Corrosion and Corrosion Protection Handbook

Corrosion and
Corrosion Protection
Handbook
CORROSION TECHNOLOGY
Editor
Philip A. Schweitzer, P.E.
Consultant
Chester, New Jersey
1. Corrosion Protection Handbook, Second Edition, Revised and Expanded,

edited by Philip A. Schweitzer, P.E.
Additional Volumes in Preparation

Corrosion and
Corrosion Protection
Handbook
Second Edition
REVISED AND EXPANDED
EDITED BY
Philip A. Schweitzer, PE.

Consultant
Chester, New Jersey
M A R C E L
MARCEL DEKKER, INC. N E W YORK • BASEL

Library of Congress Cataloging-in-Publication Data
Corrosion and corrosion protection handbook I [edited by] Philip A.
Schweitzer. -- 2nd e d . , r e v . and expanded.
p . cm. -- (Corrosion technology; 1)
Includes bibliographies and index.
ISBN 0-8247-7998-3
1. Corrosion and anti-corrosives--Handbooks, manuals, etc.
I. Schweitzer, Philip A. II. Series: Corrosion technology (New
York, N.Y.) ; 1.
TA418.74.C5928 1988
620.1 T 1223--dcl9 88-13916
CIP
Copyright © 1989 by MARCEL DEKKER, INC. All Rights Reserved
Neither this book nor any part may be reproduced or transmitted in

any form or by any means, electronic or mechanical, including photo-
copying, microfilming, and recording, or by any information storage
and retrieval system, without permission in writing from the publisher.
MARCEL DEKKER, INC.

270 Madison Avenue, New York, New York 10016
Current printing (last digit):

10 9 8 7
Preface to the Second Edition
The principles and basis on which the first edition of this book
were formulated have been followed in the second edition, and all
the chapters of the first edition have been expanded and updated
to include new developments in the field. In addition, the following
new subjects have been incorporated:
Atmospheric corrosion
Corrosion inhibitors
Sheet linings
Designing to prevent corrosion
As in the first edition, theory is only touched on to provide a

basic background.
I extend my gratitude to all the contributors who updated their
chapters and to those other authors who undertook the assignment
of updating the work of contributors to the first edition who were
unable to update their original manuscripts.
in
Preface to the First Edition
This handbook has been designed and formulated for use by practic-
ing engineers and other persons concerned with the problem of
corrosion in their day-to-day job functions. Although the theory
of corrosion is touched upon to provide a basic background for
the sections on applications, the handbook is not necessarily intended
for the use of metallurgical and other engineering personnel who
are looking for advanced theories and techniques.
The major advantages and disadvantages of the most commonly
used materials of construction are discussed and evaluated. Practical
means of use are explained and their most advantageous areas of
application discussed. Materials of construction considered include
metals, nonmetals, plastics, coating materials, and elastomers.
Practical means of determining corrosion conditions before selection,
approaches to be used for the selection of materials of construction,
and means of monitoring corrosion are also included.
In general, this handbook has been designed as a guide to be
used to:
1. Solve existing corrosion problems

2. Select the best material of construction for a specific application,
taking into account cost and service life
3. Assist in the proper initial design so as to eliminate corrosion
pitfalls from being designed into the equipment
4. Determine what corrosion problems may or may not exist
5. Establish practices to monitor corrosion of existing equipment
vi Preface to the First Edition
Based on the areas covered and the practical approach established,

this handbook should also be of interest to young engineers and
college students, who can profit from the vast experience of the
many authors who have contributed to the text.
I wish to thank all the contributors to this work for their willing-
ness to share the knowledge they have gained through their experi-
ence. A special thanks is extended to Zane B. Laycock of NRC Inc.
for supplying data for the section on tantalum and permitting use
of these data in the handbook.

Contents
Preface to the Second Edition iii

Preface to the First Edition v
Contributors xvii
1. FUNDAMENTALS AND PREVENTION OF

METALLIC CORROSION
Dean M. Berger
Introduction 1
Mechanism of Corrosion 2
Preventing Corrosion 11
Protective Coatings 16
Conclusions 22
References 22
2. ATMOSPHERIC CORROSION 23
Introduction 23
Atmospheric Types 24
vu
viii Contents
General Factors Affecting Atmospheric Corrosion 25

Specific Atmospheric Corrodants 28
Effect on Metals and Protective Measures 29
3. CATHODIC PROTECTION 33
Introduction 33
Background 33
Theory 34
Method of Application 36
Current Requirements 41
Anode Materials and Backfill 42
Testing for Completeness of Protection 42
Overprotection 44
Economics 44
4. CORROSION INHIBITORS 47
Introduction 47
Passivation Inhibitors 48
Organic Inhibitors 49
Precipitation Inhibitors 50
Inhibitor Evaluation 50
Summary 51
5. CARBON STEEL AND LOW-ALLOY STEEL 53

Introduction 53
Heat-Treating Operations 55
Effect of Alloying Elements on the Properties of Steel 56
Case Hardening 58
Atmospheric Corrosion of Steel 58
Contents ix
General Corrosion Resistance 59

Phosphating 60
Clad Steels 60
Metallic Protective Coatings 63
6. STAINLESS STEELS 69
Introduction 69
Austenitic Stainless Steels 69
Martensitic Stainless Steels 76
Ferritic Stainless Steels 79
Duplex Stainless Steels 82
Preparation for Service 85
7. NICKEL AND HIGH NICKEL ALLOYS 89

N. Sridhar and F. Galen Hodge
Introduction 89
Commercially Pure Nickel 95
Nickel-Copper 96
Nickel-Molybdenum 98
Nickel-Chromium-Iron 103
Nickel-Chromium-Iron-Molybdenum 106
Nickel-Chromium-Molybdenum 112
Alloys for High-Temperature Corrosion 119
References 123
Supplemental Reading 124
8. COPPER AND COPPER ALLOYS 125

John M. Cieslewicz and Philip A. Schweitzer, P.E,
Introduction 125
Corrosion Resistance 126
Coppers 128
x Contents
High Copper Alloys 132

Copper-Zinc Alloys 132
Copper-Tin Alloys 134
Copper-Aluminum Alloys 136
Copper-Nickel Alloys 149
Conclusions 151
References 152
9. ALUMINUM ALLOYS 153

Ernest H. Hollingsworth, Harold Y. Hunsicker,
and Philip A. Schweitzer, P.E.
Introduction 153
Aluminum Wrought Alloys and Their Resistance to
General Corrosion 154
Aluminum Casting Alloys and Their Resistance to
General Corrosion 158
Chemical Nature of Aluminum: Passivity 160
Electrochemical Aspects of the Corrosion of Aluminum 162
Stress-Corrosion Cracking 170
Exfoliation Corrosion 175
Other Types of Corrosion 176
Welded, Brazed, and Soldered Joints 177
Weathering 178
Waters 179
Cathodic Protection 180
Foods 180
Chemicals 181
Coatings 183
References 185
Suggested Reading 186
10. TITANIUM 187

Loren C. Covington and Philip A. Schweitzer, P.E.
Introduction 187
Properties of Titanium 187
Contents xi
Fabrication 209
Bonded Titanium 210
References 211
11. TANTALUM 213

Introduction 213
Source of Tantalum 213
Tantalum Manufacture 214
Properties of Tantalum 215
Fabrication 225
Suggested Applications 229
12. ZIRCONIUM 231
Te-Lin Yau
Introduction 231
Physical and Mechanical Properties 232
Corrosion Properties 240
Special Corrosion Topics 260
Corrosion Protection 263
Typical Applications 267
Fabrication Practices 270
Zirconium Products 275
References 278
13. CAST ALLOYS 283

Glenn W. George and Patricia G.Breig
Introduction 283
Iron-Carbon Alloys 285
xii Contents
Stainless Steels 292

Nickel-Based Alloys 303
Copper-Based Alloys 307
Aluminum Alloys 311
Titanium 311
Zirconium 313
Magnesium Alloys 316
Casting Production 316
References 320
14. DEVELOPMENT AND APPLICATION OF

PLASTIC MATERIALS 323
John H. Mallinson
Introduction and History 323

Forms and Products Commercially Available 327
Specific Plastic Families 328
Recommended Design Practices 334
Plastics—Their Service and Use 347
Reinforcement 351
Nonfibrous Enhancers 355
Composite Laminates 359
Chemical Attack of Plastics—The Counterpart of
Metallic Corrosion 360
Other Causes of Failure 365
Plastics: Mechanisms of Failure from Abrasion 367
Electrically Grounding Plastic Systems 368
Ducts, Scrubbers, Fans, and Stacks 373
Some Comments on Other Types of Materials Used in
Duct, Scrubber, Fan, and Stack Construction 374
Design Checkpoints for Successful Plastic Piping
Systems 375
Design Checkpoints for Plastic Tanks 376
Linings 378
Nondestructive Testing 380
Sandwich Construction 383
Illustrated Case Histories 385
References 392
Contents xiii
15. DEVELOPMENT AND APPLICATION OF

CERAMIC MATERIALS 395
Ronald A. McCauley
Fundamentals of Corrosion 395

Development and Application of Corrosion-Resistant
Ceramic Materials 416
References 423
16. DEVELOPMENT AND APPLICATION OF ELASTOMERS 429

Introduction 429
Specifications 429
Natural Rubber 430
Isoprene 431
Butyl Rubber 431
Styrene-Butadiene-Styrene 432
Styrene-Ethylene-Butylene-Styrene 432
SBR Styrene 433
Neoprene 434
NBR-Nitrile 436
Chlorosulfonated Polyethylene (Hypalon) 437
Polysulfide (Thiokol ST) 438
Polysulfide (Thiokol FA) 439
Silicone Rubbers 439
Polybutadiene 440
Urethane Rubbers 440
Polyester Elastomer 442
Perfluoroelastomers 443
Ethylene-Acrylic Elastomer 445
Ethylene-Propylene Rubber 446
Acrylate-Butadiene 448
Polyamides (Nylon) 448
Polyetherimide (ULTEM) 449
Polytetrafluoroethylene 449
Fluorinated Ethylene Propylene 450
ECTFE (Halar) 450
ETFE (Tefzel) 451
xiv Contents
17. COATINGS 453
Kenneth B. Tator
Introduction 453
Coating System Selection 454
Environmental Compliance 458
What Is a Paint/Coating? 460
Paint Systems 470
Selection of a Suitable Coating System 471
Coating Application, Inspection, and Maintenance 485
18. LIQUID-APPLIED LININGS 491
Dean M. Berger
Introduction 491
Criteria for Tank Linings 492
Coating Application 506
Performance History and Failure Analysis 511
Summary 513
Appendix 514
References 519
19. CEMENTS AND MORTARS 521

George W. Read, Jr., Curtis E. Zimmer,
and Gary R. Hall
Introduction 521
Corrosion-Resistant Masonry 522
Chemical-Resistant Mortars 524
Monolithic Linings 528
Addendum 530
20. SHEET LININGS 533
General Considerations 533

Contents xv
Shell Preparation 535

Testing of Lining 536
Elastomeric Linings 536
Thermoplastic Linings 538
Causes of Lining Failure 543
Reference 545
21. CORROSION MONITORING 547

Gene Frederick Rak and Philip A. Schweitzer, P.E.
Introduction 547
Onstream Monitoring Equipment 548
Off stream Monitoring Equipment 573
Summary 582
Glossary 583
References 585
22. CORROSION-TESTING TECHNIQUES 587

Charles G. Arnold and Philip A. Schweitzer, P.E.
Introduction 587
Dimension Change 587
Weight Change 590
Hydrogen Diffusion 604
Electrical Resistance 606
Electrochemical Techniques 609
References 616
23. SELECTING MATERIALS OF CONSTRUCTION 619

Lewis W. Gleekman and Philip A. Schweitzer, P.E.
Principles 619
Strength/Weight Ratio 623
Corrosion Considerations 624
Nonmetallic Materials 629
xvi Contents
24. DESIGNING TO PREVENT CORROSION 639

Introduction 639
Corrosion Under Insulation 642
Structures 644
Instrument Rooms 651
Electrical Components 652
Index 653
Contributors
Charles G. Arnold Dow Chemical Company, Texas Division, Free-

port, Texas
Dean M. Berger Berger Associates, I n c . , Leola, Pennsylvania
Patricia G. Breig The Duriron Company, Inc., Dayton, Ohio
John M. Cieslewicz Ampco Metal, Milwaukee, Wisconsin
Loren C. Covington* Titanium Metals Corporation of America,
Henderson, Nevada
Glenn W. George The Duriron Company, I n c . , Dayton, Ohio
Lewis W. Gleekman^ Materials and Chemical Engineering Services,
Southfield, Michigan
Gary R. Hall Sauereisen Cements Company, Pittsburgh, Pennsylvania
F. Galen Hodge Haynes International, Inc., Kokomo, Indiana
Ernest H. Hollingsworth* Alcoa Laboratories, Alcoa Center, Penn-
sylvania
Harold Y. Hunsicker* Alcoa Laboratories, Alcoa Center, Pennsylvania
John H. Mallinson J. H. Mallinson PE & Associates, Inc., Front
Royal, Virginia
*Retired.
"f* Deceased.
xvu
xviii Contributors
Ronald A. McCauley Department of Ceramic Engineering, Rutgers,

The State University, New Brunswick, New Jersey
Gene Frederick Rak Exxon Company, USA, Baton Rouge, Louisiana
George W. Read, Jr. Sauereisen Cements Company, Pittsburgh,
Pennsylvania
Philip A. Schweitzer, P.E. Consultant, Chester, New Jersey
N. Sridhar Haynes International, Inc., Kokomo, Indiana
Kenneth B. Tator KTA-Tator Inc., Pittsburgh, Pennsylvania
Te-Lin Yau Teledyne Wah Chang Albany, Albany, Oregon
Curtis E. Zimmer Sauereisen Cements Company, Pittsburgh, Penn-
sylvania
1
FUNDAMENTALS AND PREVENTION
OF METALLIC CORROSION
DEAN M. BERGER Berger Associates, Inc., Leola, Pennsylvania
INTRODUCTION
Corrosion is defined as a gradual wearing away or alteration by a

chemical or electrochemical oxidizing process. Because the process
of corrosion returns metal to its original condition, we must consider
the action degeneration, in its true or primary form. Destruction
of metals by methods other than mechanical means is, therefore,
considered to be corrosion failure.
Ordinarily, iron and steel corrode in the presence of both oxygen
and water, and corrosion usually does not take place in the absence
of either of these. Rapid corrosion may take place in water; the
rate of corrosion is accelerated by the velocity or the acidity of
the water, by the motion of the metal, by an increase in temperature
or aeration, by the presence of certain bacteria, or by other less
prevalent factors. On the other hand, corrosion is generally retarded
by protective layers (or films) consisting of corrosion products
or adsorbed oxygen; high alkalinity of the water also retards the
rate of corrosion on steel surfaces. Water and oxygen, however,
are almost always the essential factors, and the amount of corrosion
is controlled by one or the other. For instance, corrosion of steel
does not occur in dry air and is negligible when the relative humidity
of the air is below 30% at normal or lower temperatures. Prevention
of corrosion by dehumidification is based on this [1],
All structural metals corrode to some extent in natural environ-
ments. Bronzes, brasses, stainless steels, zinc, and aluminum corrode
so slowly under the service condition in which they are placed that
Berger
they are expected to survive for long periods without protection.

Corrosion of structural grades of iron and steel, however, proceeds
rapidly unless the metal is amply protected. This susceptibility
to corrosion of iron and steel is of great concern because, owing
to favorable cost and physical property considerations, vast quanti-
ties are used. Annual losses due to corrosion of steel have been
variously estimated at nearly 70 billion dollars in the United States.
It is apparent that protection against corrosion of iron and steel
is an indispensable phase of sound engineering.
MECHANISM OF CORROSION
Corrosion in metals, whether in the atmosphere, underwater, or

underground, is caused by a flow of electricity from one metal
to another metal or a recipient of some kind; or from one part of
the surface of one piece of metal to another part of the same metal
when conditions permit the flow of electricity.
Furthermore, a moist conductor or electrolyte must be present
for this flow of energy to take place. The presence of an electrolyte
is a key condition for the process of corrosion to occur. Water,
therefore, especially salt water, is an excellent electrolyte.
Simply stated, energy (electricity) passes from a negative area
to a positive area through the electrolyte medium. Thus, to have
corrosion take place in metals, one must observe an (1) electrolyte,
(2) an area or region on a metallic surface with a negative charge
in relation to a second area, and (3) the second area with a positive
charge in opposition to the first [ 2 ] .
Sometimes the situation becomes further involved. The flow of
energy (electricity) may be from one metal to another or from one
metal recipient of some kind, which might be the soil. This is due
to various environments within a given soil. Soils frequently have
contained dispersed metallic particles or bacterial pockets that pro-
vide a natural electrical pathway with buried metal. If an electrolyte
is present and the soil is negative relative to the metal, the electrical
path will occur from the metal to the soil, and corrosion results.
Types of corrosion commonly identified on metal are as follows [ 3 ] :
Uniform Corrosion fatigue

Electrochemical Intergranular
Galvanic Fretting
Concentration cell Impingement
Erosion corrosion Dezincification
Embrittlement Graphitization
Stress corrosion Chemical reaction
Filiform
1. Fundamentals and Prevention of Metallic Corrosion
Water readily dissolves a small amount of oxygen from the atmos-

phere into solution, and this may become highly corrosive. When
the free oxygen dissolved in water is removed, the water is prac-
tically noncorrosive, unless it becomes acidic or unless anaerobic
bacteria incite corrosion. If oxygen-free water is maintained neutral
or slightly alkaline, it will be practically noncorrosive to steel.
Thus, steam boilers and water supply systems are effectively pro-
tected by deaeration of the water.
Several other important facts, fundamental to the corrosion of
steel, are (1) hydrogen gas is evolved when a metal corrodes in
acid and the rate of corrosion is relatively rapid; (2) surface films,
usually inert and often invisible, may greatly decrease the rate
of corrosion (as with aluminum and stainless steel); (3) the rate
of corrosion increases with temperature and velocity of motion up
to a certain point; and (4) corrosion is rarely uniformly distributed
over the metal surface.
Electrochemical Corrosion
The cell shown in Figure 1 illustrates the corrosion process in its
simplest form. This cell includes the following essential components:
1. A metal anode
2. A metal cathode
3. A metallic conductor between the anode and cathode
4. An electrolyte (water-containing conductive salts) in contact
with the anode and cathode but not necessarily of the same
composition at the two locations
In addition, oxygen will usually be present as a depolarizing

agent. As shown in Figure 1, these components are arranged to
form a closed electrical path or circuit. In the simplest case, the
anode would be one metal, perhaps iron, the cathode another, say
copper, and the electrolyte might, or might not, have the same
composition at both electrodes. Alternatively, the electrodes could
be of the same metal if the electrolyte composition varied.
If the cell, as shown, were constructed and allowed to function,
an electrical current would flow through the metallic conductor
and the electrolyte. The anode would corrode (rust, if the anode
were iron); chemically, this is an oxidation reaction. Simultaneously,
a nondestructive chemical reaction (reduction) would proceed at
the cathode, usually producing hydrogen gas on the cathode. When
the gas layer insulates the cathode from the electrolyte, current
flow will stop, thus, polarizing the cell. However, oxygen or some
other depolarizing agent is usually present to react with the hydro-
gen, reducing this effect; hence, the cell would continue to function.
Berger
Current flow in
conductor
Metallic conductor (wire)
Anode (metal 1) Cathode (metal 2 )
Oxygen or other
depolarizer in electrolyte
Oxidation reaction \£
occurs
lectrolyte
at anode S N
(conductive solution)
Reduction reaction occurs

at cathode
Current flow through

the electrolyte
FIGURE 1 Simple cell showing components necessary for corrosion.

(From Ref. 3.)
If the metallic conductor were replaced with a voltmeter, a difference

of potential could be measured between the electrodes.
The difference in potential that causes these electric currents
is mainly due to contact between dissimilar metallic conductors or
differences in concentration of the solution, generally related to
dissolved oxygen in natural waters. Almost any lack of homogeneity
on the metal surface or in its environment may initiate attack by
causing a differential in potentials that results in more or less local-
ization of corrosion. Many other factors are involved, but the fore-
going include most of the important facts known about ordinary
corrosion and are all satisfactorily explained by application of electro-
chemical principles. The metal undergoing electrochemical corrosion
need not be immersed in a solution, but it may be in contact with
moist soil, or patches of the metal surface may be moist.
Atmospheric corrosion differs from the action that occurs in
water or underground, in that a plentiful supply of oxygen is always
present. Here, the formation of insoluble films and the presence of
moisture and deposits from the atmosphere become the controlling
factors; an additional factor that affects the corrosion rate is the
presence of contaminants such as sulfur compounds and salt particles.

Nevertheless, atmospheric corrosion is mainly electrochemical, rather
than a direct result of chemical attack by the elements. The anodic
and cathodic areas, however, are usually quite small and close
together, so that, generally, corrosion is apparently uniform, rather
than in the form of severe pitting as in water or in soil.
The larger the anodic area is in relation to the cathode, the
faster the rate of degeneration or corrosion. It follows, therefore,
that anodes and cathodes exist on all iron and steel surfaces. Surface
imperfections, grain orientation, lack of homogeneity of the metal,
variation in the environment, localized shear and torque during
manufacture, mill scale, and existing red iron oxide rust.
Technical Definition of an Electrolyte

An electrolyte is a solution containing ions, which are particles
bearing an electric charge. Ions are present in solutions of acids,
alkalis, and salts.
It is well known that the formation of rust by electrochemical
reactions may be expressed as follows:
1. 4Fe -> 4Fe2+ + 8e

4Fe + 3O2 + H2O + 2Fe2O3 • H2O (hydrated red iron rust)
2. 4Fe + 2O2 + 4H2O + 4Fe(OH)2
4Fe(OH)2 + O2 + 2Fe2O3 • H2O + 2H2O (hydrated red iron rust)
According to a number of investigations, the most stable form

of rust is Fe 2 O 3 . At higher temperatures (900 to 1300°F) Fe2O3
reverts to Fe3OLf. It is believed that the formation of FegO^ can
occur either by heating the rusted steel to high temperatures or
by oxidizing (reducing) operations.
In an acid environment, even without the presence of oxygen,
the metal at the anode is attacked at a rapid rate, whereas at the
cathode, the hydrogen gas/film is being dissolved continuously,
forming a true hydrogen gas.
When corrosion by an acid results in the formation of a salt,
the reaction is slowed conditionally because of the salt formation
on the surface that is being attacked.
Galvanic Corrosion
Better known as simply dissimilar metal corrosion, this form of
degeneration pops up in the most unusual places and often causes
the most painful professional headaches.
Berger
The Galvanic Series of Metals guide provides details of how the

galvanic current will flow between two metals and which metal will
corrode when they are in contact or near each other in the ground
[4].
If rust or mill scale is present on the surface of the steel, gal-
vanic corrosion will take place. This action is due to the dissimilarity
with the metal; here, the base metal is the anode.
A galvanic couple may be the cause of premature failure in metal
components of hydraulic structures, or it may be advantageously
exploited. Galvanizing of iron sheets is an example of the useful
application of galvanic action. For this, iron is the cathode and
is protected against corrosion at the expense of the zinc anode.
Alternatively, a zinc or magnesium anode may be located in the
electrolyte close to the structure and still be connected metallically
to the iron or steel. This is termed cathodic protection of the struc-
ture. On the other hand, iron or steel becomes the anode when
in contact with copper, brasses, and bronzes, and corrodes rapidly
while protecting the latter metals.
The mill scale formed on steel during rolling varies with the
type of operation and the rolling temperature. In general, mill scale
is magnetic and contains three layers of iron oxide, but the bound-
aries between the oxides are not sharp. The outer layer of mill
scale is essentially ferric oxide, Fe 2 O 3 , which is relatively stable
and does not easily react. The layer closest to the steel surface
and sometimes intermingled with the surface crystalline structure
of the steel itself is ferrous oxide, FeO. This substance is unstable
and the iron in ferrous oxide is easily oxidized to ferric iron, result-
ing in a chemical change to ferric oxide. This process, accompanied
by an increase in volume, may result in the loosening of the intact
mill scale. The intermediate layer of magnetic oxide is best repre-
sented by the chemical formula Fe3Oi+. The actual thickness of mill
scale on structural steel, which depends on rolling conditions, varies
from about 0.002 in. to about 0.020 in. and consists mainly of the
magnetic oxide Fe3Oif and the FeO layer. Much of the mill scale
formed at high initial rolling temperatures is knocked off in subse-
quent rolling [5].
Unfortunately, mill scale is cathodic to steel ( i . e . , the mill scale
has a more noble potential) and an electric current can easily be
produced between the steel and the mill scale. This electrochemical
action will corrode the steel and protect the mill scale (Fig. 2).
The driving force (difference of potential) available to promote
the electrochemical corrosion reaction is reflected by the galvanic
series. This is a list of a number of common metals and alloys
arranged according to their tendency to corrode galvanically. Metals
grouped together do not have a strong effect on each other, and
Electrolyte (water) —
__^ .^-Current flow
Fe2+(rust) Cathode (broken
mill scale)
Anode
(steel)
FIGURE 2 Mill scale is cathodic to steel, establishing a corrosion

cell. (From Ref. 4.)
the farther apart any two metals appear, the stronger the corroding
effect on the one higher in the list. It is possible for certain metals
to reverse their positions in some environments, but the list, as
given, will hold generally in natural waters and the atmosphere.
(The galvanic series should not be confused with the similar electro-
motive force series, which shows exact potentials based on highly
standardized conditions that rarely exist in nature [4].)
Galvanic Series
Corroded end (anodic)
Magnesium
Magnesium alloys
Zinc
Aluminum 2S
Cadmium
Aluminum 17 ST
Steel or iron
Cast iron
Chromium iron (active)
Ni-resist
18-8 Chromium-nickel-iron (active)
18-8-3 Chromium-nickel-molybdenum-iron (active)
Lead-tin solders
Lead
Tin
Nickel (active)
Inconel (active)
Hastelloy C (active)
Brass
Copper
Bronzes
Berger
Copper-nickel alloys
Monel
Silver solder
Nickel (passive)
Inconel (passive)
Chromium-iron (passive)
18-8 Chromium-nickel-iron (passive)
18-8-3 Chromium-nickel-molybdenum-iron (passive)
Hastelloy C (passive)
Silver
Graphite
Gold
Platinum
Protected end (cathodic)
Although the preceding galvanic series generally represents

the driving force available to promote a corrosion reaction, the
actual rate experienced may be considerably different from that
predicted from the driving force alone. Electrolytes may be poor
conductors, or long distances may introduce a large resistance
into the corrosion cell circuit. More frequently, scale formation
forms a partially insulating layer over the anode. A cathode having
a layer of adsorbed gas bubbles as a consequence of the corrosion
cell reaction is said to be polarized. The effect of such conditions
is to reduce the theoretical consumption of metal by corrosion.
The area relationship between the electrodes also may strongly
affect the corrosion rate; a high cathode area/anode area ratio
produces rapid corrosion, but in the reverse case, the cathode
polarizes, and the rate soon drops to a negligible level.
The passivity of stainless steels is attributed to the presence
of corrosion-resistant oxide film over the surfaces. In most natural
environments, they will remain in a passive state and, thus, tend
to be cathodic to ordinary iron and steel. Change to an active state
usually occurs only when chloride concentrations are high, as in
seawaters or in reducing solutions. Oxygen starvation also causes
the change to an active state. This occurs where there is no free
access to oxygen, such as in crevices and beneath contamination
on partially fouled surfaces. Accelerated corrosion of steel and
iron can be produced by stray currents. Direct currents in the
soil or water, associated with nearby cathodic protection systems,
industrial activities, or direct-current electric railways, can be
intercepted and carried for considerable distances by buried steel
structures. Corrosion takes place where the stray currents are
discharged from the steel to the environment, and damage to the
structure can occur very rapidly indeed [4],
Cathodic area (sieel at Oxygen diffusing into earth

top of pipe) from ground surface
Electrolyte I ( s o i l with ground

Buried pipe water high in oxygen content)
Anodic area (steel Current flow

bottom of pipe)
Electrolyte 2 (soil with ground
water deficient in oxygen content)
Fe2*(rust)
FIGURE 3 Metal pipe buried in moist soil may corrode on the bottom.
A difference in oxygen content at different levels in the electrolyte
will produce a difference of potential. Thus, anodic and cathodic
areas will develop, and a corrosion cell, called a concentration cell,
will form. (From Ref. 4.)
Differences in soil conditions, such as moisture content and

resistivity, commonly are responsible for creating anodic and cathodic
areas. Where there is a difference in the concentration of oxygen
in the water or in moist soils in contact with metal at different
areas, cathodes will develop at points of relatively high oxygen
concentrations, and anodes at points of low concentration. Strained
portions of metal reportedly tend to be anodic and unstrained portions
cathodic. Thus, under all ordinary circumstances where iron and
steel are exposed to natural environments, the basic conditions
essential to corrosion are present to a greater or lesser degree
(Fig. 3).
Pitting deserves special mention because it is the type of local
cell corrosion that is predominantly responsible for the functional
failure of iron and steel hydraulic structures. Pitting may result
in the perforation of water pipe, rendering it unserviceable, even
though less than 5% of the total metal has been lost through rusting.
Even where confinement of water is not a factor, pitting will cause
structural failure from localized weakening effects, although there
is still considerable sound metal remaining.
Pitting develops when the anodic (corroding) area is small in
relation to the cathodic (protected) area. For example, it can be
expected where large areas of the surface are generally covered
by mill scale, applied coatings, or deposits of various kinds, but
breaks exist in the continuity of the protective material. Pitting
may also develop on bare, clean metal surfaces because of irregulari-
ties in the physical or chemical structure of the metal. Localized,
10 Berger
dissimilar soil conditions at the surface of steel can also create

conditions that promote the pitting type of corrosion [4],
The main factors that cause and accelerate pitting are electrical
contact between dissimilar materials, or between what are termed
concentration cells (areas of the same metal where oxygen or conduc-
tive salt concentrations in water differ). Even in cleistomatic struc-
tures, these couples cause a difference of potential that results
in an electric current flowing through the water, or across moist
steel, from the metallic anode to a nearby cathode. The cathode
may be copper or brass, mill scale, or any other portion of the
metal surface that is cathodic to the more active metal areas. In
practice, mill scale is cathodic to steel and is found to be one of
the more common causes of pitting. The difference of potential
generated between steel and mill scale often amounts to 0.2 to 0.3 V;
this couple is nearly as powerful a generator of corrosion currents
as is the copper-steel couple. However, when the anodic area is
relatively large compared with the cathodic area, the damage is
spread out and usually negligible; when the anode is relatively
small, the metal loss is concentrated and may be serious.
On surfaces containing mill scale, the total metal loss is nearly
constant as the anode area is decreased, but the degree of penetra-
tion increases. Figure 2 shows diagrammatically how a pit forms
where a break occurs in mill scale. When contact between dissimilar
materials is unavoidable and the surface is painted, it is important
to paint both materials—especially the cathode. If only the anode
is coated, any weak points, such as pinholes or holidays in the
coating, will probably result in intense pitting [5].
Severe corrosion, leading to pitting, is often caused by concen-
tration cells, particularly when differences in dissolved oxygen
concentration occur. When a part of the metal is in contact with
water relatively low in dissolved oxygen, it is anodic to adjoining
areas in contact with water higher in dissolved oxygen. This lack
of oxygen may be caused by exhaustion of dissolved oxygen in
a crevice (Fig. 4). The low oxygen area is always anodic. Figure 4
illustrates another type of concentration cell; this cell at the mouth
of a crevice is due to a difference in concentration of the metal in
solution. These two effects sometimes blend together, as in a re-
entrant angle in a riveted seam.
As a pit, perhaps caused by broken mill scale, becomes deeper,
an oxygen concentration cell is started by the depletion of oxygen
in the pit, and, this will proportionately accelerate the rate of
penetration. Fabrication operations may crack mill scale and result
in accelerated corrosion.
A pit develops in stages, original attack, propagation, termination,
and reinitiation. After the original attack, the rate of depression
increases because of changes in the cathodic and anodic environment.
1. Fundamentals and Prevention of Metallic Corrosion 11
Low Metal Ion Concentration,
High Metal Ion Concentration
METAL ION CONCENTRATION CELL
High Oxygen Concentration
Low Oxygen Concentration
OXYGEN CONCENTRATION CELL
FIGURE 4 Corrosion caused at crevices by concentration cells.

The attacks may occur simultaneously. (From Ref. 4.)
Termination will occur with increase internal resistance of the local

cell. Frequently, the cell is filled with corrosion products, or a
drying out of the pits will result in a halt in the corrosion process.
When rewetted, corrosion may cease or commence again, depending
upon environmental conditions or differential aeration between the
main pit cavity and solutions in other minor adjoining cracks. Such
conditions can be evaluated by using microscopic techniques to
determine the extent and depth of pitting.
PREVENTING CORROSION
In the book Designing to Prevent Corrosion in the Process Industry

[6], Whitney suggests some very basic common sense approaches
to reduce or eliminate the problem of corrosion. He suggests approach-
ing the problem at the design stage and also through the use of
good maintenance procedures after start-up of the facility.
Whitney1 s recommendations call for the evaluation of
1. Plant location (coastal locations are troublesome)

2. Plant layout; check prevailing winds, fallout, and related items
3. Proper fume removal and control
12 Berger
4. Sewer treatment of effluents

5. Design of equipment to avoid
a. Galvanic corrosion
b. Crevice corrosion
For example, using Whitney's concepts in the design of tankage,

one could eliminate crevice corrosion-concentration cell corrosion
by proper design. DO NOT LAP as shown in Figure 5. If lap welding
is to be employed, the laps should be filled with fillet welding or
a suitable caulking compound designed to prevent crevice corrosion
(Fig. 6). The use of a proper butt weld will eliminate the need
for future maintenance (Fig. 7). This form of butt welding is espe-
cially suitable for tank-lining work with protective coatings. Butt
welding allows for grinding down smooth and then subsequent coating
with a uniform milage of coating. Welding with dissimilar metals can
establish a corrosion cell (Fig. 8).
The importance of organic-coating system selection and application
is stressed. Adequate paint systems or lining materials exist that
will deter the corrosion rate of carbon steel surfaces. High-
performance coatings such as epoxy, polyesters, polyurethanes,
vinyl, or chlorinated rubber help to satisfy the needs of the corro-
sion engineer. Special primers are used to provide passivation,
galvanic protection, or barrier properties that are necessary for
corrosion inhibition.
A water-soluble corrosion inhibitor will reduce galvanic action
by depassivating the metal or by laying down an insulating film on
FIGURE 5 Improper lap weld protection. (From Ref. 4.)
L
FIGURE 6 P r o p e r l a p weld p r o t e c t i o n . (From Ref. 4 . )
FIGURE 7 Butt weld. (From Ref. 4 . )

Electrolyte (water) ' 2 + (rust)

^ Current flow
Cathode
(steel)
(weld metal)
FIGURE 8 Weld metal may be anodic to steel, creating a corrosion

cell when immersed. (From Ref. 4.)
either the anode or the cathode, or both. A very small amount

of chromate, polyphosphate, or silicate added to water acts in this
way. A slightly soluble inhibitor incorporated in the primary coat
of paint may also have a considerable protective influence. Inhibitive
pigments in paint primers act well in this manner, as long as they
do not dissolve sufficiently to leave holes in the paint film.
It is believed that corrosion by chemical attack is the single
most destructive force against steel surfaces. Chemicals are used
everywhere and the chemical industry is rapidly expanding. Chemical
attack is more dramatic in that the steel literally dissolves and
erodes away. One observer, after inspection of a paper mill, said:
"The steel beams looked like they had been chewed by mice with
strong teeth." The corrosion engineer must, therefore, be concerned
with the environment and the chemicals surrounding a structure.
Halogens are particularly aggressive. The galvanized roof of one
building was completely eaten away within 6 months after erection.
This building sat downstream of an aluminum ingot plant where
fluorides were always present in the atmosphere. Selection of mate-
rials is extremely important. In this case, galvanized steel should
not have been specified.
Coatings help prevent corrosion by providing
1. Sacrificial or galvanic protection

2. Passivation of the steel using inhibitive pigments
3. A barrier against the environment
Sacrificial Coatings
Zinc-rich primers are applied at 3.0-mil dry-film thickness to provide
galvanic protection. These primers are very effective, even in chemi-
cal environments because the zinc will dissipate itself before the
steel is attacked. Adequate high-performance top coats are recom-
mended to prolong the life of the coating system.
14 Berger
Passivation and Corrosion Inhibitors

Most paint primers contain an inhibitive of partially soluble pigment,
such as zinc chromate, that reacts with the steel substrate to form
the iron salt. These salts slow down the corrosion of steel. Chro-
mates, phosphates, molybdates, borates, silicates, and plumbates
are common. Some pigments passivate by contributing alkalinity,
thereby slowing down the chemical attack on steel. Alkaline pigments,
such as metaborates, cement or lime, or red lead, are all quite
effective, provided that the environment is not too aggressive.
Many new pigments have been introduced to the paint industry.
In 1976, Hammond Lead offered a zinc phosphosilicate and Silberline
manufactured a zinc flake as examples.
Barrier Coatings
Protective coatings are the most widely used and recognized forms
of barrier materials in engineered and remedial construction. These
protective barriers may vary in thickness from thin paint films
of only a few mils to heavy mastic coatings applied about 1/4 to
1/2 in. thick to acid-proof brick linings several inches thick. Barrier
coatings are effective because they keep moisture and oxygen away
from the steel substrate. The lower the moisture vapor transmission
rate of the polymer, the more effective it is as a vehicle for protec-
tive coatings. The thicker the coating, the better moisture is kept
out. Protective barrier coatings vary considerably in composition,
performance, and applied cost.
Cathodic Protection
Simply stated, cathodic protection serves to reverse electric current
flow within the corrosion cell. Cathodic protection is used to reduce
or eliminate corrosion by connecting a more active metal to the
metal that must be protected. For example, zinc and magnesium
anodes are used to protect steel in marine environments.
The use of cathodic protection to reduce or eliminate corrosion
is a long-standing successful technique employed in marine struc-
tures, pipelines, bridge decks, sheet piling, equipment, and tankage
of all types, particularly below water or underground. Typically,
zinc and magnesium anodes are used to protect steel in marine
environments. The anodes are replaced after they are consumed.
Cathodic protection also employs the use of direct current (DC)
and a relatively inert anode. As happens in all forms of cathodic
activity, an electrolyte is needed for current flow. Cathodic protec-
tion and the use of protective coatings are most often employed
jointly, especially in marine applications and aboard ships, where
impressed current inputs usually do not exceed 1 V [7]. Beyond

that point, many coating systems tend to disbond. Current flow
for cathodic protection in soils is usually 1.5 to 2 V.
Choice of anodes for buried steel pipe depends on job conditions.
Magnesium is most commonly used for galvanic anodes; however,
zinc also can be used. Galvanic anodes are seldom used when the
resistivity of the soil is over 3000 ft-cm; impressed current is normally
used for these conditions. Graphite, high silicon cast iron, scrap
iron, aluminum, and platinum are used as anodes with impressed
current. The availability of low-cost power is often the deciding
factor in choosing between galvanic or impressed current cathodic
protection.
Protective coatings are normally- used in conjunction with cathodic
protection and should not be neglected when cathodic protection
is contemplated in new construction. Because the cathodic protection
current must protect only the bare or poorly insulated areas of
the surface, coatings that are highly insulating, very durable,
and free of discontinuities lower the current requirements and
system costs. Moreover, a good coating enables a single impressed
current installation to protect many miles of piping. Coal tar enamel,
epoxy powder coatings, and vinyl resin are examples of coatings
that are most suitable for use with cathodic protection. Certain
other coatings may be incompatible; for instance, phenolic coatings
may deteriorate rapidly in the alkaline environment created by
cathodic protection currents. Although cement mortar initially con-
ducts the electrical current freely, polarization (formation of an
insulating film on the surface as a result of the protective current)
is believed to reduce the current requirement moderately.
Cathodic protection is being used increasingly to protect buried
and submerged metal structures in the oil, gas, and waterworks
industries and has specialized applications such as the interiors
of water storage tanks. Pipelines are routinely designed to ensure
the electrical continuity necessary for effective functioning of the
cathodic protection system. Thus, electrical connections or bonds
are required between pipe sections in lines utilizing mechanically
coupled joints, and insulating couplings may be employed at intervals
to isolate electrically some parts of the line from other parts. When
needed, leads may be attached during construction to facilitate
cathodic protection installation.
Good inspection procedures are required to maintain surveillance
of cathodic protection installations. Such service is available from
suppliers of these systems.
Good engineering practice, material selection, design consideration,
and inspection will prolong the life of metal structures.
16 Berger
PROTECTIVE COATINGS
Protective coatings and lining materials are often examined by inspec-

tion personnel and found to be acceptable. Rust spotting or a few
small blisters might occur. These, in themselves, may not be a
really serious problem. The fact remains, however, that these ob-
servations are the first signs of corrosion. Most of the time they
may be corrected easily at an early stage.
The breakdown of protective coatings over steel substrates may
be analyzed by a step wise procedure. These steps usually are visually
recognized and are a part of corrosion analysis.
Protective coatings act as a barrier. They prevent moisture,
oxygen, and other chemicals from attacking the steel substrate.
Most coating films, however, permit chemicals, moisture vapor,
and oxygen to permeate them and attack the steel. This phenomena
is accentuated at temperatures between 150°F and 210°F. Gaseous
penetration occurs not only through pinholes, and other micropores,
but also through the general coating film. The movement of pene-
trants through the coating film is fostered principally by osmotic
and electroendesmotic pressures and the constant thermally induced
movements and vibrations of the coating film molecules.
First Stages of Corrosion: Spot Rusting or Blistering

Early stages of corrosion are often left unattended. They have
been described many times as rust spotting. The standards for
determining and evaluating degree of rust spotting are found in
Steel Structures Painting Council Vis-2 or ASTM D610-68. One rust
spot found in 1 sq ft may provide a 9+ rating but three or four
rust spots drop the rating to 8. That the rust spots go unattended
provides the mechanism for further corrosion to take place.
Early stages of corrosion can be recognized as blistering. Fre-
quently, blistering occurs without external evidence of rusting
or corrosion. The mechanism of blistering is attributed to osmotic
attack or a dilation of the coating film at the interface with the
steel under the influence of moisture. Water and chemical gases
pass through the film, dissolve ionic material either from the film
or the substrate, causing an osmotic pressure greater than that
of the external face of the coating. This establishes a solute con-
centration gradient, with water building up at these sites until
the film eventually blisters. Visual blistering standards are found
as ASTM D 714-56.
Blistering is also dependent upon electrochemical reactions. Water
diffuses through a coating also by an electroendesmotic gradient.
After corrosion has started, moisture is pulled through the coating
by an electrical potential gradient between the corroding area and

the protected areas that are in electrical contact. Therefore, osmosis
starts the blistering, and as soon as corrosion begins, electroendes-
motic reactions greatly accelerate the corrosion process. By adding
heat and acidic chemicals, the breakdown occurs most rapidly. At
temperatures of 150°F to 200°F the chemical reaction is accelerated.
Thus, steel will literally dissolve in a chemical environment at these
temperatures. Moisture is everpresent and often condenses on the
surface behind the blister. This condensation offers a solute for
gaseous penetrants to dissolve. In acidic environments the water
pH behind the blister can drop down as low as 1.0 to 2.0; there-
fore, the steel is subjected to severe attack.
In SO2 scrubbers, coatings often are blistered after less than
1 year service. Low pH and elevated temperatures cause premature
corrosion to occur (Fig. 9).
FIGURE 9 An SO2 scrubber flue. Early signs of corrosion failure.

