other ongoing high-energy triazine (McConnell, 1991a) (Fig.45.9). In other
physics applications (such as the Relativistic components, such as coil spacers and end
Heavy Ion Collider at Brookhaven National parts, the predominant prototyping method
Laboratory in Upton, NY, the Tevatron was machining glass fiber/epoxy, though
Collider at Fermi National Accelerator options considered included highly
Laboratory in Batavia, IL, the Tokomak crosslinked BMI doughs and other polyimide
Physics Experiment in Princeton, NJ, and the resins with chopped glass, fabricated by low-
European International Thermonuclear pressure techniques such as structural RTM.
Experimental Reactor). 'Magnets were built for SSC that were never
For SSC dipole magnets (each nearly 18 288 seen before in the world', recounts John
mm (60 ft) long and weighing 11 340 kg (12.5 Morena, who served as the primary compos-
tons)) and smaller quadrupole magnets, com- ites materials and processes advisor on the
Fig. 45.9 Glass fiber/epoxy end saddles were fabricated and tested for Superconducting Supercollider
magnets. (Source:Brookhaven National Laboratory.)
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 intriguing required; 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
1991b. Progress report: composites in space- trains. Paper 66-WA/RR-5 read at ASME
craft. Adv. Comp., July/Aug: 26-34.1992a. Flight Winter Annual Meeting Nov. 27-Dec. 1,in New
vehicles of the future. Adv. Comp., Jan/Feb: York City.
28-34. 1992b. Tough promises from cyanate Shaw, P.1993. Overview of maglev vehicle struc-
esters. Adv. Comp., May/June: 28-37. 1993a. tural design philosophy, material selection, and
Composites ride the rails. Adv. Comp., manufacturing approach. Paper read at Maglev
March/April: 28-37. 199310. Surviving space: a 93 conference May 19-21, at Argonne National
program and materials quandary. Higk- Laboratory.
Performance Composites, Nov/Dec: 22-28. 1993c: Sondericker, J.H. 1991. Alternate concepts for struc-
Focus on design: telescope structure. Higk- turally supporting the cold mass of a
Performance Composites, Nov/Dec: 54-56. superconducting accelerator magnet. Proc.
Morena, John. 1994. Invaluable materials science IlSSC 3, New York, Plenum Press, pp. 175-189.
from Super Collider. High-Performance Stein, Bland A. 1993. LDEF materials overview.
Composites, Jan/ Feb: 12-1 3. Second Post-Retrieval Symposium, LDEF-69
Nicol, Thomas H. 1992. SSC 50mm collider dipole Months in Space, NASA Conference Publication
cryostat single tube support post conceptual 3194, (ed. Arlene S. Levine), Vol. 3, pp. 741-789.
design and analysis. Proc. IISSC 4, New York: Tennyson, R.C. and Manuelpillai, G. 1993. Analysis
Plenum Press, pp. 747-755.. of LDEF micrometeroid/debris data and dam-
Nicol, Thomas H. 1993. Single tube support post age to composite materials. Second
thermal analysis and test results. Paper read at Post-Retrieval Symposium, LDEF-69 Months in
IISSC 5, May 6-8, in San Francisco, CA. Space, NASA Conference Publication 3194, (ed.
Peterson, Ivars. 1992. Flash tracks-building an eye- Arlene S. Levine), Vol3, pp. 493-512.
piece for a particle accelerator. Science News 142,
July 4: 8-9.
Powell, James and Danby, Gordon. 1966. High
speed transport by magnetically suspended
CONSTRUCTION 46
Ever J. Barber0
concrete decks that corrode rapidly under the vice for more than twenty years atest the excel-
attack from de-icing chemicals. For example, a lent corrosion resistance of fiberglass
pultruded deck was used to construct the reinforced composites. The following exam-
Wick Wire Run vehicular bridge on public ples of fiberglass reinforced isopolyester resin
road 26, in Taylor County, West Virginia (com- applications, described extensively in the
pleted August 1996).An added advantage of a excellent review by Adams and Bogner (1993),
composite deck would be the weight reduc- illustrate the feasibility of constructing com-
tion that supposedly would allow the user posite structures and using them for many
(highway department) to re-rate some bridges years. A three mile pipe of diameter 254 mm
for a higher live load without major modifica- (10 in) is reported in service since 1971. Fifteen
tions to the existing superstructure. The live miles of piping, carrying saline water with
load could be increased by approximately the temperature up to 50°C (112"F),pressure up to
same amount of dead load saved with the use lo6 N/m2 (10 bar), and exposed to sunlight has
of the composite deck minus adjustments for been in operation in Saudi Arabia since 1983
dynamic effects. Other applications where without problems. An old sewage duct was
weight savings are important are cladding of lined in 1971, then inspected in 1991 showing
buildings, rehabilitation of chimneys, etc. no sign of deterioration. More than 300 000
underground fuel tanks are in use in North
America alone. Some of these have been in
46.2 CURRENT APPLICATIONS
operation for more than 26 years without
Current applications of composites in con- problems. Internal or external lining of steel
struction can be classified by the major tanks has been common practice for more than
advantage of the composite material that is twenty years in the oil industry to protect and
exploited. The main ones are corrosion resis- reinforce the bottom of steel tanks that are cor-
tance and magnetic transparency. An roded internally because of corrosive
alternative classification may be based on the substances in the oil or externally because of
type of construction. Composites are used in contact with soil. Wine tanks have been in
the form of structural shapes (similar to steel operation for more than 20 years without
construction), as reinforcement for concrete, problems. Ducts carrying chlorine gases and
cables, and for rehabilitation of existing struc- sulphur dioxide, in use since 1962, and tanks
tures. Reinforcement of concrete may be in the holding hydrochloric acid, in use since 1964,
form of conventional reinforcement, pre- remain in perfect condition. A chimney
stressed concrete, or post-tensioned structures. exposed to organic chemicals, water vapor,
Rehabilitation applications include repairing and temperature up to 60"C, in operation since
deteriorated structures as well as increasing 1968 is reported. Chimneys are important con-
the load carrying capacity of sound structures struction applications because they are load
to re-rate them for higher load capacity. carrying structures designed for large wind
Some of the recent applications of compos- loads. A detailed account of recent applica-
ites in construction of civil infrastructure will tions of composites in construction, classified
be described in the next section. Further exam- by the type of construction, follows.
ples of applications can be found in previous
reviews (Barbero and GangaRao, 1991,
46.2.1 REINFORCEMENT OF CONCRETE
GangaRao and Barbero, 1991), professional
journals ( e g SAMPE Journal, ASCE Journal) Concrete can be reinforced with fiber rein-
and edited books (Mufti, Erki and Jaeger, forced composites, with fibers mixed in the
1991a, 1991b; Iyer, 1991, Neale and Labossiere, concrete, or by polymers added to the concrete
1992).Applications to pipes and tanks in ser- mix. This article will concentrate on the use of
984 Construction
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
I
J. I
I
reinforcement. Sen (1992) used the anchorage
developed by Iyer at South Dakota School of
Mines and Technology. Efficient utilization of
r,_
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
stress of one third the static tensile strength. on the transfer of the axial load in the cable,
by shear in the grouting material, to the
Post-tensioning anchor. Attaching the anchor to the tendons is
a labor intensive process. The resin used to
Post-tensioning of concrete with steel or com- bond the tendons to the anchor may creep,
posite tendons is performed to induce a state leading to loss of pre-stress. This anchor was
of compressive stress in the concrete similarly used to partially post-tension several bridges.
to pre-stressing, but post-tensioning is per- Cases have been reported where individual
formed at the construction site. A hole or tendons slipped and broke at the anchor dur-
some kind of access is left in the concrete to ing post-tensioning at the bridge site. Porter
thread the post-tensioning cables through. and Barnes (1991) report several anchorage
Tensile force is applied to the tendons against systems. To avoid the problems that all pot-
the concrete structure before the structure is ted type anchors have, Ahmed and Plecnik
loaded by the service loads. The anchorage (1989) developed a filament wound cable
system is subject to severe requirements. First, where continuous fibers are wound around
it must sustain the tension load for the whole the end eyes of the cable. Each cable must be
life of the structure, which requires very care- custom made for the required length, but the
ful design against creep in the anchor. Second, problems of potted type anchors are elimi-
the anchor should be resistant to corrosion as nated.