Blisters in polyester lining are the size of half dollars. Water pH
2.5 is entrapped.
18 Berger
Second Stage of Corrosion: General Rusting

After one rust spot has been observed or a few blisters are found,
the condition advances to general rust spotting. The second stage
of corrosion can be described as general rusting. This most fre-
quently is seen as red iron rust, Fe2O3. However, within SO2
scrubber systems, which do not have sufficient oxygen during
normal operation, the rusting is usually black FeO. This converts
to Fe2O3 eventually as the unit is shut down and more oxygen
is available. The second stage of rusting may therefore be more
accurately described as a number 5 or number 3 rusting condition
according to SSPC Vis-2 (Fig. 10).
Third Stage of Corrosion: Coating Disbondment

The next advanced stage of corrosion is the total disbondment of
the coating, and this results in direct exposure of the steel to the
environment. No longer is the coating protecting the steel substrate,
FIGURE 10 An SO2 scrubber flue. Second stage of corrosion. Black

iron oxide or iron sulfide appears through weakened lining.
FIGURE 11 An S02 scrubber flue. Third stage of corrosion. Lining

has lost adhesion. Spot corrosion or rusting appears beneath the
coating.
therefore, corrosion can now occur at an uninhibited rate. The

acidic conditions within the SO2 scrubber system will quickly corrode
the steel at these elevated temperatures, especially, with plenty
of moisture present. Disbondment occurs because of chemical attack
on the substrate, forcing off the coating. One might think of dis-
bondment as one immense blister (Fig. 11).
Fourth Stage of Corrosion: Pitting

Once the coating has been removed and no longer acts as a protective
barrier, the steel is left to be directly attacked. This attack most
frequently is not uniform but, rather, localized into many electro-
lytic cells. Each cell with an anode and a cathode, an electrolyte
(moisture and acid), and the steel surface provide the perfect mecha-
nism for pitting to occur: the concentration cell.
Pitting develops when the anodic (corroding) area is small relative
to the cathodic area. These concentration cells develop where oxygen
or conductive electrolyte concentrations in water differ. Mill scale,
for example, is cathodic to steel; therefore, areas surrounding
mill scale would be eaten away and pitted first. In a short time,
20 Berger
FIGURE 12 SO2 scrubber flue. Fourth stage of corrosion. Severe

pitting occurs after prolonged acidic attack.
the pitting will undercut the mill scale and flaking occurs. Pitting
will cause structural failure from localized weakening effects while
there is still considerable sound metal remaining (Fig. 12).
Fifth Stage of Corrosion: Flaking of Steel

and Development of Holes
As the corrosion cell becomes more active, the rust and pitting
become more advanced. Deep pits in steel may eventually penetrate
completely to cause holes. Such penetrations generally result in
structural loss and replacement of the steel at considerable expense
to the owner. Within the corrosion cell, pitting has occurred to
such a degree that undercutting, flaking, and delamination of the
steel is noted. Most of these pits have a conical configuration
(Fig. 13).
After the small hole develops, the electrolyte now can seek other
fresh surfaces on the reverse side. This enables corrosion to occur
on both surfaces, front and back.
FIGURE 13 An S0 2 scrubber flue. Fifth stage of corrosion. Con-
siderable loss of steel. Small hole completely through steel liner.
FIGURE 14 An SO2 scrubber flue. Final stage of corrosion. Hole

about 1 x 2 ft. A plate will be welded over this area and a new
lining applied.
22 Berger
Final State of Corrosion: Complete Loss of Steel

As the chemicals present condense on the unprotected substrate,
corrosion occurs as its most rapid and aggressive rate. Large gaping
holes are found, causing considerable structural damage (Fig. 14).
These holes are rapidly enlarged because the electrolyte is ever-
present on both front and back surfaces of the steel. Costly repairs
are necessary. Replacement of steel and welding of large plates
to the surface are necessary. Complete inspection is required to
determine the functionality of the structure.
CONCLUSIONS
Good inspection procedures and preventive maintenance practices

are required to prevent excessive corrosion. Proper design considera-
tions are necessary to provide adequate protection. Material selection
and coating systems designed to prevent corrosion are required.
REFERENCES
1. Theory of corrosion, Good Painting Practice, Vol. 1. (1968).

Steel Structures Painting Council, Pittsburgh, Chap. 1.
2. Introduction to Corrosion. (1968). Carboline Co.
3. Berger, D. M. (1974). Corrosion principles can never be forgotten
in organic finishing, Metal Finish. 72: November.
4. Kiewit, J. (1976). The Paint Manual, USDI Bureau of Reclamation,
Denver, Chap. III.
5. Speller, F. N. (1951). Corrosion Causes and Prevention, McGraw-
Hill, New York.
6. Whitney, F. L. (1959). Designing to Prevent Corrosion in the
Process Industry, 59-SA-58, American Society of Mechanical
Engineers, May.
7. Anderton, W. A. (1970). The aluminum vinyl for ships bottoms.
J. Oil Colour Chem. Assoc. 53: November.
2
ATMOSPHERIC CORROSION
PHILIP A. SCHWEITZER, P.E. Consultant, Chester, New Jersey
INTRODUCTION
Atmospheric corrosion, although not a separate form of corrosion,

is uniquely important because of the many outdoor structures, such
as buildings, bridges, towers, fences, automobiles, ships, and
innumerable other applications, that are exposed to the atmospheric
environment. Associated costs resulting from atmospheric corrosion
can be staggering. Because of these factors a considerable amount
of attention has been devoted to this subject.
Atmospheric corrosion is a complicated electrochemical process
taking place in corrosion cells consisting of base metal, metallic
corrosion products, surface electrolyte, and the atmosphere. Because
this is an electrochemical process, an electrolyte must be present
on the surface of the metal for corrosion to occur. In the absence
of moisture, which is the common electrolyte associated with atmos-
pheric corrosion, metals corrode at a negligible rate. For example,
carbon steel parts left in the desert remain bright and tarnish
free over long periods. Also, in climates where the air temperature
is below the freezing point of water or of aqueous condensation
on the metal surface, rusting is negligible because ice is a poor
conductor and does not function effectively as an electrolyte.
Atmospheric corrosion depends not only on the moisture content
present but also on the dust content and the presence of other
impurities in the air, all of which have an effect on the condensation
of moisture on the metal surface and the resulting-corrosiveness.
Air temperature can also be a factor.
23
24 Schweitzer
ATMOSPHERIC TYPES
Geographic location plays an important part in atmospheric corrosion

because corrosion rates are affected by local conditions. Hence,
atmospheres can be divided into the following categories:
Rural
Urban
Arctic
Tropical
Wet
Dry
Industrial
Marine
For all practical purposes, the more rural the area, with little or
no heavy manufacturing operations or with very dry climatic condi-
tions, the less will be the problems of atmospheric corrosion.
The air in industrial regions is laden with various sorts of con-
taminants, resulting from the burning of fossil fuels, hazardous
waste products, road traffic, and energy production.
Combustion of fossil fuels and hazardous waste products should
produce only carbon dioxide, water vapor, and inert gas as combus-
tion products. But this is seldom the case. Depending upon the
impurities contained in the fossil fuel, the chemical composition
of the hazardous waste materials incinerated, and the combustion
conditions encountered, a multitude of other compounds may be
formed.
The most common contaminant resulting from the burning of
fossil fuels is SOX. Combustion of chemical wastes produces such
pollutants as hydrogen chloride, chlorine, hydrogen fluoride, and
hydrogen bromide. When organophosphorus compounds are incinerated,
corrosive phosphorus compounds are produced. Chlorides are also
a product of municipal incinerators.
Road traffic and energy production lead to the formation of NOX
compounds. The antipollution regulations that have been enacted
do not prevent escape into the atmosphere of quantities of these
materials sufficient to eliminate corrosion problems.
Marine environments are subject to chloride attack resulting
from the deposition of fine droplets or crystals formed by evaporation
of spray that has been carried by the wind from the sea. The quan-
tity of chloride deposition from marine environments is directly
proportional to the distance from the shore. The nearer the shore,
the greater the deposition and corrosive effect.
2. Atmospheric Corrosion 25
In addition to these general air contaminants, there may also

be specific pollutants found in a localized area. These may be emitted
from a manufacturing operation on a continuous or spasmodic basis
and can result in a much more serious corrosion problem than that
caused by the presence of the general atmospheric pollutants.
Because of these varying conditions, a material that is resistant
to atmospheric corrosion in one area may not be satisfactory in
another. For example, galvanized iron is perfectly suitable for appli-
cation in rural atmospheres, but it is not as resistant when exposed
to industrial atmospheres.
GENERAL FACTORS AFFECTING

ATMOSPHERIC CORROSION
As stated previously, atmospheric corrosion is an electrochemical

process that depends upon the presence of an electrolyte. Water,
resulting from rain, dew, fog, melting snow, or high humidity,
is the usual electrolyte associated with atmospheric corrosion. Be-
cause an electrolyte is not always present, atmospheric corrosion
must be considered a discontinuous process.
Corrosion takes place during the time of wetness. This phrase
refers to the period during which the surface is covered by a film
of water (electrolyte) that permits appreciable corrosion to take
place. The time of wetness is dependent upon the frequency of
rain, fog, dew, the temperature of the metal surface, the tempera-
ture of the air, relative humidity of the atmosphere, the wind speed,
and the hours of sunshine. As can be seen, the local climatic con-
ditions are an important factor in the resulting corrosion rate.
Adsorption Layers
Adsorption of water on the metal surface may be the result of the
relative humidity of the atmosphere, of the chemical and physical
properties of the corrosion products, of the properties of materials
deposited from the air, or of a combination of all three. Industrial
atmospheres contain suspended particles of carbon, carbon com-
pounds, metal oxides, sulfuric acid, sodium chloride, and ammonium
sulfate, to mention just a few. When these substances combine with
moisture or when, because of their hygroscopic nature, they form
an electrolyte on the surface, corrosion is initiated.
This adsorption will occur above what is known as the critical
relative humidity, which corresponds to the vapor pressure above
a saturated solution of the salt present. The amount of water on
the surface has a direct effect on the corrosion rate.
26 Schweitzer
Phase Layers
Phase layers are the result of the formation of dew by condensation
on a cold metallic surface, precipitation in the form of rain or fog,
and wet or melting snow. The rate of corrosion will be dependent
upon the concentration and nature of the corrodants in the electro-
lyte, which will vary depending upon the deposition rates, frequency
of wetting, drying conditions, and degree of rain protection provided.
If the surface is wetted after a long dry spell during which there
has been a large accumulation of surface contamination, the corrosion
rate will be greater than that for a smaller amount accumulated
during a shorter dry period. Corrosion will also be affected by
the quantity of electrolyte present.
Dew
Dew is an important cause of atmospheric corrosion—more so than
rain—and particularly under sheltered conditions. Dew forms when
the temperature of the metal surface falls below the dew point of
the atmosphere. This can occur outdoors during the night when
the surface temperature of the metal is lowered as a result of radiant
heat transfer between the metal and the sky. It is also quite common
for dew to form during the early morning hours when the air tem-
perature rises faster than the temperature of the metal.
The high corrosivity of dew is a result of several factors.
1. Relatively speaking, the concentration of contaminants in dew

are higher than in rain water, which leads to lower pH values.
Heavily industrialized areas have reported pH values of dew
in the range of 3 and lower.
2. The washing effect, which occurs with rain, is usually slight
or negligible.
With little or no runoff, the pollutants remain in the electrolyte

and continue their corrosive action. As the dew dries, these con-
taminants remain on the surface to repeat their corrosive activity
with subsequent dew formations.
Rain
Rain has the ability to either increase or to decrease the effects
of atmospheric corrosion, depending upon conditions. Corrosive
action is increased by rain because a phase layer of moisture is
formed on the metal surface. This activity is increased when the
rain washes corrosion promoters, such as H+ and SO^~, from the
air. Rain has the ability to decrease corrosive action on the surface
of the metal as a result of washing away the pollutants that had
been deposited during the preceding dry spell.
Whether the rain will increase or decrease the corrosive action

is dependent upon the ratio of deposition between the dry and
wet contaminants. When the dry-period deposition of pollutants
is greater than the wet-period deposition of sulfur compounds,
the washing effect of the rain will be dominant and the corrosive
action will be decreased.
In areas where the air is not as heavily polluted, the corrosive
action of the rain will assume a much greater importance because
it will increase the corrosion rate.
Fog
In areas that have an appreciable degree of air pollution, high
acidity and high concentrations of sulfate and nitrate will be found.
The pH of fog water has been found to be in the range of 2.2
to 4.0 in highly contaminated areas. This leads to increased corro-
sivity.
Dust
The primary contaminant of air, on a weight basis, in many locations
is dust. When in contact with metallic surfaces and combined with
moisture, this dust can promote corrosion by forming galvanic or
differential aeration cells that, because of their hygroscopic nature,
form an electrolyte on the surface. This is particularly true if the
dust consists of water-soluble particles or particles on which sulfuric
acid is adsorbed. Dust-free air, therefore, is less likely to cause
corrosion.
Temperature
The effect of temperature on atmospheric corrosion has not been
the subject of many studies. It appears that the effect of tempera-
ture is greater on the atmospheric corrosion of carbon steel than
on other metals. An increase in temperature accelerates corrosive
attack by increasing the rate of electrochemical and chemical reactions
and of the diffusion process. Consequently, under constant-humidity
conditions, a temperature increase will promote corrosion.
Conversely, an increase in temperature can also cause a decrease
in the corrosion rate by causing a more rapid evaporation of the
surface moisture film. This reduces the time of wetness which,
in turn, decreases the corrosion rate. In addition, as the tempera-
ture is increased, the solubility of oxygen and other corrosive
gases in the moisture film is decreased.
When the air temperature falls below 0°C (32°F) the electrolytic
film may freeze. This freezing causes a decrease in the corrosion
rate, which is typical of atmospheric corrosion rates in arctic and
subarctic regions.
28 Schweitzer
In general, temperature is a factor influencing atmospheric corro-

sion rates, but it is of importance only under extreme conditions.
It has little effect on the atmospheric corrosion rate when materials
are subjected to long-term exposure in a temperate climate zone.
SPECIFIC ATMOSPHERIC CORRODANTS
The primary contaminants in the air that lead to atmospheric corro-

sion are:
so x
Chlorides
Oxygen
These contaminants are found in industrialized and urban areas.

In addition to these general contaminants, other pollutants may
be present in local areas.
Sulfur dioxide (SO2) is the most important corrosive contaminant

found in industrial atmospheres. It is formed as a result of the
burning of fossil fuels, such as coal and oil, and of the combustion
products from the incineration of organic and hazardous wastes.
The sulfur dioxide is oxidized by water droplets to form sulfuric
acid, which is highly corrosive in dilute concentrations.
Atmospheric corrosion resulting from sulfur pollutants is usually
confined to areas having a high population, many structures, and
severe pollution. Deposition of sulfur compounds is accomplished by:
1. Dry deposition
a. Absorption of sulfur dioxide gas on metal surfaces
b. Impaction of particles (sulfates)
2. Wet deposition
a. Removal of gas from the atmosphere by precipitation in the
form of rain or fog
The dry deposition of sulfur dioxide is the primary deposition process

responsible for the atmospheric corrosion of metallic structures.
NOX
NOX emissions are also the result of a combustion process but of
a different source than that producing SOX emissions. Energy produc-
tion and road traffic are the main sources of NOX.
During the combustion process, the nitrogen oxides are emitted

as NO, which is oxidized to NO2, which can be further oxidized
to HNO3. This latter reaction has a very slow rate; therefore,
in the immediate vicinity of the emissions, the predominant contami-
nant is NO2. At further distances the concentration of nitric acid
increases.
Chlorides
Chlorides find their way into the atmosphere from marine environ-
ments and emissions of gaseous HC1 from coal burning and municipal
incinerators.
Chloride deposition from marine environments is in the form
of droplets or crystals formed by evaporation of spray that has
been carried by the wind from the sea. This deposition decreases
with increasing distance from the shore as the droplets and crystals
are filtered off when the wind passes through vegetation or they
settle by gravity.
The gaseous HC1 is quite soluble in water and forms hydrochloric
acid which is extremely corrosive.
Oxygen
Oxygen is present naturally in the air and is readily absorbed
from the air into the water film on the metal surface, which may
be considered saturated, thus enhancing any oxidation reactions.
Hydrogen Sulfide
In some contaminated atmospheres, trace amounts of hydrogen sulfide
may be found. This can cause the tarnishing of silver and copper
by the formation of tarnish films.
EFFECT ON METALS AND PROTECTIVE MEASURES
Carbon steel is the most widely used metal for outdoor applications,
although large quantities of zinc, aluminum, and copper are also
used.
Carbon Steel
Carbon steel is so widely used because it possesses desirable physi-
cal and mechanical properties, is readily available in a variety of
forms and shapes, can be easily fabricated and joined, and is eco-
nomical.
30 Schweitzer
Carbon steel does not have the ability to form its own protective
coating, as do some other metals, except in a dry, clean atmosphere.
Under this latter condition, a thick oxide film will form that prevents
further oxidation. Initiation of corrosion is the result of the presence
of solid particles on the surface. This settled airborne dust promotes
corrosion by absorbing SO2 and water vapor from the air. Even
greater corrosive effects result when particles of hygroscopic salts,
such as chlorides or sulfates, settle on the surface and form a
corrosive electrolyte.
To protect the surface of unalloyed carbon steel, an additional
surface protection must be applied. This protection usually takes
the form of an antirust paint or other type of paint protection formu-
lated for resistance against a specific type of contaminant known
to be present in the area. On occasion, plastic or metallic coatings
are used.
Before applying any type of surface protection, it is essential
that the surface of the carbon steel be properly prepared. If not
properly prepared, it is possible for corrosion cells to develop
under the protective coating and result in the coating delaminating
and flaking off.
Paint and coating manufacturers supply detailed specifications
covering surface preparation. There may be some variation among
manufacturers but, in general, they require that all surfaces should
be abrasive blasted to white metal in accordance with 55PC Specifica-
tion Tp-5-63 or NACE Specification NACE-1. A white metal surface
condition is defined as being one from which all r u s t , scale, paint,
and such, have been removed, and the surface has a uniform gray-
white appearance. Streaks or stains of rust or any other contaminants
are not permitted. On some occasions, a near-white, blast-cleaned
surface equal to SSPC SP-10 is permitted. This is a more economical
surface preparation, but it should not be used unless specifically
allowed by the coating manufacturer. Details regarding types of
paint coatings will be found in Chapter 17.
Chapter 5 discusses various metallic coatings that may be used.
Weathering Steels
When small amounts of copper, chromium, nickel, phosphorus, silicon,
manganese, or various combinations thereof, are added to conven-
tional carbon steel, a low-alloy carbon steel results that has an
improved corrosion resistance. These steels are known as weathering
steels. The corrosion resistance of these steels is dependent upon
the climatic conditions, the pollution levels, the degree of sheltering
from the atmosphere, and the specific composition of the steel.
Upon exposure to most atmospheres, the corrosion rate becomes

stabilized within 3 to 5 years. A dark brown to violet patina, or
protective film, develops over this period. This patina is a rust
formation that is tightly adhered to the surface and cannot be wiped
off. In rural areas with little or no pollution, a longer period may
be required to form this protective film. In areas that are highly
polluted with SO2, the weathering steels exhibit a much higher
corrosion rate and loose rust particles are formed. Under these
conditions, the film formed offers little to no protection.
These steels will not produce this protective film in marine en-
vironments where chlorides are present. Corrosion rates will be
as high as for conventional carbon steels.
The formation of the patina is dependent upon a series of wet
and dry periods because periodic flushing followed by a period
of drying are necessary. In areas where the steel is sheltered from
the rain, the dark patina is not formed. In its place, a layer of
rust in lighter colors forms, which has the same effect. With con-
tinued exposure to wetness, such as in water or soil, the corrosion
rate for the weathering steels is equal to that of plain carbon steel.
Because the patina formed has a pleasant esthetic appearance,
the weathering steels can be used without the application of any
protective coating of antirust paint, zinc, or aluminum. This is
particularly true in urban or rural areas.
When employing these weathering steels, design consideration
should be given to the elimination of possible areas where water,
dirt, and corrosion products can accumulate. If pockets are present,
the time of wetness will be increased, which will lead to the develop-
ment of corrosive conditions. The design should make maximum
use of exposure to the weather. Sheltering from rain should be
avoided.
The designer should also be aware that during the period over
which this protective film is forming, rusting will proceed at a
relatively high rate, during which time rusty water is produced.
This rusty water may stain masonry, pavements, and the like.
In view of this, precautions should be taken to prevent detrimental
staining effects, such as coloring the masonry brown, so that any
staining will not be obvious.
Zinc
For many years galvanized steel (zinc coating of steel) was used
for protection against atmospheric corrosion. It performed satisfac-
torily until increasing concentrations of SO2 in the atmosphere
resulted in attack. Consequently, galvanizing offers little protection
32 Schweitzer
in industrial atmospheres. However, it still provides adequate pro-

tection in rural or urban atmospheres having little to moderate
quantities of pollutants present. Additional details on galvanized
steel will be found in Chapter 5.
Aluminum
When exposed to air, the surface of the aluminum becomes covered
with an amorphous oxide coating that provides protection against
atmospheric corrosion, particularly against SO2.
In the presence of SO2 pollution, the shiny metal appearance
will gradually disappear and the surface will become rough. A gray
patina of corrosion products will form on this surface. If esthetics
are important the original surface luster can be retained by anodizing.
This anodic oxidation strengthens the oxide coating and improves
its protective properties.
As with the weathering steels, care should be taken during
the design stage to eliminate rain-sheltered pockets on which dust
and other pollutants may collect. The collection of these pollutants
accelerates corrosion by disturbing the formation of the protective
film.
Additional information about the use of aluminum will be found
in Chapter 9.
Copper
Copper is resistant to the corrosive effects of rural, urban, marine,
and industrial atmospheres. Consequently it finds applications as
sheeting and roofing, in seawater applications, and in domestic
water systems.
It possesses many desirable properties, being malleable, machin-
able, and having excellent electrical and thermal conductivity proper-
ties. This leads to its use as an electrical conductor.
Its corrosion resistance is the result of the formation of a protec-
tive film or patina. Copper roofs are still in existence on many
castles and monumental buildings that are centuries old.
The patina formed will vary in color from a dark brown to the
characteristic blue-green, depending upon atmospheric conditions
and time. It may take 5 to 10 years for the green patina to form.
In marine atmospheres the surfaces facing the sea will develop the
green patina in a much shorter time. In areas having little or no
atmospheric pollution the formation of the patina may take hundreds
of years to form, if at all.
The one disadvantage of copper is its low mechanical properties.
However, this can be easily overcome by alloying it with zinc, alumi-
num, nickel, and other metals. Refer to Chapter 8 for more details.
3
CATHODIC PROTECTION
INTRODUCTION
A tremendous investment exists worldwide in underground metallic

structures such as pipelines, storage facilities, well casings, struc-
tural supports, communication cables * and so forth. When these
metallic members are in direct contact with the soil and unprotected,
they are subject to corrosion.
Attempts have been made to overcome this problem by the use
of various types of coatings applied to the surface. Although such
coatings can be effective, invariably small holes or holidays are
usually present. These holidays provide access to the uncovered
base metal and permit corrosion to take place.
Subsequent repairs can be extremely costly. In addition, un-
detected failure (or leakage) can cause accidents or lead to safety
hazards, such as causing roadways to collapse as a result of an
underground water leak, or to environmental hazards resulting
from oil leaks.
By cathodic protection, bare metals and holidays in coated metals
can be protected from corrosion.
BACKGROUND
Cathodic protection is a major factor in corrosion control of metals.
When an external electric current is applied, the corrosion rate
can be reduced to practically zero. Under these conditions, the
33
34 Schweitzer
metal can remain in a corrosive environment indefinitely without

deterioration.
In practice, cathodic protection can be utilized with such metals
as steel, copper, b r a s s , lead, and aluminum against corrosion in
all soils and almost all aqueous media. Although it cannot be used
above the waterline (because the impressed electric current cannot
reach areas outside of the electrolyte) it can be effectively used
to eliminate corrosion fatigue, intergranular corrosion, s t r e s s -
corrosion cracking, dezincification of b r a s s , or pitting of stainless
steels in seawater or steel in soil.
In 1824, Sir Humphry Davy reported that by coupling iron or
zinc to copper the copper could be protected against corrosion.
The British admiralty had blocks of iron attached to the hulls of
copper-sheathed vessels to provide cathodic protection. Unfortunately,
cathodically protected copper is subject to fouling by marine life,
which reduced the speed of vessels under sail and forced the ad-
miralty to discontinue the practice. However, the corrosion rate
of the copper had been appreciably reduced. Unprotected copper
supplies a sufficient number of copper ions to poison fouling orga-
nisms.
In 1829, Edmund Davy was successful in protecting the iron
portions of buoys by using zinc blocks and, in 1840, Robert Mallet
produced a zinc alloy that was particularly suited as a sacrificial
anode. The fitting of zinc slabs to the steel hulls of vessels became
standard practice as wooden hulls were replaced. This provided
localized protection specifically against the galvanic action of a
bronze propeller. Overall protection of seagoing vessels was not
investigated again until 1950, when the Canadian Navy determined
that the proper use of antifouling paints in conjunction with corrosion-
resistant paints made cathodic protection of ships feasible and could
reduce maintenance costs.
About 1910-1912 the first application of cathodic protection by
means of an impressed electric current was undertaken in England
and the United States. Since that time, the general use of cathodic
protection has been widespread. There are thousands of miles of
buried pipelines and cables that are protected in this manner.
This form of protection is also used for water t a n k s , submarines,
canal gates, marine piling, condensers, and chemical equipment.
THEORY
Cathodic protection is achieved by applying electrochemical principles

to metallic components buried in soil or immersed in water. It is
accomplished by flowing a cathodic current through a metal-electrolyte
3. Cathodic Protection 35
interface favoring the reduction reaction over the anodic metal dis-
solution. This enables the entire structure to work as a cathode.
The flux of electrons can be provided by one of two methods.
By use of a rectifier, a direct current may be impressed on an
inert anode and the components. These components receive an excess
of electrons and are, thus, cathodically protected.
The alternative method is to couple the components with a more
active metal, such as zinc or magnesium, to create a galvanic cell.
Under these conditions, the active metal operates as an anode and
is itself destroyed while protecting the components that are cathodic.
Such an anode is referred to as a sacrificial anode.
The basis of cathodic protection is shown in the polarization
diagram for a Cu-Zn cell (Fig. 1). If polarization of the cathode
is continued by use of an external current beyond the corrosion
potential to the open-circuit potential of the anode, both electrodes
reach the same potential and no corrosion of the zinc can take place.
Cathodic protection is accomplished by supplying an external current
to the corroding metal on the surface of which local action cells
operate, as shown in Figure 2. Current flows from the auxiliary
anode and enters the anodic and cathodic areas of the corrosion
cells, returning to the source of the DC current, B. Local action
(MAX)
CURRENT
FIGURE 1 Polarization for copper-zinc cell.

36 Schweitzer
llllllh
ELECTROLYTE
CORRODING AUXILIARY
METAL ANODE
FIGURE 2 Cathodic protection using impressed current on local

action cell.
current will cease to flow when all the metal surface is at the same
potential as a result of the cathodic areas being polarized by an
external current to the open-circuit potential of the anodes. As
long as this external current is maintained, the metal cannot corrode.
The corrosion rate will remain at zero if the metal is polarized
slightly beyond the open-circuit potential ^ of the anode. However,
this excess current has no value and may be injurious to amphoteric
metals or coatings. Hence, in actual practice, the impressed current
is maintained close to the theoretical minimum.
If the current should fall below that required for complete pro-
tection, some protection will still be afforded.
METHOD OF APPLICATION
A source of direct current and an auxiliary electrode are required

to provide cathodic protection. The auxiliary electrode (anode)
is usually composed of graphite or iron and is located some distance
away from the structure being protected. The anode is connected
to the positive terminal of the DC source, and the structure being

protected is connected to the negative terminal. This permits current
to flow from the anode, through the electrolyte, to the structure.
Applied voltages are not critical as long as they are sufficient to
supply an adequate current density to all parts of the protected
structure. The resistivity of the soil will determine the required
applied voltage; when the ends of a long pipeline are to be protected,
the voltage will have to be increased.
Current is usually supplied by a rectifier supplying low-voltage
direct current of several amperes.
Sacrificial Anodes
It is possible, by selection of an anode constructed of a metal more
active in the galvanic series than the metal to be protected, to
eliminate the need for an external DC current. A galvanic cell will
be established with the current direction, exactly as described,
by using an impressed electric current. These sacrificial anodes
are usually composed of magnesium or magnesium-based alloys.
Occasionally, zinc and aluminum have been used. Because these
anodes are essentially sources of portable electrical energy, they
are particularly useful in areas where electric power is not available
or where it is uneconomical or impractical to install power lines
for this purpose.
Most sacrificial anodes in use in the United States are of magnesium
construction. Approximately 10 million pounds of magnesium is used
annually for this purpose. The open-circuit potential difference
between magnesium and steel is about 1 V. This means that one
anode can protect only a limited length of pipeline. However, this
low voltage can have an advantage over higher impressed voltages
in that the danger of overprotection to some portions of the structure
is less and, because the total current per anode is limited, the
danger of stray-current damage to adjoining metal structures is
reduced.
Magnesium anode rods have also been placed in steel hot-water
tanks to increase the life of these tanks. The greatest degree of
protection is afforded in "hard" waters, in which the conductivity
of the water is greater than in "soft" waters.
Anode Requirements
To provide cathodic protection, a current density of a few milliamps
(mA) is required. Therefore, to determine the anodic requirements,
it is necessary to know the energy content of the anode and its
efficiency. From this data the necessary calculations can be made
38 Schweitzer
to size the anode, determine its expected life, and to determine

the number of anodes required. As indicated previously, the three
most common metals used as sacrificial anodes are magnesium, zinc,
and aluminum. The energy content and efficiency of these metals
are as follows:
Practical energy
Theoretical energy Anodic constant
Metal content (A h r / l b ) efficiency (%) (A h r / l b ) (PE)
Magnesium 1000 50 500

Zinc 370 90 333
Aluminum 1345 60 810
The number of pounds of metal required to provide a current

of 1 A for a year can be obtained from the following equation:
„ .... 8760 h r / y r
lb metal/A-yr = — —
For magnesium this would be
lb Mg/A-yr = — = 17.52
The number of years (YN) for which 1 lb of metal can produce

a current of 1 mA is determined from the following equation:
PE
YN = 10" 3 A 8760 h r / y r
=6
°
The life
The life expectancy
expectancy ((L)
) oof an
a anode of W lb, delivering a current
of ii mA
mA is
is calculated
calculated as
as follows:
follows:
L = YN (W)
i
L
60 W
Mg
which is based on a 50% anodic efficiency. Because actual efficiencies

tend to be somewhat less, it is advisable to apply a safety factor
and multiply the result by 0.75.
The current required to secure protection of a structure and
the available cell voltage between the metal structure and sacrificial
anode determine the number of anodes required. This can be illus-
trated by the following example:
Assume that an underground pipe line has an external area of
200 sq ft and a soil resistivity of 600 ohm cm. Field tests indicate
that 6 mA/sq ft is required for protection. To provide protection
for the entire pipe line (6 mA/ft2) (200 ft2) = 1200 mA. Magnesium
anodes used in this particular soil have a voltage of - 1.65 V,
or a galvanic cell voltage of
E
cell = EC - EA
= - 0.85 - (-1.65)
= + 0.8 V
The resistance is therefore
R = j = ~ | = 0.67 ohm.
As the number of anodes are increased the total resistance of

the system decreases. Each anode that is added provides a new
path for current flow, parallel to the existing system. The relation-
ship between the resistance of the system and the number of anodes
is shown in the Sunde equation.
R =^ ^ (2.3 log - J L - + f 2.3 log 0.656N)
where:
R = resistance in ohms
P = soil resistivity in ohm cm
N = number of anodes
L = anode length (ft)
d = diameter of anode (ft)
S = distance between anodes (ft)
Figure 3 shows the typical plotting of the results of this equation.

Different anodic shapes will have different curves.
40 Schweitzer
LJJ
o
CO
LJJ
DC
NUMBER OF ANODES
FIGURE 3 Plot of the Sunde equation.
Use with Coatings

Insulating coatings are advantageous to use with either impressed
current or sacrificial anodes when supplying cathodic protection.
These coatings need not be pore free because the protective current
flows preferentially to the exposed metal areas, which require the
protection. Such coatings are useful in distributing the protective
current, in reducing total current requirements, and in extending
the life of the anode. For example, in a coated pipeline, the current
distribution is greatly improved over that of a bare pipeline, the
number of anodes and total current required is less, and one anode
can protect a much longer section of pipeline. Because the earth
itself is a good electrical conductor and the resistivity of the soil
is localized only within the region of the pipeline or electrodes,
the limiting length of pipe protected per anode is imposed by the
metallic resistance of the pipe itself and not the resistance of the
soil.
One magnesium anode is capable of protecting approximately
100 ft (30 m) of a bare pipeline, whereas it can provide protection
for approximately 5 mi (8 km) of a coated pipeline.
In a hot-water tank, coated with glass or an organic coating,
the life of the magnesium anode is extended and more uniform protec-
tion is supplied to the tank. Without the coating, the tendency is
for excess current to flow to the sides and insufficient current

to flow to the top and bottom.
Because of these factors, cathodic protection is usually provided
in conjunction with coated surfaces.
CURRENT REQUIREMENTS
The specific metal and the environment will determine the current
density required for complete protection. The applied current density
must always exceed the current density equivalent to the measured
corrosion rate under the same conditions. Therefore, as the corrosion
rate increases, the impressed current density must be increased
to provide protection.
There are several factors that affect the current requirements.
These include
1. The nature of the electrolyte

2. The soil resistivity
3. The degree of aeration
The more acid the electrolyte, the greater will be the potential
for corrosion and the greater will be the current requirement. Soils
that exhibit a high resistance require a lower cathodic current
to provide protection. However, in areas of violent agitation or
high aeration, an increase in current will be required. The required
current to provide cathodic protection can vary from 0.5 to 20
mA/sq ft of bare surface.
Field testing may be required to determine the necessary current
density to provide cathodic protection in a specific area. However,
these testing techniques will provide only an approximation. After
completion of the installation, it will be necessary to conduct a
potential survey and make the necessary adjustments to provide
the desired degree of protection.
For cathodically controlled corrosion rates, the corrosion potential
approaches the open-circuit anodic potential and the required current
density is only slightly greater than the equivalent corrosion current.
The required current can be considerably greater than the corrosion
current for mixed control, and for anodically controlled corrosion
reactions, the required current is even greater.
When a protective current causes precipitation of an inorganic
scale on the cathode surface, such as in hard water or seawater,
the total current required is gradually reduced. This is the result
of an insulating coating being formed. However, the current density
at the exposed metal areas does not change; only the total current
density per apparent unit area is less.
42 Schweitzer
ANODE MATERIALS AND BACKFILL
The use of magnesium as a sacrificial anode has already been dis-

cussed. For use with impressed current, auxiliary anodes are usually
formed of scrap iron or graphite. Scrap iron is consumed at a con-
siderably faster rate than graphite (15-20 lb/A-yr versus 2 lb/A-yr);
however, graphite costs more both initially and in operating expense.
Graphite requires more power than scrap iron. It is also more fragile,
and greater care must be taken during installation. Under certain
conditions the advantage of the 8- to 10-times longer life far out-
weighs the added costs, particularly in areas where replacement
poses problems.
Platinum-clad or 2% silver-lead electrodes that use impressed
current have been employed for the protection of structures in
seawater. The latter anodes are estimated to last 10 years, whereas
sacrificial magnesium anodes require replacement every 2 years.
On occasion, aluminum electrodes have been used in freshwaters.
Because the effective resistivity of soil surrounding an anode
is limited to the immediate area of the electrode, this local resistance
is generally reduced by using backfill. For impressed current sys-
tems, the anode is surrounded with a thick bed of coke mixed with
three to four parts of gypsum to one part of sodium chloride. The
consumption of the anode is reduced somewhat because the coke
backfill is itself a conductor and carries part of the current. If
the anode is immersed in a river bed, lake, or ocean, backfill is
not required.
Auxiliary anodes need not be consumed to fulfill their purpose.
Conversely, sacrificial anodes are consumed no less to supply an
equivalent current than is required by Faraday1 s law.
For magnesium anodes, backfill has the advantage of reducing
the resistance of insulating corrosion-product films as well as in-
creasing the conductivity of the immediate area. A typical backfill
consists of a mixture of approximately 20% bentonite (for retention
of moisture), 75% gypsum, and 5% sodium sulfate.
TESTING FOR COMPLETENESS OF PROTECTION
There are several ways in which the effectiveness of protection

can be checked. The first two methods are qualitative and do not
provide data about whether enough or more than enough current
is being supplied. Potential measurements, the third method, is
of prime importance in practice.
Coupon Tests
A metal coupon is shaped to conform to the contour of the pipe,
weighed, and attached by a brazed-connected cable to the pipe.
Both the cable and the surface between the coupon and pipe are
coated with coal tar. The coupon is allowed to remain buried for
weeks or months, recovered, cleaned, and weighed. The weight
loss, if any, is an indication of whether or not the cathodic protec-
tion of the pipeline is complete.
Colormetric Tests
A piece of absorbent paper soaked in potassium ferricyanide solution
is placed in contact with a cleaned section of the buried pipeline
and the soil replaced. After a relatively short time the paper is
retrieved. A blue ferrous ferricyanide reaction indicates incomplete
cathodic protection, whereas an absence of blue on the paper indi-
cates that the cathodic protection is complete.
Potential Measurements
By measuring the potential of the protected structure, the degree
of protection, including overprotection, can be determined quantita-
tively. This measurement is the generally accepted criterion and
is used by corrosion engineers. The basis for this determination
is the fundamental concept that cathodic protection is complete when
the protected structure is polarized to the open-circuit anodic poten-
tial of local action cells.
The reference electrode for making this measurement should
be placed as closely as possible to the protected structure to avoid
and to minimize an error caused by internal resistance (IR) drop
through the soil. Such IR drops through corrosion product films
or insulating coatings will still be present regardless of precautions
taken, tending to make the measured potential more active than
the actual potential at the metal surface. For buried pipelines,
a compromise location is taken directly over the buried pipe at
the soil surface because cathodic protection currents flow mostly
to the lower surface and are minimum at the upper surface of the
pipe buried a few feet below the soil surface.
The potential for steel is equal to -0.85 V versus the copper-
saturated copper sulfate half-cell, or 0.53 V on the standard hydrogen
scale. The theoretical open-circuit anodic potential for other metals
may be calculated using the Nernst equation. Several typical calcu-
lated values are shown in Table 1.
44 Schweitzer
TABLE 1 Calculated Minimum Potential d> for Cathodic Protection
$ v s . Cu-CuSO^
<j>H2 reference
E° Solubility product, scale electrode
Metal (V) M(OH)2 (V) (V)
Iron 0.440 1.8 x 10" 15 -0.59 -0.91

Copper -0.337 1.6 x 10" 19 0.16 -0.16
Zinc 0.763 4.5 x 10" 17 -0.93 -1.25
Lead 0.126 4.2 x 10~15 -0.27 -0.59
Source: Uhlig, H. H. (1971). Corrosion and Corrosion Control,

2nd ed. Wiley, New York.
OVERPROTECTION
Overprotection of steel structures, to a moderate degree, usually

does not cause any problems. The primary disadvantages are waste
of electric power and increased consumption of auxiliary anodes.
When the overprotection is excessive, hydrogen can be generated
at the protected structure in sufficient quantities to cause blistering
of organic coatings, hydrogen embrittlement of the steel, or hydrogen
cracking. Damage to steel by hydrogen absorption is more prevalent
in environments where sulfides are present.
Overprotection of systems with amphoteric metals (e.g., aluminum,
zinc, lead, tin) will damage the metal by causing increased attack
instead of reduction of corrosion. This emphasizes the need for
making potential measurements of protected structures.
ECONOMICS
The cost of cathodic protection is more than recovered by reduced

maintenance costs or by reduced installation costs, or both. For
buried pipelines, the guarantee that there will be no corrosion
on the soil side of the pipe has made it economically feasible to
transport oil and high-pressure natural gas across the American
continent. It has also permitted the use of thinner-walled pipe.
Wall thicknesses need only be sufficient to withstand the internal
pressures. No extra allowance has to be added for external corrosion.
This savings alone has sometimes more than paid for the installation
of the cathodic protection equipment.
Similarly, other cathodic protection systems have more than paid

for their installation costs by reduced maintenance costs or by
longer operating periods between routine inspections and maintenance
periods.
4
CORROSION INHIBITORS
INTRODUCTION
The addition of small amounts of chemical compounds to a corrodant

that are able to reduce the corrosion of the exposed metal is a
preventative measure known as inhibition, inhibitors will reduce
the rate of either anodic oxidation, or cathodic reduction, or both
processes. This reduction is accomplished by the formation of a
protective film on the exposed surface of the metal. On this basis
it is possible to have anodic, cathodic, and mixed inhibitors.
Inhibitors can be classified in many ways according to
Their chemical nature (organic or inorganic substances)

Their characteristics (oxidizing or nonoxidizing compounds)
Their technical field of application (pickling, descaling, acid clean-
ing, cooling water systems, and the like
It is possible to use inhibitors at different pH values, from acid,

to near-neutral, to alkaline. The corrosive attack of aqueous acid
solutions on metals and alloys is usually severe. This attack can
be inhibited by the addition of many classes of organic compounds
such as triple-bonded hydrocarbons; acetylenic alcohols; sulfoxides;
sulfides and mercaptans; aliphatic, aromatic, or heterocyclic com-
pounds containing nitrogen; and many other families of simple organic
compounds.
It is postulated that inhibitors are adsorbed onto the metal surface
either by physical (electrostatic) adsorption or chemsorption.
47
Schweitzer
Physical adsorption is the result of electrostatic attractive forces

between the organic ions and the electrically charged metal surface.
Chemsorption is the transfer of, or sharing of, the inhibitor mole-
cule's charge to the metal surface, forming a coordinate-type bond.
The adsorbed inhibitor reduces the corrosion of the metal surface
by either retarding the anodic dissolution reaction of the metal,
or by the cathodic evolution of hydrogen, or both.
Inhibitors will be classified and discussed under the headings of
Passivation inhibitors
Organic inhibitors
Precipitation inhibitors
PASSIVATION INHIBITORS
Passivation inhibitors are chemical-oxidizing substances, such as

chromate (CrO£~) and nitrite (NO^), or substances such as NagPO^
or NaBrO7. These materials favor the adsorption on the metal surface
of dissolved oxygen.
Passivation inhibitors are widely used and are the most effective
of all inhibitors. Chromates are the least expensive inhibitors for
use in water systems and are widely used in the recirculating-
cooling-water systems of internal combustion engines, rectifiers,
and cooling towers. Sodium chromate, in concentrations of 0.04
to 0.1%, is used for this purpose, with the higher concentrations
being necessary at higher temperatures or in freshwater that has
chloride concentrations above 10 ppm. If necessary, sodium hydroxide
is added to adjust the pH to a range of 7.5 to 9.5. It is essential
that periodic colorimetric analyses be conducted to ensure that
the chromate concentration remains above 0.016%.
Although these are the most effective inhibitors, they must be
used with caution because they are toxic and can cause a rash
on prolonged contact with the skin. Recent environmental legislation
regulates discharge of these materials; thus, local regulations should
be checked before using.
It usually will be necessary to convert the ion from Cr+6 to
Cr+3 before discharge. The Cr+6 ion is water-soluble and toxic,
whereas the Cr+3 ion is insoluble and can be removed as a sludge.
These chromate sludges are classified as hazardous wastes and,
therefore, must be constantly monitored. As a result of these regu-
lations, the economics of using these inhibitors may not be as attrac-
tive as in the past. The cost of conversion of the chromate ions,
the constant monitoring of, and disposal of the hazardous waste
sludge must all be taken into account.
4. Corrosion Inhibitors 49
Additional legislation has also been proposed that will limit the
chromate discharge and drift through the air, because both valences
of chromate are suspected carcinogens.
Chromates have a tendency to react with organic compounds,
therefore, they cannot be used in antifreeze solutions because most
antifreeze solutions contain methanol or ethylene glycol. A common
material used for this purpose is borax (Na2BLfO7 • 10 H2O) to
which may be added sulfonated oils, to produce an oily coating,
and mercaptobenzothiazole, which is a specific inhibitor for the
corrosion of copper.
Nitrites also find application in antifreeze-type cooling water
systems because they have little tendency to react with alcohols
or ethylene glycol. They are not recommended for use in cooling-
tower waters because they are gradually decomposed by bacteria.
They are also used to inhibit corrosion by cutting oil-water emulsions
that are employed in the machining of metals, and in corrosion
inhibition of the internal surfaces of pipelines used to transport
petroleum products and gasoline. This latter application is accom-
plished by continuously injecting a 5 to 30% sodium nitrite solution
into the line. At lower temperatures, such as in underground
storage tanks, gasoline can be corrosive to steel as dissolved water
is released, which in contact with the large quantities of oxygen
dissolved in the gasoline corrodes the steel and forms large quantities
of rust. The sodium nitrite enters the water phase and effectively
inhibits the corrosion.
If passivation inhibitors are not used in sufficient quantities
(concentrations fall below minimum limits) they can actually accelerate
the corrosion and may cause pitting.
ORGANIC INHIBITORS
A variety of organic compounds are available that are capable of

providing a broad range of protection to metals in certain environ-
ments. These compounds build up a protective film of adsorbed
molecules on the metal surface, which provide a barrier to the dis-
solution of the metal in the electrolyte. The concentration of the
inhibitor in the medium is critical because the metal surface covered
is proportional to the concentration. There is an optimal concentra-
tion for each specific inhibitor in any given medium. For example,
a concentration of 0.05% sodium benzoate, or 0.2% sodium cinnamate,
is effective in water that has a pH of 7.5 and contains 17 ppm
sodium chloride or 0.5% by weight of ethyl octenol.
Ethanolamine phosphate is used in ethylene glycol cooling-water
systems as an inhibitor.
50 Schweitzer
Inhibitors that are efficient in controlling corrosion in acid solu-

tions have little or no effect in near-neutral solutions. Inorganic
compounds usually are used as inhibitors for these. Inorganic anions,
such as polysulfates, silicates, borates, and phosphates, are typically
used. Oxidizing inhibitors, such as chromates or nitrites, are also
used.
A different group of inhibitors are used in alkaline solutions.
All metals whose hydroxides are destroyed in the presence of alkalis
are subject to caustic attack. Inhibitors for this class of solution
consist of organic substances such as tannins, gelatine, saponin,
thioureas, substituted phenols and naphthols, $-diketones, and
quinalizarine.
PRECIPITATION INHIBITORS
Precipitation inhibitors are those that cause the formation of solid

precipitates on the surface of the metal, thus, providing a protective
film. Hard water, high in calcium and magnesium, is less corrosive
than soft water because of the tendency of the salts in the hard
water to precipitate on the metal surface and form a protective film.
Sodium polyphosphate, when used in a concentration of 10 to
100 ppm, after adjusting the water pH to 5 to 6, will cause a pre-
cipitate of calcium or magnesium orthophosphate to form on the
metal surface. Zinc salts can also be added to improve the inhibition.
INHIBITOR EVALUATION
Because more than one inhibitor may be suitable for use in a specific
application, it becomes necessary to have a means of evaluating
their individual performances. A comparison can be made by using
any of the corrosion-testing techniques discussed in Chapter 22
to first determine the corrosion rate of the medium without inhibitor.
The test should then be repeated with each inhibitor present in
the medium. The efficiency of each inhibitor can be calculated from
the following equation:
Ro - Rj
leff = R (100)
where I e ff = inhibitor efficiency; Ro = corrosion rate without in-

hibitor; and Ri = corrosion rate with inhibitor. The corrosion rate
can be measured in any units, such as weight loss of test piece
(mil/yr, etc.) as long as consistent units are employed.
4. Corrosion Inhibitors 51
SUMMARY
There are many other inhibitors available for use in special applica-
tions. Thiourea-type compounds are used to inhibit corrosion in
sulfuric acid pickling baths for steel, and silicates are used for
aluminum alkaline cleaners. Inhibitors are also present in antirust
paint systems. Such materials as red lead and zinc chromate are
typical examples.
Volatile inhibitors are being used for protection where there
are vapor phases.
The primary use of inhibitors is to prevent or to reduce general
corrosion. However, this is not the most important form of corrosion.
Approximately 65 to 75% of all chemical plant failures are due to
stress-corrosion cracking, corrosion fatigue, pitting, erosion corro-
sion, and only 35% are the result of general corrosion. The use
of inhibitors plays an important part in the control of corrosion
for those areas in which general corrosion is the problem.
The use of inhibitors to control corrosion requires continued
attention to be certain that the inhibitors are being constantly added
and that the proper concentrations are being maintained. A primary
advantage of inhibitor use is when existing equipment is to be used
for a new application. This may be the most economical approach,
rather than changing the materials of construction.
5
CARBON STEEL AND LOW-ALLOY STEEL
INTRODUCTION
Steel is produced from pig iron by the removal of impurities in

an open-hearth furnace, a basic oxygen furnace, a Bessemer con-
verter, or an electric furnace. In the United States over 80% of
the steel is produced in the basic open-hearth furnace.
As a result of the methods of production, the following elements
are always present in steel: carbon, manganese, phosphorus, sulfur,
silicon, and traces of oxygen, nitrogen, and aluminum. Various
alloying ingredients are frequently added, such as nickel, chromium,
copper, molybdenum, and vanadium. The most important of these
elements in steel is carbon, and it is necessary to understand the
effect of carbon on the internal structure of the steel to understand
the heat treatment of carbon and low-alloy steels.
Constitution and Structure of Steel

When heated to 910°C (1670°F), pure iron changes its internal
crystalline structure from a body-centered cubic arrangement of
atoms, alpha iron, to a face-centered cubic structure, gamma iron.
At 1390°C (2535°F) it changes back to the body-centered cubic
structure, delta iron, and at 1538°C (2802°F) the iron melts. When
carbon is added to iron, it has only slight solid solubility in alpha
iron (0.001% at room temperature). However, gamma iron will hold
up to 2.0% carbon in solution at 1130°C (2066°F). The alpha iron-
containing carbon or any other element in solid solution is called
54 Schweitzer
ferrite, and the gamma iron-containing elements in solid solution

is called austenite. Usually, when not in solution in the iron, the
carbon forms a compound Fe 3 C (iron carbide), which is extremely-
hard and brittle and is known as cementite.
Carbon steel in equilibrium at room temperatures will contain
both ferrite and cementite. The physical properties of the ferrite
are approximately those of pure iron and are characteristic of the
metal. The presence of cementite does not in itself cause steel to
be hard; r a t h e r , it is the shape and distribution of the carbides
in the iron that determine the hardness of the steel. The fact that
the carbides can be dissolved in austenite is the basis of the heat
treatment of steel, because the steel can be heated above the critical
temperature, to dissolve all the carbides, and then suitable cooling
through the cooling range will produce the desired size and distribu-
tion of carbides in the ferrite.
If austenite that contains 0.8% carbon (eutectoid composition)
is slowly cooled through the critical temperature, ferrite and cementite
are rejected simultaneously, forming alternative plates or lamellae.
This microstructure is called pearlite because when polished and
etched it has a pearly luster. If the austenite contains less than
0.80% carbon (hypoeutectoid composition), free ferrite will first
be rejected on slow cooling through the critical temperature until
the composition of the remaining austenite reaches 0.80% carbon,
when the simultaneous rejection of both ferrite and carbide will
again occur, producing pearlite. So a hypoeuctectoid steel at room
temperature will be composed of areas of free ferrite and areas
of pearlite; the higher the carbon percentage, the more pearlite
present in the steel. When austenite that contains more than 0.80%
carbon (hypereuctectoid composition) is slowly cooled, cementite
is thrown out at the austenite grain boundaries, forming a cementite
network, until the austenite contains 0.80%, carbon at which time
pearlite is again formed. Thus, a hypereuctectoid steel, when slowly
cooled, will have areas of pearlite surrounded by a thin carbide
network.
As the cooling rate is increased the spacing between the pearlite
lamellae becomes smaller; with the resulting greater dispersion of
carbide, preventing slip in the iron crystals, the steel becomes
h a r d e r . Also, with an increase in the rate of cooling, there is less
time for the separation of excess ferrite or cementite, and the
equilibrium amount of these constituents will not be precipitated
before the austenite transforms to pearlite. Thus, with a fast rate
of cooling, pearlite may contain more or less carbon than that given
by the eutectoid composition. When the cooling rate becomes very
rapid (as obtained by quenching), the carbon does not have suffi-
cient time to separate out in the form of carbide, and the austenite
5. Carbon Steel and Low-Alloy Steel 55
transforms to a highly stressed structure supersaturated with carbon,

called martensite. This structure is exceedingly hard; but brittle,
and requires tempering to increase the ductility. Tempering consists
of heating martensite to a temperature below critical, causing the
carbide to precipitate in the form of small spheroids. The higher
the tempering temperature, the larger the carbide particle size,
the greater the ductility of the steel, and the lower the hardness.
In a carbon steel it is possible to have a structure consisting
either of parallel plates of carbide in a ferrite matrix, the distance
between the plates depending upon the rate of cooling, or of carbide
spheroids in a ferrite matrix, the size of the spheroids depending
on the temperature to which the hardened steel was heated.
HEAT-TREATING OPERATIONS
The following definitions of terms have been adopted by the American

Society for Testing and Materials (ASTM), the Society of Automotive
Engineers (SAE), and the American Society for Metals (ASM) in
substantially identical form.
Heat treatment An operation, or combination of operations,
involving the heating and cooling of a metal or alloy in the solid
state for the purpose of obtaining certain desirable conditions or
properties.
Quenching Rapid cooling by immersion in liquids or gases or
by contact with metal.
Hardening Heating and quenching certain iron-based alloys
from a temperature either within or above the critical range, to
produce a hardness superior to that obtained when the alloy is
not quenched. Usually restricted to the formation of martensite.
Annealing Annealing is a heating and cooling operation that
usually implies relatively slow cooling. The purpose of such a heat
treatment may be (1) to remove stresses; (2) to induce softness;
(3) to alter ductility, toughness, electrical, magnetic, or other
physical properties; (4) to refine the crystalline structure; (5)
to remove gases; or (6) to produce a definite microstructure. The
temperature of the operation and the rate of cooling depend upon
the material being heat treated and the purpose of the treatment.
Certain specific heat treatments coming under the comprehensive
term annealing are as follows:
Process annealing Heating iron-based alloys to a temperature
below or close to the lower limit of the critical temperatures, generally
540 to 705°C (1000 to 1300°F).
Normalizing Heating iron-based alloys to approximately 50°C
(100°F) above the critical temperature range, followed by cooling
to below that range in still air at ordinary temperature.
56 Schweitzer
Patenting Heating iron-based alloys above the critical temperature

range followed by cooling below that range in air, molten lead,
or a molten mixture of nitrates or nitrites maintained at a temperature
usually between 425 and 555°C (800 and 1050°F), depending on the
carbon content of the steel and the properties required in the finished
product. This treatment is applied in the wire industry to medium
or high carbon steel as a treatment to precede further wire drawing.
Spherodizing Any process of heating and cooling steel that
produces a rounded or globular form of carbide. The following
spheroidizing methods are used: (1) prolonged heating at a tempera-
ture just below the lower critical temperature, usually followed by
relatively slow cooling; (2) for small objects of high carbon steels,
the spheroidizing result is achieved more rapidly by prolonged
heating to temperatures alternatively within and slightly below the
critical temperature range; (3) tool steel is generally spheroidized
by heating to a temperature of 750 to 805°C (1380 to 1480°F) for
carbon steels and higher for many alloy tool steels, holding at heat
from 1 to 4 hr, and cooling slowing in the furnace.
Tempering (Drawing) Reheating hardened steel to a temperature
below the lower critical temperature, followed by any desired rate
of cooling. Although the terms tempering and drawing are practically
synonymous as used in commercial practice, the term tempering is
preferred.
EFFECT OF ALLOYING ELEMENTS ON THE

PROPERTIES OF STEEL
When relatively large amounts of alloying elements are added to

steel, the characteristic behavior of carbon steel is obliterated.
Most alloy steel is medium or high carbon steel to which various
elements have been added to modify its properties to an appreciable
extent, but it still owes its distinctive characteristics to the carbon
that it contains. The percentage of alloy element required for a
given purpose ranges from a few hundredths of 1% to possibly as
high as 5%.
When ready for service these steels will usually contain only
two constituents, ferrite and carbide. The only way that any alloying
element can affect the properties of steel is to change the dispersion
of carbide in the ferrite or change the properties of the carbide.
The effect on the distribution of carbide is the most important factor.
In large sections when carbon steels fail to harden throughout the
section, even under a water quench, the hardenability of the steel
can be increased by the addition of any alloying element (except
possibly cobalt). The elements most effective in increasing the hard-
enability of steel are manganese, silicon, and chromium.
5. Carbon
TABLE 1 Trends of Influence of Alloying Elements
CO
As dispersed CO
As dissolved carbide in 2.
carbide in tempering: As fine nonmetallic p
As dissolved in austenite: high-temperature dispersion: a

Ferrite: Austenite: fine-grain strength and fine-grain o
Element strength hardenability toughness toughness toughness i
Al Moderate Mild None None Very strong

Cr Mild Strong Strong Moderate Slight
Co Strong Negative None None None CO
c?
Cb Little Strong Strong Strong None
Cu Strong Moderate None None None
Mn Strong Moderate Mild Mild Slight
Mo Moderate Strong Strong Strong None
Ni Mild Mild None None None
P Strong Mild None None None
Si Moderate Moderate None None Moderate
Ta Moderate Strong Strong Strong None
Ti Strong Strong Very strong Little Moderate
W Moderate Strong Strong Strong None
V Mild Very strong Very strong Very strong Moderate
58 Schweitzer
Elements such as molybdenum, tungsten, and vanadium are effec-

tive in increasing the hardenability when dissolved in the austenite,
but they are usually present in the austenite in the form of carbides.
The main advantage of these carbide-forming elements is that they
prevent the agglomeration of carbides in tempered martensite. Temper-
ing relieves the internal stresses in the hardened steel and causes
spheroidization of the carbide particles, with resultant loss in hard-
ness and strength. With these stable carbide-forming elements
present, higher tempering temperatures may be employed without
sacrificing strength. This permits these alloy steels to have a
greater ductility for a given strength, or a greater strength for
a given ductility, than plain carbon steels.
The third factor that contributes to the strength of alloy steel
is the presence of the alloying element in the ferrite. Any element
present in solid solution in a metal will increase the strength of
the metal. The elements most effective in increasing the strength
of the ferrite are phosphorus, silicon, manganese, nickel, molyb-
denum, tungsten, and chromium.
A final important effect of alloying elements is their influence
on the austenitic grain size. Martensite, when formed from a course-
grained austenite, has considerably less resistance to shock than
that formed from a fine-grained austenite. Aluminum is the most
effective element for fine-grained growth inhibitors.
Table 1 provides a summary of the effects of various alloying
elements. This table indicates only the trends of the elements;
the fact that one element has an influence on one factor does not
prevent it from exerting an influence on another factor.
CASE HARDENING
The production of articles having a soft ductile interior and a very

hard surface can be accomplished by carburizing a low carbon steel
at an elevated temperature and then quenching. This process is
known as case hardening.
ATMOSPHERIC CORROSION OF STEEL
Atmospheric corrosion of steel is a function of location. In country

air the products of corrosion are either oxides or carbonates. In
industrial atmospheres sulfuric acid is present, and near the ocean
some salt is in the air. Corrosion is more rapid in industrial areas
because of the presence of the acid, and it is higher both near
cities and near the ocean because of the higher electrical conductivity
of the rain and the tendency to form soluble chlorides or sulfates,
which cause the removal of protective scale. The rusting of steel

exposed to weather is subject to many variables. The protective
action of copper and other alloying elements is due to a resistant
form of oxide that forms a protective coating under atmospheric
conditions but has little or no favorable effect when immersed con-
tinuously in water.
In an industrial atmosphere, steel with 0.32% copper will corrode
only half as much after 5 years as steel with 0.05% copper. A low-
alloy, high-strength steel having the following composition (percent-
age) will corrode only half as much as steel having 0.32% copper:
c
Mn
0.12 maximum
0.20-0.50
P 0.07-0.16
S 0.05 maximum
Si 0.75 maximum
Cu 0.30-0.50
Cr 0.50-1.25
Ni 0.55 maximum
It will be noted that in addition to the copper, this high-strength

alloy also contains notable amounts of chromium and nickel, both
of which are helpful in increasing strength and adding resistance
to corrosion. Phosphorus, which it also contains, is another element
that aids in providing protection against atmospheric corrosion.
In general, the presence of oxygen or of acidic conditions will
promote the corrosion of carbon steel. Alkaline conditions inhibit
corrosion. Steel that is embedded in concrete is protected from
corrosion by the alkalinity of the products formed when cement
reacts with water. If the concrete cracks or changes chemically
through aging, the protection disappears. For a more complete
discussion of atmospheric corrosion, refer to Chapter 2.
GENERAL CORROSION RESISTANCE
The corrosion resistance of carbon steel is dependent on the forma-

tion of an oxide surface film. However, resistance to corrosion is
somewhat limited. Carbon steel should not be used in contact with
dilute acids; thus, it is not recommended with sulfuric acid below
90%. Between 90 and 98%, steel can be used up to the boiling point,
between 80 and 90% it is serviceable at room temperature. Steel
is not normally used with hydrochloric, phosphoric, or nitric acids.
If iron contamination is permissible, steel can be used to handle
caustic soda up to approximately 75% and 100°C (212°F). Stress
relieving should be employed to reduce caustic embrittlement.
60 Schweitzer
Brines and seawater corrode steel at a slow rate, and the metal
can be used if iron contamination is not objectionable.
Steel is little affected by neutral water and most organic chemicals.
Organic chlorides are an exception. Many large water tanks and
storage tanks for organic solvents are fabricated from carbon steel.
PHOSPHATING
Phosphating, by itself, does not appreciably improve the corrosion

resistance of carbon steel. However, depending upon the type of
phosphating applied, certain properties will be imparted to the
carbon steel that will improve the corrosion resistance by subsequent
treatments.
Iron or sodium/ammonium phosphating will produce a yellow/green,
violet, blue, or gray material depending upon the conditions of
treatment. The advantage of iron phosphating is in the improvement
of paint adhesion to the surface, and it is particularly suitable
for use in moderately corrosive environments.
Zinc phosphating produces a porous coating on the surface of
the steel which, when impregnated with oil, can provide protection
for rock drills and weapons. It also prevents rust from spreading
under defects in antirust paint coatings. This treatment is widely
used for products made from rolled sheet steel such as car bodies.
CLAD STEELS
A clad steel plate is a composite plate made of mild steel with a

cladding of corrosion-resistant or heat-resistant metal on one or
both sides.
The cladding may consist of various grades of stainless steels,
nickel, Monel, Inconel, cupronickel, titanium, or silver. The thick-
ness of the clad material may vary from 5 to 50% of the thickness
of the clad plate, but normally is held to 10 to 20%. The clad steels
are available in the form of sheet, plate, strip, and may be obtained
as wire.
The clad steels are used in place of solid corrosion-resistant
or heat-resistant materials. They also find application where corrosion
is a minor problem but where freedom from contamination of the
materials handled is essential. In addition to the savings in material
costs, the clad steels are frequently easier to fabricate than solid
plates of the cladding material. Their high heat conductivity is
another reason for their selection for many applications.
Clad steels are used for processing equipment in the chemical,

food, beverage, drug, paper, textile, oil, and associated industries.
Methods of Cladding
There are six basic methods of cladding ranging from the insertion
of a loose liner to explosion cladding.
Loose Lining
The installation of a thin, corrosion-resistant liner inside a process

vessel constructed of a less expensive base metal is the least ex-
pensive form of cladding. With this type of cladding the liner is
normally relatively thin, anywhere from 0.3- to 2-mm thick, and
is used only for corrosion resistance. The base metal provides all
of the structural strength.
The advantages of this method are
1. Relatively low cost.

2. Availability: providing the base metal and the liner material
are available, the finished piece of equipment can be produced
in a short time.
3. Base metal and liner material do not have to be metallurgically
compatible.
4. Repairs can be made relatively easily.
The disadvantages of a loose liner are
1. A vacuum will cause the liner to collapse. However, if the liner

is periodically attached to the base metal or its thickness is
increased, this disadvantage can be overcome, but the cost is
increased.
2. Heat transfer is reduced.
3. The liner is easily damaged.
Resistance Cladding
Resistance cladding provides a means of applying a lining to a base

metal regardless of whether or not the base metal and the liner
material are metallurgically compatible. In this process, use is made
of resistance welding and proprietary intermediate materials to bond
thin-gauge, corrosion-resistive materials to heavier, less-expensive
base metals.
This type of cladding can be applied to completed fabrications
of equipment or to components during fabrication. It is also possible
62 Schweitzer
to apply this cladding to existing used equipment. Completed fabri-

cations are relatively inexpensive.
Because of the relatively thin layer of cladding, the corrosion
rate of the process must be low. The process also does not lend
itself to providing a finished, polished surface. Economics do not
favor this process unless the cladding material is expensive.
Thermal Spraying
Thermal spraying is accomplished by heating the metal-cladding

(or nonmetallic) particles to a molten state and spraying them on
the prepared surface of the base metal. As the molten particles
impact on the surface of the base metal they form an overlapping
multilayered cladding, ranging in thickness from 0.2 to 2.5 mm.
One of the advantages of this process is that the temperature of
the base metal normally does not exceed 150 to 200°C which mini-
mizes thermal distortion of the base metal. This also does not permit
the coating to become diluted, which is essential when the cladding
material and the base metal are not metallurgically compatible. Com-
binations of certain metals form mixtures that are affected adversely
by the intermixing or interaction of the components. For example,
nickel and copper are metallurgically compatible, whereas steel and
zirconium are not. This process is relatively inexpensive and is
a common operation performed by many shops.
Certain disadvantages are prevalent with these spraying processes.
The claddings or coatings have a tendency to be porous. This can
be overcome somewhat by increasing the density of the coating.
In addition, the bond between the coating/cladding is mechanical,
and any leakage of corrodent to the base metal through a porous
section of the coating can cause the coating to "spall off." It is
also very difficult, or at times impossible, to clad complex shapes.
Weld Overlaying
Weld overlaying can be used with only cladding materials and base
metals that are metallurgically compatible, and this method is best
restricted for use on small, complex parts. Most readily available
commercial alloys, such as the stainless steels, and nickel- and
copper-based alloys, can be used to provide a corrosion-resistant
overlay.
Because of the heat required for the welding, care must be
taken not to distort the member being clad. Thought must also
be given to whether or not the welding equipment will have access
to the completed fabricated section to produce the overlay.
Roll Cladding
Roll cladding produces full-sized sheets of clad material that a fabri-

cator then forms and welds into a finished product. These sheets
are rolled at the mill. Composites are produced with cladding de-
signed to resist wear, abrasion, or corrosion. The bond formed
is part mechanical and part metallurgical, consequently metallurgically
incompatible materials normally cannot be produced. One exception
is the production of titanium-clad steel sheets being produced by
Nippon Kokan KK of Tokyo. Refer to Chapter 10.
Cladding thicknesses range from 5 to 50% of the composite thick-
ness.
Explosion Cladding
Explosion cladding produces full-sized sheets of clad material, just
as roll cladding does, that a fabricator then forms and welds into
a finished product. The bond produced is metallurgical, but by
use of an intermediate material, metallurgically incompatible materials
may be coupled. Thick plates, up to 510 mm, may be produced
by this method and, unless relatively thick sections are required,
this process is not economical.
METALLIC PROTECTIVE COATINGS
To take advantage of the physical and the mechanical properties

of carbon steel, various types of metallic coatings have been devel-
oped to provide corrosion resistance for specific types of applications.
There are several methods by which metallic coatings may be
applied.
1. By brief immersion in a molten bath of metal, called hot dipping.

2. By electroplating from an aqueous electrolyte.
3. Spraying, for which a gun is used that simultaneously melts
and propels small droplets of metal on to the surface to be coated,
similar to spray painting.
4. Cementation, in which the material to be coated is tumbled in
a mixture of metal powder and an appropriate flux at elevated
temperatures, thus allowing the metal to diffuse into the base
metal.
5. Gas phase reaction.
6. By chemical reduction of metal-salt solutions, the precipitated
metal forming an overlay on the base metal. Nickel coatings of
this type are referred to as electroless nickel plate.
Coatings from a corrosion viewpoint are classified as either noble

or sacrificial. All metal coatings contain some degree of porosity.
Coating performance is, therefore, determined by the degree of
galvanic action that takes place at the base of a pore, scratch,
or other imperfection in the coating.
64 Schweitzer
Electrolyte
Noble coating
-Base metal
FIGURE 1 Galvanic action with a noble coating.
Noble coatings, consisting of nickel, silver, copper, lead, or

chromium on steel, are noble in the galvanic series relative to steel,
resulting in galvanic current attack at the base of the pores of
the base metal and eventually undermining the coating (Fig. 1).
To reduce this rate of attack, it is important that this type
of coating be prepared with a minimum number of pores and that
any pores that are present be as small as possible. This can be
accomplished by increased coating thickness.
In sacrificial coatings consisting of zinc, cadmium and, in certain
environments, aluminum and tin on steel, the base metal is noble
in the galvanic series to the coating material, resulting in cathodic
protection to the base metal and attack on the coating material
(Fig. 2).
As long as sufficient current flows and the coating remains in
electrical contact, the base metal will be protected from corrosion.
Contrary to noble coatings, the degree of porosity of sacrificial
coatings is relatively unimportant. However, the thicker the coating,
the longer cathodic protection will be provided to the base metal.
Nickel Coatings
The most common method of applying nickel coatings is by electro-
plating, either directly on steel or over an intermediate coating
of copper. Copper is used as an underlayment to facilitate buffing,
because it is softer than steel, and to increase the required coating
thickness with a material less expensive than nickel.
Depending upon exposure conditions, certain minimum coating
thicknesses to control porosity are recommended for the coating
to maintain its appearance and have a satisfactory life
Indoor exposures 0.3 to 0.5 mil (0.008 to 0.013 mm)

Outdoor exposures 0.5 to 1.5 mil (0.013 to 0.04 mm)
Chemical industry 1 to 10 mil (0.025 to 0.25 mm)
Electrolyte
.Sacrificial
coating
Base metal
FIGURE 2 Galvanic action with a sacrificial coating.
For applications near the seacoast, thicknesses in the range

of 1.5 mil should be considered. This also applies to automobile
bumpers and applications in general industrial atmospheres.
Nickel is sensitive to attack by industrial atmospheres and forms
a film of basic nickel sulfate that causes the surface to "fog" or
lose its brightness. To overcome this fogging, a thin coating of
chromium (0.01 to 0.03 mil; 0.003 to 0.0003 mm) is electrodeposited
over the nickel, which is sometimes incorrectly referred to as chrome
plate. This finish is applied to all materials for which continued
surface brightness is desired, such as automobile bumpers.
The chemical industry is the prime user of electroless nickel
plate. Various compositions of nickel salts in sodium hypophosphite
solutions are used. When the solution is heated up to, or at the
boiling point, the nickel salts are reduced to the metal and deposited
on the base metal. By specific additions of other materials to the
solution, nickel can also be coated on glass and plastic.
Nickel electroless coatings cannot be deposited on lead, tin solder,
cadmium, bismuth, or antimony.
Lead Coatings
Lead coatings are usually applied either by hot dipping or by elec-
trodeposition. When the coating is to be applied by hot dipping,
a small percentage of tin is added to improve the adhesion to the
steel plate. If 25% or more of tin is added, the resulting coating
is termed terne plate. Lead or lead-tin alloy coatings are applied
to resist atmospheric corrosion. Pores in the coating fill with rust,
thereby inhibiting further corrosive attack. Little protection is
provided by these coatings when in contact with the soil.
Caution: Do not use lead coatings where they will come into
contact with drinking water or food products. Lead salts can be
formed that are poisonous.
66 Schweitzer
Zinc Coatings (Galvanizing)

Galvanized or zinc coating is probably one of the most common coat-
ings because it is the least expensive. They are applied either by
electrodeposition or hot dipping. Electrodeposited coatings tend
to be more ductile than hot-dipped coatings but otherwise are com-
parable in corrosion resistance, with one exception. Hot-dipped
coatings tend to pit less in hot or cold water and soils than coatings
applied by other methods. The zinc dissolves to a small extent
in the iron, and this thin film of alloy permits the outer coating
of zinc to adhere firmly to the metal. If a scratch is made on a
sheet of galvanized steel, the zinc along the edges will suffer prefer-
ential corrosion, and the iron will be protected, even if the zinc
has been removed from a strip 1/8 in. wide.
Zinc coatings stand up extremely well in rural atmospheres and
in marine atmospheres, except when saltwater spray comes into
direct contact with the coating.
In aqueous environments at room temperatures, within a pH
range of 7 to 12, good corrosion resistance will be obtained.
Any welding or forming should, if possible, be performed before
the galvanizing operation. Zinc-coated steel (galvanized) is widely
used for wire fences, water pipes, and buckets. Pipe fittings made
from cast or malleable iron are protected in the same manner.
Cadmium Coatings
Cadmium coatings are produced almost exclusively by electrodeposi-
tion. A cadmium coating on steel does not provide as much cathodic
protection to the steel as does a zinc coating because the potential
between cadmium and iron is not as great as between zinc and iron.
Therefore, it becomes important to minimize defects in the cadmium
coating.
Unlike zinc, a cadmium coating will retain a bright metallic appear-
ance. It is more resistant to attack by salt spray and atmospheric
condensate. In aqueous solutions, cadmium will resist attack by
strong alkalis, but it will be corroded by dilute acids and aqueous
ammonia.
Because cadmium salts are toxic, these coatings should not be
allowed to come in contact with food products. This coating is
commonly used on nuts and bolts.
Tin Coatings (Tinplate, Terne Plate)

Steel sheets containing less than 0.1% carbon are pickled in dilute
sulfuric acid to remove mill scale and then passed through a bath
of used zinc chloride, a bath of molten tin, and a bath of palm oil,
Steel base
Tin plate (noble) Tin plate (sacrificial)
Outside of Inside of
container container
FIGURE 3 Tin acting as both a noble and sacrificial coating on

a "tin" can.
all in one continuous operation. A standard grade of tinplate will

have 0.7 lb of tin applied to 100 sq ft of steel sheets.
When tinplate is to be used for structural purposes such as
roofs, an alloy of 12 to 25 parts of tin to 88 to 75 parts of lead
is frequently used. This is called terne plate. It is less expensive
and more resistant to the weather than is a pure tin coating.
Most of the tin plate (tin coating on steel) produced is used
for the manufacture of food containers (tin cans). The nontoxic
nature of tin salts makes tin plate an ideal material for the handling
of foods and beverages.
An inspection of the galvanic series will indicate that tin is more
noble than steel and, consequently, the steel would corrode at
the base of the pores. On the outside of a tinned container this
is what happens—the tin is cathodic to the steel. However, on the
inside of the container there is a reversal of polarity because of
the complexing of the stannous ions by many food products. This
greatly reduces the activity of the stannous ion, resulting in a
change in the potential of tin in the active direction.
This change in polarity is absolutely necessary because most
tin coatings are thin and, therefore, porous. To avoid perforation
of the can, the tin must act as a sacrificial coating. Figure 3 illus-
68 Schweitzer
trates this reversal of activity between the outside and inside of

the can.
Tin will react with both acids and alkalis, but it is relatively-
resistant to a neutral or near-neutral medium.
It is extremely resistant to soft waters and, consequently, has
found wide use as a piping material for distilled water. Only its
cost and availability have precluded it from monopolizing this market.
Aluminum Coatings
Aluminum coatings on steel are applied primarily by hot dipping
or by spraying. Silicon is usually added to the molten bath to retard
the formation of a brittle alloy layer. Organic lacquers or paints
are used as sealers over sprayed coatings.
Hot-dipped coatings are used mostly to provide oxidation resistance
at moderately elevated temperatures, e.g., oven construction. They
find limited application as protection against atmospheric corrosion
because of the higher cost, compared with zinc, and because of
a variable performance.
Chrominizing
Chrominizing of low carbon steel is effective in improving corrosion
resistance by developing a surface containing up to 40% chromium.
Some forming operations can be carried out on chrominized material.
6
STAINLESS STEELS
INTRODUCTION
Stainless steel is probably the most widely known and most commonly
used material of construction for corrosion resistance. For many
years stainless steel was the only material available to provide any
degree of resistance to corrosive attack.
Stainless steel is not a singular material, as its name might imply,
but rather a broad group of alloys, each of which exhibits its own
physical and corrosion-resistant properties. There are more than
70 standard types of stainless steels and many special alloys.
These steels are produced both as cast alloys [Alloy Casting
Institute (ACI) types] and wrought forms [American Iron and Steel
Institute (AISI) types]. Generally, all are iron-based with 12 to
30% chromium, 0 to 22% nickel, and minor amounts of carbon, colum-
bium, copper, molybdenum, selenium, tantalum, and titanium. They
are corrosion- and heat-resistant, noncontaminating, and easily
fabricated into complex shapes. The 70+ types can be divided into
three basic groups.
1. Austenitic
2. Martensitic
3. Ferritic
AUSTENITIC STAINLESS STEELS
Austenitic stainless steels contain both nickel and chromium. The

addition of substantial quantities of nickel to high chromium alloys
69
70 Schweitzer
stabilizes the austenite at room temperature. This group of steels

contain 16 to 26% chromium and 6 to 22% nickel. The carbon content
is kept low (0.08%) to minimize carbide precipitation. The most
common composition is 18 Cr and 8 Ni (known as 18-8). However,
many other compositions have been developed to meet special condi-
tions and for special applications. Refer to Table 1, which gives
the chemical compositions of the various austenitic stainless steels.
Table 2 provides the physical properties of the austenitic stainless
steels.
Type 302 is the basic alloy of this group.
Mechanical Properties
The austenitic stainless steels cannot be hardened except by cold
work. Heat treatment will not cause hardening. In the annealed
condition the tensile strength is approximately 85,000 psi. Austenitic
stainless steels are both tough and ductile. Table 3 lists the mechan-
ical properties.
All plain carbon steels and low-alloy steels become increasingly
brittle as the temperature is reduced and should be used with caution
if the operating temperature is expected to be much less than -18° C
The austenitic stainless steels are almost exempt from this low
temperature brittleness, and consequently stainless steels are widely
used in equipment operating at low temperatures. The higher the
percentage of nickel p r e s e n t , the lower the allowable operating
temperature.
All standard methods of fabrication can be used to work these
steels; however, the austenitic grades are difficult to machine b e -
cause they work-harden and gall. Rigid machines, heavy c u t s ,
and high speeds are necessary. Welding is readily performed,
although the heat of welding may cause chromium carbide precipita-
tion, which depletes the alloy of some chromium in t h e area of the
weld and lowers its corrosion resistance in liquid service. High-
temperature properties are not affected. This is not serious for
mild service, b u t for severe corrosive service, the carbides must
be put back into solution by heat treatment, which is not always
possible with field welds.
The Removal of Precipitated Carbides from Type 304

The removal of precipitated carbides from type 304 to restore maxi-
mum corrosion resistance can be accomplished by annealing [at 980
to 1180°C (1800 to 2150°F)] (above the sensitizing range) followed
by rapid cooling. Stress relieving a weldment at 1500 to 1700°F
will not restore corrosion resistance and, in fact, may foster carbide
TABLE 1 Chemical Composition of Austenitic Stainless Steels
Stai
AISI Nominal composition (%)
type C max. Mn max. Si max. Cr Ni Others 8
CO
CO
201 0.15 7.5 b 1.00 16.00-8.00 3.50-5.50 0.25 max. N Co
202 0.15 10.00 c 1.00 17.00-19.00 4.00-6.00 0.25 max. N c?
205 0.25 15.50 d 0.50 16.50-18.00 1.00-1.75 0.32/0.4 max. N 2-
301 0.15 2.00 1.00 16.00-18.00 6.00-8.00
302 0.15 2.00 1.00 17.00-19.00 8.00-10.00
302B 0.15 2.00 3.00 e 17.00-19.00 8.00-10.00
303 0.15 2.00 1.00 17.00-19.00 8.00-10.00 0.15 min. S
303(Se) 0.15 2.00 1.00 17.00-19.00 8.00-10.00 0.15 min. Se
304 0.08 2.00 1.00 18.00-20.00 8.00-12.00
304L 0.03 2.00 1.00 18.00-20.00 8.00-12.00
304N 0.08 2.00 1.00 18.00-20.00 8.00-10.50 0.1/0.16 N
305 0.12 2.00 1.00 17.00-19.00 10.00-13.00
308 0.08 2.00 1.00 19.00-21.00 10.00-12.00
309 0.20 2.00 1.00 22.00-24.00 12.00-15.00
309S 0.08 2.00 1.00 22.00-24.00 12.00-15.00
310 0.25 2.00 1.50 24.00-26.00 19.00-22.00
310S 0.08 2.00 1.50 24.00-26.00 19.00-22.00
314 0.25 2.00 3.00 f 23.00-26.00 19.00-22.00
316 0.08 2.00 1.00 16.00-18.00 10.00-14.00 2.00-3.00 Mo
316F 0.08 2.00 1.00 16.00-18.00 10.00-14.00 1.75-2.50 Mo
316L 0.03 2.00 1.00 16.00-18.00 10.00-14.00 2.00/3.00 Mo
316N 0.08 2.00 1.00 16.00-18.00 10.00-14.00 2.00-3.00 Mo
317 0.08 2.00 1.00 18.00-20.00 11.00-15.00 3.00-4.00 Mo
(continued) -sj
(Table 1, continued)
AISI
type C max. Mn max. Si max. Cr Ni Others a
317L 0.03 2.00 1.00 18.00-20.00 11.00-15.00 3.00-4.00 Mo

321 0.08 2.00 1.00 17.00-19.00 9.00-12.00 5XC min Cb-Ta
330 0.08 2.00 1.5& 17.00-20.00 34.00-37.00 0.10TA
0.20 Cb
347 0.08 2.00 1.00 17.00-19.00 9.00-13.00 10XC min. Cb-Ta
348 0.08 2.00 1.00 17.00-19.00 9.00-13.00 10C min. Cb-Ta
2.0 Mo
20Cb3 0.07 0.75 1.00 20.0 29.0 3.0 Cu
904L 0.02 21.0 25.5 8XC Min. Cb-Ta
4.7 Mo
1.5 Cu
a
Other elements in addition to those shown are as follows: Phosphorus is 0.03% max. in type 205; 0.06%
max. in types 201 and 202; 0.045% max. in types 301, 302, 302B, 304, 304L, 304N, 305, 308, 309, 309S,
310, 310S, 314, 316, 316N, 316L, 317, 317L, 321, 330, 347, and 348; 0.20% max. in types 303, 303(Se),
and 316D. Sulfur is 0.030% max. in types 201, 202, 205, 301, 302, 302B, 304, 304L, 304N, 305, 308,
309, 309S, 310, 310X, 314, 316, 316L, 316N, 317, 317L, 321, 330, 347, and 348; 0.15% min. in type
303; 0.10% min. in type 316D.
D
Mn range 4.40 to 7.50.
c
Mn range 7.50 to 10.00.
d
Mn range 14.00 to 15.50. c?
e
Si range 2.00 to 3 . 0 0 . |
f
Si range 1.50 to 3 . 0 0 . 2.
TABLE 2 Physical Properties of Austenitic Stainless Steels
Thermal
Specific expansion Thermal Tensile
Stain- heat coefficient conductivity Electrical modulus
less Hard- Melting (32-212°F) (32-212°F) (32-212°F) resistivity of
steel Form and ness Density Specific point (BTU/lb (x 10"6 [BTU(ft)(hr) (68°F) elasticity
type condition (Brinell) (lb/in.3) gravity (°F) <5 F) in./in. °F) (°F/in.)] (fi/cir mil) (x
201 Annealed 194 0.,28 7.7 255-2650 0.,12 113 414 28.6
202 Annealed 184 0.,28 7.7 2550-2650 0.,12 113 414 28.6
205 Annealed 217
301 Annealed 160
0.,29 8.02 2550-2590 0.,12 9.4
Cold-rolled 186
302 Annealed 160
i n n 0<.29 8.02 2550-2590 0..12 112.8 435 28
Cold-rolled <
Up t o 100
302B Annealed 165
303 Annealed 165
303(Se) Annealed 160
304 Annealed 160
.29 8.02 2550-2650 0,.12 9.6 113 435 28
Cold-rolled Up to 400
304L Annealed 150
Cold-rolled 277 0,.29 8.02 2550-2650 0,.12 9.6 113 435 28
304N Annealed 160
305 Annealed 156
308 Annealed 150
309 Annealed 165
0,.29 8.02 2550-2650 0,.12 8.3 96 470 29
Cold-rolled 275
(continued)
Thermal
Stain- heat coefficient conductivity Electrical modulus
less Hard- Melting (32-212°F) (32-212°F) (32-212°F) resistivity of
steel Form and ness Density Specific point (BTU/lb (x 10"6 [BTU(ft)(hr) (68°F) elasticity
type condition (Brinell) (lb/in. 3 ) gravity (°F) °F) i n . / i n . °F) (°F/in.)] (ft/cir mil) (
309S Annealed 165