the tendon itself if the non-corrosive proper- The Bachigawa-Minami-Bashi bridge (Koga
ties of the system are the objective of replacing et al., 1992) uses both pre-stressing and post-
steel tendons. The reduced weight of the ten- tensioning carbon fiber tendons. The
dons is not very important because the heavy Schiessbergstrasse bridge in Germany and the
weight of the concrete structure. While the Notch bridge in Austria (Wolf and Miesseler,
stress losses of fiberglass tendons are smaller 1992), use partial post-tensioning with fiber-
than those of steel cables, it is difficult to jus- glass cables. Some of the tendons that form a
tify the use of more expensive and novel cable contain sensors (copper wire or fiber
composite tendons for this reason alone. optical gauges) to monitor the strain level,
Therefore, corrosion resistance is the main integrity of the tendon, and location of even-
objective of using composite tendons. In this tual damage. A demonstration bridge was
case the anchorages should be resistant to cor- built in 1990 by the Sumimoto Construction
rosion. Also, the structure to be post- Co. in Oyama, Japan, using a single concrete
tensioned is usually made of reinforced con- box girder, post-tensioned with aramid com-
crete (although the reinforcement is not posite rods produced by Teijin Co. The
sufficient to carry all the load). If corrosion is internal tendons are placed in a parabolic
a problem, the conventional reinforcement housing in each web and post-tensioned with
(not pre-stressed or post-tensioned) may also steel grouted anchorages to a permanent stress
have to be made of composite material rebars. of 25% of the static tensile strength of the ten-
Anchors for post-tension applications are dons. The external tendons are placed at the
still being developed and evaluated. bottom of the box girder and post-tensioned,
Meisseler and Preis (1989) report on an with grouted anchorages built with composite
anchor developed to hold glass reinforced casings for added corrosion protection, to a
tendons. The anchor is of the potted type, in permanent stress of 10% of the static strength.
which the tendons comprising a cable are Besides the composite post-tension cables, the
spread at each end and potted in a steel regular reinforcement of the girder uses epoxy
anchor with some grouting material, usually coated rebars. Further details are given by
a polymer. The potted type anchors are based Mufti, Erki and Jaeger (1991a).
988 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
three bridges of 6.1 m (20 ft), 9.75 m (32 ft), of the pultruded glass-polyester deck (Fig.
and 15.24m (50 ft) (Fig. 46.7) using their 46.8). The bridge is 113m (370ft) long and
design and construction method, called 2.23 m (7.3 ft) wide, with a main span of 63 m
PRESTEK. Given the low stiffness of E-glass (206 ft). The deck and towers are constructed
reinforced pultruded composites when com- with Maunsell's interlocking panels (ACCS
pared to steel, conventional steel or concrete System by Designer Composites Technology
designs are not efficient when implemented Ltd), pultruded with 70% volume of fiberglass
with composites. The PRESTEK system uses a reinforcement and isophthalic polyester resin,
beam-truss geometry of pultruded tubes pre- then bonded together with an epoxy adhe-
stressed with aramid or steel cables. The three sive. The cable stays are Parafil ropes, a
bridges are a king-post truss, a queen-post Kevlar fiber core in a polyethylene sheath.
truss and a bow-string truss respectively. The bridge deck was designed to be modular
Maunsell Structural Plastics in Beckenham, so that every component could be handled by
Kent, England, with the participation of GEC hand. The heaviest module, a 6 m (19.7 ft) by
Reinforced Plastics (pultrusion manufactur- 0.6 m (2 ft) plank weighed only 66 kg (145 lb).
ing), Scott Bader Co. Ltd (resin supplier), The weight of the deck is only 150kg/m
Vetrotex UK (glass reinforcement), Ciba Geigy (lOOlb/ft) and each tower weighs only
Plastics (adhesives), Linear Composites 2500 kg (5511 lb), facilitating erection and
(Parafil cable stays), R. O'Rourke and Sons reducing the cost of the foundation. The com-
(construction management), and University posite system has class 2 fire resistance rating.
of Dundee, constructed a pedestrian bridge
over the river Tay in Aberfeldy, Scotland. The
Bridge enclosures
pultruded deck is cable stayed from two A-
frame towers, 17.5m (57 ft) high, to provide The A19 Tees Viaduct in Middlesbrough, UK, is
for adequate stiffness despite the low stiffness a steel-concrete bridge with 117 m (383 ft) span
Current applications 993
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 Fig. 46.9, over the railway station. Pultruded
steel plate girders was taking place. plank and connector sections are joined to form
Maintenance (e.g. painting) and rehabilitation a floor system suspended from the steel girders
work are difficult since the viaduct spans over of the bridge. Pleasant appearance was
railroad tracks. A composite material enclosure required since the bridge is located in a resi-
was built in 1989 to prevent further deteriora- dential area and over the railway station. Light
tion by isolating the bridge from the weight and low maintenance costs were cited
environment and to facilitate maintenance and as additional advantages of composites for this
rehabilitation. A floor area of 16000m2 application.
(172 200 ft2)using 250 metric tons (275 US tons)
of composite material was created under the
Cooling towers
bridge by interlocking pultruded panels
wrapped around the steel girders of the bridge The resistance of composite materials to
to create a box. The enclosure system was humidity and creep under sustained loads has
designed by Maunsell StructuralPlastics Ltd, of been demonstrated by their successful appli-
Beckenham, Kent, UK. The system uses inter- cation to cooling towers, in operation for more
locking panels designed by Maunsell and than twelve years (Fig. 46.10). Cooling towers
fabricated by GEC Reinforced Plastics Ltd, are permanently loaded with the heavy
while the main contractor was Fairclough weight of the ceramic filling used for cooling.
Construction Ltd. The enclosure system has These towers are built by Ceramic Cooling
been also used in the construction in 1992 of the Towers of Forth Worth, TX, entirely of com-
enclosure to the Bromley South Bridge, seen in 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.)
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.
Design considerations 997
The sigruficance of the shear deflection with the length of the member. Lateral forces (e.g.
respect to the bending deflection varies with wind forces) and bending moments (e.g.
the span, the larger the span the lesser the influ- eccentric loading) are considered secondary
ence of shear. Sometimes, properties of beams forces, which are dealt with separately.
are reported without distinction between the Column performance is limited by one of two
bending and shear components, using an failure mechanisms, crushing and buckling.
apparent value of modulus Eapp= Dy/lyy,where Crushing is the failure of the material because
D,, is the bending stiffness with respect to the of excessive compressive stress, similar to
strong axis. The bending stiffness with respect yield of steel. Buckling is more frequent in
to the weak axis Dx cannot be accurately composite columns because thin-walled sec-
obtained as Dx = EapIxx. The apparent stiffness tions are preferred. A thin-walled section may
Eappis then used in &e classical deflection for- experience at least three different types of
mulas (for steel) that do not account for shear buckling, which are described next.
deformations. The reported values are usually Long and slender columns fail in a global
based on three-point bending tests, performed sense when the axial load reaches a critical
at the factory with a specific span, which is sel- value P,, For load values lower that the criti-
dom reported. The results of using the classical cal load the column remains straight. When
(steel) deflection formulas for spans or loading the load reaches critical value, the column
other than that of the test are only approximate. experiences sudden lateral deflection. The
The main modes of failure of beams in axial stiffness after buckling is much lower
bending are: (a) compression crushing of the than the stiffness before buckling. Therefore,
compression flange; (b) local buckling of the the lateral deflections are quite large and they
compression flange; (c) tensile rupture of the usually precipitate another mode of failure
tension flange; (d) shear failure of the web; like crushing of parts of the cross section, lead-
and (e) web buckling. Since each part (panel) ing to collapse.
of the cross section can be built with different The concept of slenderness allows us to
materials, the failure mode can be controlled compare members of different cross sections
by design. Local buckling modes can be elimi- and column lengths for their tendency to
nated by increasing the thickness and buckle. For a composite column, the slender-
choosing the fiber orientations properly ness is defined as
(Barber0 and Raftoyiannis, 1993). The com-
pression strength of composites is lower than = L&) (46.1)
the tensile strength. Therefore, a symmetric
section is not the most efficient cross section. where P, is the local buckling load, D is the
Symmetric sections fail in the compression bending stiffness, and Le is the effective
flange first. Tensile failure may occur in length of the column, which is used to
unsymmetric sections, when the compression account for different end conditions (Gere
flange works with composite action with a and Timoshenko, 1990, p. 589).
deck, etc. Shear failure is less likely to occur in Short and stubby columns, which have a
sections with multiple webs. Incorporation of low Slenderness value, are less likely to buckle
off-axis fibers (cloth, mats, etc.) increases the in a global mode as described previously.
shear strength. However, individual parts (flange or web) of
the cross section may buckle locally. Local
buckling is very likely to occur in composite
46.3.2 COLUMNS
columns because they are commonly thin
Columns are structural members subjected walled. The compressive stress required to trig-
primarily to compression forces acting along ger local buckling increases with the thickness
998 Construction
of the cross section and the local stiffness of the 0.5 and 1.5 show some type of interactive phe-
material. The narrower the flange or web nomenon. The interaction occurs between the
under consideration, the higher the local buck- local mode, the global mode, and crushing.
ling load P,. The wavelength of local buckling Interaction results in lower buckling loads
is independent of the length of the column for than those predicted by any of the modes act-
columns of practical lengths. ing alone.