0.29 8.02 2550-2650 0.12 8.0 96 470 29
310 Annealed 165
310S Annealed 170
314S Annealed 170
316 Annealed 165
Cold-rolled 275 0.29 8.02 2500-2550 0.12 8.9 113 445 28
316F Annealed
316L Annealed 150
Cold-drawn 275 0.29 8.02 2500-2550 0.12 8.9 113 445 28
316N Annealed
317 Annealed 160
317L Annealed 160
321 Annealed 160
Cold-rolled 300 0.286 7.92 2550-2600 0.12
0.12 9.3 110 435 28
330 Annealed 156
347 Annealed 160
0.286 7.92 2550-2600 0.12
0.12 9.3 110 435 28
Cold-rolled 300
348 Annealed 160
20CB3 Annealed 160 0.289 8.02 0.12 8.6 145.2 451 28
904L Annealed 140 0.288 7.9 0.105 8.4 94 480 28.4
TABLE 3 Mechanical Properties of Austenitic Stainless Steels
Stainless Yield strength Tensile Elongation

steel Form and (0.2% offset) strength in 2 in.
type condition (x 106ip) (x 10S) (%)
201 Annealed 55 115 55

202 Annealed 50 100 60
205 Annealed 69 120 58
301 Annealed 30 100 72
Cold rolled a Up to 165 Up to 200 15b
302 Annealed 30 90 60
Cold rolled a Up to 165 Up to 190 8^
302B Annealed 40 95 50
Cold rolled Up to 160 Up to 185
303 Annealed 35 90 50
303(Se) Annealed 35 90 50
304 Annealed 30 85 62
Cold rolled Up to 160 Up to 185 8«
304L Annealed 30 80 60
Cold drawn 95 125 25
304N Annealed 48 90 50
305 Annealed 85 37 55
308 Annealed 85 35 55
309 Annealed 30 82 50
Cold rolled Up to 120 Up to 140 4b
309S Annealed 90 40 45
310 Annealed 40 100 50
310S Annealed 95 40 45
314 Annealed 100 50 45
316 Annealed 30 90 50
Cold rolled Up to 120 Up to 150 8^
316F Annealed 38 85 60
Cold drawn 60 90 45
316N Annealed 48 90 48
317 Annealed 90 40 50
321 Annealed 30 85 50
330 Annealed 38 80 40
347 Annealed 30 85 50
348 Annealed 92 35 50
20Cb3 35 85 50
a
The cold-rolled properties depend on composition; types 302 and
304 are not often rolled in excess of 175,000 $ tensile strength
b
The values for elongation (percentage in 2 in.) are obtainable
in steel cold rolled to the maximum stated yield strength and tensile
strength. For lower values of tensile strength, elongation will be
correspondingly higher.
76 Schweitzer
precipitation in stainless steels that do not have a low carbon con-

tent or are not stabilized.
To avoid this problem, special stainless steels have been developed
by adding titanium, columbium, or tantalum to stabilize the carbon
and prevent precipitation (types 321, 347, and 346).
Alternative to the use of these alloys is to use the low carbon
alloys such as types 304L and 316L, which have maximum carbon
contents of 0.03%.
Corrosion Resistance
The austenitic stainless steels perform best under oxidizing conditions
because their resistance is dependent on an oxide film that forms
on the surface of the alloy. Reducing conditions and chloride ions
destroy this film and cause rapid attack. Chloride ions, combined
with high tensile stresses, cause stress-corrosion cracking.
These alloys have excellent resistance to nitric acid at practically
all concentrations and temperatures. Type 304 is used in the con-
struction of most nitric acid plants. To handle sulfuric acid, without
inhibitors, type 316 stainless steel has limited application. Below
5% and above 85% it can be used only at temperatures below the
boiling point.
MARTENSITIC STAINLESS STEELS
The martensitic stainless steels contain 12 to 20% chromium, controlled

amounts of carbon, and other additives. Table 4 gives the chemical
composition of the various martensitic alloys, and Table 5 gives
the physical properties.
Type 410 is a typical member of this group.
Martensitic stainless steels can be hardened by heat treatment,
which can increase the tensile strength from 80,000 to 200,000 psi.
A high hardness can be achieved by this heat treatment.
A hardening temperature range depends on the composition but,
in general, the higher the quenching temperature, the harder the
article. Oil quenching is preferable, but with thin and intricate
shapes, hardening by cooling in air should be undertaken.
Tempering at 425°C (800°F) does not reduce the hardness of
the part, and in this condition these alloys show an exceptional
resistance to fruit and vegetable acids, lye, ammonia, and other
corrodants to which cutlery may be subjected.
Table 6 lists the mechanical properties of the martensitic stainless
steels.
TABLE 4 Chemical Composition of Martensitic Steels CO
CO
C/
AISI Nominal composition (%) CO
Si max. Other a
CO
type C Mn max. Cr Ni «—
05
403 0.15 max. 1.00 0.50 11.50-13.00

410 0.15 max. 1.00 1.00 11.50-13.50
414 0.15 max. 1.00 1.00 11.50-13.50 1.25-2.50
416 0.15 max. 1.25 1.00 12.00-14.00 0.15 S min.
416(Se) 0.15 max. 1.25 1.00 12.00-14.00 0.15 S min.
420 0.15 min. 1.00 1.00 12.00-14.00
431 0.20 max. 1.00 1.00 15.00-17.00 1.25-2.50
440A 0.60-0.75 1.00 1.00 16.00-18.00 0.75 Mo max.
440B 0.75-0.95 1.00 1.00 16.00-18.00 0.75 Mo max.
440C 0.95-1.20 1.00 1.00 16.00-18.00 0.75 Mo max.
501 0.10 min. 1.00 1.00 4.00-6.00 0.40-0.65 Mo
502 1.10 max. 1.00 1.00 4.00-6.00 0.40-0.65 Mo
a
Other elements in addition to those shown are as follows: Phosphorus is 0.06% max. in types 416
and 416(Se); sulfur is 0.03% max. in types 403, 410, 414, 420, 431, 440A, 440B, 440C, 501, and 502.
TABLE 5 Physical Properties of Martensitic Stainless Steels
Thermal
heat coefficient conductivity Electrical modulus
Stainless Hard- Melting (32-212°F) (32-212°F) (32-212°F) resistivity of
steel Form and ness Density Specific point (BTU/lb (x 10"6 [BTU(ft 2 )(hr) (68°F) elasticity
type condition (B rinell) (lb/in. 3 ) gravity (°F) °F) i n . / i n . °F) (°F/in.)] (ft/cir mil) (x 106i/O
403 Annealed 155

Heat-treated 410
410 Annealed 150
0.28 7.75 2700-2790 0.11 5.5 173 340 29
Heat-treated 410
414 Annealed 217
0.28 7.75 2600-2700 0.11 6.1 173 420 29
Heat-treated 387
416 Annealed 155
Heat-treated 410
Heat-treated 410
420 Annealed 180
0.28 7.75 2650-2750 0.11 5.7 173 330 29
Heat-treated 480
431 Annealed 250
0.28 7.75 2600-2700 0.11 6.5 140 430 29
Heat-treated 400
440 Annealed 215
Heat-treated 570
440B Annealed 220
Heat-treated 590
440C Annealed 230
Heat-treated 610
501 Annealed 160
502 Annealed 150
6. Stainless Steels 79
TABLE 6 Mechanical Properties of Martensitic Stainless Steels
Yield
Stainless strength Tensile Elongation
type condition (x 103xp) (x io3i/,) (%)
403 Annealed 75 40 30
410 Annealed 40 75 30
Heat-treated 115 150 15
414 Annealed 80 100 22
416 Annealed 75 40 30
420 Annealed 60 98 28
431 Annealed 85 120 25
440A Annealed 105 60 20
440B Annealed 107 62 18
440C Annealed 110 65 13
501 Annealed 70 30 28
502 Annealed 70 30 30
The corrosion resistance of the martensitic stainless steels is inferior
to that of the austenitic stainless steels. These alloys are generally
used in mildly corrosive services such as atmospheric, freshwater,
and organic exposures.
Because of the ability to heat treat these alloys to a high degree
of hardness and because of their resistance to oxidation, they are
used extensively for cutlery, razor blades, surgical and dental
instruments, springs for high-temperature operations, ball valves
and seats, and similar applications.
FERRITIC STAINLESS STEELS
The ferritic stainless steels contain 15 to 30% chromium with a low

carbon content (0.1%). Table 7 lists the chemical composition of the
members of this group, and Table 8 gives the physical properties.
Type 430 is a typical member of this group.
TABLE 7 Chemical Composition of Ferritic Steels
AISI Nominal Composition (%)

type C max. Mn max. Si min.
Cr Other a
405 0.08 1.00 1.00 11.50-14.50 0.10-0.30 Al
403 0.12 1.00 1.00 14.00-18.00
430F 0.12 1.25 1.00 14.00-18.00 0.15 S min.
430 (Se) 0.12 1.25 1.00 14.00-18.00 0.15 Se min.
444 0.025 1.00 1.00 (max) 17.5-19.5 1.75-2.50 Mo
446 0.20 1.50 1.00 23.00-17.00 0.25 max. N
a
Other elements in addition to those shown are as follows: Phosphorus is 0.06% max. in types 430F and
430 (Se); sulfur is 0.030% max. in types 405, 430, 444, and 446; 0.15% min. in type 430F; nickel 1.00%
max. in type 444; titanium + niobium 0.80% max. in type 444.
TABLE 8 Physical Properties of Ferritic Stainless Steels
Thermal Thermal
Specific expansion conduc- Tensile
heat coefficient tivity Electrical modulus
Hard- Melting (32-212°F) (32-212°F) (32-212°F) resistivity of
AISI Form and ness Density Specific point (BTU/lb (x 10"6 [BTU(ft 2 )(hr) (68°F) elasticity
type condition (Brinell) (lb/in. 3 ) gravity (°F) °F) in./in. °F) (°F/in.)] (ft/cir mil) (x 10H)
405 Annealed 150

430 Annealed 165
0.28 7.75 2600-2750 0.11 6.0 180 360 29
Cold-rollec1 225
430F Annealed 170
444 Annealed 217 0.28 7.75 0.102 6.1 186
446 Annealed 165 0.27 7.45 2600-2750 0.12 5.8 145 405 29
The strength of ferritic stainless steels can be increased by cold
working but not by heat treatment. These alloys possess considerable
ductility, ability to be worked hot or cold, and excellent corrosion
resistance, and they are relatively inexpensive.
Alloys containing 16 to 18% chromium are probably the most useful
of the straight chromium steels because of their forming and medium-
deep drawing properties. They are used extensively for kitchen
equipment, dairy machinery, interior decorative work, automobile
trimmings, and chemical equipment to resist nitric acid corrosion.
The mechanical properties are given in Table 9.
Corrosion resistance is rated good, although ferritic alloys do not
resist reducing acids such as HC1. Mildly corrosive solutions and
oxidizing media are handled satisfactorily. Type 430 finds wide
application in nitric acid plants. Increasing the chromium content
to between 25 and 30% improves the resistance to oxidizing conditions
at elevated temperatures. These alloys are useful for all types of
furnace parts not subjected to high stress. Because the oxidation
resistance is independent of the carbon content, soft, forgeable
alloys low in carbon can be rolled into plates, shapes, and sheets,
and hard and wear-resistant castings can be made from higher
carbon nonforgeable alloys.
TABLE 9 Mechanical Properties of Ferritic Stainless Steels
Stain- Yield
less strength Tensile Elongation
type condition (x 103ip) (x 103ip) (%)
405 Annealed 70 40 30
430 Annealed 75 45 30
Cold drawn
430F Annealed 40 70 350
Cold rolled 95 110 10
444 Annealed 40 60 20
446 Annealed 50 80 30
82 Schweitzer
DUPLEX STAINLESS STEELS
The duplex stainless steels are those alloys whose microstructure

is a mixture of austenite and ferrite. These alloys were developed
to improve the corrosion resistance of the austenitic stainlesses,
particularly in the areas of chloride stress-corrosion cracking and
in maintaining corrosion resistance after welding. Typical of the
first duplexes developed are type 329 and CD-4M Cu, both of which
have been in use for many years. However, although having improved
corrosion resistance over the austenitic stainlesses they do not
possess all of the desired improvements in corrosion resistance,
and welding of these alloys present several problems. Heat treating
after welding must be performed if the corrosion resistance in the
weld area is to be maintained.
To overcome these shortcomings, additional research was under-
taken which produced a series of duplexes that have the desired
improvement in corrosion resistance both before and after welding.
Specific improvements in corrosion resistance are found in the area
of pitting, crevice corrosion resistance, and chloride stress-corrosion
cracking.
The original duplex stainless steels did not have nitrogen added
specifically as an alloying ingredient. By adding 0.15 to 0.25% nitro-
gen the chromium partitioning between the two phases is reduced,
resulting in the pitting and crevice corrosion resistance of the
austenite being improved. This nitrogen addition also improves the
weldability of the stainless steel without losing any of its corrosion
resistance. It is not necessary to heat treat these duplexes after
welding.
Table 10 shows the chemical composition of the duplex stainless
steels.
Because the duplex stainless steels are a mixture of austenite and
ferrite it is only logical that their physical properties would lie
between the comparable properties of these microstructures. The
duplexes have better toughness than ferritic grades and higher
yield strengths than the austenitics. Tables 11 and 12 show these
properties.
Because of the large amounts of ferrite present in the duplexes,
they are magnetic. However, unlike the ferritics, they have a high
degree of toughness along with their high strength.
Because the duplexes have a higher yield strength than the
austenitics, they provide certain economic advantages. Money can
be saved by using thinner-walled sections for piping and equipment
TABLE 10 Chemical Composition of Duplex Stainless Steels

Nominal composition ( %)
Type Cr Ni Mo Cu N Other
3E60 18.5 4.7 2.7 1.7 SI

Uranus 50 21.0 7.0 2.5 1.5
329 26.0 4.5 1.5
CD-4MCu 25.0 5.0 2.0 3.0
44LN 25.0 6.0 1.7 — 0.15
DP3 25.0 7.0 3.0 0.5 0.15 0.3 W
Alloy 2205
CD-3MN 22.0 5.0 3.0 — 0.15
Ferralium 255 25.0 6.0 3.0 2 0.20
7Mo PLUS 26.5 4.8 1.5 0.20
Atlas 958
COR 25 25.0 7.0 4.5 0.25
TABLE 11 Physical Properties of the Duplex Stainless Steels
Thermal Tensile
expansion Thermal modulus
Duplex coefficient conductivity of
stainless (68-212°F) (68°F) elasticity
type (x 10"6 in./in. °F) [BTU-ft/(hr)(°F/in.)] (x loS)
3E60 6.8 11.5 28
329 5.6 8.8 29
CD-4MCU 6.3 8.8 29
44LN 7.8 11.5 29
DP-3 8.3 12 28
Alloy 2205 7.5 11 27.5
CD-3MN 7.5 11 27.5
Ferralium 255 6.1 7.8 31
7MO PLUS 6.4 8.6 29
84 Schweitzer
TABLE 12 Mechanical Properties of Duplex Stainless Steels
Yield
Duplex strength Tensile Elongation
stainless (0.2% offset) strength in 2 in.
type 3
(X 10 !/,) (X 10 3 !/,) (%)
3RE60 65 90 30
Uranus 50 55 90 25
329 70 90 15
Cd4-MCu 70 100 16
44LN 65 100 25
DP-3 65 90 30
Alloy 2205 65 90 25
Ferralium 255 80 110 15
7MO-PLUS 70 90 15
Atlas 958 75 100 18
Cor 25 75 100 18
without sacrificing operating pressures. Conversely, equipment

manufactured from these stainless steels using conventional wall
thicknesses can be operated at higher pressures. The thinner wall
thicknesses result in lighter weights that provide additional savings
in terms of supports and other peripheral equipment.
Corrosion Properties
The high chromium and molybdenum contents of the duplex stainless
steels are particularly important in providing resistance in oxidizing
environments and are also responsible for the exceptionally good
pitting and crevice corrosion resistance, especially in chloride
environments. In general these stainless steels have greater pitting
resistance than type 316, and several have an even greater resistance
than alloy 904L.
The resistance to crevice corrosion of the duplexes is superior
to the resistance of the 300 series austenitics. They also provide
an appreciably greater resistance to stress-corrosion cracking.
However, under very severe conditions, such as boiling magnesium
chloride, the duplexes will crack, as will 20Cb3, and like 20Cb3,
they are resistant to chloride stress-corrosion cracking in chloride-
containing process streams and cooling water.
To achieve the desired microstructure, the nickel content of
the duplexes is below that of the austenitics. Because the nickel
content is a factor for providing corrosion resistance in reducing
environments, the duplexes show less resistance in these environ-

ments than do the austenitics. However, the high chromium and
molybdenum contents partially offset this loss and, consequently,
they can be used in some reducing environments, particularly dilute
and cooler solutions.
PREPARATION FOR SERVICE
The excellent resistance of stainless steel is the result of the highly

tenacious, durable, and self-healing protective film of chromium
oxide that is formed. In the presence of oxygen, this film can be
damaged. On occasion, fabrication or postfabrication cleanup prac-
tices can disturb this film. The most common causes of problems
are
Iron contamination
Organic contamination
Welding contamination
Iron Contamination
On occasion, rust is noticed on new stainless steel vessels shortly
after delivery from a fabricator—the result of embedded iron in
the stainless. When exposed to a moist or humid atmosphere the
iron corrodes leaving streaks of rust on the stainless. These em-
bedded particles can initiate crevice corrosion. To minimize the
presence of embedded iron the following steps can be taken.
1. Purchase specifications for the surface finish should be com-
plete. Sheet, strip, and pipe can be specified to have a 2B finish,
or equivalent. Under normal circumstances plate is furnished hot
rolled, annealed, and pickled and is not furnished with a 2B finish.
If the pickling is carried out properly, embedded iron, if present,
will be removed.
Proper specifications can go a long way toward eliminate embedded
iron.
2. In most instances, the stainless steel sheet or plate is received
in a satisfactory condition, but care must be exercised in the storage
and handling of this material such that it will not be contaminated
with embedded iron. If cleanliness of the surface is extremely impor-
tant, such as in a pharmaceutical or food environment, where product
contamination would be detrimental, the sheet or plate can be ordered
with a protective adhesive paper on the surfaces. Leaving this
paper in place during fabrication will reduce the amount of time
required for cleanup after fabrication.
86 Schweitzer
The sheet and plate should be stored upright and not laid on
the floor. The dragging of plates over each other and foot traffic
are prime causes of damaging scratches or embedded iron.
3. During fabrication, it is good practice to use cardboard or
plastic sheets on carbon steel layout and cutting tables, forming
roll aprons, and rollout benches. This will go a long way in prevent-
ing or reducing iron embedment. The use of plastic, wood, or alumi-
num guards on slings, hooks, and the forks of forklift trucks will
further reduce the chance of iron embedment.
Organic Contamination
Organic contamination is the result of grease, construction markings
(crayon), oil, paint, adhesive tape, sediment, and other sticky
substances being allowed to remain on the stainless. If not removed,
they may cause crevice corrosion if the stainless is exposed to
extremely corrosive atmospheres. During the fabrication stage,
there is little that can be done to prevent this contamination from
occurring. The only solution is to ensure that all such deposits
are removed during final cleanup.
Welding Contamination
In corrosive environments, surface imperfections in stainless plate
can be the source from which corrosion will be initiated. This corro-
sion can occur in the presence of media to which the stainless steel
is normally resistant. Such surface imperfections can be caused by
Weld splatter
Welding slag from coated electrodes
Arc strikes
Welding stop points
Heat tint
Weld splatter produces small particles of metal that adhere to

the surface, at which point the protective film is penetrated, forming
minute crevices where the film has been weakened the most. If
a splatter-prevention paste is applied to either side of the joint
to be welded, this problem will be eliminated. Splatter will then
easily wash off with the paste during cleanup.
Whenever coated electrodes are used, there will be some slag
around the welded joints. This slag is somewhat difficult to remove,
but if it is not done, the small crevices formed will be points of
initiation of corrosion.
Arc strikes and weld stop points are more damaging to stainless
steel than embedded iron because they occur in the area where the
protective film has already been weakened by the heat of welding.

Weld stop points create pinpoint defects in the metal, whereas arc
strikes form crevicelike imperfections in or adjacent to the heat-
affected zone.
It is possible to avoid weld stop defects by employing extensions
at the beginning and end of a weld (runout tabs) and by beginning
just before each stop point and welding over each intermediate stop
point.
An arc can be struck initially on a runout tab or on weld metal,
providing the filler metal will tolerate this. If the filler metal will
not tolerate the striking of an arc, then the arc must be struck
adjacent to it, in or near the heat-affected zone, when it is necessary
to strike an arc between runout tabs.
Heat tint results in the weakening of the protective film beneath
it and can be the result of the welding of internals in a vessel
or the welding of external attachments. The heat tint must be r e -
moved to prevent corrosion from taking place in the tinted area.
Cleanup Procedures
The cleanup procedures to be followed will be dependent somewhat
on the service to which the vessel is to be put. In very corrosive
media, a greater degree of cleanup will be required than in relatively
mild media.
Good commercial practice will always include degreasing and
removal of embedded iron, even if not detailed in the specification.
A complete specification for the procurement of a vessel should
include the desired cleanup procedures to be followed, even if only
degreasing and removal of embedded iron are required.
Removal of Organic Contamination

The removal of organic contamination is best accomplished by the
use of a nonchlorinated solvent. It is vital that the solvent does
not contain chlorides because residual chlorides remain in crevices
and can lead to stress-corrosion cracking. Proprietary degreasing
solvents should be tested for chlorides before use.
It is essential that all organic contamination be removed because
any grease remaining could prevent or hinder the removal of embedded
iron which follows the degreasing operation.
Removal of Embedded Iron

Embedded iron removal is accomplished by pickling. The normal
pickling solution is a nitric/hydrofluoric acid bath at 120°F. The
pickling solution removes the surface layer (<1 mil) by corrosion,
leaving the pickled surface in its most corrosion-resistant condition.
88 Schweitzer
Low carbon or stabilized grades of stainless are best suited for

this operation because the process may cause intergranular corrosion
in heat-affected zones of unstabilized grades of stainless. This
procedure will also remove heat tint.
Removal of Welding Contamination

Welding contamination removal is best accomplished by the use of
abrasive disks and flapper wheels. Although grinding has been
used, this procedure tends to overheat the surface, thereby reducing
its corrosion resistance; hence, its use should be avoided.
7
NICKEL AND HIGH NICKEL ALLOYS
N. SRIDHAR and F. GALEN HODGE Haynes International, Inc.

Kokomo, Indiana
INTRODUCTION
No class of alloys shows as wide a range of applications as the

Ni-based alloys. These alloys are used as corrosion-resistant alloys,
heating elements, controlled expansion alloys, creep-resistant alloys
in turbines and jet engines, and high-temperature corrosion-resistant
alloys. What makes this array of applications possible is not only
the electrochemical properties of nickel but also its crystallographic
characteristics that enable it to accommodate large amounts of alloy-
ing elements that, in turn, lend these alloys their unique properties.
This chapter will be devoted to the alloys developed mainly for
their corrosion resistance. These alloys are mainly solid-solution-
strengthened alloys supplied in the fully annealed condition. How-
ever, some precipitation hardenable Ni-based alloys will also be
discussed where their corrosion properties are of importance. The
purpose overall will be to present the strengths and weaknesses
of these alloys and their areas of application. Discussion of corrosion
mechanisms and physical metallurgy will be kept to a minimum.
However, references, which elaborate the physical metallurgy and
corrosion mechanisms, are cited under each alloy category.
The element nickel is nobler than iron but more active than
copper in the electrochemical series. In reducing environments,
such as dilute sulfuric acid, nickel is more corrosion-resistant than
iron but not as resistant as copper or nickel-copper alloys. The
nickel-molybdenum alloys are more corrosion-resistant to reducing
acids than nickel or Ni-Cu alloys. Nickel can form a protective,
89
90 Sridhar and Hodge
passive film in some environments and, hence, exhibit moderate

corrosion resistance. However, the passive film is not particularly
stable and, hence, nickel cannot generally be used in oxidizing
environments such as nitric acid. Alloying with chromium can result
in a much more stable passive film and corrosion resistance to a
variety of oxidizing environments. However, the nickel-chromium
alloys can corrode in environments containing appreciable amounts
of chloride or other halides, especially if oxidizing species are pres-
ent. The form of corrosion will be pitting. Alloying with molybdenum
and tungsten is necessary to improve the resistance to corrosion
by oxidizing chloride solutions.
One of the important attributes of nickel is its metallurgical
compatibility with a variety of alloying elements such as chromium,
copper, and molybdenum. A comparison of the phase diagram of
nickel with chromium, for example, with the phase diagram of iron
with chromium would indicate that chromium dissolves to a much
greater extent in nickel. This translates to greater homogeneity
and lack of embrittlement caused by the precipitation of deleterious
second phases. Hence, nickel-based alloys, generally, contain more
alloying elements and are more corrosion-resistant than the iron-
based alloys. The high nickel-containing alloys, both nickel-based
alloys and austenitic stainless steels containing high nickel content,
are also often used in applications requiring stress corrosion-cracking
resistance to chloride-containing environments. This is usually
attributed to the effect of nickel in altering the plastic deformation
mode of low nickel austenitic stainless steels.
Nickel-based alloys can be subjected to precipitation of carbides
and intermetallic phases when exposed to temperatures lower than
their recommended annealing temperatures. In some alloys designed
for high-temperature applications, grain boundary precipitation
of carbides is encouraged for resistance to creep. However, the
alloys used in corrosion-resistant applications usually contain low
carbon to delay precipitation of carbides. In some alloys, such
as alloy 625, niobium, tantalum, or titanium is added to stabilize
the alloy against precipitation of Cr, Mo carbides. These elements
combine with carbon instead of chromium or molybdenum. In other
alloys, the presence of niobium or tantalum has been found to in-
crease precipitation of deleterious intermetallic phases. Here, carbon
is lowered to a very small level through changes in the melting
practice, thus, obviating or minimizing the use of stabilizers. Many
of these alloys are also subjected to an electroslag remelting operation
to lower the sulfur levels and, thereby, the inclusion content.
A list of various commercially available nickel-based alloys is
shown in Table 1. Where available, the UNS number [1] is also
shown. Tables 2 and 3 list the nominal physical and mechanical prop-
erties, respectively, of various alloys in the mill-supplied condition.
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Chemical composition (wt %)

Category Alloy UNS No. C Cb Cr Cu Fe Mo Ni Si Ti W Others
Ni-Si D 0.12 a - 1.0 a 3.0 2.0a - 86 9.5 -

Precipitation
Hardenable K-500 NO5500 0.25 a — — 29 2.0a — 63 0.5 a 0. 6 - A l , 2.7
R-41 NO7041 0.09 — 19 — 5.0 a 10.0 52 0.5 a 3. 1 - A l , 1.5
718 NO7718 0.05 5.0 18 — 19 3.0 52.5 — 0. 4a _
925 0.02 — 22.5 1.8 28 3.0 43.0 — 2. 1 -
Cast alloys
B 0.12 a — 1.0 a — 5.0 26.5 Bal. 0.6 — 0.3 V
Chlorimet 2 0.07 a — 1.0 a — 2.0 31.0 Bal. 0.6 — —
Alloy C 0.12 a — 16.0 — 6.0 16.5 Bal. 0.6 4.0 0.3 V
Chlorimet 3 0.07 a — 18.5 _ 3.0a 18.5 Bal. 0.6 _ —
Alloy C-4C 0.02 a — 16.5 — 2.0a 16.5 Bal 0.6 — CO
Alloy C-22C 0.02 a — 22 — 3.0a 13.0 Bal. 0.8 a 3.0 —
a
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TABLE 2 Typical Physical Properties at Room Temperature
Specific Thermal expansion Electrical Thermal r-«.

o
Density heat (x 10~6 m/m-K, resistivity conductivity ?r
Alloy (g/m) (J/kg-K) 20-93°C) (yft-m) (W/m-K) £.
Nickel 8.89 456 13.3 0.095 74.9 a:

Nickel 201 8.89 456 13.3 0.076 79.3 r-i.
Monel alloy 400 8.84 427 13.8 0.509 21.8 ;y
Monel alloy K-500 8.48 418 13.7 0.614 17.4 i?

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Hastelloy alloy B-2 9.22 389 10.3 1.38 12.2 ?r
Inconel alloy 600 8.42 444 13.3 1.03 14.8
Incoloy alloy 800 7.95 502 14.2 0.988 11.5
Incoloy alloy 825 8.15 — 14.0 1.13 11.1
Hastelloy alloy G 8.31 456 13.4 1.18 10.1 CO
Hastelloy alloy X 8.28 486 13.8 1.18 9.1

Inconel alloy 625 8.45 410 12.8 1.29 9.8
Hastelloy alloy C-276 8.89 427 11.2 1.30 10.2
Hastelloy alloy S 8.76 414 11.5 1.25 10.8
Hastelloy alloy G-3 8.30 464 14.60 1.13 10.00
Hastelloy alloy G-30 8.22 12.80 1.16 10.20
Hastelloy alloy N 8.93 418 11.60 1.21 11.50
Hastelloy alloy W 6.29
Haynes alloy No. 230 8.83 419 12.70 1.25 8.90
Haynes alloy No. 214 8.05 13.30 1.36
Haynes alloy No. 556 8.23 475 14.70 0.95 11.10
CO
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TABLE 3 Typical Mechanical Properties a (Annealed Sheet)
Yield Ultimate Dynamic modulus

strength strength Elongation Hardness Hardness of elasticity, RT
Alloy [Ksi (MPA)] [Ksi (MPA)] (Brinell) [Rb (BHN)] [103 x Ksi (GPa)]
Nickel 200 22 (152) 67 (462) 47 105

Nickel 201 17 (117) 55 (379) 50 87
Monel alloy 400 37 (255) 80 (552) 48 130
Monel alloy K500** 50 (345) 100 (689) 35 162
Hastelloy alloy B-2 60 (414) 130 (896) 60 210
Inconel alloy 600 40 (276) 90 (620) 45 142
Incoloy alloy 800 45 (310) 87 (600) 45 152
Incoloy alloy 825 50 (345) 95 (655) 40 150
Hastelloy alloy G 46 (317) 102 (703) 61 169
Hastelloy alloy X 52 (358) 114 (786) 43 176
Inconel alloy 625 70 (483) 135 (931) 42 192
Hastelloy alloy C-276 42 (290) 100 (689) 56 190
Hastelloy alloy C-4 53 (365) 113 (779) 55 190
Hastelloy alloy S 49 (338) 116 (800) 65 180
Hastelloy alloy G-3 45.1 (311) 100.4 (692) 58 885 28.9 (199)
Hastelloy alloy G-30 45.0 (310) 100.0 (689) 65 29.3 (202)
Hastelloy alloy N 45.5 (313) 115.1 (793) 50.7 896
Hastelloy alloy W
Hastelloy alloy C-4
Hastelloy alloy C-22 54.0 (372) 114 (785) 62 895 29.9 (206)
Haynes alloy No. 230 57.4 (395) 125.4 (865) 49.60 30.6 (211)
Haynes alloy No. 214 83.2 (574) 134.6 (928) 42 C20 31.6 (218)
Haynes alloy No. 556 54.6 (375) 116.4 (805) 51.40 29.7 (205)
7. Nickel and High Nickel Alloys 95
COMMERCIALLY PURE NICKEL

Alloys 200 and 201
Alloys 200 and 201 are the major examples of this class. Alloy 201
is the low carbon version of alloy 200 and is used in applications
involving temperatures above 315°C (600°F). The low carbon prevents
formation of the grain-boundary graphitic phase, which reduces
ductility tremendously. A major area for use of alloys 200 and 201
is in caustic evaporators because of their outstanding resistance
to hot alkalis [1]. Alloy 201 tubular evaporators have been used
to evaporate concentrated caustic to anhydrous at temperatures
of 400°C (750°F). The corrosion rate is dependent on impurities
such as chlorates and hypochlorites in the caustic. Presence of
these impurities has been shown to adversely affect the resistance
of alloy 200 and 201. Another area of use is in hot, dry chlorine
and hydrogen chloride gas for which nickel can be used for con-
tinuous service up to temperatures of 510 to 540°C (950 to 1000°F).
The high resistance is attributed to the formation of protective
nickel chloride film. Similar resistance can be obtained in dry fluorine
and bromine. However, when moisture is present, the resistance
of the material decreases. Nickel is not attacked by anhydrous
ammonia or ammonium hydroxide concentrations < 1%. Stronger
concentrations cause rapid attack through formation of soluble nickel-
ammonium complexes. Nickel is also used in handling food and syn-
thetic fibers for maintaining product purity. For food products,
the presence of nickel ions is not detrimental to the flavor and
is nontoxic. For many organic chemicals, such as phenol and viscose
rayon, nickel does not discolor the solutions, unlike iron and copper.
Other Alloys
Other alloys in this family are not specifically used for their corro-
sion resistance. Alloy 270 is a high-purity, low-inclusion version
of alloy 200. Alloy 301 (also referred to by the trade name of
Duranickel) is a precipitation hardenable alloy containing aluminum
and titanium. Alloy 300 (also called by the trade name Permanickel)
is a moderately precipitation hardenable alloy, containing titanium
and magnesium, that also possesses higher thermal and electrical
conductivity.
Applicable Specifications
Nickel 200 (UNS NO2200) and Nickel 201 (UNS NO2201)
Sheet, plate, and strip: ASTM B162-80, ASME SB162
Rod and bar: ASTM B160-81, ASME SB 160
Fittings: ASTM B366-77
Seamless pipe: ASTM B161-75, ASME SB 161
Seamless tubing: ASTM B163-80, ASME SB 163
Sridhar and Hodge
NICKEL-COPPER
Nickel and copper are completely soluble in each other so that a

series of alloys have been available. This section will discuss the
alloys in the nickel-rich side of the compositions. Most widely used
of these alloys is alloy 400 (popularly called Monel).
Alloy 400
The alloying of 30 to 33% copper with nickel produces Monel alloy
400 that shares many of the characteristics of commercially pure
nickel but improves on others. Water handling, including brackish
and seawaters, is a major area of application. It gives excellent
service under high-velocity conditions, as in propellers, propeller
shafts, pump shafts, impellers, and condenser tubes. The addition
of iron to the composition improves the resistance to cavitation
erosion in condenser tube applications. The alloy can pit in stagnant
seawater as does nickel 200; however, the rates of attack are sig-
nificantly diminished. The absence of chloride stress-corrosion
cracking is also a factor in the selection of the alloy for this service.
The general corrosion resistance of alloy 400 in the nonoxidizing
acids, such as sulfuric, hydrochloric, and phosphoric, is improved
over that of pure nickel. The influence of the presence of oxidizers
is, however, the same as for nickel. The alloy is not resistant
to oxidizing media, such as nitric acid, ferric chloride, chromic
acid, wet chlorine, sulfur dioxide, or ammonia.
Alloy 400 does have excellent resistance to hydrofluoric acid
solutions [2] at alloy concentrations and temperatures, as shown
in Figure 1. Again aeration or the presence of oxidizing salts in-
creases the corrosion rates. The alloy is widely used in HF alkyla-
tion, is comparatively insensitive to velocity effects, and is widely
used for critical parts, such as bubble caps or valves, that are
in contact with flowing acid. Alloy 400 is, in common with some
other high nickel alloys, subject to stress-corrosion cracking in
moist, aerated hydrofluoric or hydrofluosilicic acid vapor. Cracking
is unlikely, however, if the metal is completely immersed in the
acid.
Alloy 400 also exhibits stress-corrosion cracking in high-
temperature, concentrated caustic and in mercury.
Other Alloys
Alloy 405 is a higher sulfur grade in which sulfur is added for
machinability. The corrosion resistance of alloys 400 and 405 are
approximately the same.
250
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I ^^Boiling
200
I Point Curve
1
\ Air-free, \
\ <20 mpy
\
i \
Aerated,
i \
>20 mpy
\
150 •
\
\ \
S \
Air-free, Aerated,
\ < 10 mpy <25 mpy
\
100
\
A>
\
4
Air-free, Aerated,
<1 mpy <10 mpy
50
20 30 40 50 60 70 { 90 100
Acid C o n c e n t r a t i o n , w e i g h t p e r c e n t
FIGURE 1 Isocorrosion diagram for Monel alloy 400 in hydrofluoric

acid.
Alloy K-500
Monel alloy K-500 is an age-hardenable alloy that combines the
excellent corrosion-resistant characteristics of Monel alloy 400 with
the added advantage of increased strength and hardness. Age hard-
ening increases its strength and hardness; however still higher
properties can be achieved when the alloy is cold worked before

the aging treatment. Alloy K-500 has good mechanical properties
over a wide range of temperatures. Strength is maintained up to
about 649°C (1200°F), and the alloy is strong, tough, and ductile
at temperatures as low as -235°C (-423°F). It also has low permea-
bility and is nonmagnetic to -134°C (-210°F). Typical applications
include pump shafts, impellers, doctor blades and scrapers, oil
well drill collars and instruments, electronic components, springs,
and valve trim.
In certain stress corrosion-cracking situations, precipitation-
hardening treatment has led to increased susceptibility to cracking
of this alloy. For example, alloy K-500 oil well drill collars have
been found to be susceptible to hydrogen embrittlement when gal-
vanically coupled to steel components [3],
Monel alloy 400 (UNS NO4400)
Sheet, plate, and strip: ASTM B127, ASME SB 127, AMS 4544C
Rod and bar: ASTM B164, ASME SB 164, AMS 4675A
Fittings: ASTM B366
Seamless pipe: ASTM B165-80, ASME SB 165
Seamless tubing: ASTM B163, ASME SB 163
All product forms: DIN 17743, Werkstoff No. 2.4360
NICKEL-MOLYBDENUM
Hastelloy Alloy B-2
Within the nickel-molybdenum series there is one major alloy: Hastel-
loy alloy B-2. Alloy B-2 is a low carbon and silicon (0.02%, 0.08%
maximum) version of Hastelloy alloy B. The alloy is uniquely differ-
ent from other corrosion alloys because it does not contain chromium.
Molybdenum is the primary alloying element and provides significant
corrosion resistance to reducing environments.
Alloy B-2 was developed to be resistant to hydrochloric acid
and is used in many applications in the distillation, condensation,
and handling of this acid. Alloy B-2 is recommended for service
in handling all concentrations of hydrochloric acid in the temperature
range 70 to 100°C (158 to 212°F) and for handling wet hydrogen
chloride gas as shown in Figure 2.
Alloy B-2 has excellent resistance to pure sulfuric acid at all
concentrations and temperatures below 60% acid and good resistance
to 100°C (212°F) above 60% acid as shown in Figure 3 [4], The
alloy is resistant to a number of nonoxidizing environments, such
as hydrofluoric and phosphoric acids and numerous organic acids
i i i
- 125
250
Corrosion rates in parentheses are in mm/year.
Boiling Point Curve

^N
*T - 100
200 0-5 mpy
/
o - 5 mpy LU
LLJ Q
Q (0.13)
LU LLT
DC
DC
D / D
< 5-20 mpy - 75 <
DC DC
LU (0.13-0.51) LU
CL
150 -
/ \
/ \
\
*
5 mpy \
(0.13) V
0-5 mpy
(0-0.13)
100
i I i
10 20 30 40
CONCENTRATION, WEIGHT PERCENT
FIGURE 2 Isocorrosion diagram for Hastelloy B-2 in hydrochloric

acid.
such as acetic, formic, and cresylic. It is also resistant to many

chloride-bearing salts (nonoxidizing), such as aluminum chloride,
magnesium chloride, and antimony chloride.
Because alloy B-2 is nickel rich (approx. 70%) it is resistant
to chloride-induced stress-corrosion cracking (SCC). Alloy B-2,
for example, is used as spray nozzles for a magnesium chloride
dryer. By virtue of the high molybdenum content, it is highly
resistant to pitting attack in acid chloride environments.
Stress-corrosion cracking has been observed in alloy B-2 in
20% magnesium chloride environment at temperatures exceeding 260°C
(500°F). Other environments in which stress-corrosion cracking
of this alloy has been observed include high-purity water at 177°C
(350°F), molten lithium at 157°C (315°F), oxygenated deionized
water at 204°C (400°F), 1% HI at 17 to 232°C (62 to 450°F), and
10% HC1 at 204°C (400°F). In some environments, such as concen-
trated ammonia at 25 to 60°C (77 to 140°F) cracking has been
I I I I i I I I !
400- Corrosion rates in parentheses are in mm/year.

/ Over 50 mpy -200
/ (Over 1 .27)
/
3 5 0- 50 mpy
/ <
20 mpy
Boiling Point Curve / ^ ^ (0.51) ^20 v -150 O
3 0 0-
X
O 5 mpy
LU LU
Q ((D.13)^V. r Q
LU
_= 250
< 0-5 mpy
DC _ _ • — (0-0.13) DC
LU
Q_
-100 LU
Q_
200-
~~ LU
5-10 mpy
(0.13-0.25) 5 mpy
150- (0.13)
-50
CO
100- Si
i i i i i i i
10 20 30 40 50 60 70 80 90 100
a:
FIGURE 3 Isocorrosion diagram for Hastelloy B-2 in sulfuric acid. o
a,
"8
observed if the alloy was aged at 750°C (1382°F) for 24 hr before

the test. Precipitation of an ordered intermetallic phase, Ni^Mo has,
been attributed to be the cause of the increased embrittlement.
Alloy B-2 is not recommended for elevated temperature service,
except in specific circumstances. There is no chromium in the alloy
and, therefore, the alloy scales heavily at temperatures above 760°C
(1400°F) in air. A nonprotective layer of molybdenum trioxide (MoO3)
forms and results in a heavy green oxidation scale. In a chlorine-
containing environment, however, alloy B-2 has demonstrated good
resistance. Alloy B-2 has excellent elevated temperature [> 900°C]
(1650°F) mechanical properties because of the high molybdenum content,
and it has been used for mechanical components in reducing environ-
ments and vacuum furnaces. Because of the formation of the inter-
metallic phases Ni Mo and Ni Mo after longtime aging, the use of
alloy B-2 in the temperature range of 600 to 850°C (112 to 1562°F)
is not recommended, regardless of environment.
The major factor that limits the use of alloy B-2 is the poor
corrosion resistance in oxidizing environments. It has virtually
no corrosion resistance to oxidizing acids, such as nitric and chromic,
or to oxidizing salts, such as ferric chloride or cupric chloride.
The presence of oxidizing salts in reducing acids must also be given
attention. Oxidizing salts, such as ferric chloride, ferric sulfate,
or cupric chloride, even when present in the part per million range
can significantly accelerate the attack in hydrochloric or sulfuric
acids as shown in Figure 4. Even dissolved oxygen has sufficient
oxidizing power to affect the corrosion rates for alloy B-2 in hydro-
chloric acid. This alloy also shows excellent resistance to pure
phosphoric acid, and it has found wide acceptance in a number
of key chemical processes by virtue of its resistance to corrosive
catalysts. The application typically involves the halogens (Cl, F, Br)
with or without the presence of reducing-type acids, such as hydro-
chloric, hydrofluoric, bromic, or sulfuric acids. The alloy has unique
resistance to the aluminum chloride catalysts used in the alkylation
of benzene to ethyl benzene (Friedel-Crafts-type processes). The
ethyl benzene is used for production of styrene and cumene. The
isomerization of paraffin hydrocarbons, such as butane to isobutane,
uses antimony chloride-aluminum chloride catalysts.
The halide catalyst systems used in the newer processes for
acetic acid and ethylene glycol have demonstrated substantial cost
reductions for producing these chemicals. Alloy B-2 is demonstrating
excellent corrosion resistance in this equipment, and it is considered
to be a prime factor in making these both viable chemical processes.
Alloy B-2 can be welded using a matching alloy B-2 filler metal.
Although this alloy was developed for use in the as-welded condition,
where corrosion resistance is critical, postweld annealing may be
necessary to improve the corrosion resistance of the weld.
10,000 I I I I Mill I I I i 11 Mi I I I I I I I L
Corrosion rates in parentheses are in mm/year. 1
Boiling 20% HCI

4,000
Boiling 30% H 2 SO 4
/ _
/
1,000
M i l l 1
_ ' /
/
400 - / -
/ /
/
y/ -
/
100
/ /
1 1
-
50 mpy
(1 .27)
40 1
1n I i l l i i I 11 i i i i i I III I I i I | 1 1 1
4 6 810 20 40 60 80100 200 400 600800
FERRIC ION CONCENTRATION, PPM
FIGURE 4 Effect of ferric ions on corrosion rates for Hastelloy

alloy B-2.
Hastelloy alloy B-2 (UNS N10665)
Sheet, plate, and strip: ASTM B333, ASME SB333
Rod and bar: ASTM B335, ASME SB335
Fittings: ASTM B366
Welded pipe: ASTM B619, ASME SB619
Welded tubing: ASTM B626, ASME SB626
Seamless pipe and tubing: ASTM B622, ASME SB622
Castings
Castings for use in conjunction with alloy B-2 equipment are available
in two compositions, both of which are listed in ASTM A494. The
N-12M-1 version corresponds to old alloy B, whereas the N-12M-2

version corresponds to Chlorimet 2. For good consistent corrosion
resistance the carbon composition range for the N-12M-1 is too
broad, and some castings are encountered that have poor inter-
granular corrosion resistance but are within the specification.
The corrosion resistance of alloy B castings, in general, is not,
even with the identical composition, the same as the wrought version.
This is because of the significant interdendritic segregation and
carbides that exist in the as-cast structure. It is less of a problem
with the N-12M-2 composition because of the lower carbon content
and the higher molybdenum content. A comparison of the isocorrosion
diagram in hydrochloric acid [5] shows that there is still a minor
difference.
Alloy B ASTM A494 grade N-12M-1
Chlorimet 2 ASTM A494 grade N-12M-2
NICKEL-CHROMIUM-IRON
Inconel Alloy 600
Inconel alloy 600 is a nickel-based alloy with about 16.0% chromium
and 7.0% iron that is primarily used to resist corrosive atmospheres
at elevated temperatures. The alloy is slightly less resistant to
oxidation than the 20% Cr-Ni alloy, but it has excellent physical
properties, is readily fabricated and welded, and can be used in
air up to about 2000°F (1093°C). Although resistant to oxidation,
the presence of sulfur in the environment can substantially increase
the rate of attack. The mode of attack is generally intergranular
and, therefore, the attack proceeds more rapidly, and the maximum
use temperature is restricted to about 600°F (315°C). Typical appli-
cations include furnace muffles, carburizing baskets, and fixtures.
Alloy 600 has excellent resistance to dry halogens at elevated
temperatures, and it has been used successfully for chlorination
equipment at temperatures up to 1000°F (538°C). When arrangements
can be made for cooling the metal surface, the alloy can be used
at even higher gas temperatures.
Resistance to stress-corrosion cracking is imparted to alloy 600
by virtue of its nickel base. The alloy, therefore, finds considerable
use in handling water environments where stainless steels fail by
cracking. Because of its resistance to corrosion by high-purity
water, it has a number of uses in nuclear reactors, including steam
generator tubing and primary water piping. The lack of molybdenum
in the alloy restricts its use in applications for which pitting is the
primary mode of failure.
In certain high-temperature caustic applications in which sulfur

is present, alloy 600 is substituted for alloy 201 because of its
improved resistance. Alloy 600 i s , however, subject to stress-
corrosion cracking in high-temperature, high-concentration alkalies.
Hence, the alloy should be stress relieved before use and the
operating stresses kept at a minimum. Alloy 600 is almost entirely
resistant to attack by solutions of ammonia over the complete range
of temperatures and concentrations.
The presence of chromium in the alloy provides corrosion resistance
in mildly oxidizing aqueous media, and the absence of molybdenum
limits the usefulness of the alloy in reducing acid solutions. The
usefulness of the alloy is in its high-temperature applications.
Inconel alloy 600 (UNS NO6600)

Sheet, plate, and strip: ASTM B168, ASME SB168, AMS 5540H
Rod and bar: ASTM B166, ASME SB166, AMS 5665H
Fittings: ASTM B366
Welded tubing: ASTM B516
Seamless pipe: ASTM B167, ASME SB167
Seamless tubing: ASTM B163, ASME SB163
Wire: AMS 5687G
All product forms: DIN 17742, Werkstoff No. 2.4816
Incoloy Alloy 800

Incoloy alloy 800 contains about 20% chromium, 32% nickel, and 46%
iron as a balance. The alloy is used primarily for its oxidation
resistance and strength at elevated temperatures. It is particularly
useful for high-temperature equipment in the petrochemical industry
because the alloy does not form the embrittling sigma phase after
long exposures at 1200 to 1600°F (649 to 871°C). High creep and
rupture strengths are other factors that contribute to its performance
in many applications.
An upper-use temperature for the alloy in oxidation applications
is approximately 2000°F (1093°C). Considerable experimentation
has shown that the alloy could have extensive application in the
coal gasification area when the environments contain mixtures of
sulfur and oxygen. In strongly reducing mixtures of H2S and H 2 ,
the alloy, like most others, has little utility. Typical applications
are heat exchangers, process piping, carburizing fixtures, and
retorts. Two applications that consume substantial quantities of
material are for electric range heating element sheathing and for
extruded tubing for ethylene- and steam methane-reforming furnaces.
The latter is usually specified in alloy 800H that has a slightly

narrower carbon range and higher-temperature anneal.
In aqueous corrosion service, alloy 800 has general resistance
that falls somewhere between types 304 and 316 stainless steels.
Thus, the alloy is not widely used for aqueous service. The stress
corrosion-cracking resistance of alloy 800 is, while not immune,
better than that of the 300 series stainless steels, and substitution
has been made on that basis in the past.
Incoloy alloy 800 (UNS NO8800)
Fittings: ASTM B366
Seamless pipe: ASTM B407, ASME SB407
Seamless tubing: ASTM B163, ASME SB163
Wire: AMS 5687G
All product forms: DIN Werkstoff No. 1.4876
Incoloy Alloy 825

Incoloy alloy 825 is very similar to alloy 800; however, the composi-
tion has been modified to provide for improved aqueous corrosion
resistance. These modifications include 1.8% copper, 3.0% molybdenum,
a higher nickel content of about 42%, and a titanium level of 0.90%.
The combination of Ni-Cr-Mo-Fe with the 1.8% copper added
provides good resistance for alloy 825 in pure dilute sulfuric acid.
Given test results [6] and service experience, the alloy should
have useful resistance in sulfuric acid solutions up to 40% by weight
at boiling temperatures and at all concentrations at a maximum temper-
ature of 150°F (66°C). In dilute solutions the presence of oxidizing
salts, such as cupric or ferric, actually lower the corrosion rates
experienced. Alloy 825 has only limited use in hydrochloric acid
or hydrofluoric acid. It has good resistance to phosphoric acid
and has been used in some commercial acid applications.
The alloy is not fully resistant to stress-corrosion cracking when
tested in the boiling magnesium chloride solution, but it has good
resistance in neutral chloride environments. Therefore, it is some-
times substituted for the 300 series stainless steels when localized
corrosion is a problem. The increased nickel content gives the alloy
better pitting resistance; however, it is not as resistant [7] as a
number of other commercially available alloys in that category.
Typical applications for alloy 825 include phosphoric acid evapora-
tors, pickling tank heaters, pickling hooks and equipment, chemical
process equipment, spent nuclear fuel element recovery, propeller
shafts, tank trucks, and oil and gas tubulars.
Incoloy alloy 825 (UNS NO8825)
Fittings: ASTM B366
Stainless pipe: ASTM B423, ASME SB423
Seamless tubing: ASTM B 163, ASME SB613
Alloy 800H
Alloy 800H is a controlled carbon version of alloy 800, in which
the carbon level is maintained between 0.05 and 0.1%. This gives
the alloy better elevated-temperature, creep and stress rupture
properties. Alloy 800H is used in a variety of high-temperature
applications in the refining and heat treatment industries.
Alloy 800H (UNS NO8810)
Sheet, plate, and strip: ASTM B409, ASME SB409, BSI BS 3072-
NA15(H)
Rod and bar: ASTM B408, ASME SB408, BSI BS 3076-NA15 (H)
Seamless pipe and tubing: ASTM B 407, ASME SB407
Heat exchanger tubing: ASTM B163, ASME SB 163
All forms: ASME Code Case 1325 (*00H), DIN Werkstoff No. 1.4876
Other Alloys
Inconel alloy 690 is a higher chromium version of alloy 600 that
contains about 30% chromium. It is used in pressurized-water steam
generator tubing and has shown some potential to be used in nuclear
waste disposal systems. Alloy 671 is another high chromium version
containing about 48% chromium and is used where oxidation resistance
is required, such as in boiler tubes.
NICKEL-CHROMIUM-IRON-MOLYBDENUM
The addition of molybdenum to the Ni-Cr-Fe alloys results in an

increase in corrosion resistance to environments containing chlorides
and to moderately corrosive reducing environments, such as dilute
sulfuric and phosphoric acids. The presence of iron makes these
alloys less expensive than the Ni-Cr-Mo alloys but also limits the
amount of molybdenum that can be alloyed because of embrittlement
resulting from precipitation of intermetallic phases.
Alloy G
Hastelloy alloy G has a nickel base with additions of 22% chromium,
19% iron, 6.5% molybdenum, and 2% copper, stabilized with 2% colum-
bium plus tantalum. Although some competitive materials use only
8 or 10 times the carbon content, a larger amount of columbium
is used in alloy G to promote more satisfactory stabilization. It
is the intent to have alloy G used in the as-welded condition, even
under the circumstance of multipass welding. The columbium addition
has also been noted to provide better resistance in highly oxidizing
environments than do titanium additions. Because of the nickel base,
the alloy is resistant to chloride-induced stress corrosion cracking.
The 2% copper addition is effective in enhancing the corrosion
resistance of the alloy in reducing acids, such as sulfuric and phos-
phoric [8]. The isocorrosion diagram for alloy G in sulfuric acid
(Fig. 5) compares favorably with that of alloy C-276 at the dilute
end (< 50%). Other less-expensive alloys will also resist pure dilute
sulfuric acid; however, alloy G will also resist combinations of sul-
furic and halides. This alloy has excellent resistance to phosphoric
acid and has been used as wet-process acid evaporators, agitator
shafts, pumps, and superphosphoric acid evaporators.
In many applications, alloy G is being replaced by alloys G-3
and G-30. In addition to its traditional application for sulfuric and
phosphoric acids, alloy G had found wide acceptance in other types
of chemical applications, such as HF manufacture and processing
of organic chemicals, particularly those with chlorides present.
However, the largest growth of applications in the past had been
in pollution control equipment. Alloy G demonstrated excellent per-
formance in municipal garbage incinerator systems, including fans,
ducts, and scrubber equipment. The SO2 scrubbing systems for
power plants that use water or alkaline quench have been incorporat-
ing alloy G as a major material of construction because of its resist-
ance to sulfuric acid and conditions during which the chloride ion
can concentrate. The recent scrubber equipment has used higher
alloys, such as C-22, C-276, 625, and H, because the scrubber
conditions have become more severe over the years.
Cast components for use with alloy G wrought equipment can
be obtained from material of the same composition. Castings in alloy
G suffer from similar problems encountered in other cast nickel-
based alloys: lower corrosion resistance than the equivalent wrought
alloys. Fewer intermetallic phases form, but carbides have been
observed to form on grain boundaries, and a solution anneal after
casting is required.
Hastelloy alloy G (UNS NO6007)
400 Corrosion rates in parentheses are in mm/year. 200
350
Boiling Point Curve
O 300
LU
LJJ
DC
Z)
250
<
DC
LU
Q_
LU 200 LU
0-5 mpy C/3

(0-0.13)
100 3.
0 10 20 30 40 50 60 70 80 90 100 ft
a:
FIGURE 5 Isocorrosion diagram for Hastelloy G in sulfuric acid. o

Fittings: ASTM B366
Hastelloy Alloy G-3
The addition of columbium is a double-edged sword. Although colum-

bium stabilized alloy G from formation of chromium-rich carbides
in the heat-affected zones of the welds, secondary carbide precipita-
tion still occurred when the primary columbium carbides dissolved
at high temperatures, and the increased carbon in the matrix in-
creases the tendency of the alloy to precipitate intermetallic phases.
Hastelloy alloy G-3 was invented with lower carbon (0.015 max. v s .
0.05 max. for alloy G) and lower columbium (0.3 max. v s . 2 for
alloy G). The alloy also possesses slightly higher molybdenum (7%
v s . 6.5% for alloy G). The corrosion resistance of alloy G-3 is about
the same as alloy G. However, the thermal stability is much better [ 9 ] .
Hastelloy alloy G-3 (UNS No. 6985)

Fittings: ASTM B366
Seamless tube and pipe: ASTM B622, ASME SB622
Bare welding rods: AWS A5.14 (ERNICrMo-9)
All forms: DIN 17744, DIN Werkstoff No. 2.4619
Hastelloy Alloy X
Hastelloy alloy X is a major material of construction in the hot section

of gas turbine engines. Applications include parts such as burner
cans and transition ducts. Alloy X owes its oxidation resistance
to the formation of a complex chromium oxide spinel that provides
good resistance up to temperatures of 1177°C (2150°F). Alloy X
is also used in chemical plants for its combination of high strength
and excellent oxidation resistance.
A typical application in the process industries is the nitric acid
catalyst grid supports operating at 900°C (1650°F). The high-
temperature strength and resistance to warpage and distortion
provide outstanding performance. Alloy X is also used as distributor
plates in the manufacture of magnesium chloride. Other high-
temperature applications include flare nozzles, thermowell protection
tubes, expansion bellows, furnace internals retorts, muffles, and trays.
The catalyst regenerator for high-density polyethylene is con-

structed of alloy X because high temperatures and pressures are
required to revitalize the catalysts. Unfortunately, this continued
temperature cycling eventually reduces the room-temperature ductility
in alloy X so that repair welding becomes difficult without solution
annealing. The improved stability in alloy S has been demonstrated
in this application; thus, future equipment to be built in areas
of the world where annealing furnaces are not available may be
constructed from alloy S.
Hastelloy alloy X (UNS NO6002)
Sheet, plate, and strip: ASTM B435, ASME SB435, AMS 5536G
Rod and bar: ASTM B572, ASME SB572, AMS 5754G
Fittings: ASTM B366
Wire: AMS 5798A
Hastelloy Alloy G-30

Hastelloy alloy G-30 is a higher chromium modification of alloy G.
The chromium content of 29.5% in this alloy endows it with higher
resistance to oxidizing environments than other alloys in its class.
The presence of 5.5% molybdenum and 2.5% tungsten yield resistance
to the presence of moderate amounts of chlorides and fluorides in
these environments. Thus, in acid mixtures, such as nitric plus
hydrofluoric and sulfuric plus nitric acids, alloy G-30 shows the
highest resistance of this class of alloys (Table 4 ) . The alloy is
also being used in the evaporators of commercial wet-process phos-
phoric manufacturing systems. In these environments, which are
complex mixtures of phosphoric, sulfuric, and hydrofluoric acids
and contain various oxides, alloy G-30 has shown the lowest corrosion
rate of a number of alloys tested (Table 5).
TABLE 4 Corrosion Resistance of Hastelloy Alloy G-30

in Nitric Acid + Hydrofluoric Acid Mixture a
Alloy Corrosion rate, mm/yr (mpy)
Hastelloy alloy G-30 4. 43 (177)

Haynes alloy 625 60. 0 (2400)
a
20% HNO3 + 6% HF at 80°C (176°F).
TABLE 5 Corrosion Resistance of Hastelloy Alloy G-30

in Commercial, Wet-Process Phosphoric Acid a
Alloy Corrosion rate mm/yr (mpy)

Haynes alloy 625 0. 40 (16)
a
54% P 2 O 5 at 116°C (240°F).
Hastelloy alloy G-30 (UNS NO6030)
Bar: ASTM B581, ASME B581
Fittings: ASTM B366, ASME SB366
Covered welding electrodes: AWS A 5 . l l ER (NiCrMo-11*)
Bare welding rods: AWS A5.14 ER (NiCrMo-11*)
All forms: DIN 17744 No. 2.4603
Hastelloy Alloy H-9M

Alloy H-9M can be considered either as a modification of alloy G-3
or of alloy 625. The direction of the modification is to improve the
localized corrosion resistance of both alloys, G-3 and 625. The
alloy has higher molybdenum content than alloy G-3 and higher
tungsten content than alloy 625. Copper that was present in alloy
G-3 was removed in alloy H to increase the localized corrosion
resistance also. The critical pitting temperature of these alloys
TABLE 6 Critical Pitting Temperature of Hastelloy Alloy

H-9M in Comparison to Other Alloys a
Critical pitting temperature

Alloy (°C) (°F)
H-9M 95 203
625 90 194
G-3 75 167
a
S o l u t i o n : 4% NaCl + 0.1% F e 2 ( S O t + ) 3 + 0.01M HC1
in an oxidizing, acidic chloride mixture is shown in Table 6. The

critical pitting temperature indicates the temperature above which
pitting is observed in the solution, and the higher the temperature,
the better the alloy in pitting resistance. Because of its high pitting
resistance and relatively lower cost compared with the Ni-Cr-Mo
alloys, alloy H-9M has been evaluated for a number of applications,
especially pollution control systems.
NICKEL-CHROMIUM-MOLYBDENUM
Inconel Alloy 625
Inconel alloy 625 has been extensively used in sheet form in high-
temperature gas turbine applications. Because of its combination
of chromium, molybdenum, carbon, and columbium plus tantalum,
the alloy retains its strength and oxidation resistance to elevated
temperatures.
Typical applications include ducting systems, thrust reverser
assemblies, and afterburners. Use of the alloy has been considered
in the high-temperature gas-cooled reactor; however, after long
aging in the temperature range 590 to 760°C (1100 to 1400°F), the
room-temperature ductility is significantly reduced.
Resistance to aqueous solutions is good in a variety of applica-
tions, including organic acid, sulfuric acid, and hydrochloric acid
at temperatures below 65°C (150°F). The alloy has satisfactory
resistance to hydrofluoric acid, and it has been used in a liner
in a hydrofluoric acid generator that reacts sulfuric acid with
fluorspar. Although nickel-based alloys are not generally used in
nitric acid service, alloy 625 is resistant to mixtures of nitric-
hydrofluoric, where stainless loses its resistance. Alloy 625 can
be rated to be more resistant than alloy C-276 but less than alloy
G-30.
Alloy 625 has excellent resistance to phosphoric acid solutions.
Actual field operating information has shown this alloy to have
excellent resistance to commercial grades of acid that contains
fluorides, sulfates, and chlorides in the production of superphos-
phoric acid (72% P 2 O 5 ).
The columbium and tantalum stabilization (3.65%) makes the alloy
suitable for corrosion services in the as-welded condition. The
high nickel content provides good resistance to chloride SCC. Alloy
625 has a relatively high molybdenum content (9%), and field-testing
data place its performance somewhere between alloys G and H-9M
in pitting and crevice corrosion resistance.
Alloy 625 has been utilized in several new pollution control appli-
cations, such as reheaters for SO2 scrubbing systems on coal-fired
power plants and bottoms of electrostatic precipitators that are
flushed with seawater. In one installation, the interior of a stack
has been lined to provide resistance to the wet sulfur-containing gases.
Inconel alloy 625 (UNS NO6625)
Sheet, plate, and strip: ASTM B443, ASME SB 443, AMS 5599B
Rod and bar: ASTM B446, ASME SB446, AMS 5666A
Hastelloy Alloy C-276

Hastelloy alloy C-276 is a low carbon (0.01% maximum) and silicon
(0.08% maximum) version of Hastelloy alloy C. Alloy C-276 was
developed to overcome the corrosion problems associated with the
welding of alloy C. When used in the as-welded condition, alloy C
was often susceptible to serious intergranular corrosion attack in
many oxidizing and chloride-containing environments. The low C
and Si content of alloy C-276 prevents precipitation of continuous
grain-boundary precipitates in the weld heat-affected zone. Thus,
alloy C-276 can be used in most applications in the as-welded condi-
tion without suffering severe intergranular attack.
The descriptions of the applications for alloy C-276 in the process
industries are extensive and diverse. The alloy is extremely versatile
because it possesses good resistance in both oxidizing and reducing
media, and this includes conditions with halogen ion contamination.
The pitting and crevice corrosion resistance of alloy C-276 makes
it an excellent choice when dealing with acid chloride salts, whether
in the process or in merely handling hot seawater in heat exchangers.
Isocorrosion diagrams for alloy C-276 have been developed for
a number of inorganic acids: for example, for sulfuric acid (Fig. 6).
Rather than having one or two acid systems in which the corrosion
resistance is exceptional, as with alloy B-2, alloy C-276 is a good
compromise material for a number of systems. For example, in sul-
furic acid coolers handling 98% acid from the absorption tower,
alloy C-276 is not the optimum alloy for the process-side corrosion,
but it is excellent for the water-side corrosion and allows the use
of brackish water or seawater. Concentrated sulfuric acid is used
to dry chlorine gas. The dissolved chlorine will accelerate the corro-
sion of alloy B-2, but alloy C-276 has performed quite satisfactorily
in a number of chlorine-drying installations.
Another example is the spray application of alloy C-276 powder
to steam plant boiler tubes to prevent liquid-phase corrosion. A
complex alkali-iron-sulfate that forms a liquid slag in the range
570 to 700°C (1060 to 1290°F) was attributed to causing the rapid
attack experienced on the chrome-moly steel tubes. A spray applica-
tion, without removal of the tubes, of a thin coating of alloy C-276
was measured as reducing the rate of attack from 41 mil/yr (mpy)
to 3 mpy.
Many new applications for alloy C-276 have evolved as a result
of increased activity in scrubbers for the pollution control industry.
i i i 1 1 i i i i
400
- 200
Corrosion rates in parentheses are in mm/year.
/
350 Over 200 mpy

(Over 5.08)
Boiling Point Curve -.
300 200 mpy / Over 200 mpy - 150
o (5.08).. / (Over 5.08)
-^_ y LU
LU Q
Q — 50-200 mpy
LLT "^"50 mpy (1-27-5.08) —200 mpy
DC 250 (5.08) ^
D 20-50 mpy*^v. 50-200 mpy
< *20 mpy -^dUl'^'^
(1.27-5.08) ^ ^
CC
20-50 mpy (1.27) ^ ^
LU -100
v^^^_^—
Q_
200 (0.51-1.27) Q_
20 mpy LU
^ 5-20 mpy
' V (0.13-0.51)
150 -
5 mpy
(0.13) - 50
0-5 mpy
(0-0.13)
100 _ S
I I I i i i | i i
10 20 30 40 50 60 70 80 90 100
3
a:
o
FIGURE 6 Isocorrosion diagram for Hastelloy alloy C-276 in sulfuric acid.
Induced-draft fans represent a particularly aggressive environment

because they are exposed to wet/dry conditions. Alloy C-276 has
functioned very satisfactorily for years in an induced-draft fan
for a municipal incinerator in Grosse Point, Michigan. Alloy C-276
has been indicated as a satisfactory material for scrubber construc-
tion where problems of localized attack have occurred with the
Ni-Cr-Mo-Fe-Cu alloys because of pH, temperature, or chloride
content.
Hastelloy Alloy C-4

Hastelloy alloy C-4 was developed for improved stability relative
to precipitation of both carbides and intermetallic phases. The con-
trol of these secondary phases results in excellent high-temperature
stability, such that the corrosion resistance and mechanical properties
in the thermally aged condition are similar to the annealed condition
properties. Although alloy C-276 is resistant to precipitation of
carbides, precipitation of the intermetallic mu-phase can still occur.
This latter precipitation was reduced in alloy C-4 by reducing the
tungsten content to low levels [10].
Within the broad scope of chemical processing, numerous examples
exist for which oxidizing and reducing conditions can cause serious
intergranular corrosion of a sensitized (precipitated) microstructure.
The sensitized structure can result from several sources, such
as (1) improper anneal; (2) welding; (3) thermomechanical process-
ing, such as hot-forming or rolling operations; (4) stress relief
or normalizing treatments required for carbon steel backing of clad
materials; or (5) operation of process equipment in the sensitizing
range. Alloy C-4 represents a substantial improvement because
the alloy can be subjected to temperatures in the normal sensitizing
range of 550 to 1090°C (1022 to 1994°F) for extended periods without
experiencing the severe corrosion attack that plagues the common
austenitic alloys.
As shown in Table 1, the composition of alloys C-4 and C-276
is, with the exception of iron and tungsten, approximately the same.
Similarly, the general corrosion resistance of the two alloys is
generally the same. In a strongly reducing medium, such as hydro-
chloric acid, alloy C-4 has slightly higher rates than alloy C-276,
but in an oxidizing medium the results are reversed. Apparently,
these differences relate to the effects of iron and tungsten; however,
the data are not conclusive. Alloy C-4 offers good corrosion resist-
ance to a wide variety of media, including organic acids and acid
chloride solutions. Isocorrosion diagrams for alloy C-4 have also
been developed for a series of inorganic acids.
Hastelloy alloy C-276 (UNS N10276) and Hastelloy alloy C-4 (UNS
NO6455)

Fittings: ASTM B366
Hastelloy Alloy C-22
Alloy C-22 represents the latest in the development of the C-family

of alloys. Although Hastelloy alloy C-276 is a versatile alloy, its
chief limitations are in oxidizing environments containing low amounts
of halides and in environments containing nitric acid. In addition,
the thermal stability of the alloy was not sufficient to enable it
to be used as a casting. Although Hastelloy alloy C-4 has much
higher thermal stability, because of the absence of tungsten in
this alloy, its corrosion resistance to chloride-containing environ-
ments suffered. Hastelloy alloy C-22 was invented to improve the
resistance to oxidizing environments, such as nitric acid, and also
to improve the thermal stability sufficiently to enable it to be used
as casting [11]. The higher chromium level in this alloy not only
made it superior in oxidizing environments containing nitric acid
but also improved the pitting resistance over that of alloy C-276.
This is shown in Table 7. The areas of applications of alloy C-22
are many of the same as those for alloy C-276. It is being used
in pulp and paper bleaching systems, pollution control systems,
various areas in the chemical process industry, and is being con-
sidered for oil and gas applications
Fittings: ASTM B366, ASME SB366

Rod: ASTM B574, ASME SB 574
Plate, sheet, and strip: ASTM B575, ASME SB575
TABLE 7 Critical Pitting and Crevice Corrosion Temperatures

of Ni-Cr-Mo Alloys
24-hr pitting test a 100-hr crevice corrosion 0

Alloy °C °F °C °F
625 75 167 25 77
C-4 90 194 45 113
C-276 110 230 80 176
C-22 120 248 101 214
a
7 Vol. % H 2 SO 4 + 3 vol. % HC1 + 1% Fe.Cl3 + 1% CuCl 2 .
°4% NaCl + 0.01M HC1 + 0.1% Fe 2 (SO l f ) 3 .
Welded pipe: ASTM B 619, ASME SB 619

Seamless tubing: ASTM B 622, ASME SB 619
Welded tubing: ASTM B626, ASME SB 626
Bare welding rods: AWS A5.14 ER (NiCrMo-10*)
Covered welding electrodes: AWS A5.ll ER (NiCrMo-10*)
All forms: DIN 17744 No. 2.4602
All forms: TUV Werkstoffblatt 479
Hastelloy Alloy S
Hastelloy alloy S was developed (1973) primarily for gas turbine

applications requiring good alloy stability, oxidation resistance,
and a low thermal expansion coefficient. Its composition is much
like that of alloys C-276 and C-4, and it has similar corrosion
resistance; however, the carbon content may preclude its use in
some aqueous media in the as-welded condition.
Because of the combination of stability and oxidation resistance,
alloy S has shown considerable promise as a welding filler metal
in dissimilar metal joint applications. One example is in the welding
of centrifugaily cast furnace tubes to pigtails and in turn to the
header. After 10,000 hr of aging in the temperature ranges typically
encountered in this application, the alloy S welds exhibited 80%
of their original ductility.
Sheet, plate, and strip: AMS 5873

Rod and bar: AMS 5711
Wire: AMS 5838
Castings
Castings for use in conjunction with alloys C-276 or C-4 are cur-
rently available in two compositions that are listed in ASTM A494.
The CW-12M-1 version corresponds to old alloy C, and the CW-
12M-2 version corresponds to Chlorimet 3. For good consistent
corrosion resistance the carbon composition range for the CW-12M-1
is too broad, and some castings are encountered that have poor
inter granular corrosion resistance but are within the specification.
Castings of Hastelloy alloy C-22 are also available.
A further problem associated with the corrosion resistance of
cast alloy C is the precipitated intermetallic phases in the inter-
dendritic areas. These phases are not homogenized with a solution
heat treatment and promote localized attack in some media. Figure
7 shows the interdendritic attack that occurred in cast alloy C
bolts in a pulp and paper, chlorine-containing environment. Bolts
made from wrought bar stock had corrosion rates of less than 1
mpy. Similar experiences have been encountered with cast pipe
fittings and valves.
FIGURE 7 Localized corrosion on a cast alloy C bolt.
Modification of the composition of alloy C to produce alloy C-4

has eliminated the presence of the intermetallic phases in the wrought
alloy and minimized its presence in the cast alloy. The CW-12M-2
composition is closer to being stable by virtue of the absence of
the tungsten; however, the chromium, molybdenum, and iron levels
can also produce the metallurgical instability.
Hastelloy alloy C-4C has been developed that couples low carbon
with a balanced composition to avoid the intermetallic phases. Corro-
sion resistance of castings made from this alloy approaches that
of wrought alloys.
Because alloy C-4C lacks tungsten, its resistance to pitting
corrosion is not as good as that of alloy C-276. In alloy C-22, the
higher thermal stability enables it to be made into castings that
possess much higher pitting resistance and resistance to oxidizing
environments than for alloy C-4C castings.
Alloy C: ASTM A494, grade CW-12M-1
Chlorimet 3: ASTM A494, grade CW-12-2
Hastelloy alloy C-4C: ASTM A494, grade CW-2M

Hastelloy alloy C-22C: none
ALLOYS FOR HIGH-TEMPERATURE CORROSION

Haynes Alloy No. 556
The Haynes Fe-Ni-Co-Cr alloy (No. 556) exhibits useful resistance
to a wide variety of high-temperature corrosive atmospheres as
well as molten salts. The presence of 18% cobalt results in more
resistance to sulfidation than many Ni-based alloys, such as Hastelloy
alloy X and Incoloy alloy 800H. This is illustrated in Figure 8,
where results from 215-hr tests in a reducing, sulfidizing environ-
ment at 1800°F (982°C) are shown [12]. In pure oxidation, the
alloy shows good resistance, but it is superseded in performance
by other alloys such as alloys X and 214. In chlorine-bearing
oxidizing environments, the alloy shows better resistance than
alloys 800H and X but not as good as alloy 214. The resistance
to carburizing environments is shown in Figure 9 [13]. The alloy
TOTAL DEPTH OF ATTACK (MM/SIDE)

0- 0.1 0.2 0.3 0.4 0.5
982°C (1800°F)/215 H
25.6 MILS
3 >21.7 MILS
\
/ / / / / / / / / / / / / / I >17.7 MILS
/ / / / / / / / / / / / / / / /*\> 21.7 MILS
' / / / / / / / / / / / / / / / /~\> 21.7 MILS
/ / / / / / / / / / / / / / / / 7\ > 21.7 MILS
' / / / / / / / / / A > 2 5 . 6 MILS
5 10 15 20
MILS/SIDE
0 METAL WASTAGE
1 I INTERNAL ATTACK
FIGURE 8 Results of sulfidation tests performed at 982°C (1800°F)

for 215 h r . (From Ref. 12.)
is better than 310 stainless steel and some Ni-based alloys, such
as alloys X and 617, but not as good as the aluminum-containing
alloys, such as alloy 214. Typical applications of the alloy include
internals of municipal waste incinerators and refractory anchors
in a refinery tail-gas-burning unit.
Haynes alloy No. 556 (UNS No. R30556)
Sheet, plate, and strip: SAE AMS 5874
Sheet and plate: ASTM B 435
Rod: ASTM B 572
Welded pipe: ASTM B 619
Seamless pipe and tube: ASTM B 622
Welded tubes: ASTM B 626
Sheet, plate, bar, pipe and tube: ASME Code Case No. 2010
Haynes Alloy N o . 214
The primary attribute of this Ni-based alloy is its high oxidation

resistance, a result of a tenacious aluminum oxide layer at the
surface. The alloy possesses the highest oxidation resistance to
both static and dynamic environments among the Ni-based alloys,
as illustrated in Figure 10 [14]. The alumina film also lends superior
resistance to carburizing environments and complex environments
containing chlorine and oxygen. The resistance to carburization
is shown in Figure 9 and resistance to oxy-chlorination is shown
in Figure 11 [15]. However, as typical of many high-temperature
alloys, the alloy does not possess good resistance to aqueous chloride
solutions, so dew-point conditions must be avoided. Typical applica-
tions of this alloy include mesh belts for supporting chinaware while
being heated in a kiln, strand annealing tubes for making medical-
grade stainless wire, and honeycomb seals in turbine engines.
All forms: DIN Werkstoff No. 2.4646
Haynes Alloy No. 230

Originally developed for its high-temperature strength, thermal
stability, and oxidation resistance, the alloy has found a niche
in the chemical process industry because of its superior nitridation
resistance. The nitridation resistance is shown in Table 8. This
property along with high creep strength has enabled use of the
alloy as a catalyst support grid in the manufacture of nitric acid.
Other properties of the alloy include good resistance to carburization.
Because of its Ni matrix, the alloy does not possess adequate resist-
ance to sulfidizing environments.
MASS OF CARBON PICKUP PER UNIT AREA
y MULTIMET
Fe- 556
Base 800H
JL 31 OSS
0 0.2 0.4 2.2 2.4
FIGURE 9 Results of carburization tests conducted at 871°C (1600°F)

for 215 h r . (From Ref. 13.)
2000°F - 500 Hours

Burner Rig Exposure
5 10 15 20 25 30 35
Average Metal Affected (Mils]
FIGURE 10 Oxidation damage sustained by various alloys exposed

for 500 hr in a burner rig running at 2000°F (1093°C) burning
No. 2 fuel oil. (From Ref. 14.)
CORROSION RATE (MILS/WEEK)

0 10 20 30 40 50 60 70 80 90 100
i i i I i r
CABOT^
ALLOY N O . 214 IMETAL LOSS
CABOT ALLOY
N O . R-41 ] • CONTINUOUS
PENETRATION
CABOT
ALLOY
N O . 600
7A I
UL
TYPE 310SS
J
HASTELLOY
ALLOY S
HASTELLOY
ALLOY X 77771 J
'////////77///777A
HASTELLOY
ALLOY C-276
®
777X
HAYNES
ALLOY
N O . 188
0 0.5 1.0 1.5 2.0 2.5
CORROSION RATE (mm/week)
FIGURE 11 Corrosion rates of various alloys obtained from tests

conducted at 900°C (1650°) for 8 hr in argon-containing 20% O2
and 2% Cl 2 (volume %). (From Ref. 15.)
TABLE 8 Nitridation Resistance of Alloy No. 230 a
Nitrogen absorption
Alloy (Mg/cm2)
230 0.7
600 0.8
617 1.3
X 1.7
a
Tested in flowing NH3 at 1200°F for 168 h r .
Source: Ref. 16.
Haynes alloy No. 230 (UNS NO6230)
Sheet and plate: ASTM B 435*
Rod: ASTM B 472*
Welded pipe: ASTM B 619*
Seamless pipe and tube: ASTM B 622*
Welded tube: ASTM B 626*
ACKNOWLEDGMENT
The authors are grateful to Mrs. Rebecca Dague for typing this
manuscript and the Haynes International, Inc. for permission to
publish the paper.
REFERENCES
1. Inco Alloys International. Bulletin CEB - 2, Corrosion Resistance

of Nickel and Nickel-Base Alloys in Caustic Soda and Other
Alkalies. Huntington, West Virginia.
2. Inco Alloys International. Resistance to Corrosion, Bulletin S-37.
Huntington, West Virginia.
3. Efird, K. D. (1985). Failure of Monel alloy K-500 bolts in sea-
water. Matr. Perf. April, p p . 37-40.
4. Haynes International. Brochure H-2006, Hastelloy alloy B-2.
Kokomo, Indiana.
5. The Duriron Company I n c . , Bulletin A/3C, Chlorimet 2, Dayton,
Ohio.
6. Lee, T. S., and Hodge, F. G. (1976). Matr. Perf. 15:29-36.
7. Asphahani, A. I. (1980). Matr. Perf. 19:9-21.
8. Sridhar, N. (1987). "Behavior of High Performance Alloys in
Sulfuric Acid Streams." Corrosion/87, Paper No. 19, NACE,
Houston, Texas.
9. Sridhar, N . , Wu, J. B. C , and Manning, P. E. (1985). Corro-
sion resistant Ni-base alloys. J. Metals 37:51-53.
10. Kirchner, R. W., and Hodge, F. G. (1973). Werkstoffe Korrosion
24:1042-1049.
11. Manning, P. E . , Sridhar, N . , and Asphahani, A. I. (1983).
"New Developmental NiCrMo Alloys," CORROSION/83, Paper
No. 21, NACE.
12. Lai, G. Y. (1984). High Temperature Corrosion in Energy Sys-
tems, M. F. Rothman ( e d . ) . TMS-AIME.
13. Lai, G. Y. (1985). J. Metals 37:14-19.
14. Lai, G. Y. et al. (1983). J. Metals 35:24-29.
15. Haynes International. Brochure H-3000A, Haynes alloy no. 230.
Kokomo, Indiana.
SUPPLEMENTAL READING
Books
Friend, W. Z. (1980). Corrosion of Nickel and Nickel-Base Alloys.
Wiley & Sons, New York.
Handbook of Corrosion, Vol. 13, ASM Metals Handbook Series, 9th
ed. ASM International.
Betteridge, W. (1984). Nickel and Its Alloys. Ellis Harwood Ltd.,
Chichester, England.
Brochures
Publications of Haynes International, I n c . , Kokomo, Indiana
Brochure H-2019B, Hastelloy Alloy C-22.
Brochure H-2002A, Hastelloy Alloy C-276.
Brochure H-2007, Hastelloy Alloy C-4.
Brochure H-2009, Hastelloy Alloy G-3.
Brochure H-2028A, Hastelloy Alloy G-30.
Brochure H-1019, Haynes Alloy 625.
Brochure H-2006, Hastelloy Alloy B-2.
Brochure H-3003, Hastelloy Alloy S.
Brochure H-3009, Hastelloy Alloy X.
Brochure H-3000A, Haynes Alloy No. 230.
Brochure H-3008A, Haynes Alloy No. 214.
Brochure H-3013, Haynes Alloy No. 556.
Publications of Inco Alloys International, Huntington, West Virginia

Bulletin CEB-1, Resistance of Nickel and High Nickel Alloys to
Sulfuric Acid.
Caustic Soda and Other Alkalis.
Hydrochloric Acid, Hydrogen Chloride, and Chlorine.
Phosphoric Acid.
Hydrofluoric Acid, Hydrogen Fluoride, and Fluorine.
Organic Acid and Related Compounds.
Bulletin T-5, T-9, Monel Alloys.
Bulletin T-7, Inconel Alloy 600.
Bulletin T-15, Nickel 200 and 201.
Bulletin T-40, Incoloy Alloy 800.
Bulletin T-37, Incoloy Alloy 825.
Bulletin T-42, Inconel Alloy 625.
8
COPPER AND COPPER ALLOYS
JOHN M. CIESLEWICZ Ampco Metal, Milwaukee, Wisconsin