Flange buckling of open section members is There are many situations of practical inter-
triggered by pure compression.It occurs during est for which the buckling loads required to
compression of columns and on the compres- produce two or more failure modes (Euler,
sion flange of beams in bending. Web buckling local, crushing) may be very close. In this case
is initiated by shear and it occurs during bend- the failure modes interact. That is, the proxim-
ing of beams. Web buckling of open section ity of the stresses to more than one mode of
columns is not common because most open sec- failure causes the structure to fail at a lower
tions have wide flanges that buckle first. There stress value that predicted by either of the
is of course no distinction between flanges and modes involved should they be acting sepa-
webs in closed section columns. Unlike steel rately. Euler and local modes interact to give
structural shapes, composite closed sections are an overall strength deterioration. Interaction
easier to produce and structurally more effi- must be taken into account because the
cient than open section members. strength values predicted by either isolated
Local buckling can be prevented by choos- mode fit are not conservative. The failure load
ing the section geometry and material of a column (Po) taking into account local,
properties. Global buckling can be prevented global, and interaction phenomena simultane-
by a combination of section geometry, material ously can be obtained from the following
properties and bracing. If all buckling modes design equation (Barbero and Tomblin, 1993)
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 The column properties needed to use this
thickness of the flange or web and the geome- design equation are: the local buckling load PL;
try of the section. As for any composite the interaction constant c; and the bending
property, it depends of the constituents (fiber stiffness D, which along with the length of the
and resin) and the arrangements of the fibers column enter in the computation of the slen-
inside the material (orientation, fiber volume derness 1 (46.1). All these properties can be
fraction, stacking sequence). The crushing determined experimentally or predicted ana-
strength is usually determined experimentally lytically. The bending stiffness D and the local
but the main factors that influence its value buckling load P,, can be predicted analytically,
can be highlighted by predictive equations while an analytical study of the interaction
(Tomblin, 1994; Barbero, 1998). phenomenon is presented by Raftoyiannis
A slender column buckles in a global (1993). The design equation does not have any
(Euler) mode. A not-so-slender column may safety factor included. Typical properties of
fail in a local buckling mode. A thick-walled wide-flange pultruded structural shapes are
stubby column may fail due to crushing. given in Table 46.1 where the interaction con-
Columns with a slenderness ratio less than 0.5 stant is c = 0.84 for all sections reported.The
fail in a local buckling mode. For slenderness length at which maximum interaction occurs
larger than 1.5 the mode is purely global is denoted by L‘.
(Euler). Columns with slenderness between
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
by Sen, Issa, and Mariscal (1992) to pre-stress many years of service, mostly in adverse con-
concrete piles. Seven 3 mm (0.125in) diameter ditions. Composites are being used
rods were twisted with one turn every 30 cm extensively for applications where the advan-
(12 in) to create a seven wire strand. The tages significantly justify their higher initial
strands were used to pre-stress concrete piles cost. Composites have been successful when
to be used in marine environment. To simulate the design and manufacturing of a product
marine environment, the piles were subjected was performed by a single company or group
to wet and dry seven-day cycles in a 15% of companies, using the integrated design
sodium chloride solution, then tested to failure approach typical of the aerospace industry.
in bending. To facilitate the moisture ingress, The use of composites in the traditional civil
four out of eight glass composite reinforced engineering environment, where individuals
piles were pre-cracked at the mid-span prior create unique structures from standard com-
to testing. The bending strength of specimens ponents, has been slow, with the exception of
subjected to the wetting cycles, specially those markets where corrosion resistance offsets
pre-cracked, reduced significantly over time. higher costs and less than optimum perfor-
From the pre-stressing force applied, it is pre- mance. Large markets have not developed
dicted that 1.6% strain was induced in the rod, partly because of lack of design codes and
while larger values of strain may have been specifications and lack of awareness of com-
induced during the precracking of the beams. posites advantages by structural engineers. A
Additionally, radial stresses produced by the number of factors, including the decline of
twist of the rods in the strand and by the mois- military industry and the need for rehabilita-
ture ingress in the resin may have caused tion of USA infrastructure, have produced a
cracking. Although the neat resin failure strain flurry of activity in this area, which undoubt-
is reported at 4%, the strain applied to the edly will produce significant progress in the
composite rods may have produced cracking application of composites in construction.
of the matrix, thus facilitating the ingress of
moisture carrying the alkaline solution to the
glass fibers. Scanning electron microscopy REFERENCES
micro-photographs clearly show degradation Adams, R.C. and Bogner, B.R. 1993. Long-term use
of the glass fibers along with some cracking of of isopolyesters in corrosion resistance. Proc.
the matrix. An additional pile was fabricated 48th Annual Conf, Section 1-C. New York:
with pultruded fiberglass rods for which an Composites Institute, The Society of the Plastics
additional coating resin was added to provide Industry Inc., pp. 1-5.
a smooth finish. This pile performed signifi- AGA NGV2. 1992. Proposed American National
Standard, basic requirements for compressed
cantly better than the other four after a nine
natural gas vehicle (NGV) fuel containers. Draft
month exposure, perhaps because of the 8. American National Standards Institute.
added protection of the finishing resin. It is Ahmed, S.H. and Plecnik, J.M. 1989. Transfer of
concluded that the alkalinity of the environ- composite technology to design and construc-
ment (eg. concrete), the availability of water tion of bridges. Washington, DC: US
or other solvent, and the protection provided Department of Transportation, Federal
by the resin must be evaluated for each spe- Highway Administration, Office of University
Research, Contract DTRS 5683400043.
cific application.
Bank, L.C. 1989. Flexural and shear modulii of full-
section fiber reinforced plastic (FRP) pultruded
46.4 CONCLUSIONS beams. J. Testing Evaluation, 17(1),4045.
Barbero, E.J. and GangaRao, H.V.S. 1991. SAMPE J.
Composite materials have been used for many Part I(12) 1991. Part II(1) 1992
structures that have performed well over Barbero, E.J. 1998. Introduction to Composite Materials
1002 construction
Design. Washington, DC: Taylor and Francis. CFRP rods to a post-tensioned pre-stressed con-
Barbero E.J. and Raftoyiannis, I. 1993. Local buck- crete bridge, in Advanced Composite Materials in
ling of FRP beams and columns. ASCE J. Mater. Bridges and Structures, (eds. K.W. Neale and P.
Civil Engng, 5(3), 339-355. Labossiere).Montreal: The Canadian Society for
Barbero, E.J. and Tomblin, J. 1992. A phenomeno- Civil Engineering, pp. 405-414.
logical design equation for FRP columns with Martine, E.A. 1993. Long-term tensile creep and
interaction between local and global buckling. stress rupture evaluation of unidirectional fiber-
Thin-Walled Structures. Composite Technol., 18, glass-reinforced composites. Proc. Composites
117-131. Institute 48th Ann. Conf., pp. 9-A/1-4.
Composite Technology Inc. 1992. Meisseler, H-J and Preis, L. 1989. High performance
Creative Pultrusions. 1989. Creative Pultrusions glass fiber composite bars as reinforcements, in
Design Guide. Alumn Bank, PA: Creative Concrete and Foundation Structures. Strabag Bau-
Pultrusions Inc. AG information brochure.
Davalos, J.F. and Salim, H A. 1992. Design of stress- MMFG. 1992. EXTREN Fiberglass Structural Shapes
laminated T-system timber bridges. Timber Design Manual. Bristol, VA: Morrison Molded
Bridge Information Resource Center, USDA Fiberglass Co.
Forest Service, Northeastern Area. Mochida, S., Tanaka, T. and Yagi, K. 1992. The
Morgantown, WV. Development And Application Of A Ground
Faza, S and GangaRao, H.V.S. 1993. Pultruded fiber Anchor Using New Materials. Advanced
reinforced plastic bars, an alternative to steel Composite Materials in Bridges and Structures,
reinforcement of concrete, Section 13-D, Proc. (eds. K.W. Neale and P. Labossiere), Montreal:
48th A n n . Conf, pp. 1C-5C. New York: The Canadian Society For Civil Engineering,
Composites Institute, The Society of the Plastics pp. 393-402.
Industry, Inc. Mufti, A.A., Erki, M-A. and Jaeger, L.G. (eds). 1991.
Fibergrate. 1992. Structural Fiberglass Products and Advanced Composite Materials With Application To
Systems. Dallas, TX: Fibergrate. Bridges. Montreal: The Canadian Society for
GangaRao, H.V.S. and Barbero, E.J. 1991. Civil Engineering.
Construction: structural applications, in Mufti, A.A., Erki, M-A. and Jaeger, L.G. 1992.
Encyclopedia of Composites (6), (ed. S. Lee). New Advanced Composite Materials In Bridges And
York VCH Publishers. Structures In Japan Montreal: The Canadian
Glaser, R.E., Moore, R. and Chiao, T.T. 1983. Life Society for Civil Engineering.
estimation of an E-glass epoxy composite under Munipalle, U.M. 1992. Analysis And Testing Of
sustained tensile loading. Composites Technology Wood-Glass Fiber Reinforced Plastic Adhesive
Review, 5(1), 21-26. Interface. M. S. Thesis. West Virginia University,
Head, P. 1988. Use of fiber reinforced plastics in Morgantown, W.
bridge structures. Helsinki: XI11 International Neale, K.W. and Labossiere, P. (eds). 1992.Advanced
Association for Bridge Structures Engineering Composite Materials In Bridges And Structures.
(IABSE),pp. 123-128. Montreal: The Canadian Society For Civil
Iyer, S.L. 1993. First composite cable pre-stressed Engineering.
bridge in the USA. Proc. 38th Int. SAMPE Symp. Noritake, K., Kumagai, S., Mizutani, J. and Mukae,
May 10-13, pp. 1766-1771. K. 1992. Construction of a pre-stressed barge
Iyer, S.L. (ed). 1991. Advanced Composite Materials in using aramid FRP rods, in Advanced Composite
Civil Engineering Structures, (ed. S.L. Iyer). New Materials in Bridges and Structures, (eds. K.W.
York American Society of Civil Engineers. Neale and P. Labossiere), Montreal: The
Kakihara, R., Kamiyoshi, M., Kumagai, S. and Canadian Society For Civil Engineering, pp.
Noritake, K. 1991. A new aramid rod for the 533-541.
reinforcement of pre-stressedconcrete struc- Pletcher, D. 1991. Consider structural composites,
tures, in Advanced Composite Materials in Civil Chem. Eng. Progress, November, 4449.
Engineering Structures, (ed. S.L. Iyer). New York Porter, M.L. and Barnes, B.A. 1991. Tensile testing of
American Society of Civil Engineers, pp. glass fiber composite rod, in Advanced Composite
132-142. Materials In Civil Engineering Structures, (ed. S.L.
Koga, M., Okano, M., Kawamoto, Y., Sakai, H. and Iyer). New York American Society Of Civil
Yagi, K. 1992. Application of a tendon made of Engineers, pp. 123-131.
References 1003
Priestley, M.J.N., Seible, F. and Fyfe, E. 1992. Gere, J.M. and Timoshenko, S.P. 1990. Mechanics of
Column seismic retrofit using fiberglass-epoxy Materials, 3rd Edn. Boston: PWS-KENT
jackets, in Advanced Composite Materials in Publishing Co.
Bridges and Structures, (eds. K.W. Neale And P. Tomblin, J. 1991. A Universal Design Equation For
Labossiere). Montreal: The Canadian Society Pultruded Composite Columns. M.S. Thesis. West
For Civil Engineering, pp. 287-298. Virginia University, Morgantown, WV.
Raftoyiannis, L. 1993. Buckling Mode Interaction in Tomblin, J. 1994. Compressive Strength Models For
Fiber Reinforced Composite Structures. Ph.D. Pultruded Fiber Reinforced Composites. Ph.D.
Thesis. West Virginia University, Morgantown, Dissertation, West Virginia University,
WV. Morgantown, WV.
Rostasy, F.S., Hankers, C. and Ranisch, E-H. 1992. TUFSPAN. 1991. Technical Data and Design Guide,
Strengthening of R/C- and P/C-structures with Forth Worth Tufspan, p. 8.
bonded FRP plates, in Advanced Composite Wolf, R. and Miesseler, H-J. 1992. Experience with
Materials in Bridges and Structures, (eds. K.W. glass fiber pre-stressing elements for concrete
Neale and P. Labossiere). Montreal: The bridges, in Advanced Composite Materials in
Canadian Society For Civil Engineering, pp. Bridges and Structures, (eds. K.W. Neale And P.
253-263. Labossiere). Montreal: The Canadian Society
Saadatmanesh and Ehsani. 1990. Fiber composite For Civil Engineering, pp. 425433.
plates can strengthen beams. Concrete
International. Farmington Hills, MI: American ACKNOWLEDGEMENTS
Concrete Institute, pp. 65-71.
Sen, R., Issa, M. and Mariscal, D. 1992. Feasibility of My sincere gratitude to Prof. G. Turvey for his help
Fiberglass Pretensioned Piles in a Marine researching applications in Europe, to all the con-
Environment. Report No. CEM/ST/92/1, tributors of information for this article, and to West
University of South Florida, Tampa, FL 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
For aerospace equipment and instrument and/or are going to be used for aerospace
structures, generally, thermoplastic versions of equipment and instrument structures.
GFRP have not seen as much application as Table 47.4 compares the mechanical and
the thermosets due to high investment costs in thermal properties of candidate materials for
tooling and facilities. Considering the rela- aerospace equipment and instrument struc-
tively small quantities that are usually bought, tures. One could ask, from the obvious
thermoplastic applications are not often cost property advantage of beryllium, why all such
effective. Also, the required high temperature structures are not made from beryllium? If not
cures subject the laminate to microcracking beryllium, why not metal matrix composites
instabilities. or carbon-carbon (C/C) or silicon carbide
Metal matrix composite applications have (Sic)? The answer is that raw material cost,
been limited, and knowledge of material prop- fabrication cost, practical size, and other criti-
erties and processes has been restricted due to cal properties all come into play for any
their use on classified programs. Materials like specific application. Table 47.5 shows typical
silicon carbides and carbon-carbon find lim- design requirements for various applications
ited, but important, use in aerospace and indicates which materials typically satisfy
structures, particularly mirrors. Design selec- the critical requirement.
tion criteria plays an extremely important role The primary reason that GFRP is a material
in determining what type of material is used candidate for most applications is the wide
on any particular component of aerospace range of material systems that are currently
equipment and instrument structures. The pri- available that can compare with Kevlar, alu-
mary reasons for choosing a composite minum, Invar, beryllium, metal matrix
material, rather than a metal, are weight, composites, silicon carbide, and carbon-car-
dynamic stability and thermal stability. bon.
Table 47.1 categorizes some of the desirable
and undesirable characteristics that con-
47.2 HISTORICAL PERSPECTIVE AND
fronted the early users of GFRP. Table 47.2
PROGRESS
addresses the undesirable properties listed in
Table 47.1 and indicates how the aerospace From a historical perspective, and to illustrate
equipment and instrument designers have rec- where significant progress has been made in
ognized the barriers or problems with GFRP the use of composites for aerospace structure,
and found work-around techniques to allow the following areas of interest will be
their usage. Table 47.3 illustrates several struc- addressed:
tural applications where GFRP have been used
Desirable Undesirable
Low density Low short transverse properties
Coefficient of thermal expansion(CTE near Hygroscopic
zero) High material cost
High specific strength High fabrication cost
High specific stiffness Low impact strength
Readily formable Subject to microcracks (translaminarstress
Crack growth resistant relief)
Adaptable laminate properties Low peel strength
Easily repairable
1006 Aerospace equipment and instrument structure
where c = moisture concentration; t = time; Dz maximum moisture pick-up for the composite
= moisture diffusivity; and z = thickness coor- (Mcm)may
be calculated by the following equa-
dinate. tion:
Diffusivity is dependent on resin type and
temperature but is independent of moisture
MCm= (Mrn)[x wr (47.2)
concentration or laminate orientation. where Wr = resin weight YOand (MJr is the
Figure 47.2 illustrates the importance of maximum moisture pick-up for the neat resin
temperature in determining the diffusivity of a for a given relative humidity condition.
laminate. Figure 47.3 illustrates the moisture The moisture content as a function, Iw,can
absorption behavior as a function of tempera- be represented by:
ture for this same laminate. Note that this is Mcm= A (WB (47.3)
for a 100% relative humidity (RH) exposure.