INTRODUCTION
Copper is a unique material. It has excellent electrical and thermal

conductivity, and it is malleable and machinable. However, it has
low mechanical properties and must be cold worked or alloyed to
obtain strength. Copper is classed as a noble metal and is, therefore,
corrosion-resistant. It is resistant to urban, marine, and industrial
atmospheres and finds use as sheeting, roofing, and the like, in
these environments. It is resistant to water and finds use in domestic
and industrial systems and in seawater applications.
To increase the strength of copper and, therefore, its engineer-
ing usefulness, copper is alloyed with other elements, such as zinc,
aluminum, nickel, tin, and so on. There are hundreds of copper
alloys. To bring order and to identify the many alloys, the Copper
Development Association [1], together with the American Society
of Testing and Materials and the Society of Automotive Engineers,
developed a five-digit system. This system is part of the Unified
Numbering System for metals and alloys. In this system, the numbers
C10000 through C79999 denote the wrought alloys: The cast copper
and copper alloys are numbered from C80000 through C99999.
Within the two preceding categories, the compositions are grouped
into the following families: copper, 99.3% minimum copper; high
copper alloys, 94% minimum copper; brasses, which contain zinc
as the principal alloying element; bronzes, which contain tin, alumi-
num, or silicon as the principal alloying element; and copper nickels,
in which nickel is the principal alloying element. Other families are
125
126 Cieslewicz and Schweitzer
nickel-silvers, leaded copper (20% or more lead), and special alloys,

but these three families are of little importance in corrosion engineer-
ing. A more complete description of the families is given elsewhere
[ 1 ]. We will look at these families and discuss their uses in corrosion
engineering.
CORROSION RESISTANCE
Copper and copper alloys exhibit good corrosion resistance. The

corrosion of metal is usually an electrochemical reaction involving
solution of the metal as ions at anodic areas and deposition of hydro-
gen from the electrolyte at cathodic areas. Copper, being a noble
metal, does not normally displace hydrogen from a solution containing
hydrogen ions. With copper and its alloys the predominant cathodic
reaction is the reduction of oxygen to form hydroxide ions. There-
fore, the presence of oxygen or other oxidizing agent is essential
for corrosion to take place.
Many of the corrosion products formed on copper and copper
alloys have a low solubility and produce adherent, relatively im-
pervious films that provide the corrosion protection. However, copper
and copper alloys are sensitive to velocity effects. Turbulently
flowing solutions are capable of corroding these metals, even though
these same metals may be resistant under stagnant conditions. Oxy-
gen or oxidizing agents, if present, will generally increase the
corrosion rate of copper and copper alloys.
Copper, when exposed to the atmosphere over long periods,
will form a coloration on the surface known as patina, which in
reality is a corrosion product that acts as a protective film against
further corrosion. Initially, the patina has a dark color that gradu-
ally turns green. The length of time required to form the patina
depends upon the atmosphere because the coloration is given by
copper hydroxide compounds. In a marine atmosphere, the compound
is a mixture of copper/hydroxide/chloride and in urban or industrial
atmospheres copper/hydroxide/sulfate. These compounds will form
in approximately 7 years. When exposed in a clean rural atmosphere,
tens or hundreds of years may be required to form the patina.
Brass alloys of copper can be subject to dealloying (dezincifica-
tion); a type of corrosion in which the brass dissolves as an alloy
and the copper constituent redeposits from solution onto the surface
of the brass as a metal in a porous form. The zinc constituent
may be deposited in place as an insoluble compound or carried away
from the brass as a soluble salt. The corrosion can be either local
8. Copper and Copper Alloys 127
or take place uniformly. The former, called plug-type dealloying,

is more likely to occur in alkaline, neutral, or slightly acid environ-
ments, whereas the latter, called layer-type dealloying, is more
prevalent in acid environments.
If the brass alloy contains less than 15% zinc, it will be resistant
to dealloying. Additives, such as tin and arsenic, will inhibit this
form of corrosion.
Pure copper is immune to stress-corrosion cracking, but copper
alloys containing more than 15% zinc are particularly subject to
this type of corrosion.
Moist ammonia in the presence of air will cause stress-corrosion
cracking of copper alloys. The quantity of ammonia present need
not be great, as long as the other factors are present. Relative
resistance of the various copper alloys to stress-corrosion cracking
is as follows:
Low resistance
Brasses containing > 15% zinc
Brasses containing > 15% zinc
and small amounts of lead, tin, or aluminum
Intermediate resistance
Brasses containing < 15% zinc
Aluminum bronzes
Nickel-silvers
Phosphor bronzes
Good resistance
Silicon bronzes
Phosphorized copper
High resistance
Commercially pure copper
Cupronickels
Stress-corrosion cracking can also be the consequence of residual

stresses remaining in the metal as a result of cold forming. These
stresses can be removed by heating the metal to a temperature
high enough to recrystallize the metal. It is also possible to provide
a stress-relieving anneal at a lower temperature without substantially
changing the mechanical properties of the cold-worked material.
Based on results of a 30-min heat test, examples of recrystallizing
temperatures and relief-annealing temperatures are shown in Table 1
for several of the more commonly used alloys.
The corrosion resistance of specific alloys to general classes
of and specific corrodants is discussed under the heading of each
alloy.
TABLE 1 Examples of Annealing Temperatures for Copper Alloys
Stress-relief Recrystalliza-
anneal tion anneal
Alloy °C op °C °F
Phosphorized arsenical copper 142 350 662 580 1076
Cartridge brass 260 275 527 326 617
Arsenical Admiralty 443 400 752 470 878
Ambraloy 687 400 752 550 1022
Cupronickel 30% 625 1157 775 1427
Cupronickel 20% 625 1157 700 1292
Cupronickel 10% 600 1112 725 1337
Red brass 400 752 550 1022
Ambronze 400 752 550 1022
COPPERS
The coppers contain a minimum of 99.3% copper. The elements silver,

arsenic, phosphorus, antimony, tellurium, nickel, cadmium, lead,
sulfur, zirconium, magnesium, boron, and bismuth may be present
singly or in combination. The primary uses of the coppers, because
of their good electrical properties, are in electrical or electronic
applications such as bus bars, waveguides, wire, switches, and
transistor components. Because copper is a noble metal, it also
finds many uses in corrosive environments. Table 2 gives the chemi-
cal composition of some of the coppers usually used in corrosion
applications.
The coppers are resistant to urban, marine, and industrial
atmospheres, so it is only logical that these materials are used
architecturally. Coppers such as UNS numbers C11000, C12500,
and C13000 are used as building fronts, downspouts, flashing,
gutters, roofing, and screening. Because of their good thermal
conductivity and corrosion resistance, the coppers are ideal for
solar panels and related tubing and piping used in solar energy
conversion.
Also, because of the excellent thermal properties, inherent
resistance to various atmospheres and engine coolants, and their
ease of joining by brazing and soldering, radiators are commonly
made of copper. The silver-bearing coppers, such as C10400, C11300,
and C12500, are used in radiator construction. Tubing for brakes
and hydraulic and fuel lines are commonly made of copper.
o
o
TABLE 2 Chemical Composition of Coppers: Maximuma Composition (%)
Copper Ag,
UNS no. Cu min. As Sb Te Others o
o
T3
C10200 99.95
C10300 99.95 0.001-0.005
C10400 99.95 0.027
C10800 99.95 0.005-0.012 Co
C11000 99.90
C11300 99.90 0.027
C12000 99.90 0.004-0.012
C12200 99.90 0.015-0.040
C12500 99.88 0.012 0.003 0.025 0.050 Ni
0.003 Bi
0.004 Pb
C13000 99.88 0.085 0.012 0.003 0.025 0.050 Ni
0.003 Bi
0.004 Pb
C14200 99.4 0.015-0.040 0.15-0.50
a
Unless shown as a range.
Source: Ref. 1.
The beverage industry makes use of the coppers in brewery

and distilling operations. Brew kettles, heating vessels, heating
coils, and piping are to be found in these operations.
The inherent resistance of copper to potable waters, its ease
of fabrication, and its nonflammability all make it an ideal material
for plumbing environments, both domestic and commercial. Since
1950 [2], over 10 billion pounds of plumbing tube and pipe has
gone into plumbing systems in the United States. Copper UNS num-
bers C10200, C10300, C10800, C12000, and C12200 are those most
commonly used. These are covered by ASTM Standard Specifications
B42, B88, B302, and B447. ASTM B306 covers copper drainage tube.
Occasional failures with copper plumbing tube have been en-
countered. Lyman and Cohen [2] reported that in a 5-year period,
an average of 71 incidents per year have been documented in the
United States at a time when the yearly total use of copper plumbing
tube was 450 million pounds. The two most common causes of failure
were pitting (24 cases) and corrosion erosion (12 cases). Most of
the pitting failures occurred in cold-water lines, and aggressive
well waters were involved. Surface waters, unless mixed with well
waters, are usually not involved in cold-water pitting.
Cohen [3] reports on a computer-aided study of 120 aggressive
well waters that were known to have caused pitting. The tentative
conclusion of this study was that pitting waters had the following
characteristics: the pH is less than 7.8, carbon dioxide is in excess
of 25 ppm, the sulfate ion is over 17 ppm, and the sulfate/chloride
ratio is about 3:1. There was also an apparent increase in pitting
if one or more of the following ions were found: less than 42 ppm
potassium, less than 25 ppm nitrate, and more than 26 ppm silicate.
Alleviation of the pitting problem is accomplished by either
changing the character of the water or abandoning the aggressive
well. Water characteristics can be changed by dilution of the aggres-
sive water by a nonpitting water or by water treatment. Water
treatment as simple as aeration to release the free carbon dioxide
or raising the pH can alleviate the problem.
Although hot-water pitting is rare, when it occurs a soft water
is usually involved, and the pH is below 6.5, the carbon dioxide
content is 10 to 50 ppm, and the water is low in chloride, sulfate,
and nitrate ions.
Corrosion-erosion failure of copper water tube is the result
of this excessively high velocity and turbulence that develop when
sudden changes in direction or cross section occur. This is easily
remedied by proper design and sizing of the system so that maximum
velocity is kept at 4-5 ft/sec. Good workmanship is also essential
so that a burr or an improperly prepared tube end does not cause
turbulence.
Copper and Copper• Alloys
TABLE 3 High Copper Alloys : Maximuma Composition (%)
Copper
alloy
UNS no. Cu Fe Ni Co Be Pb P Zn Sn Si Al
C17000 Rem b b b 1. 6-1,.79 — — — - — 0 .20 0 .20

C17200 Rem b b b 1. 8-2,.00 — — — — — 0 .20 0 .20
C17300 Rem b b b 1. 8-2,.00 0.20-0.60 — - — - 0 .20 0 .20
c
C18000 Rem 0.10 2.5 — — — — — — 0.4 0 .7 —
C19200 98.7 min. 0. 8-1.2 — — — — 0.01-0.04 — - — — —
C19400 97.0 min. 2. 1-2.6 — — — 0.03 0.015-0.15 0.05-0.20 — — — —
a
Unless shown as a range or minimum
b
Ni + Co, 0.20% min.; Ni + Fe + Co, 0.60% max.
c
Also available in cast form as copper alloy UNS C81540.
Source: Ref. 1.
HIGH COPPER ALLOYS
The high copper alloys contain a minimum of 96% copper if wrought

and 94% copper in the cast form. Like the coppers, the principal
use of the high coppers is in electrical and electronic applications.
The corrosion resistance of the high copper alloys is about
the same as that of the coppers. When they are used in corrosion
service, they are used where mechanical strength and corrosion
resistance are needed. Table 3 gives the composition of some of
the high copper alloys.
C19400 is essentially copper with the addition of about 2.4%
iron. The iron addition enhances corrosion resistance, and the
alloy1 s first use was as seam-welded condenser tubing in desalting
service.
C18000 is a new alloy developed to replace beryllium copper,
C17500, in the resistance welding field. Corrosion tests in plating
solutions have indicated that the alloy may be useful. Tests in
a tinplating solution at room temperature gave a corrosion rate
of 0.02 mil/yr (mpy) for C18000, and tests at room temperature
in a zinc-plating solution gave a corrosion rate of 1.4 mpy.
COPPER-ZINC ALLOYS
Brasses contain zinc as their principal alloying ingredient. Other

major alloying additions are lead, tin, and aluminum. Lead is added
to improve machinability, and its presence does not enhance corro-
sion resistance. The addition of tin, nominally about 1%, increases
strength and the dealloying resistance of the alloys. Aluminum is
added to stabilize the protective surface film. Table 4 lists some
of the brasses used in corrosion engineering. Alloys containing
in excess of about 15% zinc are susceptible to dealloying in many
environments. These environments include acids, both organic and
inorganic, dilute and concentrated alkalies, neutral solutions of
chlorides and sulfates, and mild oxidizing agents such as hydrogen
peroxide. As stated earlier, the addition of small amounts of tin
improves the dezincification resistance of these alloys. The Admiralty
brasses, copper alloy UNS C44300 through C44500, and the naval
brasses, C46400 through C46700, owe their dealloying resistance
to the presence of tin. In addition, minor additions, usually less
than 0.10%, of arsenic, antimony, or phosphorus are added to the
Admiralty brasses to further enhance dealloying resistance.
The high zinc brasses, such as C27000, C28000, C44300, and
C46400, resist sulfides better than do the low zinc brasses. Dry
H2S is well resisted. Because of this resistance to sulfides, alloys
o
o
7
TABLE 4 Copper-Zinc Alloys: Maximuma Composition (%)
Copper O
alloy o
UNS no. Cu Pb Fe Zn Sn P Al Others 73
TO
C27000 63.0-68.5 0.10 0.07 Rem

C28000 59.0-63.0 0.30 0.07 Rem — —
C44300 70.0-73.0 0.07 0.06 Rem 0.8-1.2 — 0.02-0.10 As CO
C44400 70.0-73.0 0.07 0.06 Rem 0.8-1.2 — 0.02-0.10 Sb

C44500 70.0-73.0 0.07 0.06 Rem 0.8-1.2 0.02-0.10
C46400 59.0-62.0 0.20 0.10 Rem 0.50-1.0 —
C46500 59.0-62.0 0.20 0.10 Rem 0.50-1.0 — 0.02-0.10 As
C46600 59.0-62.0 0.20 0.10 Rem 0.50-1.0 — 0.02-0.10 Sb
C46700 59.0-62.0 0.20 0.10 Rem 0.50-1.0 0.02-0.10
C68700 76.0-79.0 0.07 0.06 Rem — — 1.8-2.5 0.02-0.10 As
a
Source: Ref. 1.
Co
Co
such as the Admiralty and naval brasses find use in petroleum

refinery applications, where H2S is commonly found.
Alloys containing 15% or less of zinc resist dealloying and are
generally more corrosion-resistant than the high zinc-bearing brasses.
These alloys are resistant to many acids, alkalies, and salt solutions
that cause dealloying in the high zinc brasses. Dissolved air, oxi-
dizing materials, such as chlorine and ferric salts, compounds that
form soluble copper complexes ( e . g . , ammonia), and compounds
that react directly with copper ( e . g . , sulfur, mercury) are deleteri-
ous to the low zinc brasses. The alloys are more resistant to stress-
corrosion cracking than the high zinc-containing alloys.
The brasses are widely used as plumbing hardware in valves,
elbows, and piping. The inhibited brass alloy C44300 is a common
condenser tube alloy, and tube sheets are C46400. Many commercial
vessels use these materials, whereas most naval vessels use copper-
nickels. Another excellent condenser tube alloy is aluminum brass,
C68700, which contains 2% aluminum.
COPPER-TIN ALLOYS
Alloys of copper and tin are known as tin bronzes or phosphor

bronzes. Tin is the principal alloying ingredient, but phosphorous
is always present in small amounts, usually less than 0.5%, because
of its use as a deoxidizer. Other secondary alloying elements are
lead, zinc, and nickel. The microstructure of the alloys can range
from solid solution alpha to complex structures of alpha plus alpha-
delta eutectoid, beta, and gamma. These alloys are available in
both cast and wrought form and some alloys respond to heat treat-
TABLE 5 Wrought Copper-Tin Alloys: Maximuma Composition (%)
Copper
alloy
UNS no. Cu Pb Fe Sn Zn P
C51000 Rem 0.05 0.10 4.2-5.8 0.30 0.03-0.35

C51100 Rem 0.05 0.10 3.5-4.9 0.30 0.03-0.35
C52100 Rem 0.05 0.10 7.0-9.0 0.20 0.03-0.35
C52400 Rem 0.05 0.10 9.0-11.0 0.20 0.03-0.35
C54400 Rem 3.5-4.5 0.10 3.5-4.5 1.5-4.5 0.01-0.50
a
Source: Ref. 1.
Copper and Coppe
TABLE 6 Cast Copper-Tin Alloys: Maximuma Composition (%)
Copper
alloy
UNS no. Cu Sn Pb Zn Fe Sb Ni S P Al Si
C90300 86.0-89.0 7.5-9.0 0.30 3.0-5.0 0.20 0.20 1.0 0.05 0.05 0.005 0.005
C90500 86.0-89.0 9.0-11.0 0.30 1.0-3.0 0.20 0.20 1.0 0.05 0.05 0.005 0.005
C92200 86.0-90.0 5.5-6.5 1,.0-2. 0 3.0-5.0 0.25 0.25 1.0 0.05 0.05 0.005 0.005
C93700 78.0-82.0 9.0-11.0 8,.0-11 .0 0.8 0.15 0.55 1.0 0.08 0.15 0.005 0.005
C93800 75.0-79.0 6.3-7.5 13,.0-16 .0 0.8 0.15 0.8 1.0 0.08 0.05 0.005 0.005
C93900 76.5-79.5 5.0-7.0 14,.0-18 .0 1.5 0.40 0.50 0.8 0.08 1.5 0.005 0.005
b
C94700 85.0-90.0 4.5-6.0 0.10 1.0-2.5 0.25 0.15 4.5-6.0 0.05 0.05 0.005 0.005
a
b
Mn 0.20.
Source: Ref. 1.
Co
Cn
ment. Tables 5 and 6 list some of the tin bronzes used in corrosion
applications.
The tin bronzes are probably the oldest alloys known. They
are the bronzes of the Bronze Age. There are many bronze artifacts
in existence today, such as statues, swords, vases, and bells.
These have survived hundreds of years exposure to various atmos-
pheres, waters, and soils, testifying to the corrosion resistance
of the tin bronzes to a wide variety of environments.
Modern use of tin bronzes is primarily as valves, valve com-
ponents, impellers, pump casings, and so on, in water service.
These alloys are used in fire protection systems because of their
corrosion resistance in stagnant waters.
COPPER-ALUMINUM ALLOYS
Alloys consisting primarily of copper and aluminum are commonly

referred to as aluminum bronzes. They are available in both cast
and wrought form, some of them respond to heat treatment, and
they can be joined by brazing and welding. The aluminum bronzes
find use where combinations of strength, corrosion resistance, and
wear resistance are of importance. Tables 7 and 8 list the alloys
generally used in corrosion applications.
The development of the aluminum bronzes has progressed from
a simple alloy of copper and aluminum to complex alloys with the
addition of iron, nickel, silicon, manganese, and other elements.
The microstructure of these bronzes is controlled primarily by the
aluminum content. In alloys containing up to approximately 8% alumi-
num, the microstructure consists of the single-phase alpha structure,
in which some minor intermetallics may be included. When the alumi-
num content is increased, other constituents appear. They may be
beta, alpha-gamma eutectoid, or a combination of these constituents,
depending on the aluminum content, the cooling rate from solidifica-
tion, and the heat treatment. The addition of iron generally forms
an iron-rich intermetallic compound, whereas the addition of nickel,
above 2%, tends to introduce the additional kappa phase.
The corrosion characteristics are affected by the microstructure
of the alloy. A small amount of tin added to C61300 will inhibit
inter granular stress corrosion. The importance of microstructure
is particularly apparent in the dealloying resistance of the alloys.
Dealloying is rarely seen in all-alpha, single-phase alloys such
as copper alloy UNS C60800, C61300, or C61400, and when seen,
conditions of low pH and high temperature are usually present.
However, duplex structures are more prone to dealloying. Proper
heat treatment can control dealloying in these duplex alloys. As
o
o
O
a
TABLE 7 Wrought Copper-Aluminum Alloys: Maximum Composition (%) Q
Copper o
alloy o
UNS no. Cu Al Fe Ni Mn Si Sn Zn Others CO
C60800 92.5-94.8 5.0-6.5 0.10 — 0.02-0.^$5 As

0.10 Pb
C61000 90.0-93.0 6.0-8.5 0.50 — — 0.10 — 0.20 0.02 Pb cc
C61300 88.6-92.0 6.0-7.5 2.0-3.0 0.15 0.10 0.10 0.20-0.50 0.05 0.01 Pb
C61400 88.0-92.5 6.0-8.0 1.5-3.5 — 1.0 — — 0.20 0.01 Pb
C61500 89.0-90.5 7.7-8.3 — 1.8-2.2 — — — — 0.01J> Pb
C61800 86.9-91.0 8.5-11.0 0.5-1.5 — — 0.10 — 0.02 0.02 Pb
C62300 82.2-89.5 8.5-11.0 2.0-4.0 1.0 0.50 0.25 0.60 — —
C63000 78.0-85.0 9.0-11.0 2.0-4.0 4.0-5.5 1.5 0.25 0.20 0.30 —
C63200 75.9-84.5 8.5-9.5 3.0-5.0 4.0-5.5 3.5 0.10 — — 0.02 Pb
a
Source: Ref. 1.
Co
•si
CO
00
TABLE 8 Cast Copper-Aluminum Alloys: Maximum8 Composition (%)
Copper
alloy
UNS no. Cu Al Fe Ni Mn Si Others
C95200 86.0 min. 8.5-9.5 2.5-4.0 1.0 total

C95300 86.0 min. 9.0-11.0 0.8-1.5 — — 1.0 total
C95400 83.0 min. 10.0-11.5 3.0-5.0 2. 5 0 .50 — 0.5 total
C95500 78.0 min. 10.0-11.5 3.0-5.0 3. 0-5. 5 3 .5 — 0.5 total
C95700 71.0 min. 7.0-8.5 2.0-4.0 1. 5-3. 0 11 .0-14.0 0.10 0.5 total b
C95800 79.0 min. 8.5-9.5 3.5-4.5 c 4. 0-5. 0 0 .8-1.5 0.10 0.5 total d
a
Unless shown as a range or minimum. o
^Maximum Pb 0.03.
c
Iron content shall not exceed the nickel content.
d
Maximum Pb 0.02. o"
Source: Ref. 1.
2
CO
an example, C95400, with a structure of alpha plus eutectoid is

susceptible to dealloying. A simple heat treatment above the critical
temperature will transform the susceptible eutectoid to beta, which
can be realigned by rapid cooling, making the alloy more resistant
to dealloying. It is possible to improve the alloy still further by
quenching it from a high temperature 890°C (1650°F), then tempering
it at a temperature, say 649°C (1200°F), above the critical. This
will give a structure of martensitic beta with acicular reprecipitated
alpha scattered through the beta. Table 9 gives the results of alter-
nate immersion (aerated) laboratory tests in a 3% NaCl solution
for C95200, C95300, and C95400.
The addition of about 4% nickel coupled with a lower aluminum
content is also advantageous in deterring dealloying. This addition
plus heat treatment is the basis for Mil-B-24480 (Ships, January
1973), Table 10.
This alloy has been and is used in many seawater applications,
such as valves, fittings, and pump casings. Pumps of temper-
annealed C95800 are used in saltwater desalination units aboard
both naval and commercial vessels.
The aluminum bronzes, particularly C61300, C61400, and C63000,
are used as condenser tube sheets in both fossil-fueled and nuclear
power plants handling fresh, brackish, and seawaters for cooling.
These tube sheets are compatible with most condenser tube alloys,
such as C70600, C71500, C68700, and titanium.
Recent work has indicated that aluminum bronzes may be useful
in geothermal energy applications. Tests were run at various locations
in the Madison Aquifer of western South Dakota [4], Water analyses
are given in Table 11 and test results in Table 12. These tests
indicate that aluminum bronze, nickel-aluminum bronze, and Admiralty
brass, C44300, will resist these waters. Where crevice or incipient
crevice corrosion was observed, the bronzes consistently exhibited
very good resistance. Copper and C71500, cupronickel, were the
least resistant of the copper alloys tested.
Aluminum bronze alloys are generally resistant to chloride potash
solutions. Tables 13 and 14 give the results of on-site tests in
several types of potash ores. As these data show, the alloys are
affected by aeration and pH. This is shown in Table 14. Where
the aeration is 100% and the pH low (Table 14, test 1), the corrosion
rate is near 50 mpy. As aeration decreases and pH increases (Table
14, tests 2 and 3), the corrosion rate drops to less than 10 mpy.
A potash crystallizer was constructed of C61400 and was in service
for 15 years in the New Mexico area. The original plate thickness
was 12.4 mm (0.5 i n . ) , and upon dismantling the plant, the plate
thickness was 11.6 mm (0.457 i n . ) . This is a loss of 0.8 mm (0.043
in.) in 15 years, giving a corrosion rate of 2.8 mpy. Other success-
ful applications are in the Middle East Dead Sea area and in Spain.
TABLE 9 3% NaCl, 15 Days Exposure, Alternate Immersion
Copper
alloy
UNS no. Thermal treatment a Before cleaning After cleaning Fracture appearance
C95200 As cast 100% of surface Red areas over Irregular dealloying 1.5 mm
covered with 90% of surface (0.059 in.) in depth max.
brown-red product
C95200 621°C (1150°F) 1 hr, WQ 90% of surface Red areas over Irregular dealloying 1.3 mm
510°C (950°F) 1 hr, WQ covered with 90% of surface (0.051 in.) in depth max.
brown-red product
C95200 621°C (1150°F) 1 hr, WQ 5% of surface Red spots over Plug-type dealloying 0.25 mm
covered with about 5% of (0.010 in.) in depth max.
brown-red spots surface
C95200 899°C (1650°F) 1 hr, WQ No brown-red No red areas No dealloying o
spots or product CO
covered with 90% of surface (0.059 in.) in depth max. 8
Q
brown-red product
C95300 621°C (1150°F) 1 hr, WQ 75% of surface Red areas over Irregular dealloying 1.0 mm O
brown-red product TO
C95300 621°C (1150°F) lhr, WQ No brown-red spots No red areas No dealloying

C95300 899°C (1650°F) 1 hr, WQ No brown-red spots No red areas No dealloying
649°C (1200°F) 1 hr, WQ o
o
brown-red product
C95400 621°C (1150°F) 1 hr, WQ 75% of surface Red areas over Irregular dealloying 1.3 mm
510°C (950°F) 1 hr, WQ covered with 75% of surface (0.031 in.) in depth max. O
O
brown-red product
C95400 621°C (1150°F) 1 hr, WQ 10% of surface Red areas over Plug-type dealloying 0.38 mm
covered with about 10% of (0.015 in.) in depth max.
brown-red product surface
C95400 890°C (1650°F) 1 hr, WQ A few brown-red A few red spots Shallow plug-type dealloying
649°C (1200°F) 1 hr, WQ spots 0.08 mm (0.003 in.) in
depth max.
a
WQ, water quenched.
Source: Maersch, R. E. and Cieslewicz, J. M. (1974). Heat treatments reduce dealuminification of aluminum
bronzes in saline solution. Mater. Prot. 3(7).
TABLE 10 Mil-B-24480 (Ships) a January 1973
Cu 79.0 min.
Al 8.5-9.5
Fe 3.5-4.5
Ni 4.0-5.0
Mn 0.75-1.5
Si 0.10 max.
Pb 0.03 max.
a
The nickel content should exceed the iron
content. All castings must be temper annealed
at 677°C (1250°F) for at least 6 hr and air
cooled.
Source: military Standard Mil-B-24480 (ships),
January 1973.
TABLE 11 Range in Water Analysis for Madison Aquifer

in South Dakota
Concentration ppm, except pH,

Species temperature, and depth
so2- 120-1426
2
S " 0.02-0.20
cr 0.6-269
HCO3 103-274
TDS 189-2710
2+
Ca 31-572
2+
Mg 16-120
pH 6.5-8.13
Temperature, °C (°F) 11-71 (52-160)
Depth, m (ft) 229-1481 (751-4859)
Source: Ref. 4.
TABLE 12 Weight Loss Results for the Coupon Tests in Madison

Aquifer Corrosion Rate (mpy)
Madison Aquifer test sites

Edgemont Philip Diamond Ring
Copper alloy Days Days Days
UNS no • 149 308 457 148 460 608 97 317 414
C61300 0.10 0.15 0.05 0.24 0.16 0.28 0.39 0.42 0.39
C61300 welded 0.15 0.16 0.09 0.43 0.17 0.24 0.59 0.47 0.48
C95800 as cast 0.13 0.16 0.04 0.51 0.35 0.48 0.33 0.18 0.57
C95800 annealed 0.36 0.15 0.14 — — 0.57 0.32 0.35
C95800 welded 0.15 0.16 0.11 0.60 0.35 0.46 0.52 0.24 0.36
Copper 0.24 0.25 0.16 0.13 0.15 0.17 3.42 4.45 3.23
C44300 0.43 0.42 0.41 0.12 0.05 0.09 0.74 0.37 0.55
C71500 0.45 0.39 0.33 0.32 0.28 0.30 1.46 1.78 0.47 a
a
A black coating could not be removed, resulting in lower weight loss
and corrosion rate.
Source: Ref. 4.
TABLE 13 Aluminum-Bronze Alloys in KC1: On-Site Spool Test a
Copper alloy Corrosion rate,

UNS no. (mpy) Remarks
C61400 2.7 Etched with machining marks

discernible
C61400 welded 2.6 Etched with machining marks
discernible
discernible
C95300 1.4 Three to four incipient de-
alloyed plugs
discernible
discernible
a
48 daysT exposure in submerged combustion evaporator. Vapor from
evaporation of KC1 brine. Consists of combustion products-natural
gas plus air, water-vapor-entrained KC1, NaCl, and MgCl2. Average
temperature 97°C (206°F). pH slightly acid from CO2 in combustion
gas.
TABLE 14 Aluminum-Bronze Alloys in MgCl2: On-Site Spool Tests
1. 26-days T exposure in vapor phase of submerged combustion

evaporator. Vapor from evaporation of MgCl2 brine consists of
combustion products-natural gas with 100% excess air, water
vapor, entrained MgCl2 brine with NaCl solids; HCl-contaminated.
Temperature 104°C (220°F), pH 0.5 to 3.4.
Corrosion rate
UNS no. (mpy) Remarks
C61300 47 All samples thinned with rough-

ened surfaces
C61300 welded 46
C95800 annealed 43
2. 31-day T s exposure in liquid in discharge position. 24% MgCl2,

4% CaCl, 3% NaCl, 1.5% KC1 at 81°C (178°F), pH 3.5 to 4.5.
Corrosion rate
UNS no • (mpy) Remarks
C61300 0.77 Etched

C61300 welded 0.77 Etched
C95200 0.70 Incipient de alloying
C95800 annealed 0.47 Etched
3. 34-day T s exposure in crystallizer. Multicomponent slurry and

brine consisting of MgCl2, NaCl, KC1, CaCl 2 , and some MgO
and HC1, 45% solids. Temperature 67°C max. (150°F), pH 3.5
to 5.0.
Corrosion rate
UNS no • (mpy) Remarks
C61300 9.6 Etched

C61300 welded 10.0 Etched
C95200 8.1 Etched and incipient dealloying
C95400 annealed 10.4 Etched
TABLE 15 Corrosion Rate (mpy) of Aluminum Bronze Alloys C61400 and C95300 in Various Concentra-
tions of Sodium Hydroxide
Immersion Room temperature 52 (125) a 80 (175) a

condition C61400 C95300 C61400 C95300
Constant 0.6 1.4 x

Alternate 0.5 0.5 — — o
Constant — 0.5 — —
Alternate 1.8 1.2 — —
Constant 0.9 1.1 — —
__ _ -S
Alternate — — — —
Constant 1.3 0.9 — — ~~ ~~ o1
Alternate 7.2 4.2 - - 03
10 Constant 1.5 0.7 4.9 3.8 8.1 8.9

Alternate 15.7 11.4 — —
15 Constant 0.5 0.6 3.1 2.3 7.2 3.1
Alternate 10.3 10.2 —
- —
- - -
20 Constant 0.3 0.5 1.7 0.7 7.1 1.9
Alternate 6.7 5.8 - - - -
25 Constant 0.2 0.4 0.9 0.6 4.8 0.4
Alternate 4.6 3.8 — — — —
30 Constant 0.1 0.4 0.5 0.3 7.5 0.2
Alternate 3.7 2.4 -— -— — —
35 Constant 0.1 0.4 0.2 0.2 3 0.1
Alternate 0.7 0.5 -
— -
— - -
45 Constant 0.1 0.3 0.1 0.3 2.1 0.3
Alterna
Alternate 0.3 0.3
a
Temperature, °C
Alkalis, such as sodium and potassium hydroxides, can be

handled by aluminum bronze alloys. Laboratory tests of various
concentrations of sodium hydroxide (Table 15) give rates ranging
from 0.1 to 15 mpy, depending on concentration, aeration, and
temperature.
These alloys are resistant to nonoxidizing mineral acids, such
as sulfuric and phosphoric. Their resistance to these acids is con-
trolled by the presence of oxygen or an oxidizing agent. Alloys
such as C95300 and C95400 are used as pickling baskets, hooks,
and chain in sulfuric acid pickling operations. Table 16 gives the
results of tests on C95400 in various concentrations of sulfuric
acid, and Table 17 gives results in phosphoric acid.
Aluminum bronzes are resistant to many organic acids, such
as acetic, citric, formic, and lactic. In some instances, its uses
in these media are limited because of the possibility of copper pickup
in the finished product. This pickup, although very low, may, as
an example, discolor the product. However, a polishing step such
as charcoal filtration easily removes the color contaminant. Tables
18 and 19 give corrosion rates (generally low) for aluminum bronzes
in various organic acids. Vessels are fabricated from alloy C61300
for acetic acid containment. Its good corrosion resistance, strength,
and heat conductivity make it an appropriate choice for acetic acid
processing.
TABLE 16 C95400 in Sulfuric Acid, Laboratory Tests
Acid Exposure time Temperature Corrosion rate

(%) (days) [°C (OF)] (mpy)
0.5 31 32.0 (90) 1.6

1.0 31 32.0 (90) 1.6
2.0 31 32.0 (90) 1.6
5.0 31 32.0 (90) 1.4
5.0-7.0 30 38.0 (100) 2.9
10.0 31 32.0 (90) 1.1
10.0 28 22.0 (72) 3.7
35.0 28 22.0 (72) 1.7
35.0 31 30.0 (86) 0.3
35.0 34 90.0 (194) 42.0
50.0 28 22.0 (72) 2.5
50.0 31 30.0 (86) 0.3
TABLE 17 Alloys in Phosphoric Acid, Laboratory Tests

1. C95400 in phosphoric acid, laboratory tests
Acid Exposure time Temperature Corrosion rate
(%) (days) [°C (°F)] (mpy)
10.0 28 22.0 (72) 2.8
10.3 la 81.0 (178) 31.8
25.7 la 81.0 (178) 23.0
35.0 28 22.0 (72) 1.8
35.0 34 90.0 (194) 13.8
50.0 28 22.0 (72) 1.1
50.8 la 81.0 (178) 20.1
Crude 1*> 79.0 (174) 35.7
2. C95300 in phosphoric acid. Laboratory tests at 32°C (90°F).
Constant immersion, 30 days. Alternate immersion, 10 days.
Corrosion rate in mpy.
Acid Immersion condition
Constant Alternate0
26.0 0.8 177.5
50.0 0.6 85.5
85.0 0.3 23.4
a
Aerated and agitated.
b
Some agitation.
c
Dealloying noted to varying degrees.
Source: Data from private communications from International Nickel
Co., Inc., and Ampco Metal Division.
As stated previously in the section on coppers, architectural

uses of the coppers have many successful applications. Smith [5]
has reported on a development of an aluminum-bronze alloy for
architectural use. This alloy is designated copper alloy UNS C61500
and is reported to have a film resistance 20 times that of C11000.
TABLE 18 Corrosion Rates in Acetic Acid
1. Acetic acid, 20 days, constant immersion, room temperature,

Acid Alloy (corrosion rate, mpy)
<%) C61400 C63200 Remarks
10 2.5 2.6 Slight etch, no dealloying

20 2.5 2.6
30 3.8 2.6
40 3.2 2.6
2. In experimental pressure vessel, 25% acetic acid, vapor zone,

126°C (258°F), 26 psig.
Exposure time Corrosion rate
Alloy (days) (mpy)
C61400 56 5.6 Light etch

C61400 187 2.8
C61400 Welded 56 5.6 Light etch
C61400 Welded 187 3.1
C95300 56 5.8 Incipient dealloying
C95300 187 2.7
C95400 56 5.7 Incipient dealloying
C95400 187 2.7
C95500 56 5.5 Light etch
C95500 187 2.5
3. Acetic acid, various concentrations, alloy C95400.

Acid Exposure conditions Corrosion rate
<%) Days Temp. (mpy)
10 31 30°C (85°F) 3.1

10 28 22°C (72°F) 2.2
27a 15 room temperature 0.4
35 31 30°C (85°F) 4.3
35 28 22°C (72°F) 3.1
35 34 89°C (102°F) 19.5
50 31 30°C (85°F) 7.8
50 28 22°C (72°F) 3.9
Glacial b 15 118°C (244°F) 2.3
a
Acid solution renewed each day; no aeration or agitation.
Âcid solution renewed each day; agitated by boiling.
Co., I n c . , and Ampco Metal Division.
TABLE 19 C95400 in Citric, Formic, Lactic, and Tartaric Acids
Exposure
Acid time Temperature Corrosion rate (mpy)
<%) (days) [°C (°F)] Citric Formic Lactic Tartaric
10 28 22.0 (72) 2.0 2.3 1.7 0.8
35 34 89.0 (192) 1.8 18.9 16.6 1.9
35 28 22.0 (72) 1.3 2.7 1.3 0.5
50 28 22.0 (72) 0.8 2.5 1.1 0.3
Co., Inc.
COPPER-NICKEL ALLOYS
The copper-nickels are single-phase solid solution alloys, with nickel

as the principal alloying ingredient. Alloys containing 10 and 30%
nickel are those of importance in corrosion engineering. Table 20
lists these cast and wrought alloys. Iron, manganese, silicon, and
niobium may be added. Iron enhances the impingement resistance
of these alloys if it is in solid solution. The presence of iron in
small microprecipitates can be detrimental to corrosion resistance.
Niobium is added to the cast alloys to aid weldability.
The cupronickels are useful in waters ranging from fresh to
brackish to sea. However, they find their greatest use in saltwater
service. Here they are used as piping, fittings, condenser tubes
and plates, and pump castings. Their biofouling resistance is excel-
lent. General corrosion rates for C70600 and C71500 in seawater
are about 1 mpy. Maximum design velocities for condenser tubes
are 3.6 m/sec (12 ft/sec) for C70600 and 4.6 m/sec (15 ft/sec)
for C71500. Popplewell [6] gives typical pitting rates in seawater
of 0.5 to 2 mpy for C70600 and 0.5 to 10 mpy for C71500. Sulfides
[7] as low as 0.007 ppm in seawater can induce pitting of both
C70600 and C71500, and both alloys are highly susceptible to accel-
erated corrosion as the sulfide concentration exceeds 0.01 ppm.
Hack and Gudos [8] inhibited this attack to some degree by the
use of ferrous sulfate additions to sulfide-contaminated seawater.
Efrid and Lee [9] have proposed that the formation of carbon on
the surface of these alloys in the presence of sulfide and oxygen
in polluted waters is responsible for many cases of pitting and
accelerated corrosion.
The copper-nickels are highly resistant to stress-corrosion
cracking. Of all the copper alloys, they are the most resistant to
stress-corrosion cracking in ammonia and ammoniacal environments.
TABLE 20 Chemical Composition of Cupronickels (%)
Copper
alloy
UNS no. Cu Ni Fe Nb Si Mn Others
C70600 Bal 9.0-11.0 1.0-1.8 — — 1.0 max. Pb 0.05 max.