Typical moisture absorption values (primarily where A and B are coefficients obtained from
by the resin) are 3 . 5 4 % by weight for epoxy empirical data. Figure 47.4 depicts the per-
and 1-1.3% by weight for cyanate ester. The cent of moisture pick-up for various levels of
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 - - - -
(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 ~
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 47.7 Prior work-around technique for addressing the hygroscopic nature of graphite/epoxy
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
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:
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,
CROSSING RIB THICKNESS
for example, the Hubble Telescope could be
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-
fabricate the tooling can be as important to the ment and instrument structures (Tables 47.8
success of the hardware as the hardware and 47.9). The photograph of the Hubble Space
design itself. The aerospace structural designer Telescope (Fig. 47.10) only shows the metering
must stay in touch with technological develop- truss structure for the telescope; substantially
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.
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)
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).
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 48
Richard N . Hadcock
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)
v)
Z
1
7
1000
100
i”’
MILITARY TRANSPORTS
AIRLINERS
BUSINESSNC
0.01
1000 10000 100000 1000000
OPERATING EMPTY WEIGHT, kg
a
CIVIL
v)
Z
0
i
1
7
te
W-
0
a
a
Fig. 48.3 Aircraft costs and prices. (a) Fixed wing aircraft; (b) helicopters. (01994 RNH Associates.)
Structural applications 1027
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 upper branch includes most of the Western
aircraft, Fig. 48.4(a), appears to have leveled European airliners and the Boeing 777; the
between 22% and 26%. The Lockheed F-22A lower branch includes the McDonnell MD-11,
airframe is composed of 26% composites, 30% Ilushin 11-96 and the Boeing 737X. The latter
titanium and 14% aluminum; the McDonnell aircraft is reported to have less composites
Douglas F/A-l8E structural weight is 22% than the Boeing 737-300 because many of the
composites, 15%titanium, 29% aluminum and operators will be the smaller airlines which do
14%steeP. not have composite maintenance and repair
Composite weight fractions for other pro- facilities12.
duction and technology demonstrator military Weight savings provided by composites
aircraft, such as the Grumman A-6E (which vary considerably with the type of aircraft and
has a CFRP wing designed and manufactured component. Weight savings, in terms of com-
by Boeing), Northrop B-2A bomber and YF- posite weight fraction, are shown in Fig. 48.5.
23A fighter, General Dynamics F-16XL, These tend to decrease as the overall compos-
Grumman X-29A, Rockwell/MBB X-31A, IAI ite weight fraction increases. These data were
Lavi, the British Aerospace EAP, the obtained from different sources, primarily
Eurofighter 2000 and the Mitsubishi FS-X, are References 7, 9 and 12-18. It should be noted
not included because of space limitations or that the weight savings for the AV-8B are
availability of weight data. based on a weight estimate for comparable
The composites weight fraction for civil aluminum wing, and not the AV-8A aluminum
transports, Fig. 48.4(b), has two branches: the wing, which is smaller15.
A
TACTICAL AIRCRAFT
I
TRANSPORT AIRCRAFT
I-
10 20 30
COMPOSITES, % STRUCTURE WEIGHT
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.
because a comprehensive design database was and access panels. The aircraft is currently
available for the material from Air Force being extensively redesigned and enlarged.
development programs and was less expen- Designated the F/ A-1 8E / F, carbon / epoxy
sive than carbon/epoxy. During the accounts for 18%of the structure weight com-
intervening years, this situation has changed. pared to 10% for the F/A-18A. Because of its
Extensive design data have been generated for higher strength and stiffness, the new
many different carbon/epoxy systems and IM7/977-3 carbon/epoxy system is being
prices are now significantly lower than for used for the wing and empennage skins
boron/epoxy, instead of AS4/3501-6’J2. F/A-l8E/F material
Carbonlepoxy was selected for the hori- usage is shown in Fig. 48.721.
zontal and vertical stabilizers covers of the In 197677, McDonnell Douglas extensively
General Dynamics F-16. These covers are redesigned the British Aerospace AV-8A
bolted to aluminum substructure. More than Harrier vertical take off and landing (VTOL)
3000 F-16s have been produced between since fighter/attack aircraft for the US Marine Corps
1976. to improve range/payload capability.
McDonnell Douglas, with Northrop as the Carbon/epoxy was utilized for the complete
major subcontractor, was awarded the Navy wing, horizontal stabilizer and forward fuse-
Air Combat Fighter contract in 1976 with the lage. Designated the AV-8B Harrier 11, the
F/A-l8A, an enlarged and extensively modi- composite wing weight is about the same as the
fied version of the Northrop YF-17. To save aluminum wing of the AV-8A but has 19%more
weight and offset the increased weight of the area, a 50% increase in internal fuel capacity
landing gear and other components required and a supercritical airfoil. Range-payload capa-
for carrier operation, carbon/epoxy materials bility was increased by 100%. Because of high
were used for the wing, tail, control surfaces temperatures from the exhaust in the VTOL
Percent of Structural Weight
FIA-18CID FlA-18UF
UAlurninurn 49 ________ 31
HSteel ___________ 15________ 14
NUilTitaniurn 13 ________ 22
Carbon EDOXV.--10 ________ 18
Fig. 48.7 McDonnell Douglas F/A-l8E/F material usage. (Courtesy of McDonnell Douglas.)
1032 Aircraft applications
mode, carbon/bismaleimide is used for the account for 44% and 7% respectively of the
skins of the inboard flaps and the strakes, structure and rotor weight of the aircraft, are
which are mounted under the fuselage9J2. estimated to have provided a 25% weight sav-
Usage of composites, which account for 26% of ing relative to a comparable metal airframe1*J4.
the airframe weight, is shown in Fig. 48.8.2l Because weight is so critical to performance of
Composites are also used on other US tacti- this aircraft, much of the structure is currently
cal aircraft. The Navy funded Boeing to design being redesigned to further reduce weight and
a CFRP wing for the Grumman A-6E in 1987 costs'*.
because fatigue of the aluminum wings lim- The outer skin and much of the substruc-
ited the life of the aircraft. Boeing built 179 ture of the large Northrop B-2A bomber is
composite wings in Seattle, which were made from carbon/epoxy. The B-2A was
installed on the last batches of 21 A-6 aircraft. designed and produced by a team composed
An additional 158 aircraft were retrofitted of Northrop, Vought and Boeing. The B-2A,
with CFRP wings. A follow-on program for which has a wing span of 52 m (172 ft), a wing
120 wings was canceled by the Navy in area of 464 m2 (5000 ft') and a gross weight of
September 1993. 180 metric tomes (4000001b), first flew on
The first production application of car- July 17,1989 and is by far the largest 'compos-
bon/thermoplastic composites was the ite' aircraft to fly to date9J2.
stabilizers of the Lockheed F-117A interdictor. McDonnell Douglas is using 6800 kg
The complete fleet of F-117A aircraft are being (15 000 lb) of composite materials for control
filled with these stabilizers to extend the flight surfaces, stabilizer leading edges, the tail cone,
envelope9J2. landing gear doors and pod, engine nacelles,
The wing, fuselage, tail and the rotors of the and the wing-fuselage fairing of the US Air
Bell/Boeing V-22 Osprey multi-mission VTOL Force C-17A transport.
tilt-rotor aircraft are almost entirely made These components, shown shaded in Fig.
from CFRP and GFRP. Composites, which 48.9, account for 8% of the structure weight
Fig. 48.8 McDonnell Douglas/BAe AV-8B material usage. (Courtesy of McDonnell Douglas.)
Structural components 1033
and are made by McDonnell Douglas and 26% weight saving26. The Dassault Mirage
many different American and European sub- 2000, which first flew in 1978, has a CFRP fin
contractors including Grumman (ailerons, designed and built by Aerospatiale, a
elevators, rudders), Heath Techna (fairings), CFRP/BFRP hybrid rudder, and CFRP
Beechcraft (landing gear doors), elevons, nose landing gear doors and some
Aerostructures Hamble (flap hinge fairings equipment doors. Composites account for
and trailing edge panels) and Northwest about 12% of the structure weight and provide
Composites (main landing gear pods). a 25% weight savings of that total. About 350
Since 1970, more than 7500 fixed wing US Mirage 2000 had been delivered by the end of
military aircraft have been produced which 1993133.
utilized composites for safety-of-flight compo- Dassault Rafale C and M tactical combat air-
nents, such as horizontal stabilizers, wings craft are now in production with CFRP wings,
and control surfacess. forward fuselage, vertical stabilizer, fin, and
Composite materials have also been used control surfaces with an AFRP radome and jet
for many structural components of European pipe fairings, accounting for about 25% of the
and other military aircraft. In France, Avion structure. Other advanced materials include
Marcel Dassault-Breguet Aviation and superplastic formed-diffusion bonded tita-
Aerospatiale have been involved in composite nium leading edge flaps and canards and
structures development programs with the aluminum-lithium fuselage panels9J3.
French government support since 1972. A British Aerospace (BAe) designed and built
boron/epoxy rudder was flown on a Dassault a CFRP wing for the SEPECAT Jaguar and
Mirage I11 in 1975; horizontal stabilizers were teamed with MBB, in Germany, to design,
flown on the Mirage F I in 1976 and composites build and fly a CFRP taileron for the Panavia
first entered production in 1978 with CFRP Tornado in the early 1980s. The British gov-
ailerons for the Mirage F I, which provided ernment authorized BAe to go-ahead by with
NONSTRUCTURALPARTS,
LINERS, TROOP SEATS
7
. .
GFRPlNomex Core
KevladFoam Core
Kevlar/Nomex
Fig. 48.9 McDonnellDouglas C-17A composite applications.(Unpublished:all rights reserved under copy-
right law by McDonnell Douglas. Reprinted with permission.)
1034 Aircraft applications
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,
Nose
radome
Fig. 48.11 Boeing 777 composite structure. (Courtesyof the Boeing Company.)
honeycomb sandwich ribs and non-structural ment programs, which included components
forward torque boxes. They are designed for for military aircraft and a complete CFRP wing
simple repair. The horizontal stabilizer has a for the Falcon 10, Airbus Industrie began
span of 21.3m (70 ft) and the projected tail using carbon/epoxy for the A-300-600 spoilers
area is 101 m2 (1090 ft2),about twice the span in 1983 and for the complete vertical stabilizer,
and four-times the area of the AV-8B ~ i n g ~ , rudder,
~ ~ . elevators and spoilers of the A310-300
Following successful airline service of the in 1985. The vertical stabilizer is used as a fuel
DC-10 CFRP rudders and fin, deployed under tank on extended range aircraft26.
the ACEE program, and production experi- The entire tail, control surfaces, and cabin
ence from composite components on the floor of the A320, A321, A330 and A340 are car-
MD-80, McDonnell Douglas extended use of bon/epoxy. The A300 medium-range narrow-
composites on the MD-11 wide-body airlineP. body airliner entered airline service in 1988 the
Almost 5000 kg (11000 lb) of composite larger A330 and A340 wide-body airliners
materials are used on the MD-11 of which entered service in 1993 and 1991 respectively.
4400 kg (9700 lb) is structural (primarily car- Composite applications on the A320 are
bon/epoxy). Weight savings of 20-30% have shown in Fig. 48.1326.
been achieved after trading some weight sav- The Airbus CFRP horizontal stabilizers are
ings for improved reliability, maintainability, designed and manufactured by CASA in Spain
durability and producibility. Most of the com- and the vertical stabilizers are manufactured
posite structure is solid-skin or Rohracell foam by Deutsche Airbus in germ an^^,^^.
sandwich construction. Honeycomb sandwich Avions de Transportation Regionale (ATR),
construction has been avoided because of sus- the Aerospatiale/ Alenia consortium, uses car-
ceptability to impact damage and moisture bon/epoxy for all the control surfaces and
penetration into the core1*.MD-11 composite Kevlar/epoxy for many components of the
components are shown in Fig. 48.12. ATR 42 regional airliner which was certifi-
As a result of the very successful French cated in 1985.
Dassault-Aerospatiale composites develop-
Structural components 1037
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 Many thousands of structural components
outer wing boxes of the ATR 72, a stretched made from composites are currently in airline
version of the ATR 42, the first airliner with a service. Damage assessment and repair has
CFRP wing box to be fully certificated in been a major problem to the airlines. Too many
Europe and the USA. It first flew in 1988 and different fiber-matrix systems are currently
was certificated and entered airline service in being used, even by the same OEM; prepreg
1989. The wing box, which is a fuel tank, is materials are expensive and have a limited life;
made by Aerospatiale at Nantes. The weight of damage assessment requires special non-
the wing box was reduced by 130 kg (286 lb) destructive test equipment and experienced
using CFRP instead of a l u m i n ~ m ' ~ , ~ ~ . technicians; minor repairs need special skilled
Composite materials used on the ATR 72 mechanics; major repairs must be made in an
and details of the CFRP wing box are shown in autoclave and take many days to complete;
Fig. 48.14. cost of replacement parts or leasing spares are
Domier chose CFRP for the complete tail much higher than metal part^^^,^^.
and rear fuselage of the Domier 328 regional IATA sent a questionnaire to the airlines to
airliner, which also has an AFRP pressure bulk- obtain information on composites maintain-
head. The 328 was fully certificated and ability in December 1991. The ATA/IATA/SAE
entered airline service in 1993. Material distrib- Commercial Aircraft Composite Repair
ution and details of the CFRP rear fuselage/fh Committee (CACRC) was formed the follow-
box structure are shown in Fig. 48.15. ing year. Committee members include
The de Havilland Canada Dash 8, Embraer representatives from the FAA, airlines, OEMs,
Brizilia, SAAB 340 and other regional airliners NASA and material s ~ p p l i e r s ~ ~ .
are using AFRP or CFRP for many secondary
structure components.
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
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
(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
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.
Fig.48.16 (a) Beech starship 2100; (b) starship wing
upper cover. (Courtesyof Raytheon Aircraft Co.) 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%
aircraft include the British Slingsby T67 Firefly composites for the rotor system; and has
trainer (USAF T-3A), the German Grob G115 shifted from 22% magnesium to 28% compos-
and FFT Eurotrainer. The Russian Sukhoi Su- ites for the drive system. Carbon/epoxy
26 and Su-31 aerobatic competition aircraft accounts for 44% of the airframe weight; the
have carbon/epoxy wings and tails. rotor blades are made from carbon/epoxy-
CFRP and GFRP materials have been used glass/epoxy broadgoods; the main gear box
for many experimental and home-built and kit housings are made from carbon/bismaleimide
aircraft. These include the Voyager, designed using resin transfer molding (RTM);and the
by Burt Rutan and built by Scaled Composites, tail drive shaft is filament-wound
which made the first unrefuelled non-stop carbon/ epoxf9.
flight around the world in December 1986. Composites are being used extensively for
rotor blades and airframes many other new
American, Western European and Russian heli-
48.6.4 HELICOPTER APPLICATIONS
copters including the McDonnell Douglas
Glass/epoxy main helicopter rotor blades Explorer, Eurocopter BO 108 and the Kamov
were initially developed in the late 1960s by Ka-62 g.
Structural components 1041
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.)
During the past 20 years, advanced corn- 15. Schier,J.F. and Juergens,R.J., They Force a Fresh
posite structures have become light-weight, Look at the Design Process. Aeronautics b
&ptember 1983.
reliable, low-risk alternatives to conventional
16. Watson, James C., AV-8B Composite Fuselage
aluminum and titanium structures. Their use Design. Aircraft, March 1982.
will continue to grow. 17. Lubin, George and Dastin, Samuel J. Aerospace
Applications of Composites. Handbook of
REFERENCES Cimposites, (ed. George Lubin), Chap 20, New
York Van Nostrand Reinhold, 1982.
1. Federal Aviation Regulations (FAR), Subchapter C 18. Ashizawa, Moto, Composite Technology
- Aircraft. 14 CFR Chapter 1, US Department of Growth Leading to the MD-11 Application and
Transportation, Federal Aviation to the Civil Transport Aircraft of Tomorrow.
Administration, Washington DC. Proc. SAMPE Meeting, Japan, 1991.
2. Abbott, Ric, Design and Certification of the All- 19. Brenner, Lothar and Johst, Eberhard, The
Composite Airframe. SAE paper 892210, SAE Airframe of the Dornier 328 - Proven Progress.
Tech. C o d , September 1989. DGLR Jahrbuch 1989 I.
3. The All-Composite Airframe Design and 20. Hadcock, Richard N. and Huber, John. Specific
Certification.Aerospace Engrzg, April 1990. Examples of Aerospace Applications of
4. A. Barrio Cardaba, et al., Design and Fabrication Composites. Lecture Series No. 124, Advisory
of the Carbon Fiber/Epoxy A-320 Horizontal Group for Aerospace Research and Development
Tailplane. SAMPE J., Jan./Feb. 1990. (AGARD), October 1982.