Zn 1.0 max.
C71500 Bal 29.0-33.0 0.40-0.7 — — 1.0 max. Pb 0.05 max.
Zn 1.0 max.
C71900 Bal 29.0-32.0 0.25 max. 0.5-1.0 Cr 2.6-3.2
Zr 0.08-0.2
Ti 0.02-0.08
C96200 Bal 9.0-11.0 1.0-1.8 1.0 max. 0.25 max. 1.5 max. a
Pb 0.03 max. o
a CO
C96400 Bal 28.0-32.0 0.25-1.5 1.0 max. 0.70 max. 1.5 max. Pb 0.03 max.
a
For welding grades the lead must not exceed 0.01%.
Source: Ref. 1.
2
Dealloying or parting corrosion has rarely been observed in

the copper-nickels. When it has been observed, a condition of high
temperature has existed. Parting has been reported in C71500 used
as feedwater preheaters under high oxygen conditions and at "hot
spots" in condenser tubing.
C71900 is a chrome-bearing cupronickel developed for naval
use. The addition of chrome allows the alloy to be strengthened
by spinodal decomposition. This increases the yield strength from
137.9 MPa (20.0 ksi) for C71500 to 310.3 MPa (45.0 ksi) for C71900.
The alloy also has superior resistance to impingement, with possible
design velocities of 7.6-9.1 m/sec (25-30 ft/sec). There is, however,
some sacrifice in general corrosion resistance, pitting, and crevice
corrosion under stagnant or low-velocity conditions.
Although these alloys are resistant to some nonoxidizing acids,
alkalies, neutral salts, and organics, they are not commonly used
in these environments. Possibly the high cost of the cupronickels
and the availability of lower-cost materials limits their use.
CONCLUSIONS
As can be seen, the available copper alloys for corrosion service

are many and there may be several alloys indicated as resistant
to a particular environment. Because of this, other criteria may
be needed to select the right alloy. Fortunately, the coppers and
copper alloys offer a wide range of chemical, physical, and mechani-
cal properties to meet most needs. Some of these materials may
be available in many cast forms, such as sand, centrifugal, perma-
nent mold, and continuous cast. Others may be available in wrought
form as wire, rod, pipe, tube, sheet, and plate. Many can be joined
by welding, brazing, or soldering. Some are more machinable than
others. Cost will vary with composition, form, and other factors.
The selection process, then, involves many criteria for obtaining
optimum service from copper and its alloys.
ACKNOWLEDGMENTS
The author thanks the Management of Ampco Metal Division, Ampco-

Pittsburgh Corporation, for permission to engage in this project.
He is particularly indebted to C. W. Dralle for encouragement in
this task; to R. J. Sever son, R. J. Cox, and P. A. Tully for
their helpful criticism, comments, and suggestions; and to Sharon
Southart for her patience in typing the several drafts of this con-
tribution .
REFERENCES
1. Application Data Sheet: Standard Designations for Copper and

Copper Alloys, Copper Development Association, Inc., New York.
2. Lyman, W. S., and Cohen, A. (1972). Service Experience with
copper plumbing tube, Matr. Prot. Perform. 48-52, February.
3. Cohen, A. (1978). Copper for hot and cold potable water systems.
Heat./Piping/Air Cond. May.
4. Howard, S. M., Carda, D. D., and Cieslewicz, J. M. (1980).
"Corrosion in Geothermal Waters of Western South Dakota," Paper
No. 208, NACE Corrosion/80, Chicago, March 3-7.
5. Smith, R. D. (1978). "Staining and Tarnishing of Copper Alloys
in Architectural Applications," Paper No. 93, NACE Corrosion/78,
Houston, March 6-10.
6. Popplewell, J. W. (1978). "Marine Corrosion of Copper Alloys:
An Overview," Paper No. 21, NACE Corrosion/78, Houston,
March 6-10, 1978.
7. Gudas, J. P . , and Hack, H. P. (1978). "Parametric Evaluation
of Susceptibility of Copper Nickel Alloys to Sulfide Induced Corro-
sion," Paper No. 22, NACE Corrosion/78, Houston, March 6-10.
8. Hack, H. P . , and Gudas, J. P. (1978). "Inhibition of Sulfide
Induced Corrosion of Copper-Nickel Alloys with Ferrous Sulfate,"
Paper No. 23, NACE Corrosion/78, Houston, March 6-10.
9. Efrid, K. D . , and Lee, T. S. (1978). "The Carbon Mechanism
for Aqueous Sulfide Corrosion of Copper Base Alloys," Paper
No. 24, NACE Corrosion/78, Houston, March 6-10.
9
ALUMINUM ALLOYS
ERNEST H. HOLLINGSWORTH and HAROLD Y. HUNSICKER* Alcoa

Laboratories, Alcoa Center, Pennsylvania
INTRODUCTION
In terms of production and consumption, aluminum is now second

only to iron as the most important metal of commerce in the United
States. Its position relative to most other metals can be expected
to increase as the resources of these metals are depleted further.
Aluminum is the third most abundant metal in the crust of the earth,
almost twice as abundant as the next metal, iron. Furthermore,
resources from which aluminum can be extracted are literally inex-
haustible, and even though its extraction from newer resources
may be more expensive than from bauxite, the resource used pres-
ently, it will still be economically feasible. The greater cost of
extraction will also be offset substantially by greater recycling
of aluminum (which saves 95% of the energy required for extraction)
and by new smelting processes requiring less energy [1].
In addition to low cost, aluminum and its alloys provide a high
strength/weight ratio, and they are fabricated and joined readily
by most of the methods commonly used. They have a high resistance
to corrosion by most atmospheres and waters and by many chemicals
and other materials. Their salts are not damaging to the ecology;
they are nontoxic, permitting applications with foods, beverages,
and Pharmaceuticals; and they are white or colorless, permitting
applications with chemicals and other materials without discoloration.
* Retired.
153
154 Hoilingsworth, Hunsicker, and Schweitzer
Other characteristics of aluminum and its alloys important for certain

applications are high electrical conductivity, higher thermal conduc-
tivity, high reflectivity, and noncatalytic action. Aluminum and
its alloys are also nonmagnetic.
ALUMINUM WROUGHT ALLOYS AND THEIR

RESISTANCE TO GENERAL CORROSION
The nominal chemical compositions of representative aluminum wrought

alloys are given in Table 1. Typical tensile properties of these
alloys in tempers representative of their most common use are given
in Tables 2 and 3.
Wrought alloys are of two types: non-heat-treatable of the 1XXX,
3XXX, 4XXX, and 5XXX series and heat-treatable of the 2XXX,
6XXX, and 7XXX series. In the non-heat-treatable type, strengthen-
ing is produced by strain hardening, which may be augmented
by solid solution and dispersion hardening. In the heat-treatable
type, strengthening is produced by (1) a solution heat treatment
at 460 to 565°C (860 to 1050°F) to dissolve soluble alloying elements,
(2) quenching to retain them in solid solution, and (3) a precipita-
tion or aging treatment, either naturally at ambient temperature,
or more commonly, artificially at 115 to 195°C (240 to 380°F), to
precipitate these elements in an optimum size and distribution.
Strengthened tempers of non-heat-treatable alloys are designated
by an "H" following the alloy designation, and of heat-treatable
alloys, by a "T"; suffix digits designate the specific treatment
(e.g., 1100-H14 and 7075-T651). In both, the annealed temper
representing a condition of maximum softness is designated by an
"0".
All non-heat-treatable alloys have a high resistance to general
corrosion. Therefore, selection is usually based on other considera-
tions. Aluminums of the 1XXX series, representing unalloyed alumi-
num, have a relatively low strength. Alloys of the 3XXX series
(Al-Mn, Al-MN-Mg) have the same desirable characteristics as those
of the 1XXX series and somewhat higher strength. Practically all
the manganese in these alloys is precipitated as finely divided phases
(intermetallic compounds), but corrosion resistance is not impaired
because the negligible difference in electrode potential between
the phases and the aluminum matrix in most environments does
not create a galvanic cell. Magnesium, added to some alloys in this
series, provides additional strength through solid-solution hardening,
but the amount is low enough that the alloys still behave more like
those with manganese alone than like the stronger Al-Mg alloys of
the 5XXX series. Alloys of the 4XXX series (Al-Si) are low-strength
9. Aluminum Alloys 155
TABLE 1 Nominal Chemical Compositions of Representative Aluminum

Wrought Alloys
Alloy Si Cu Mn Mg Cr Zn Ti V Zr
Non-heat-treatable alloys
1060 99.60% min. A
1100 99.00% min. A
1350 99.50% min. A
3003 0.12 1.2
3004 1.2 1.0
5052 2.5 0.25
5454 0.8 2.7 0.12
5456 0.8 5.1 0.12
5083 0.7 4.4 0.15
5086 0.45 4.0 0.15
7072a 1.0
Heat-treat able alloys

2014 0.8 4.4 0.8 0.50 0.06 0.10 0.18
2219 6.3 0.30
2024 4.4 0.6 1.5
6061 0.6 0.28 1.0 0.20
6063 0.4 0.7
7005 0.45 1.4 0.13 4.5 0.04 0.14
7050 2.3 2.2 6.2
7075 1.6 2.5 0.23 5.6
a
Cladding for Alclad products.
alloys used for brazing and welding products and for a cladding
in architectural products that develops a gray appearance upon
anodizing; the silicon, most of which is present in elemental form
as a second-phase constituent, has little effect on corrosion.
Alloys of the 5XXX series (Al-Mg) are the strongest non-heat-
treatable aluminum alloys, and in most products they are more
economical than alloys of the 1XXX and 3XXX series in terms of
strength per unit cost. Magnesium is one of the most soluble elements
in aluminum and, when dissolved at an elevated temperature, it is
largely retained in solution at lower temperatures, even though
its equilibrium solubility is greatly exceeded. It produces considerable
solid-solution hardening; additional strength is produced by strain
156 H oiling sworth, Hunsicker, and Schweitzer
TABLE 2 Typical Tensile Properties of Representative Non-Heat-

Treatable Aluminum Wrought Alloys in Various Tempers a
Alloy and Strength (MPa) Elongation (%)

temper Ultimate Yield In 50 m m b In 5D C
1060 -0 70 30 43
-H12 85 75 16
-H14 100 90 12
-H16 115 105 8
-H18 130 125 6
1100 -0 90 35 35 42
-H14 125 125 9 18
-H18 165 150 5 13
3003 -0 110 40 30 37
-H14 150 145 8 14
-H18 200 185 4 9
3004 -0 180 70 20 22
-H34 240 200 9 10
-H38 285 250 5 5
5052 -0 195 90 25 27
-H34 260 215 10 12
-H38 290 255 7 7
5454 -0 250 115 22
-H32 275 205 10
-H34 305 240 10
-Hill 260 180 14
-H112 250 125 18
5456 -0 310 160 22
-Hill 325 230 16
-H112 310 165 20
-H116, H321 350 255 14
5083 -O 290 145 20
-H116, H321 315 230 14
5086 -0 260 115 22
-H116, H32 290 205 12
-H34 325 255 10
-H112 270 130 14
a
Averages for various sizes, product forms, and methods of manu-
facture; not to be specified as engineering requirements or used
for design purposes.
frl.60-mm thick specimen.
C
12.5-mm diameter specimen.
TABLE 3 Typical Tensile Properties of Representative Heat-

Treatable Aluminum Wrought Alloys in Various Tempers a
Alloy and Strength (MPa) Elongation (%)

temper Ultimate Yield In 50 m m D In 5D C
2014 -O 185 95 16
-T4, T451 425 290 18
-T6, T651 485 415 11
2219 -O 170 75 18
-T37 395 315 11
-T87 475 395 10
2024 -0 185 75 20 20
-T4, T351 470 325 20 17
-T851 480 450 6
-T86 515 490 6 7
6061 -O 125 55 25 27
-T4, T451 240 145 22 22
-T6, T651 310 275 12 15
6063 -O 90 50
-T5 185 145 12
-T6 240 215 12
-T83 255 240 9
7005 -O 195 85 20
-T63, T6351 370 315 11
7050 -T76, T7651 540 485 10
-T736, T73651 510 455 10
7075 -O 230 105 17 14
-T6, T651 570 505 11 9
-T76, T7651 535 470 10
-T73, T7351 500 435 11
a
Averages for various sizes, product forms, and methods of manu-
facture; not to be specified as engineering requirements or used
for design purposes.
^1.60-mm thick specimen.
C
12.5-mm diameter specimen.
158 Hollingsworth, Hunsicker, and Schweitzer
hardening. Alloys of this 5XXX series not only have the same high
resistance to general corrosion of other non-heat-treatable alloys
in most environments but, in slightly alkaline ones, a better resist-
ance than that of any other aluminum alloy. They are used widely
because of their high as-welded strength when welded with a com-
patible 5XXX series filler wire, reflecting the retention of magnesium
in solid solution.
Among heat-treatable alloys, those of the 6XXX series, which
are moderate-strength alloys based on the quasi-binary Al-Mg2Si
(magnesium silicide) system, provide a high resistance to general
corrosion equal to or approaching that of non-heat-treatable alloys.
A high resistance to general corrosion is also provided by heat-
treatable alloys of the 7XXX series (Al-Zn-Mg) that do not contain
copper as an alloying addition.
All other heat-treatable wrought alloys have a significantly
lower resistance to general corrosion. These include all alloys of
the 2XXX series (Al-Cu, Al-Cu-Mg, Al-Cu-Si-Mg) and those of
the 7XXX series (Al-Zn-Mg-Cu) that contain copper as a major
alloying element. As described later, the lower resistance is caused
by the presence of copper in the alloys, which are designed primarily
for aeronautical applications, where strength is a requisite and
where protective measures, wherever needed, are justified.
ALUMINUM CASTING ALLOYS AND THEIR

RESISTANCE TO GENERAL CORROSION
The nominal chemical compositions of representative aluminum casting

alloys are given in Table 4. Typical tensile properties of these
alloys in tempers representative of their most common usage are
given in Table 5.
Aluminum casting alloys are also of two types: heat treatable,
corresponding to the same type of wrought alloys where strengthen-
ing is produced by dissolution of soluble alloying elements and
their subsequent precipitation, and non-heat-treatable, in which
strengthening is produced primarily by constituent (intermetallic
compounds) of insoluble or undissolved alloying elements. As with
wrought alloys, tempers of heat-treatable casting alloys are desig-
nated by an "F." Alloys of the heat-treatable type are usually
thermally treated subsequent to their casting, but in a few, in
which a substantial amount of alloying elements is retained in solution
during casting, they may not be given a solution heat treatment
after casting; thus, they may be used in both the "F" and fully
strengthened "T" tempers.
TABLE 4 Nominal Chemical Compositions of R e p r e s e n t a t i v e Aluminum
Casting Alloys
Alloying elements (%)

Alloy Si Cu Mg Ni Zn
Alloys not normally heat treated

360.0 9.5 0.5
380.0 8.5 3.5
443.0 5.3
514.0 4.0
710.0 0.5 0.7 6.5
Alloys normally heat treated

295.0 0.8 4.5
336.0 12.0 1.0 1.0 2.5
355.0 5.0 1.3 0.5
356.0 7.0 0.3
357.0 7.0 0.5
TABLE 5 Typical Tensile Properties of Representative Aluminum

Casting Alloys in Various Tempers a
Alloy and Strength (MPa) Elongation

temper Type casting Ultimate Yield in 50 mmb (%)
295.0 - T 6 Sand 250 165 5

336.0 - T 5 Permanent mold 250 195 1
355.0 - T 6 Sand 240 170 3
-T6 Permanent mold 375 240 4
-T61 Sand 280 250 3
-T62 Permanent mold 400 360 1.5
356.0 - T 6 Sand 230 165 3.5
-T7 Sand 235 205 2
357.0 -T6 Sand 345 295 2
-T7 Sand 275 235 3
360.0 -F Pressure die 325 170 3
380.0 — 17 Pressure die 330 165 3
443.0 -F Pressure mold 160 60 10
514.0 -F Sand 170 85 9
710-O -F Sand 240 170 5
a
Averages for separate cast test bars; not to be specified as engi-
neering requirements or used for design purposes.
b
1.60-mm thick specimen.
Aluminum casting alloys are produced by all casting processes,

of which die, permanent mold, and sand casting account for the
greatest production. Unlike wrought alloys, their selection involves
consideration of casting characteristics as well as of properties.
As with wrought alloys, copper is the alloying element most
deleterious for general corrosion. Alloys such as 356,0, A356.0,
B443.0, 513.0, and 414.0 that do not contain copper as an alloying
element have a high resistance to general corrosion comparable to
that of non-heat-treatable wrought alloys. In other alloys, resistance
becomes progressively less the higher the copper content. More
so than with wrought alloys, a lower resistance is compensated
for by the use of thicker sections, usually necessitated by require-
ments of the casting process.
CHEMICAL NATURE OF ALUMINUM: PASSIVITY
Aluminum is an active metal whose resistance to corrosion depends

on the passivity produced by a protective oxide film. In aqueous
solutions, the thermodynamic conditions under which the film develops
are expressed commonly by the potential-pH diagram according to
Pourbaix (Fig. 1). As this diagram shows, aluminum is passive
only in the pH range of about 4 to 9. The limits of passivity depend
on the temperature, the form of oxide present, and the low dissolu-
tion of aluminum that must be assumed for inertness (because this
value theoretically cannot be zero for any metal). The various forms
of aluminum oxide all exhibit minimum solubility at about pH 5.
The protective oxide film formed in water and atmospheres at
ambient temperature is only a few nanometers thick and structure-
less. At higher temperatures, thicker films are formed; these may
consist of a thin structureless barrier layer next to the aluminum
and a thicker crystalline layer next to the barrier layer. Relatively
thick, highly protective films of boehmite, aluminum oxide hydroxide
(A1OOH), are formed in water near its boiling point, especially if
it is made slightly alkaline, and thicker, more protective films are
formed in water or steam at still higher temperatures.
Because the form of aluminum oxide produced depends on con-
ditions, its identification is sometimes useful in establishing the
cause of corrosion. At lower temperatures, the predominant form
produced by corrosion is bayerite, aluminum trihydroxide A1(OH)3,
whereas at higher temperatures, it is boehmite. During the complex
course of the aging of aluminum hydroxide, which is first formed
during corrosion in an amorphous form, still another aluminum tri-
i i i i
1.2 ' ' '
0.8
CORROSION
Q 0.4 -
O
or
\- PASSIVATION
o
UJ
-0.4 - CORROSION -
-0.8
ujor
I- Q -1.2 - -
Q-I
Q -1.6 - -
or
-2
IMMUNITY
-2.4
I I 1 1
-2 0 2 6 8 10 12 14 16
pH
FIGURE 1 Potential-pH diagram according to Pourbaix for aluminum
at 25°C (77°F) with an oxide film of hydrargillite. (From Ref. 2.)
hydroxide, gibbsite or hydrargillite, may also be formed, especially

if ions of the alkali metals are present.
Beginning at a temperature of about 230°C (445°F), a protective
film no longer develops in water or steam, and the reaction pro-
gresses rapidly until eventually all the aluminum exposed in these
media is converted into oxide. Special alloys containing iron and
nickel have been developed to retard this reaction, and these
alloys may be used up to a temperature of about 360°C (680°F)
without excessive attack [3].
Reflecting its amphoteric nature, and as illustrated in Figure 1,
aluminum corrodes under both acidic and alkaline conditions; in
the first case to yield trivalent Al 3+ ions, and in the second case
to yield A1O2 (aluminate) ions. There are a few exceptions, either
when the oxide film is not soluble in an acidic or alkaline solution,
or when it is maintained by the oxidizing nature of the solution.
Two exceptions, acetic acid and sodium disilicate, are shown in
Figure 2. Ammonium hydroxide above 30% concentration by weight,
nitric acid above 80% concentration by weight, and sulfuric acid
of 98 to 100% concentration are also exceptions.
1 1 1 1 1 i
2.5
a Acetic acid
b Hydrochloric acid
—
c Hydrofluoric acid —
2.0 k d Nitric acid (1
O
e Phosphoric acid If
1.5-- f Sulfuric acid 1
g Ammonium hydroxide \\
1 h Sodium carbonate /(
1.0- 1 j Sodium disilicate /i^-k
C
1 k Sodium hydroxide / p
o b
l 1
8 0.5
* f
8 10 12 14
pH
FIGURE 2 Relation to pH of the corrosivities of various chemical

solutions toward 1100-H14 alloy sheet.
ELECTROCHEMICAL ASPECTS OF THE

CORROSION OF ALUMINUM
As with other metals, corrosion of aluminum is controlled by the

electrochemical relation of an anodic reaction (oxidation) that leads
to metallic dissolution and a cathodic reaction (reduction) of environ-
mental species, that does not. The intersection at which the anodic
reaction occurs in aluminum and, thus, leads to its corrosion, is
shown in Figure 3. The anodic polarization curve shown is typical
for aluminum and its alloys when they are polarized anodically in
an electrolyte free of a readily available cathodic reactant (e.g.,
in a deaerated electrolyte), whereas the polarization curves for
the cathodic reactions are only schematic. The corrosion current
developed by the two reactions (which determines the rate of corro-
sion of the aluminum) is indicated by the intersection of the anodic
polarization curve for aluminum with one of the cathodic polarization
curves. Aluminum and its alloys do not corrode in the reverse event,
in which only a cathodic reaction occurs, either because of coupling
to a more anodic metal or because of polarization cathodically by
means of a current impressed on them from a rectifier or other
external source.
Aluminum may corrode because of defects in its protective oxide
film. Resistance to corrosion improves considerably as purity is
increased, but the oxide film on even the purest aluminum still
contains a few defects where minute corrosion can develop. In less-
pure aluminums of the 1XXX series and in aluminum alloys, the
presence of second phases becomes the more important factor.
CATHODIC
t
POTE NTIA L, VOLTS
—^ Ep "
J
/
ANODIC REACTION
CATHODIC REACTION
ANODIC
110"-8 i
10,-7 10"
i i
10"
CURRENT DENSITY, A / m m 2
FIGURE 3 Typical anodic polarization curve (solid lines) for an

aluminum alloy in an electrolyte free of a readily available cathodic
reactant (commonly oxygen); Ep is the pitting potential of the alloy.
The intersection of the curve with one of the cathodic polarization
curves (schematic) determines the corrosion current on an alloy.
[From Hollingsworth, E. H. and Hunsicker, H. Y. (1979). Corrosion
resistance of aluminum alloys. Metals Handbook; Properties and
Selection; Non-Ferrous and Pure Metals, Vol. 2, 9th ed. (D. Benja-
min, e d . ) , American Society for Metals, Metals Park, Ohio, p . 205.]
164 Hoilingswor'th, Hunsicker, and Schweitzer
These phases are present as an insoluble constituent of intermetallic

compounds produced primarily from iron, silicon, and other impurities,
and a smaller precipitate of compounds produced primarily from
soluble alloying elements. Most of the phases are cathodic to aluminum,
but a few are anodic. In either circumstance, they produce galvanic
cells because of the potential difference between them and the alumi-
num matrix.
Pitting Corrosion
Any corrosion of aluminum in the pH range at which it is passive
may be of the pitting type, as with other passive metals. Corrosion
of this type is produced most commonly by halide ions, of which
chloride is the one most frequently encountered in service.
Whether or not pitting develops in aluminum depends on whether
or not it is polarized to its pitting potential [4], As shown in
Figure 3, this potential corresponds to the plateau in the anodic
polarization curve for aluminum. Pitting develops in aluminum only
when it is polarized to, or above, its pitting potential; when it
is not, pitting does not develop. Aluminum may develop pitting
in aerated solutions of halides simply because the reactions occurring
on its cathodic regions are sufficient to polarize it to its pitting
potential, as reflected by the development of an electrode potential
that is equal to the pitting potential upon immersion in the solutions.
Conversely, aluminum does not develop pitting in solutions of most
other salts because the reactions occurring on its cathodic regions
in these solutions are not sufficient to polarize it to its pitting
potential.
Invariably, the development of pitting can be prevented by
removal of the reducible species required for a cathodic reaction.
In neutral solutions, this species is usually oxygen. Thus, its
removal by deaeration will prevent the development of pitting in
aluminum even in most halide solutions because, in its absence,
the cathodic reactions are not sufficient to polarize aluminum to
its pitting potential.
Metallurgical structure has little effect on the pitting potential
of aluminum nor do second phases in the amounts present in its
alloys. Severe cold work makes the potential more anodic by a few
millivolts, and this change, although small, is sufficient to affect
the degree to which pitting develops (e.g., in a greater degree
of pitting on machined or sheared edges) [5].
Pitting of aluminum diminishes with either increasing acidity
or with alkalinity beyond its passive range, and corrosion attack
becomes more nearly uniform.
Small pits will occur in polluted outdoor atmospheres, pits that

are almost invisible to the naked eye. During the first few years
of exposure, the growth is relatively rapid, but it eventually stops,
and it seldom exceeds 200 \im. Although these pits have no effect
on the mechanical strength of the structure, the bright appearance
of the surface is gradually replaced by the gray patina of corrosion
products. In areas where quantities of soot are present, the soot
will become absorbed by the corrosion products and the patina
will become dark. Exterior portions of buildings, when exposed
to rain, will generally age uniformly, but sections sheltered from
the washing action of the rain will corrode and produce an uneven
gray discoloration. This condition can be prevented by regularly
washing these sections.
Galvanic Relations
Table 6 is a galvanic series of aluminum alloys and other metals
representative of their electrochemical behavior in seawater and
in most natural waters and atmospheres. Figure 4 shows the effect
of alloying elements in determining the position of aluminum alloys
in the series; these elements, primarily copper and zinc, affect
electrode potential only when they are in solid solution.
As is evident in Table 6, aluminum (and its alloys) becomes
the anode in galvanic cells with most metals and corrodes sacrificially
to protect them. Only magnesium and zinc are more anodic and
corrode to protect aluminum. Because they have nearly the same
electrode potential, neither aluminum nor cadmium corrodes sacrifi-
cially in a galvanic cell.
The degree to which aluminum corrodes when coupled to a more
cathodic metal depends on the degree to which it is polarized in
the galvanic cell. It is especially important to avoid contact with
a more cathodic metal where aluminum is polarized to its pitting
potential because, as is evident in Figure 3, a small increase in
potential produces a large increase in corrosion current. In particu-
lar, contact with copper and its alloys should be avoided because
of the low degree of polarization of these metals. In atmospheric
and other mild environments, aluminum may be used in contact
with chromium and stainless steel with only slight acceleration of
corrosion; in these environments, the two metals polarize highly
so that the additional corrosion current impressed onto aluminum
with them in a galvanic cell is small.
To minimize corrosion of aluminum in contact with other metals,
the ratio of the exposed area of aluminum to that of the more cathodic
metal should be kept as high as possible (because such a ratio
reduces the current density on the aluminum). Paints and other
TABLE 6 Electrode Potentials of Representative Aluminum Alloys

and Other Metalsa
Aluminum alloy or other metal*3 Potential (V)
Chromium +0.18 to -0.40

Nickel -0.07
Silver -0.08
Stainless steel (300 series) -0.09
Copper -0.20
Tin -0.49
Lead -0.55
Mild carbon steel -0.58
2219-T3, T4 -0.64 c
2024-T3, T4 -0.69 c
295.O-T4 (SC or PM) -0.70
295.O-T6 (SC or PM) -0.71
2014-T6, 355.O-T4 (SC or PM) -0.78
355.O-T6 (SC or PM) -0.79
2219-T6, 6061-T4 -0.80
2024-T6 -0.81
2219-T8, 2024-T8, 356.O-T6 (SC or PM),
443.0-F (PM), cadmium -0.82
1100, 3003, 6061-T6, 6063-T6, 7075-T6, c
443.0-F (SC) -0.83
1060, 1350, 3004, 7050-T73, c 7075-T73c -0.84
5052, 5086 -0.85
5454 -0.86
5456, 5083 -0.87
7072 -0.96
Zinc -1.10
Magnesium -1.73
a
Measured in an aqueous solution of 53 g of NaCl and 3 g of H2O2
per liter at 25°C; 0.1 N calomel reference electrode.
^The potential of an aluminum alloy is the same in all tempers wher-
ever the temper is not designated.
c
The potential varies ±0.01 to 0.02 V with quenching rate.
-0.66
Sol:53 g/l NaCI + 3 g/l H 2 O 2
IN EXCESS OF
SOLID SOLUTION
I
2 3 4 5 6 7 8
ADDED ELEMENT, WT %
FIGURE 4 Effect of alloying elements on the electrode potential

of aluminum.
coatings for this purpose may be applied to both the aluminum and
the cathodic metal, or to the cathodic metal alone. But they should
never be applied to only the aluminum because of the difficulty in
applying and maintaining them free of defects.
Galvanic corrosion of aluminum by more cathodic metals in solu-
tions of nonhalide salts is usually less than in solutions of halide
ones because the aluminum is less likely to be polarized to its pitting
potential. In any solution, galvanic corrosion is reduced by removal
of the cathodic reactant. Thus, the corrosion rate of aluminum
coupled to copper in seawater is reduced greatly when the seawater

is deaerated. In closed multimetallic systems, the rate, even though
it may be high initially, decreases to a low value whenever the
cathodic reactant is depleted. Galvanic corrosion is also low where
the electrical resistivity is low, as in high-purity water.
Some semiconductors, such as graphite and magnetite, are
cathodic to aluminum, and in contact with them, aluminum corrodes
sacrificially.
Reduction of Ions of Other Metals by Aluminum

Aluminum reduces ions of many metals, of which copper, cobalt,
lead, mercury, nickel, and tin are the ones encountered most
commonly. Not only is a chemical equivalent of aluminum oxidized
for each equivalent of ion reduced, but galvanic cells are also set
up because the metal reduced from the ions plates onto the aluminum.
Reducible metallic ions are of most concern in acidic solutions;
in alkaline solutions they are of less concern because of their greatly
reduced solubilities.
Ions of copper are encountered most frequently in applications
of aluminum; a common source in weathering is runoff from copper
products upstream (e.g., rainwater entering aluminum gutters from
roofs with copper flashing). The threshold concentration generally
accepted for reduction of copper ion by aluminum is 0.02 ppm.
The resistance to corrosion of aluminum alloys is impaired by the
presence of more than about 0.25% copper as an alloying element
because the alloys reduce the copper ions in any corrosion product
from them.
Aluminum reduces ions of ferric iron, but these ions are not
encountered frequently because of their reaction with oxygen and
water to form insoluble oxides and hydroxides of iron. The most
anodic aluminum alloys reduce ions of ferrous iron, but these ions
also are not encountered frequently because they exist only in
deaerated or other solutions free of oxidizing agents [6].
Mercury, whether reduced from its ions or introduced directly
in the metallic form, can be severely damaging to aluminum whenever
stress is present, as shown in Figure 5. The effect is caused by
amalgamation of mercury with aluminum which, once initiated, pro-
gresses for long periods because the aluminum in the amalgam oxidizes
immediately in the presence of water so that the mercury is continu-
ously regenerated. A "safe" level of mercury is difficult to determine
because of the difficulty in initiating attack of aluminum by mercury.
Any concentration in a solution of more than a few parts per billion,
however, should be viewed with suspicion—and in an atmosphere
where attack initiates less readily, that is any concentration exceed-
FIGURE 5 Cracking of a welded "cruciform" specimen of 5083-H131

alloy plate by mercury brought into contact with the plate only
within the circled region. [From Hollingsworth, E. H., and Hun-
sicker, H. Y. (1979). Corrosion resistance of aluminum and aluminum
alloys. Metals Handbook; Properties and Selection; Non-Ferrous
and Pure Metals, Vol. 2, 9th ed. (D. Benjamin, e d . ) , American
Society for Metals, Metals Park, Ohio, p . 212.]
ing that allowed by Environmental Protection Agency (EPA) regula-

tions. No amount of metallic mercury should ever be allowed to
come into contact with aluminum [7].
Alclad Products
Alclad products consist of a core alloy and a more anodic cladding
alloy, usually representing 10% or less of the total thickness,
metallurgically bonded to one or both surfaces of the core alloy.
Because of the cathodic protection afforded the core by the cladding,
any corrosion progresses only to the cladding/core interface and
then spreads laterally. Alclad products are used extensively where
perforation of a product cannot be tolerated, especially in thinner
ones where it is most likely to develop.
STRESS-CORROSION CRACKING
Only aluminum alloys with appreciable amounts of soluble alloying

elements of copper, magnesium, silicon, and zinc are subject to
stress-corrosion cracking [8]. In aluminum alloys, this cracking
characteristically is intergranular. According to the electrochemical
theory, the requisite for the development of stress-corrosion cracking
is a condition along grain and other boundaries that makes them
anodic to the rest of the microstructure so that corrosion propagates
selectively along them [9]. This condition may be produced whenever
dissolved alloying elements precipitate along grain boundaries and
deplete the regions adjacent to them of these elements. Resistance
to stress-corrosion cracking in aluminum alloys subject to this process
is achieved by metallurgical treatment, either to prevent or minimize
decomposition of solid solution, or more commonly, to produce it
uniformly throughout the microstructure.
Research more than 40 years ago demonstrated inadequacies
in the electrochemical theory of stress-corrosion cracking, and
the complex interaction of the factors related to the stress-corrosion
cracking of aluminum alloys is not yet fully understood [10]. Re-
search in recent years has been directed toward establishing a
possible effect of atomic hydrogen produced by the reaction of
aluminum with water or its vapor, but the results are inconclusive
[11]. Despite this and other more recent research, there is still
general agreement that one factor in the stress-corrosion cracking
of aluminum alloys in aqueous solutions is electrochemical. Strong
evidence is provided by the fact that the process can be retarded
greatly, if not eliminated completely, by cathodic protection.
Metallurgical treatment that improves resistance to stress-

corrosion cracking also improves resistance to intergranular corrosion,
but the optimum treatments for the two processes usually are not
the same. Thus, resistance to intergranular attack usually is not
a satisfactory criterion for predicting resistance to stress-corrosion
cracking. Resistance to this corrosion also cannot be reliably pre-
dicted from an examination of microstructure, even though progres-
sive changes resulting from decomposition of solid solution may be
observed as an alloy is treated to improve its resistance to stress-
corrosion cracking.
Factors Affecting Resistance to Stress-Corrosion Cracking

As with other metals, stress-corrosion cracking of an aluminum
alloy in a susceptible temper is determined by the magnitude and
duration of a tensile stress acting on its surface. In most wrought
alloys, it is also determined by the direction of stressing, as shown
in Figure 6. The effect of stressing in different directions is caused
by the highly directional grain structure (Fig. 7) that is typical
of many wrought products [12]. As evident in these figures, resist-
MINIMUM LONG TRANS. Y . S . FOR 3 IN THICK PLATE
LONGITUDINAL;
0 90
DAYS TO FAILURE ( 3 . 5 % NaCI ALTERNATE IMMERSION)
FIGURE 6 Effect of testing direction on the resistance to stress-

corrosion cracking of 7075-T651 alloy plate. The bands indicate
the range of values for the numerous specimens tested in the three
principal directions. (From Ref. 12.)
100/im
FIGURE 7 Composite micrograph of the three-dimensional grain

structure of 38-mm thick 7075-T6 alloy plate.
ance to stress-corrosion cracking is highest for stressing parallel

to the direction of elongation of grains (longitudinal) and lowest
for stressing across the minimum thickness of grains (short trans-
verse). Thus, in wrought alloys with an elongated grain structure,
and in products thick enough for stressing in all directions, resist-
ance to stress-corrosion cracking in the short transverse direction
may be the controlling factor in applications of the alloys.
Directions of stressing usually has little effect on casting alloys
because the grains in these alloys are equiaxed.
The "threshold" values indicated by curves of the type in
Figure 6 provide valid comparisons of the relative susceptibilities
of aluminum alloys to stress-corrosion cracking only under the con-
ditions of a specific environment and test procedure. They may
not be valid, therefore, for other conditions.
Water or water vapor is a requisite for the stress-corrosion

cracking of aluminum alloys and, in its absence, cracking does
not occur. Among species that accelerate cracking further, halides
have the greatest effect [10].
Alloys and Tempers

Wrought alloys of the 2XXX, 5XXX, 6XXX, and 7XXX series contain
soluble alloying elements in amounts sufficient to make them subject
to stress-corrosion cracking. Stress-corrosion cracking can be pro-
duced in 6XXX series alloys by special treatment, but cracking
in commercial alloys has never been reported. For alloys of the
other three series, tempers providing a high to very high resistance
to stress-corrosion cracking (Table 7) have been developed.
In naturally aged T3 and T4 tempers, thicker products of alloys
of the heat-treatable 2XXX series have a low resistance in the short
transverse direction, reflecting localized decomposition of solid solu-
tion during quenching. Heating all products of the alloys in these
tempers for short periods may impair resistance. Heating for longer
periods improves resistance, with the artificial-aging treatment
for the T6 temper producing an intermediate to very high resistance
in the short transverse direction, and that for the T8 temper, a
high to very high resistance.
The same sequence holds for heat-treatable alloys of the 7XXX
series that contain copper as an alloying element. Resistance improves
progressively with the severity of artificial aging, in the order of
T6, T76, and T73 tempers, with the last temper being practically
TABLE 7 Relative Stress-Corrosion Ratings
Rating Explanation
Very high Stress-corrosion cracking highly unlikely

High Stress-corrosion cracking unlikely at sustained
tensile stresses not exceeding 50% of the minimum
yield strength specified for the alloy
Intermediate Stress-corrosion cracking unlikely at sustained
tensile stresses not exceeding 25% of the minimum
yield strength specified for the alloy
Low Stress-corrosion cracking likely at any sustained
tensile stress in the most susceptible direction
of an alloy
ft** * ***** c*i'.
••- ^ V - ^ •• ' . . _ .;
(b)
FIGURE 8 Microstructure of annealed 5083 alloy plate that was

(a) first stretched 1% and (b) then heated 40 days at 12l°C (250° F)
(original magnification 500X).
immune to stress-corrosion cracking. The improvement is accompanied

by a decrease in strength in the same order. Alloys of this series
without copper do not respond as well to artificial aging, and resist-
ance is produced only by special heat-treating practices.
Although not heat treatable in the usual sense, alloys of the
5XXX series in most tempers do contain magnesium in a supersaturated
solid solution that may decompose selectively along boundaries and
result in susceptibility to stress-corrosion cracking. Except under
rare conditions, significant decomposition does not develop in alloys
with less than about 3% magnesium. Decomposition in alloys with
more magnesium depends on the magnesium content, the period
and temperature of exposure, and especially on the degree of a
strain hardening, as shown in Figure 8. In strain-hardened tempers
subject to such decomposition selectively along boundaries, these
alloys may develop susceptibility to stress-corrosion cracking after
long periods at ambient temperature or shorter ones at elevated
temperatures. In annealed and other strain-hardened tempers where
appreciable decomposition of solid solution has been produced uni-
formly throughout the microstructure, the alloys do not develop
susceptibility after long periods at ambient or slightly elevated
temperatures.
Stress-corrosion cracking of casting alloys in service has occurred
only in those of the Al-Mg and Al-Zn-Mg types with large amounts
of soluble alloying elements to produce the highest strength.
EXFOLIATION CORROSION
In certain tempers, wrought products of some aluminum alloys are

subject to exfoliation corrosion which causes a leafing or delamination
of the products (Fig. 9). This type of corrosion develops in products
that have a pronounced directional structure, similar to that in
Figure 9, in which grains are elongated highly and thin relative
to their length and width. Alloys of the 2XXX, 5XXX, and 7XXX
series are those most prone to exfoliation corrosion. In alloys of
this series, both exfoliation corrosion and stress-corrosion cracking
are associated with decomposition of solid solution selectively along
boundaries. Thus, metallurgical treatment that improves resistance
to stress-corrosion cracking also improves that to exfoliation corro-
sion, but resistance to exfoliation corrosion usually is achieved
first. As with stress-corrosion cracking, resistance to inter granular
attack usually is not a satisfactory criterion for predicting resistance
to exfoliation corrosion.
Exfoliation corrosion is infrequent and less severe in wrought
alloys of the non-heat-treatable type.
**-* • Vfc ~&* — > t "
-rv* '
FIGURE 9 Exfoliation corrosion in 7178-T651 alloy plate exposed

in a seacoast environment (original magnification 100X).
OTHER TYPES OF CORROSION
The fatigue strength of aluminum alloys is lower in a corrosive

medium than in a noncorrosive one, especially under low stresses
for longer periods. As shown in Figure 10, the effect is less for
the more-corrosion-resistant alloys (5XXX and 6XXX series) than
for the less-corrosion-resistant ones (2XXX and 7XXX series).
In contrast to stress-corrosion cracking, corrosion fatigue is not
affected much by a directional grain structure and the fracture
is predominantly transgranular.
Reflecting their greater hardness, high-strength aluminum alloys
have the highest resistance to cavitation and other types of erosion
in a noncorrosive medium when the only action is mechanical. In
a corrosive medium, such as seawater, however, more-corrosion-
resistant, lower-strength alloys may have a higher resistance be-
cause, as with fatigue, the effect of such a medium is less for
those alloys.
As with other metals, although to a smaller extent than with
some, corrosion of aluminum alloys may be promoted by conditions
that develop concentration cells, most commonly those in which
a galvanic current is produced by a difference in the concentration
of oxygen. These conditions are developed most frequently by
0.7
MINIMUM STRESS
R = 0
~ MAXIMUM STRESS -°
FREQUENCY- 1100 cpm
0.6 NaCI
§ 0.5
:£ 0.4
II
". 0.3
0.2
0.1
0.0
5086 5086 6061 7075 2024
H34 -H36 -T6 -T73 -T3
FIGURE 10 Axial-stress fatigue strengths of aluminum alloy sheet

in air and seawater<
crevices in wet mechanical joints, but they may also be developed

by contact with wet porous or fibrous materials, even though the
materials themselves may be inert. In milder environments, the
corrosion produced by such conditions usually is slight. In more
corrosive environments, these conditions should be avoided, insofar
as possible, and where not possible, protective measures, such
as painting and sealing, should be used.
Corrosion of aluminum alloys may also be promoted by contact
with wet materials (e.g., certain types of insulation) that produce
leaches more alkaline than a pH of about 9. Alkalinity sufficient
to cause corrosion may also be produced by the application of an
excessively high current in the cathodic protection of aluminum
alloys because the usual cathodic reaction occurring on the alloys
(reduction of oxygen) produces hydroxyl ions.
WELDED, BRAZED, AND SOLDERED JOINTS
The resistance to corrosion of weldments in aluminum alloys is affected

by the alloy welded and by the filler alloy and welding process used
[14]. Galvanic cells that cause corrosion may be created because of
potential differences among the parent alloy, the filler alloy, and
the heat-affected regions where microstructural changes have been
produced. Incomplete removal of fluxes after welding with processes
using them may also cause corrosion.
Weldments in non-heat-treatable alloys generally have a good
resistance to corrosion. Microstructural changes in the heat-affected
region in these alloys have little effect on potential, and the filler
alloys recommended have potentials close to those of the parent
alloys. In some heat-treatable alloys, however, the effect on potential
of microstructural changes may be large enough to cause appreciable
corrosion in more aggressive environments; the corrosion is selective,
either in the weld bead or in a restricted portion of the heat-affected
region. To a considerable degree, the effect on corrosion of micro-
structural changes in the heat-affected zone can be eliminated by
postweld heat treatment.
Stress-corrosion cracking in weldments subject to this process
usually is caused by residual stresses introduced during welding,
but its occurrence is rare. Stresses sufficient to cause cracking
can be avoided by the use of welding procedures that minimize
restraint of the alloy being welded.
Brazed joints in aluminum alloys also have a good resistance
to corrosion. Excessive corrosion usually is caused by fluxes from
processes using them that are not removed completely or that are
removed by a treatment that, together with the fluxes, may cause
corrosion.
Soldered joints have a resistance to corrosion satisfactory for
applications in milder environments but not for those in more aggres-
sive ones.
WEATHERING
Except for those that contain copper as a major alloying element,

aluminum alloys have a high resistance to weathering in most atmos-
pheres, as demonstrated by their extensive use for architectural
applications in commercial, industrial, and residential buildings.
In many cases, paints and other coatings are applied to products
of the alloys to enhance appearance as well as to provide additional
protection, but in many others, they are not.
As shown in Figure 11, the depth of attack during the weather-
ing of aluminum alloys characteristically decreases to a low rate
after the initial period of exposure. The loss in strength also
decreases in the same manner after the initial period, but not to
as low a rate. The difference is a consequence of the fact that
while older sites of attack tend to become inactive, newer ones
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54
0.20 i I I i i I I I I I I I
EXPOSURE TIME, YEARS
FIGURE 11 Weathering data for 1100, 3003, and 3004 alloys in

the industrial atmosphere at New Kensington, Pennsylvania (curves)
and at various other localities.
develop. The newer sites of attack decrease the cross-sectional

area on which strength depends and the average depth of attack
but not the maximum depth.
This "self-limiting" characteristic of corrosive attack during
weathering is also typical of the behavior of aluminum alloys in
many other environments. The characteristic, therefore, should
always be appreciated whenever data from exposure tests of short
duration are used to predict long-time performance. Many times,
long-time performance will be much better than predicted from short-
duration data.
Numerous weathering data for aluminum alloys exposed at locations
throughout the world have been published [15,16].
WATERS
The more resistant aluminum alloys, such as wrought alloys of the

1XXX, 3XXX, and 5XXX series, have an excellent resistance to
corrosion by high-purity water [16]. A slight reaction takes place
when the alloys are first exposed to the water, but it decreases
to a low rate within a few days upon formation of a protective oxide
film of equilibrium thickness on the alloys; pickup of aluminum by
180 H oiling sw or th, Hunsicker, and Schweitzer
water then becomes negligible. Resistance of the alloys is not affected

significantly by carbon dioxide and oxygen dissolved in the water
or by the chemicals added to it to minimize corrosion of steel because
of the presence of these gases.
The same types of alloys are also resistant to many natural
waters [16]. In general, resistance is higher in neutral or slightly
alkaline waters, and less in acidic ones, especially if they also
contain ions of reducible metals such as copper; other factors affect-
ing resistance were described earlier. Correlations of the compositions
of various waters with their corrosivities to aluminum alloys have
been developed, but none predict the corrosivities of other waters
with dependability [17].
Numerous worldwide exposure tests demonstrate the high resist-
ance of the same alloys to seawater, as does service experience
in pipelines, structures, ships, and other marine applications [16,
18]. Corrosion of aluminum alloys in seawater is mainly the pitting
type, as would be expected from its salinity and enough dissolved
oxygen as a cathodic reactant to polarize the alloys to their pitting
potentials. Rates of pitting usually range from 3-6 ym/yr during
the first year and from 0.8-1.5 ym/yr averaged over a 10-year
period; the lower rate for the longer period reflects the tendency
for older pits to become inactive. General corrosion is minimal,
with the total loss in thickness usually amounting to only a fraction
of the depth of pitting.
The corrosion behavior of aluminum alloys in deep seawater,
judging from tests at 1.6 km, is generally the same as at the surface,
except that the effect of crevices is greater [19].
Among wrought alloys, those of the 5XXX series have the highest
resistance to seawater, and considering their other desirable charac-
teristics, they are used most widely for marine applications. Among
casting alloys, those of the 356.0 and 514.0 types are used exten-
sively for marine applications.
CATHODIC PROTECTION
Pitting of aluminum structures in water can be guarded against

by providing cathodic protection. In seawater, zinc sacrificial anodes
can be used, whereas magnesium anodes are recommended for use
in fresh- or brackish waters. The latter are also used to protect
unpainted surfaces underground.
FOODS
The widespread usage of the more-corrosion-resistant aluminum

alloys for household cooking utensils attests to their compatibility
with most foods, as does their extensive use for the commercial
handling and processing of foods. Sometimes, unsatisfactory perform-
ance is caused by the use of improper cleaners, rather than by
incompatibility with the foods themselves. Because they may cause
excessive corrosion, alkaline cleaners should not be used for aluminum
equipment unless they are inhibited.
Large quantities of aluminums and aluminum alloys such as foil,
foil laminated to plastics, and cans, are used for the packaging
of foods and beverages. Most cans for beverages, both those of
all-aluminum construction and those with steel bodies, have easy-open
ends of aluminum. For most applications, lacquers and plastically
laminated coatings are applied to the alloys because only the minutest
corrosion can be tolerated in view of the long periods of exposure,
the effect of corrosion on the food packaged, and the thinness
of the container.
CHEMICALS
Aluminum alloys that do not contain copper as a major alloying ele-

ment have high resistance to corrosion by many chemicals, and
they are used extensively in the chemical process industry.
The resistance of aluminum alloys to corrosion by a large number
of chemicals, representative of practically all classifications, has
been established in laboratory tests and, usually, by service experi-
ence as well. Data are readily available from handbooks, from company
literature, and from publications by trade organizations. Aluminum
and Foods, published by the Aluminum Association, is especially
useful [20].
Aluminum alloys are compatible with dry salts of most inorganic
salts and, within their passive range of pH 4 to 9, with aqueous
solutions of many of them. Corrosion of the pitting type is produced
by aqueous solutions, mostly of halide salts, under conditions at
which the alloys are polarized to their pitting potentials, but not
in most other solutions where conditions that polarize the alloys
to these potentials are less likely.
Aluminum alloys are not suitable for most inorganic acids, bases,
and salts with a pH outside the passive range of the alloys, as
shown in Figure 2 and as described earlier.
Aluminum alloys are resistant to a wide variety of organic com-
pounds, including most aldehydes, esters, ethers, hydrocarbons,
ketones, mercaptans, and other sulfur-containing compounds, and
nitro compounds. They are also resistant to most acids, alcohols,
and phenols, except when these compounds are nearly dry and
near their boiling points; carbon tetrachloride also exhibits the
same behavior. As shown by the data for phenol in Figure 12,
which are typical of the behavior, corrosion is prevented by the
4X10"
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TEMPERATURE, °C
FIGURE 12 Resistance to corrosion of 1100-H14 alloy sheet to phenol.