5. Waggoner, Gary and Erbacher, Herman, 21. Information supplied by the author by
Damage Tolerance Program for the B-1 McDonnell Douglas Aerospace, St. Louis,
Composite Stabilizer. AlAA Paper 77-464, Missouri. Reproduced with permission.
AIAA/ASME 18th Structures, Structural 22. Rosato, Dominic V. and Lubin, George, Plastics
Dynamics and Materials Conf., March 1977. in Aircraft and Aerospace. Handbook of Fiberglass
6. Weinberger, Robert A. et al., US Navy and Advanced Plastics Composites, (ed. George
Certification of Composite Wings for the F-18 Lubin), Chap 29, New York: Van Nostrand
and Advanced Harrier Aircraft. AlAA Paper 77- Reinhold, 1969.
466, AIAA/ASME 18th Structures, Structural 23. Hadcock, Richard N., Boron/Epoxy Aircraft
Dynamics and Materials Conference, March Structures. Handbook of Fiberglass and Advanced
1977. Plastics Composites, (ed. George Lubin), Chap 24,
7. Hadcock, Richard N. Design and Analysis of New York Van Nostrand Reinhold, 1969.
Advanced Composite Structures. Handbook of 24. Hadcock, Richard N., Status and Analysis of
Composites, (ed. George Lubin), Chap 20, New Advanced Composite Aerospace Structures
York Van Nostrand Reinhold, 1982. Programs. Composites Technical Note No. CTN-
8. Aerospace Facts and Figures 1992-2993(and many 466-35. G m a n Aerospace Corp. May 1971.
previous editions). Aerospace Industries 25. Chaumette, D. Flight Qualification of
Association of America, Washington, D.C. Composite Structures at Avions Marcel
9. Jane’s AI1 The World’s Aircraft, 1993-94 (and pre- Dassault - BrCguet Aviation. AlAA Paper 82-
vious editions), (ed. Mark Lambert). Coulsdon, 0755,1982.
England: Jane’s Information Group Ltd. 26. Information supplied to the author by Avions
10. Ted G. Nicholas. US Military Aircraft Data Book. de Transport Regional, Blagnac Cedex, France.
Various editions. Data Search Associates. Used with permission.
11. Current Aircraft Prices ’88 (and other editions) 27. Information supplied to the author by SAAB
Interavia Publishing. Military Aircraft, Scania AB, Linkoping,
12. Aviation Week and Space Technology: Various Sweden. Used with permission.
issues. 28. DeAngelis, V. Michael, In-Flight Deflection
13. Defense News, Flight International, Aerospace, Measurement of the HiMat Aeroelastically
Aeronautics B Astronautics, Aerospace Tailored Wing. J. Aircraft, December 1982.
Engineering, Air International: Various Issues. 29. Hadcock, Richard N., X-29 Composite Wing.
14. Aerospace Composites B Materials, 1988-1991 and Evolution of Aircraft/Aerospace Structures and
Aerospace Materials, 1992-1993, Burnham, Materials Con5 Air Force Museum/AIAA, April
England: The Shephard Press. 1985.
References 1043
300
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.)
Introduction 1045
rackets have been fabricated by braiding. The bath, along the fiber path between the ten-
braiding process for composites is identical to sioning system and the delivery eye, through
braiding textiles, except that the fiber is usu- which the dry fibers are pulled. Both wet
ally braided as a prepreg. Prince introduced winding and prepreg winding are widely
the Vortex tennis racket, braided with co-min- used. The choice of technique depends on the
gled nylon and carbon fibers, in the late 1980s. application, cost and quality requirements.
Ski poles, kite tubes, arrow shafts, and similar Composites that have directionally oriented
hollow or solid shafts are made by the pultru- continuous fibers are analyzed by techniques
sion process. Pultrusion of composites is such as netting analysis, rule of mixtures, clas-
similar to extruding metals. The resin and sical lamination theory, and micromechanics.
fiber material are pulled through a heated die These analysis techniques all account for the
that forms the composite to shape and cures fact that composites have material properties
the resin in one continuous process. Since the that depend on the fiber directions of each ply.
fibers are essentially all aligned down the axis The overall directional properties of the lami-
of the part there is little transverse or hoop nate are calculated by adding the relative
strength unless hoop fibers or other off-axis effects of each ply. The analyses are more com-
reinforcement such as mats are added during plicated than with isotropic materials such as
the process. Arrow shafts have shattered on steel and aluminum. However, the wide-
impact because of this lack of strength in the spread use of computers has made the task of
hoop direction. analyzing composites relatively simple.
Resin transfer molding (RTM) consists of Composites are in many cases much
injecting resin into a mold containing fiber in a stronger and stiffer than metals such as steel,
preform pattern. Resin transfer molding is aluminum or titanium. When one takes into
usually used in conjunction with a fiber place- account the much lower density of composites
ment technique such as hand lay-up, braiding as compared to metals, composites have an
or filament winding. Some tennis rackets are even greater performance advantage over
fabricated using the resin transfer molding metals. To compare material properties on an
process4. equal weight basis (instead of an equal volume
The filament winding process is the basis), a property such as ultimate strength is
machine controlled technique of applying a divided by the density of the particular mater-
controlled amount of resin and oriented fiber ial. The resultant is termed specific strength.
on a mandrel that provides the finished com- The same can be applied to stiffness (modulus)
ponent shape. The mechanics of filament and is called specific modulus. Comparing
winding are illustrated in Fig. 49.2 The ten- materials this way is very important when
sioned fiber bands are accurately placed on designing weight critical parts.
the mandrel using numerically computer Figures 49.3 and 49.4 show the strength,
controlled or chain and gear mechanical modulus, and specific properties of represen-
winding machines. Fig. 49.2 shows the fiber tative composites and metals. The composite
being pulled from tensioned spools through data are for composites with all fibers oriented
the delivery eye onto the rotating mandrel. in one direction (unidirectional ply data). The
The resin can either be pre-applied on the fiber test loads are applied to the specimens in the
in an off-line operation (pre-impregnation, or same direction as the fibers. Also, all compos-
wet prepreg) or applied during the winding ite data presented here are for 60% fiber and
operation (wet winding). Prepregging usually 40% resin by volume samples. This ratio is
requires storing the material at low tempera- typical for advanced composite laminates. The
ture until required for winding to retard the epoxy resin used to make the samples is not
curing process. Wet winding uses a resin indicated specifically because its effect on the
Manufacturing techniques 1047
-MACHINE DRIVE
Fig. 49.2 Layout of a typical filament winding machine (Courtesyof Composites Machines Company.)
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
-
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
Tube and lug frames are relatively simple to helps to reduce the seam effect on perfor-
manufacture. However, the frames can have mance consistency.
durability problems if the tubes and tube to Grafalloy introduced a filament wound
lug joint are not properly designed to prevent shaft for the 1993 season. Filament wound
significant stiffness mismatches. Galvanic cor- shafts provide superior performance at low
rosion potential is a concern. Filament weight and cost compared to roll-wrapped
winding offers an inexpensive method for shafts available with comparable performance
manufacturing frame tubes. Wet winding specifications. Those familiar with the indus-
techniques allow using the required materials try believe filament winding will be the
in the lowest cost form. Since the process is process of choice in manufacturing golf shafts
machine controlled, labor requirements are in the next few years.
minimized. Currently the most widespread Player tests and mechanical golfer testing
manufacturing method is roll-wrapping. Roll- have proven the performance improvements
wrapping requires cutting prepreg plies of of a filament wound shaft over roll-wrapped
composite and hand wrapping them around a shafts. Many original equipment manufactur-
metal mandrel prior to curing. ers are evaluating filament wound shafts for
Frame tubes are not the only use of com- their product lines. One factor where roll-
posites in the bicycle industry. Handlebars are wrapped shafts can have an advantage over
filament wound, removed from the mandrel, filament wound shafts is in tip durability.
and then cured in a mold to provide the Filament winding can introduce more voids in
proper shape and curvature. An internal blad- the composite laminate than roll-wrapping.
der provides the compaction pressure. Seat Special attention is needed by filament
posts, swing arms, and handlebar extensions winders to insure that their product has suffi-
can be made using this process. Titanium cient tip strength.
tubes in some front wheel suspension systems ASTM is working to establish test methods
are reinforced with composite tubing. Wheels for golf shafts. Standard tests will allow for a
and spokes are also being made of composite better comparison of products and give the
materials using combinations of roll wrap- customer more confidence in the quality and
ping, hand lay-up and resin transfer molding. performance of the product being purchased.
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
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 environmental considerations. Key among
usage matrix systems in advanced composites these characteristics are: temperature, frac-
are considered as candidates for typical prop- ture toughness, compression after impact,
erties. In addition, for typical properties of crack propagation, humidity, stress concen-
advanced composites for structural applica- trations, interlaminar shear, mechanical
tions, only structural resin systems are fasteners in laminates, holes in laminates,
candidates. Structural resins are defined as creep, damage tolerance and compatibility
resins that have similar modulus and tensile with fiber finish. In determining typical prop-
strength as standard epoxy systems. For exam- erties, these characteristics are not included
ple, an applicable resin for structural but, as applicable, need to be considered for
composites would have a modulus of approx- the final design.
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,
cp o o /
1989).
A comparison for composites with different L
400
epoxy sizing from different manufacturers and -
0
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.)
Selecting the use of typical properties
As can be seen in Fig. A.5, the typical fiber A.4 SELECTING THE USE OF TYPICAL
fracture composite properties (ultimate fail- PROPERTIES
ure) are not affected by large variations in the
properties of the resin. However, for resin sen- A.4.1 WHERE TYPICAL PROPERTIESARE
sitive properties, for example, the first ply ACCEPTABLE
failure (limit) of the 90" plies, the resin prop-
The acceptability of material properties in the
erty is influential.
design of structures is based on a number of
For the fiber fracture controlled composites,
factors. If a design is being produced for a cus-
which are the main interest in structures, typi-
tomer, the customer is often the final word on
cal composite material properties are valid
the acceptability of the material properties uti-
over a wide variation in resin characteristics.
lized. An alternate possibility is that the
A.3.2 MATRIX CONTROLLED TYPICAL customer is not interested in accepting or
PROPERTIES rejecting the material properties used, but
would rather accept the product against a
The main interest in structural components is specification. Final acceptance is a qualifica-
the high strength and modulus obtainable tion of the product through testing.
from the fiber reinforcing of the matrix. The third case is where a product is pro-
Therefore in the design of the laminate, for duced by the company itself and sold to the
most of the applications, the resulting failure consumer directly. Of course the consumer
modes are fiber fracture critical. Unfortunately, (public) is not interested in accepting or rejec-
there are cases where the matrix is the critical tion the material properties database. An
element in the failure mode for all laminate example of this is the automobile industry.
orientations. This does not mean that the fiber In the case of a company that subcontracts
does not contribute to reinforcing the matrix in the design and fabrication of composite struc-
both strength and modulus, but only that the tures, the company may either want to review
ultimate failure is the result of failure in the the subcontractor's material properties data-
matrix. base, or be able to review the design of the
Among the cases where the matrix is the subcontractor with the use of the company's
critical failure mode are laminates that are typical properties database.
subjected to shear, the first ply failure (limit In each of the above cases, a typical mater-
load) of a laminate (Fig. A.5, first ply failure ial properties database can be used for cost
curves and Berg, 1982) and most cases of the and weight trade-offs, selection of the best
transverse strength property of a laminate materials, optimizations studies and prelimi-
with no 90" plies. Even for these cases, a typ- nary design.
ical property can be determined utilizing the It is important to note that the final design
typical set of unidirectional properties repre- would always go through an extensive test
sented by most of the epoxy systems in use program to verify the material properties
by the prepreg manufacturers as well as most selected, the final design, the manufacturing
of the structural epoxies sold. A typical set of process and to determine the variability of the
unidirectional properties for high strength product.
carbon composites, for example would be: Thus, a typical material properties database
Strength 0" 90" is acceptable and useful to reduce the cost of
Tension 2100 MPa 55 MPa engineering design, reduce the cost of testing
Compression 1380 MPa 190 MPa and allow a more intelligent and less time con-
In-plane shear 55 MPa suming approach to the final design.
Modulus 138 GPa 9.7 GPa
Shear modulus 6 GPa
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 APPENDIX B
STANDARDS FOR POLYMER
COMPOSITES
Frank T. Traceski
organizations that develop them. It is limited several military specifications and standards
to consensus-type standards and does not for polymer composite materials. Other pri-
include private sector specifications which are vate sector organizations, such as the
generally not available. Aerospace Industries Association (AIA) and
Composite Materials Characterization (CMC),
Inc., are involved in the standardization of
B.2 STANDARDS-DEVELOPING
composite materials and tests in order to reap
ORGANIZATIONS
long-term economic savings.
The two principal organizations which Japan, Germany, France and UK are also
develop test methods for composites in the major players in composites technology. The
USA are the American Society for Testing and European Association of Aerospace
Materials (ASTM) and the Suppliers of Manufacturers (known as AECMA in Europe)
Advanced Composite Materials Association produces European Norm (EN) standards for
(SACMA). The Society of Automotive aerospace composites. Japanese Industrial
Engineers (SAE) Polymeric Materials Standards (JIS) serve as a basis for standard-
Committee is the organization which pub- ization of composites in Japan. Germany has
lishes Aerospace Material Specifications issued DIN standards for composite materials.
(AMS) for advanced polymer composites. The France has AFNOR standards and the UK has
Department of Defense (DoD) has also issued British Standards.
Standards used in USA 1061
Engineering standards for polymer com- standards for determining the physical and
posites also promote international commerce. mechanical properties of polymer composites.
In the global arena, the International ASTM standards are developed by a consensus
Standardization Organization (ISO) is the process and are widely used. The ASTM
body which develops international standards. Committee D20 on Plastics also has developed
The ISO/TC 61 Subcommittee (SC) 13 on standards which may be used for testing plastic
Composites and Reinforcements Fibers is cur- resins and reinforced plastics.
rently coordinating new standards for glass
and carbon fiber composites. USA participa-
8.3.2 SACMAMETHODS
tion with IS0 not only promotes international
commerce but also enhances USA global com- The SACMA has developed recommended test
petitiveness in the composites industry. methods for determining the physical, mechan-
ical, and chemical properties of composite
materials (Table B.3). Although SACMA is not a
B.3 STANDARDS USED IN USA
standards-setting body, it works actively with
ASTM, SAE, ISO, DoD, AIA and others towards
B.3.1 ASTM STANDARDS
standardization of composite test methods.
The ASTM Committee D30 on High-Modulus SACMA does not regard its SRMs to be ’stan-
Fibers and their Composites develops standard dards’ in the truest sense because they have not
test methods for advanced polymer compos- been developed by a consensus process which
ites. Table B.2 lists the principal ASTM is typical of standard-developing bodies.
Table B.2 ASTM Standards for advanced polymer composites
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
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
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
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
Non-US Standards in use 1065
Table B.7 FAA Advisory circulars for composites compressive, and shear loadings at selective
hygrothermal test conditions. CMC also works
AC 20-10A Composite Aircraft Structures with other national organizations to promote
AC 21-26 Quality Control for the Manufacture of composites standardization.
Composite Structures
AC 145-6 Repair Stations for Composite and
Bonded Aircraft Structure B.4 NON-US STANDARDS IN USE
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 DIN 29965 Aerospace; Carbon Fibres, High
JIS R 7602 Testing Methods for Carbon Woven Performance Carbon Fibre Filament
Fabrics Yams, Technical Specification
JIS K 7071 Testing Methods for Prepreg, DIN 29971 Aerospace; Unidirectional Carbon
Carbon Fiber and Epoxy Resins Fibre-Epoxy Sheet and Tape Prepreg,
JIS K 7073 Testing Method for Tensile Technical Specification
Properties of Carbon Fibre DIN 65090 Aerospace; Textile Glass,
Reinforced Plastics Preimpregnated Filament Glass Cloth
JIS K 7074 Testing Methods for Flexural for E-Glass (Prepreg),Technical
Properties of Carbon Fibre Specification
Reinforced Plastics DIN 65426 Aerospace; Aromatic Polyamide
Part 1: (Aramid) - Preimpregnated Woven
Fabric, High-Modulus Filament Yam
(Prepreg);Dimensions, Masses
DIN 65426 Aerospace; Aromatic Polyamide
National Standards Institute (ANSI). Table Part 2 (Aramid)- Woven Filament Fabric
8.13 lists draft and published (ISO) standards Prepreg from High-Modulus Filament
for composites. Yam and Epoxy Resin, Technical
Specification
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
Page numbers in bold type refer to figures; those in italics refer to tables
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
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
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