Note that no corrosion occurred in a closed vessel from which evapo-
ration of water was prevented.
presence of a trace of water, which appears to be needed to maintain

a protective oxide film on the alloys. The degree of dryness required
for such corrosion is difficult to obtain in lower-molecular-weight
compounds.
Conditions to ensure safety should be established before aluminum
alloys are used with halogenated organic compounds. Under most
conditions, especially at ambient temperature, the alloys are resistant
to these compounds, but under certain others, they may react rapidly
with some of them; under some conditions, especially when the
alloys are finely divided, a violent reaction may occur. If water
is present, the compounds may hydrolyze to produce mineral acids
that, in turn, may corrode the alloys to produce aluminum halides
that can act as a catalyst for reactions of the organic compounds
themselves; highly reactive aluminum alkyls occasionally may be

formed. These reactions, once initiated, may also become autocata-
lytic.
Aluminum alloys are most resistant to organic compounds haloge-
nated with fluorine, followed in order of decreasing resistance with
those of chlorine, bromine, and iodine. They are resistant to highly
polymerized compounds, reflecting the high degree of stability of
these compounds.
It is also important to recognize that the compatibility of aluminum
alloys with mixtures of organic compounds cannot always be predicted
from their compatibility with each of the compounds. For example,
some aluminum alloys are corroded severely in mixtures of carbon
tetrachloride and methyl alcohol, even though they are resistant
to each compound alone. Caution also should be exercised in using
data for pure organic compounds to predict performances of the
alloys with commercial grades that may contain contaminants. Ions
of halides and reducible metals, commonly chloride and copper,
frequently have been found to be the cause of excessive corrosion
of aluminum alloys in commercial grades of organic chemicals that
would not have been predicted from their resistance to the pure
chemicals.
COATINGS
Paints and other coatings are applied to aluminum alloys for decora-
tive purposes as well as to provide protection [14], Almost any
type of paint for metals (acrylic, alkyl, polyester, vinyl, etc.)
is suitable; the performance of a particular paint, when applied
properly, is better than that on steel. As with any metal, surface
preparation is important. Conversion coatings, either of the chromate
or phosphate type are recommended for the preparation of aluminum
alloys. For milder environments, the paint may be applied onto
the conversion coating; for more aggressive environments such
as those with chlorides, a chromated primer should be applied first.
Aluminum alloys are especially amenable to water-based paints,
which are being used increasingly because of environmental considera-
tions. Many products precoated in a variety of colors for agricultural,
industrial, and residential applications are available commercially.
Although more expensive, and restricted to in-plant application,
anodized coatings provide excellent protection to aluminum alloys
[14]. They also are sometimes used as a base for paints. The many
monumental buildings with outer walls of anodized aluminum alloys
attest to the durability of the coatings in weathering. Anodized
coatings also provide a variety of colorations, most commonly shades

of gray and bronze, produced by selection of both alloy and anodiz-
ing process.
The coatings are produced by an electrolytic process in which
the surface of an alloy made the anode is converted to aluminum
oxide, bound as tenaciously to the alloy as the natural oxide film,
but much thicker. The thickness of coatings to provide resistance
to corrosion ranges from 5 to 30 ym; little or no additional protection
is provided by thicker coatings.
Although many electrolytes have been used to treat aluminum,
most of the processes are based on four solutions
Sulfuric acid
Chromic acid
Boric acid
Oxalic acid
Of the four, the most widely used is the solution based on sulfuric
acid. This process for anodization of aluminum had continued accept-
ance since it was patented in 1937. The hard, protective anodic
coating is clear and transparent on pure aluminum, but serves
as a good base for dyeing. For maximum corrosion resistance the
coating must be sealed. Nickel or cobalt acetate solutions provide
excellent sealing media. Coatings produced in sulfuric acid are
highly recommended for the protection of electropolished surfaces
for which retention of reflectivity is important.
This process is not recommended for configurations containing
joints or dead spots that can trap the electrolyte when removed
from the bath. Such areas will become sites for corrosion.
Chromic acid anodizing is the only process that can safely be
used on fabrications containing joints, blind holes, or other difficult -
to-rinse areas. Although sulfuric acid anodizing tends to reduce
fatigue strength of the metal, chromic acid anodizing increases
the fatigue strength. In general, the coatings produced by this
process tend to be relatively unattractive when compared with those
produced by the sulfuric acid process. They are opaque, gray,
or iridescent. Colorless or transparent coatings are possible when
0.03% sulfate is present. Because these coatings have little porosity
and are thin they are difficult to dye.
This process is used extensively in the aircraft industry. A
unique application employs the chromic acid electrolyte to detect
cracks in propeller blades. The acid seeps into the crack, permitting
observation of the defect after anodizing.
The primary application of boric acid electrolytes is in the form-
ing of thin dielectric films on electrolytic condensers, which are
essentially nonporous. Coatings produced by the oxalic acid process

are harder and more abrasion-resistant than those produced by
the conventional sulfuric acid process, but they are not as hard
as those specially produced under certain conditions in the sulfuric
acid process.
The coatings produced from the oxalic acid electrolytes are
usually yellow and are used both for decorative and protective
purposes.
As with the alloys themselves, anodized coatings are not resistant
to most environments with a pH outside the range 4 to 9. Within
this range, the resistance to corrosion may be improved by an
order of magnitude or more; in atmospheric weathering tests, the
number of pits that developed in the base metal was found to de-
crease exponentially with the thickness of coating. As a general
rule, however, anodized coatings do not provide protection sufficient
to make aluminum alloys suitable for environments where, without
the coatings, the alloys themselves are unsuitable because of their
inherently poor resistance in them.
REFERENCES
1. New aluminum smelting process (1973). Light Metal Age 31:8.

2. Pourbaix, M. (1966). Atlas of Electrochemical Equilibria in
Aqueous Solutions. Pergamon Press, New York.
3. Brown, M. H., Brown, R. H., and Binger, W. W. (1960).
Aluminum alloys for handling high temperature water. High
Purity Water Corrosion of Metals ( N . E . Hammer, e d . ) , P u b l .
No. 60-13, National Association of Corrosion Engineers, Houston,
p . 82.
4. Bohni, H., and Uhlig, H. H. (1969). Environmental factors
affecting the critical pitting potential of aluminum. J. Electrochem.
Soc. 116:906.
5. Mears, R. B . , and Brown, R. H. (1941). Causes of corrosion
currents. Ind. Eng. Chem. 33:1001.
6. Cook, E. H., and McGeary, F. L. (1964). Electrodeposition
of iron from aqueous solutions onto an aluminum alloy. Corrosion
20:llt.
7. Binger, W. W., Brown, R. H., and Brown, M. H. (1952).
Mercury and its compounds—a corrosion hazard. Corrosion 8:155.
8. Sprowls, D. O., and Brown, R. H. Stress-corrosion mechanisms
for aluminum alloys. Fundamental Aspects of Stress-Corrosion
Cracking (R. W. Staehle, A. J. Forty, and D. Van Rooyen,
e d s . ) , National Association of Corrosion Engineers, Houston,
p . 466.
9. Dix, E. H. J r . (1940). Acceleration of the rate of corrosion

by high constant stresses. Trans. AIME 137:11.
10. Spiedel, M. O. (1975). Stress corrosion cracking of aluminum
alloys. Metal Trans. A 6A:631.
11. Spiedel, M. O. (1974). Hydrogen embrittlement of aluminum
alloys. Hydrogen in Metals (L. M. Bertsein and A. W. Thompson,
e d s . ) , American Society for Metals, Metals Park, Ohio, p . 249.
12. Sprowls, D. O. (1976). High strength aluminum alloys with
improved resistance to corrosion and stress corrosion cracking.
Proceedings of the 1976 Tri-Service Conference on Corrosion
(S. J. Ketcham, e d . ) , The Naval Advisory Council on Materials,
Washington, p . 89.
13. ASTM (1979). Standard Method of Test for Exfoliation Corrosion
Susceptibility in 2XXX and 7XXX Series Aluminum Alloys (EXCO
Test), Standard Test Procedure G34-39, Annual Book of ASTM
Standards, Part 10, American Society for Testing and Materials,
Philadelphia.
14. Van Horn, K. R. (ed.) (1967). Aluminum Vol. Ill: Fabrication
and Finishing, American Society for Metals, Metals Park, Ohio.
15. Boyd, W. K., and Fink, F. W. (1974). Corrosion of Metals
in the Atmosphere, Rep. MCIC, Battelle Laboratories, Columbus,
Ohio.
16. Goddard, H. P . , Jepson, W. B . , Bothwell, M. R., and Kane,
R. L. (1967). The Corrosion of Light Metals. Wiley and Sons,
New York.
17. Pathak, B. R., and Goddard, H. P. (1968). Equations for
predicting the corrosivity of natural waters to aluminum. Nature
215:893.
18. Boyd, W. K., and Fink, F. W. (1975, 1978). Corrosion of Metals
in Marine Environments, Rep. MCIC-75-245R, Battelle Labora-
tories, Columbus, Ohio, Rep. MCIC-78-37.
19. Reinhart, F. M. (1976). Corrosion of Metals and Alloys in the
Deep Ocean, Rep. R834, U.S. Naval Engineering Laboratory,
Port Hueneme, Calif.
20. The Aluminum Association. (1975). Aluminum with Food and
Chemicals, 3rd e d . , Washington, D.C.
SUGGESTED READING
Hollingsworth, E. H., and Hunsicker, H. Y. (1979). Corrosion

resistance of aluminum and aluminum alloys. Metals Handbook;
Properties and Selection: NonFerrous Alloys and Pure Metals,
Vol. 2, 9th ed. (D. Benjamin, e d . ) , American Society for Metals,
Metals Park, Ohio.
10
TITANIUM
LOREN C. COVINGTON* Titanium Metals Corporation of America,

Henderson, Nevada
INTRODUCTION
Titanium is quite plentiful in the earth's crust, being the ninth most
abundant element. It is the fourth most abundant metal and is more
plentiful than chromium, nickel, or copper, which are commonly
employed in alloys used to resist corrosion. However, in spite of
early recognition of its light weight, strength, and corrosion resist-
ance, titanium metal is a relative newcomer to the industrial scene.
Commercialization of the Kroll process made titanium sponge avail-
able in about 1950. Aerospace requirements subsequently speeded
development of titanium as a structural metal. The industrial uses
for titanium developed more slowly at first. However, the lowering
of cost, the availability of product forms and new corrosion-resisting
alloys, coupled with the development of fabrication techniques,
have resulted in a rapidly expanding industrial market for titanium.
The industrial utilization of titanium results mainly from the
excellent corrosion resistance that this metal offers. The strength
properties of titanium alloys are also utilized, but to a smaller extent.
PROPERTIES OF TITANIUM
Alloys Available
The compositions of representative titanium grades, as covered
by American Society of Testing and Materials (ASTM) specifications,
* Retired.
187
00
00
TABLE 1 Chemical Composition of Titanium Alloys
Ti-50A a Ti-6Al-4V a Ti-Pd Ti-Code 12 a

Element (ASTM grade 2) (ASTM grade 5) (ASTM grade 7) (ASTM grade 12)
Nitrogen, max. 0.03 0.05 0.03 0.03

Carbon, max. 0.10 0.10 0.10 0.08
Hydrogen, max. 0.015 0.015 0.015 0.015
Iron, max. 0.30 0.40 0.30 0.30
Oxygen, max. 0.25 0.20 0.25 0.25
Aluminum — 5.5-6.75 — —
Vanadium — 3.5-4.5 — —
Palladium — — 0.12-0.25 —
Molybdenum — — — 0.2-0.4 o
Nickel — — — 0.6-0.9 o
Titanium Remainder Remainder Remainder Remainder
a
Timet designation.
o
00
o
10. Titanium 189
are given in Table 1. Unalloyed titanium, represented by ASTM

grade 2 in Table 1, is most often used for corrosion resistance.
Other unalloyed grades (ASTM grades 1, 3, and 4), containing
more or less iron and oxygen than grade 2, are available if better
formability or higher strength are required.
The titanium-palladium alloy (grade 7) offers improved corrosion
resistance compared with unalloyed titanium. This alloy, as grade 11,
is also available with low oxygen and iron content for improved
formability. Ti-Code 12 (ASTM grade 12), containing 0.8% nickel
and 0.3% molybdenum, is a recent Timet development, which is
a low-cost alternate for Ti-Pd for some applications. The Ti-6A1-4V
alloy (grade 5) is a general-purpose alloy, widely used in aerospace
applications that require higher strength or fatigue resistance.
The Ti-6A1-4V alloy, in general terms, has corrosion resistance
somewhat inferior to that of unalloyed titanium.
All of the alloys listed in Table 1 are available in various product
forms covered by the ASTM specifications listed in Table 2. Heat
exchanger tubing is most readily available as unalloyed titanium
(grade 2) and as the Ti-Code 12 (grade 12) and Ti-Pd (grade 7)
alloys.
The minimum room-temperature tensile properties for the various
titanium alloys, as defined by the ASTM specifications, are given
in Table 3. Strength and ductility, comparable with other corrosion-
resistant alloys, are available in titanium and its alloys. The Ti-Code
TABLE 2 ASTM Titanium Specifications
ASTM B 265-76 Titanium and Titanium alloy strip, sheet, and

plate
ASTM B 337-76 Seamless and welded titanium and titanium alloy
pipe
ASTM B 338-76 Seamless and welded titanium and titanium alloy
tubes for condensers and heat exchangers
ASTM B 348-76 Titanium and titanium alloy bars and billets
ASTM B 363-76 Seamless and welded unalloyed titanium welding
fittings
ASTM B 367-69 (1974) Titanium and titanium alloy castings
ASTM B 381-76 Titanium and titanium alloy forgings
190 Covington and Schweitzer
TABLE 3 Minimum Mechanical Properties of Annealed Titanium Alloys
Tensile 0.2% yield Elongation,

strength strength 2 in.
Alloy (ksi) (ksi) (%)
T1-50A (grade 2) 50 40 20
Ti-6A1-4V (grade 5) 130 120 10
Ti-Pd (grade 7) 50 40 20
Ti-Code 12 (grade 12) 70 50 18
12 alloy (grade 12) is seen to offer improved strength compared

with grade 2 or grade 7 titanium. Unfortunately, both of these
alloys have only moderate strength, which limits their application
in many industrial areas. A new heat-treatable alloy, Beta C, has
been developed. The heat treatment develops high strength and
a corrosion resistance comparable with grade 12. This alloy fills
a void in many applications.
Allowable stress values from the ASME Pressure Vessel Code
for titanium alloys as a function of temperature are given in Table 4.
The values for the Ti-Code 12 alloy (grade 12) are seen to fall off
less rapidly relative to unalloyed titanium (grade 2) and Ti-Pd
(grade 7) with increase in temperature. At 260°C (500°F), the
design stress for Ti-Code 12 (grade 12) is 70% greater than that
of grade 2 or grade 7. The Ti-6A1-4V alloy is not code-covered.
The effects of temperature on the strength, ductility, and tough-
ness of unalloyed titanium (grade 2) and annealed Ti-6A1-4V alloy
(grade 5) are shown in Figure 1. Titanium and its alloys maintain
excellent properties to low temperatures.
The fatigue properties of titanium are excellent. As shown in
Table 5, the fatigue strength/tensile strength ratio for titanium
and its alloys at ambient temperature is high, in the range 0.5
to 0.6. In addition, unlike many metals, the fatigue properties
of titanium are relatively unaffected by many corrosive media.
Cotton and Downing, for instance, have shown that the fatigue
limit of unalloyed titanium in distilled water or simulated seawater
was actually higher than that for air [1].
Physical Properties
Physical properties for titanium are given in Table 6. Titanium
is a light metal with a density slightly over half that of iron or
copper-based alloys. The modulus of elasticity of titanium is also
TABLE 4 Design Stresses for Titanium Plate a £*
2
For metal
temperatures Allowable stress values (ksi)
not exceeding Ti-50A Titanium Ti-Pd Ti-3A1-2.5V Ti-0.3MO-0.8Ni
(°F) (grade 2) (grade 3) (grade 7) (grade 9 ) c (grade 12) b
100 12.5 16.3 12.5 24.3 17.5

200 10.9 10.9 16.4
300 9.0 11.7 9.0 20.0 14.2
400 7.7 7.7 12.5
500 6.6 6.6 11.4
600 5.7 6.0 5.7 16.6
a
ASME Section VIII, Division 1-Pressure Vessels.
b
Case BC78-326.
c
Estimated values—grade 9 in the process of being qualified.
250
200
'150
100
50 02%
YIELD
STRENGTH
60
1
UNALLOYED
O 40
Ti ^*
% ELONGATION
S 20
Ti-6AI-4V
~""
u 0 • i i i i i i
-200 0 200 400 600

TEMPERATURE,°F
FIGURE 1 Effect of temperature on strength, ductility, and tough-
ness of unalloyed titanium (grade 2) and Ti-6A1-4V alloy (grade 5).
TABLE 5 Fatigue Strength of Titanium
Tensile strength Fatigue strength, Ratio

Alloy strength (ksi) 10% cycles (ksi) FS/TS
Unalloyed Ti 52.6 32.7 0.62

Unalloyed Ti 92.2 47.1 0.51
Ti-6A1-4V 140.7 85.5 0.60
Ti-6A1-4V 163.4 92.8 0.56
o
TABLE 6 Physical Properties of Titanium
Ti-50A Ti-6A1-4V Ti-Pd Ti-Code 12

Property (grade 2) (grade 5) (grade 7) (grade 12)
Modulus of elasticity, tension 14.9 16.5 14.9 15.0

(106 psi)
Modulus of elasticity, torsion 6.5 6.1 6.5 6.2
(106 psi)
Density (lb/in. 3 ) 0.163 0.160 0.163 0.164
Specific heat at 75°F 0.125 0.135 0.125 0.130
(BTU/lb °F)
Thermal conductivity at 75°F, 114 50 114 132
[BTU/(ft 2 )(hr°F)(in.)]
Coefficient of expansion, 32- 5.1 5.1 5.1 5.4
600°F (10"6 in./in. °F)
Electrical resistivity at 75°F 56 171 56.7 52
(]iQ-cm)
CO
CO
TABLE 7 Relative Costs-Titanium Alloy Plate
Relative costs a
Material 1 ft2 of 1/4-in. plate
Ti-50A (ASTM grade 2) 1.0

Ti-Code 12 (ASTM grade 12) 1.2
Ti-Pd (ASTM grade 7) 1.7
a
Ratio of base price of 1 ft 2 of alloy to that of Ti-50A (ASTM
grade 2).
about half that of steel. Specific heat and thermal conductivity

are similar to those of stainless steel. Titanium has a relatively
high electrical resistivity and low expansion coefficient. It is impor-
tant that these physical properties, particularly the modulus of
elasticity and coefficient of expansion, be carefully considered when
designing or fabricating process equipment of titanium.
Material Costs
Cost is always an important consideration when selecting a material.
Relative costs for titanium alloy plate are given in Table 7. Compared
with other materials, titanium is more costly than stainless steels
but less than nickel-based alloys. In many applications, titanium1 s
corrosion resistance permits it to be used without a corrosion allow-
ance. Thinner sections, coupled with decreased maintenance require-
ments and longer life expectancy in many applications, permit titanium
equipment installations to be cost-effective, despite a higher initial
cost.
Oxide Film
Titanium's corrosion resistance is due to a stable, protective, strongly
adherent oxide film that covers its surface. This film forms instantly
when a fresh surface is exposed to air or moisture. It is transparent
and not easily detected visually. A study of the corrosion resistance
of titanium is basically a study of the properties of the oxide film.
Additions of alloying elements to titanium affect corrosion resistance
because these elements alter the composition of the oxide film.
The oxide film on titanium, although very thin, is very stable
and is attacked by only a few substances, most notable of which
is hydrofluoric acid. Because of its strong affinity for oxygen,
10. Titanium 195
titanium is capable of healing ruptures in this film almost instantly

in any environment where a trace of moisture or oxygen is present.
Thus, we find that titanium is impervious to attack in moist chlorine
gas. If the moisture content of dry chlorine gas falls below a critical
level of about 0.5%, however, rapid or even catastrophic attack can
occur.
Anhydrous conditions, in the absence of a source of oxygen,
should be avoided with titanium because the protective film may
not be regenerated if it is damaged.
Velocity Effects
For most metals, there is a critical water velocity beyond which
protective films are swept away and accelerated corrosion attack
occurs, this is known as erosion corrosion. The velocity at which
the protective film strips off differs greatly from one material to
another. Erosion corrosion occurs on some metals at velocities as
low as 2 to 3 ft/sec. The critical velocity for titanium in seawater
is in excess of 90 ft/sec [2]. Numerous corrosion-erosion tests
have been conducted; all have shown titanium to have outstanding
resistance to this form of attack [3,4], Experiments with sand-laden,
rapidly moving seawater have demonstrated titanium to be 20 times
more resistant to erosion than the best copper-based alloys.
Corrosion in Waters
Titanium is immune to corrosion in all natural waters, including
highly polluted seawater, at temperatures up to the boiling point.
Nearly 20 years of service in such environments have now been
accumulated and, as far as is known, no failures because of corrosion
have occurred. Titanium has replaced copper-based alloys that were
corroding in the presence of sulfides, as well as stainless steels
that were suffering from pitting and stress-corrosion cracking caused
by chlorides.
Titanium also stands up to steam up to temperatures as high
as 315°C (600°F) and pressures up to 2000 psi. Resistance to erosion
by wet steam has been shown to be as good as that of 18Cr-8Ni
stainless steels [2]. The Ti-6A1-4V (grade 5) exhibited significantly
better resistance to erosion by steam than did 18Cr-8Ni stainless
steel.
Resistance to Fouling
Because of its hardness and corrosion resistance, which maintains
a smoother surface, titanium has excellent resistance to fouling or
deposit buildup in most environments. Observations of titanium tubing
in service in natural cooling waters confirm that the resistance

to fouling of titanium equals or exceeds the performance of stainless
steels. The thin oxide film present on the surface of titanium gener-
ally does not react with cooling waters to form mineral deposits,
as sometimes happens with some materials. When cleaning is necessary,
conventional acid cleaning cycles may be used, provided that proper
inhibitors are present. For these reasons, heat exchangers tubed
with titanium have been found to maintain high heat-transfer effi-
ciency indefinitely.
Galvanic Corrosion
The coupling of titanium with dissimilar metals usually does not
accelerate the corrosion of the titanium. The exception is in reducing
TABLE 8 Galvanic Series in Flowing Seawater a
Metal Potential 0
T304 stainless steel (passive) 0.08

Monel 0.08
Hastelloy C 0.08
Unalloyed titanium 0.10
Silver 0.13
Nickel 0.20
70-30 cupronickel 0.25
90-10 cupronickel 0.28
Admiralty brass 0.29
G. bronze 0.31
Aluminum brass 0.32
Copper 0.36
Naval brass 0.40
T410 stainless steel (active) 0.52
Carbon steel 0.61
Cast iron 0.61
Aluminum 0.79
Zinc 1.03
a
13 ft/sec at 75°F.
kSteady-state potential negative to saturated
calomel half-cell.
10. Titanium 197
2 5 0 0 HR IN SEAWATER
ANODE/CATHODE
18/8 STAINLESS AREA RATIO
CIO 10:1
60/40 BRASS(MUNTZ)
ALUMINUM BRASS
MONEL
NORMAL GALVANIC
80/20 CUPRO-NICKEL UNCOUPLED ATTACK
CORROSION ADDITIONS
70/30 CUPRO-NICKEL
LOW CARBON STEEL
0 1 2 3 4 5 6 7^ 27
CORROSION RATE, MPY
FIGURE 2 Galvanic corrosion of titanium in seawater.
environments where titanium does not passivate. Under these condi-

tions, titanium has a potential similar to aluminum and will undergo
accelerated corrosion when coupled to more noble metals.
Titanium occupies a place high on the passive, or noble end,
of the galvanic series in seawater, as shown in Table 8. In most
environments, titanium will be the cathodic member of any galvanic
couple. Accelerated corrosion of the other member of the couple
may occur, but usually, the titanium will be unaffected. Figure 2
shows the accelerating effect on the corrosion rate of various metals
when they are galvanically connected to titanium in seawater. If
the area of the titanium exposed is small relative to the area of
the other metal, the effect on corrosion rate of the other metal
is negligible. If, however, the area of the titanium (cathode) greatly
exceeds the area of the other metal (anode), severe corrosion may
result on the anodic metal.
To avoid problems with galvanic corrosion, it is best to construct
equipment of a single metal. If this is not practical, attempts should
be made to select two metals that are close together in the galvanic
series. Insulation of the dissimilar metal joint or cathodic protection
of the less noble metal are other preventive measures that can be
taken. If contact of dissimilar metals with titanium is necessary,
the critical parts should be constructed of titanium, because it is
usually not attacked. The use of large areas and heavy sections
of the less noble metal, to allow for increased corrosion, also helps
to keep galvanic corrosion effects to a minimum.
Chlorides
Titanium is immune to all forms of corrosive attack in seawater and
chloride salt solutions at ambient temperatures. It is also very
resistant to attack in most chloride solutions at elevated temperatures
[5,6]. Under certain conditions in chloride solutions, titanium has
been observed to undergo attack in the form of pitting and crevice
corrosion. The temperature at which attack occurs is determined
mainly by the pH of the solution, although chloride ion concentration
has been observed to have a minor effect (more concentrated solu-
tions, causing attack at lower temperatures). Figure 3 shows the
relationship between the temperature and the pH of saturated brine,
at which corrosive attack initiates on unalloyed titanium. This curve
was drawn from laboratory data and is confirmed by service experi-
ence.
Figures 4 and 5 show the pH-temperature relationship for Ti-Pd
(grade 7) and the Ti-Code 12 (grade 12) alloys. Note the greatly
improved resistance to crevice corrosion of these alloys compared
with unalloyed titanium over the pH range 9 to 0.5. The data in
Table 9 further illustrate this point.
1 ' ~Û ; . | .
^^^^ HYDROGEN PICKUP AND
12 ^ ^ ^ WEIGHT LOSS
10 NO HYDROGEN PICKUP
OR CORROSION
6 -
CREVICE CORROSION
4
2 -
. ! I . I . 1 , 1
100 200 300 400 500 600
TEMPERATURE,°F
FIGURE 3 Effect of temperature and pH on crevice corrosion of
unalloyed titanium (grade 2) in saturated brine.
10. Titanium 199
14
HYDROGEN PICKUP AND

12 WEIGHT LOSS
10
x NO HYDROGEN PICKUP
o. OR CORROSION
"^CREVICE .
CORROSION
100 200 300 400 500 600

TEMPERATURE ,°F
Ti-Pd (grade 7) in saturated NaCl brine.
14
HYDROGEN PICKUP AND

12 LOSS
10
NO HYDROGEN PICKUP
i OR CORROSION
o. \
CREVICE
CORROSION
100 200 300 400 500 600

TEMPERATURE/F
Ti-Code 12 (grade 12) in saturated NaCl brine.
TABLE 9 Crevice Corrosion of Titanium in Boiling Solutions
Crevice test r e s u l t s 8
Environment pH Ti-50A Ti-Code 12 Ti-Pd
ZnCl 2 (saturated) 3.0 F R —

10% A1C13 — F R R
MgCl2 4.2 F R R
10% NH^Cl 4.1 F R R
NaCl (saturated) 1.0 F R R
10% Na2SOi+ 1.0 F R R
10% FeCl 3 0.6 F F R
a
F , failed (samples showed crevice corrosion); R, resisted (samples
showed no evidence of corrosion).
Crevice corrosion has not been observed when pH values are

higher than 9. Failures have been observed at elevated temperatures
in chloride solutions with pH 10 or higher, b u t these have been
due to hydrogen embrittlement. Apparently, t h e oxide film on titanium
is not stable in highly basic solutions and is replaced by a hydride
film that is protective at ambient temperatures. This may cause
hydrogen embrittlement; therefore, t h e use of titanium in p u r e
caustic solutions should be limited to temperatures of 200°F (93°C),
or lower. The presence of chlorate or hypochlorite appears to inhibit
the corrosion of titanium in caustic.
Chlorine, Hypochlorites, and Other Chlorine Chemicals

Titanium has excellent resistance to moist chlorine gas. Hence,
it is used extensively in chlorine cells, heat exchangers, piping,
reactors, pumps, valves, and other equipment in chlorine plants
and in industrial processes that employ moist chlorine. Chlorine
in solution tends to have a passivating effect on titanium by moving
the corrosion potential in the positive direction. Thus, titanium
is widely employed to handle chlorinated brines and hypochlorites.
Some corrosion rates for titanium in hypochlorite solutions are given
in Table 10. Titanium is also used in bleach sections of pulp plants
to handle corrosion caused by chlorine dioxide.
Titanium is not resistant to dry chlorine gas. It is attacked
rapidly and can ignite and burn if the moisture content is sufficiently
low. The amount of moisture required for passivation depends on
environmental conditions [8,9]. About 1% H2O is sufficient under
static conditions at room temperature. Somewhat less is required if
the chlorine is flowing. About 1.5% water is required at 200°C (392°F).
10. Titanium 201
TABLE 10 Corrosion of Titanium in Hypochlorite Solutions
Tempera- Test Corrosion

ture duration rate
Environment (°F) (days) (mpy) Pitting
17% hypochlorous acid, 50 203 <0.1 —

with free chlorine and
chlorine monoxide
16% sodium hypochlorite 70 170 <0.1 None
18-20% calcium hypochlorite 70-75 204 Nil None
1.5-4% sodium hypochlorite, 150-200 72 0.1 None
12-15% sodium chloride, 1%
sodium hydroxide
Source: Ref. 7.
Acid Solutions
In general terms, titanium offers excellent resistance to oxidizing
acids. It has limited resistance to reducing acids. The presence
of oxidizing agents that induce passivity improves resistance in
these reducing environments. Hydrofluoric acid, in very small
amounts, will attack titanium.
Oxidizing Acids
Titanium offers excellent resistance to oxidizing acids such as nitric
and chromic acids. It has been used for reactors, heat exchangers,
thermowells, and other equipment employed in producing nitric
acid [10] because of the low corrosion rates experienced over a
wide range of conditions. Solutions containing 20 to 70% HNO3,
at temperatures from boiling to 315°C (600°F), have been handled
in titanium equipment. Godard et al. [9] has cited an example of
a titanium heat exchanger that handled 60% HNO3 at 195°C (380°F)
and 300 psi and showed no signs of corrosion after more than 2
years of operation.
Figure 6 shows the results of a Huey-type corrosion test for
unalloyed titanium (grade 2), Ti-Pd (grade 7), and Ti-Code 12
(grade 12), in which the nitric acid solution is changed every 24 hr.
Note that in this oxidizing environment, the resistance of the Ti-Pd
alloy is no better than that of unalloyed titanium. The Ti-Code 12
alloy, however, shows a significantly lower corrosion rate.
I I I I I 1 1
-TiCode 12
32 -
• -Ti-50A ""
- Ti Pd
24
<
DC
16
O
QC
— \
DC
O 8
O
10 20 30 40 50 60 70
% HNO 3
BOILING HNO3 SOLUTION CHANGED EVERY

24 HR (TOTAL EXPOSURE 480 HR)
FIGURE 6 Boiling HNO3 solution changed every 24 hr—exposure

480 hr.
In hot nitric acid, titanium may show a short period of relatively

high corrosion rate followed by almost complete passivation. Appar-
ently, a small amount of titanium ion in solution acts to passivate
titanium against further attack. This is illustrated by the data
in Table 11. Contrary to effects on stainless steel, the presence
of chromium ions also passivates titanium against attack by nitric
acid as shown in Table 12.
TABLE 11 Effect of Dissolved Titanium on the Corrosion

Rate of Titanium in Boiling Nitric Acid Solutions a
Titanium ion Corrosion rate (mpy)

added (mg/L) 40% HNO3 68% HNO3
.0 29.5 31.8
10 0.8
20 8.6 2.4
40 1.9 0.4
80 0.8 0.4
a
Duration of test, 24 hr.
Source: Ref. 11.
20. Titanium 203
TABLE 12 Effect of Chromium on Corrosion of Stainless

Steel and Titanium in Boiling 68%a (Nitric Acid)
Cr (%) AISI 304L (annealed) Unalloyed Ti
0.0 12-18 3.5-3.8

0.0005 12-20 -
0.005 60-90 0.9-1.6
0.05 980-1600 -
a
Exposed for three 48-hr periods, acid changed each period.
Source: Ref. 12.
Degnan [12] has pointed out that titanium is considered to be

an outstanding material for equipment for heating nitric acid solutions.
Stainless steels, for instance, show accelerated attack in a hot-wall
test or a continuous Huey test, because of the chromium ions gener-
ated by corrosion. Titanium, on the other hand, is passivated against
further attack by even the slightest degree of corrosion. One word
of caution: Titanium is not recommended for use in red fuming
nitric acid, particularly when the water content is less than about
1.5% and the nitrogen dioxide content is above 2.5% [12]. Pyrophoric
reactions have occurred in this environment.
Reducing Acids
Titanium is attacked by such reducing environments as hydrochloric,
sulfuric, and phosphoric acids. However, it is passivated by small
amounts of multivalent metal ions such as copper and iron. Many
industrial acid-process streams contain sufficient metal ion content
to permit excellent performance with titanium in fairly strong solutions
of these acids. The presence of dissolved oxygen, chlorine, nitrate,
chromate, or other oxidizing species also serves to passivate titanium
and reduce the corrosion rate in acids.
Isocorrosion data for unalloyed titanium (grade 2), Ti-Code 12
(grade 12), and Ti-Pd (grade 7) are shown in Figure 7 for hydro-
chloric acid without passivating species. The palladium-alloyed titanium
offers best resistance to HC1 under these conditions.
The effect of ferric ion on passivating unalloyed titanium against
attack in 5 wt% HC1 is shown in Figure 8. As little as 150 ppm
ferric ion can provide protection for unalloyed titanium in this con-
centration of acid, reducing the corrosion rate from more than 1000
mpy to less than 10 mpy. Further effects of ferric ion on passivating
1200 -
25 50 75 100 125 150 175

ppm
FIGURE 7 Corrosion of titanium in HC1 solution.
unalloyed titanium, Ti-Code 12, and Ti-Pd against attack by 3 and

4 wt% hydrochloric acid are shown in Table 13. In general, these
data illustrate that if metal-ion concentration is sufficient to passivate
effectively, the corrosion rate for unalloyed titanium will be as low
as for the more expensive Ti-Pd alloy.
Corrosion data in boiling sulfuric acid solutions are given in
Table 14. Although the Ti-Code 12 (grade 12) alloy offers some
improvement over unalloyed titanium, the Ti-Pd alloy again offers
best resistance. Ferric, cupric, and other heavy-metal ions will
passivate titanium against attack by sulfuric acids. The effect of
cupric ion on corrosion by sulfuric acid of unalloyed titanium at
100°C (212°F) is shown in Table 15. Similar effect of ferric ion
in passivating titanium against corrosion by 10 wt% hydrochloric
acid is also shown by data in Table 15.
The resistance of titanium to corrosion by phosphoric acid is
similar to resistance to sulfuric and hydrochloric acids. Unalloyed
titanium will handle up to 30 wt% phosphoric acid at room tempera-
ture and 1 wt% acid at the boiling point, with a corrosion rate of
10 mpy. The Ti-Pd alloy can handle up to 10 wt% phosphoric acid
at the boiling point, with a corrosion rate of about 5 mpy. The
presence of heavy-metal ions and oxidizing agents in phosphoric
10, Titanium 205
I I I
Ti-.2Pd
Ti-CODE 12
Ti-50A
250 - 5 mpy ISOCORROSION LINES

-BOILING POINT
225
200
tr.
•D
175
a:
UJ
o.
UJ
I
10 15 20 25 30 35
WT % HCI
FIGURE 8 Effect of ferric ion on corrosion of unalloyed titanium

in 5 wt% boiling HCI.
acid serves to passivate titanium in a manner similar to that demon-

strated for the other reducing acids.
A new alloy, Ti-5Ta, is under development and shows promise
of having improved corrosion resistance in both oxidizing and reduc-
ing acids. This represents the first titanium alloy that is capable
of resisting both oxidizing and reducing media.
TABLE 13 Effect of Ferric Chloride Inhibitor on Corrosion

in Boiling HC1
Corrosion rate (mpy)

Wt% HC1 Alloy No FeCl 3 2g/L FeCl 3
3.32 Ti-50A 740 0.2

3.32 Ti-Code 12 606 1.0
3.32 Ti-Pd 3 0.1
4.15 Ti-50A 843 0.4
4.15 Ti-Code 12 1083 2.3
4.15 Ti-Pd 6 0.3
TABLE 14 Corrosion Rates of Titanium Alloys in Boiling H 2 SO 4
Wt% H2SOIf Ti-Pd Ti-Code 12 Unalloyed, Ti-50A
0.54 0.1 0.6 252

1.08 0.2 35.4 440
1.62 2.1 578 713
2.16 3.8 759 945
2.70 14.9 1331 1197
5.40 29.8 2410 2047
TABLE 15 Effect of Inhibitors on Acid Corrosion of Titanium
Temperature Corrosion rate

Environment (°F) (mpy)
10% HC1 Boiling >2360

10% HC1 + 16 g/L FeCl 3 Boiling 8
20% H 2 SO 4 212 >2360
20% H2SOif + 2.5 g/L C u S ( \ 212 >2
10. Titanium 207
Organic Chemicals
Titanium generally shows good corrosion resistance to organic com-
pounds. In anhydrous environments where the temperature is high
enough to cause dissociation of the organic compound, hydrogen
embrittlement of the titanium is a consideration. Many organic com-
pounds are absorbed on titanium surfaces and act as inhibitors.
Because of its resistance to corrosion in organic environments,
titanium is finding steadily increasing uses in equipment used to
handle these chemicals. Godard et al. [9] has pointed out that
titanium is a standard construction material for the Wacker process,
used to produce acetaldehyde by oxidation of ethylene in an aqueous
solution of metal chlorides.
Organic Acids
Titanium is, in general, quite resistant to organic acids. Its behavior
is dependent on whether the environment is reducing or is oxidizing.
Only a few organic acids are known to attack titanium. Among these
are hot nonaerated formic acid, hot oxalic acid, concentrated tri-
chloracetic acid, and solutions of sulfamic acid. Aeration improves
the resistance of titanium in most of these nonoxidizing acid solutions.
In formic acid, it reduces the corrosion rates to very low values.
Titanium is resistant to acetic acid [9] over a wide range of
concentrations and to temperatures well beyond the boiling point.
It is being used in terephthalic acid and adipic acid up to 215° C
(400°F) and 67% concentration. Good resistance is observed in citric,
tartaric, carbolic, stearic, lactic, and tannic acids.
Some data for boiling organic acid solutions are given in Table 16.
As shown, the Ti-Code 12 (grade 12) and Ti-Pd (grade 7) alloys
will sometimes offer low corrosion rates when unalloyed titanium
does not.
TABLE 16 Resistance of Titanium to Boiling Nonaerated Organic Acids
Unalloyed
Acid solution titanium Ti-Code 12 Ti-Pd
20% acetic 0
50% citric 14 0.5 0.6
10% sulfamic 538 455 14.6
45% formic 433 Nil Nil
10% oxalic 3700 4100 1270
Stress-Corrosion Cracking
Titanium and its alloys have been relatively free of failures because
of stress-corrosion cracking. One of the reasons for this is that
environments that cause stress cracking have been recognized and
use of titanium has been restricted in these.
Unalloyed titanium with an oxygen content of less than 0.2%
(ASTM grades 1 and 2) appears to be susceptible to cracking only
in methanol and higher alcohols (liquid and vapor), in certain liquid
metals such as cadmium and possibly mercury, and in red fuming
nitric acid. The presence of halide ion in the alcohols accelerates
cracking tendencies. The presence of water (>2%) tends to inhibit
stress cracking in alcohols and in red fuming nitric acid.
Titanium alloys, including Ti-6A1-4V (grade 5), are more suscepti-
ble to stress-corrosion cracking. In addition to the environments
that affect unalloyed titanium, the alloys are also susceptible to
hot salts, as well as certain aqueous solutions and halogenated
hydrocarbons [13].
Hydrogen Embrittlement
Under most conditions, the oxide film on titanium acts as an effective
barrier to penetration by hydrogen. However, under conditions that
allow hydrogen to enter titanium and exceed the concentration needed
to form a hydride phase (about 100 to 150 ppm), embrittlement can
occur. Hydrogen absorption has been observed in alkaline solutions
at temperatures above the boiling point. Acidic conditions that cause
the oxide film to be unstable may also result in embrittlement under
conditions in which hydrogen is generated on the titanium surface.
Coupling of titanium to a metal low in the galvanic series can result
in generation of hydrogen on titanium as the cathode, as can an
impressed current from a cathodic protection system. In any event,
it appears that embrittlement occurs only if the temperature is suffi-
ciently high [ i . e . , above 75°C (170°F) to allow hydrogen to diffuse
into the titanium. Otherwise, if surface hydride films do form,
they are not detrimental. However, they may reduce ability to resist
erosion, resulting in higher corrosion rates.
Titanium tubing is being used effectively in a variety of environ-
ments where it is installed in a variety of tube sheet materials [14],
Hydrogen embrittlement of the titanium has been rare and has usually
occurred when active corrosion was progressing on the dissimilar
tube sheet and iron particles had been smeared into the titanium
surface. The iron smears destroy the protective oxide surface,
thereby allowing access of available hydrogen to the underlying
titanium. Contact of titanium with soft iron that might result in
10. Titanium 209
pickup of iron particles should be guarded against. Anodizing is

sometimes used to remove iron and to build up oxide film thickness.
Embrittlement of titanium in gaseous hydrogen atmospheres has
not been a problem. The presence of as little as 2% moisture effec-
tively prevents the absorption of molecular hydrogen up to tempera-
tures as high as 315°C (600°F). Anhydrous environments and those
lacking a source of oxygen to maintain the oxide film intact on
titanium should be avoided, because absorption of hydrogen will
occur at temperatures above 75°C (170°F).
FABRICATION
Titanium is routinely being fabricated into various types of process

equipment by many fabricators. Techniques required to fabricate
titanium are essentially the same as those required for other highly
alloyed materials. These techniques, usually, simply represent good
fabrication practice. Lack of attention to good practice for titanium,
as with other metals, can lead to difficulties.
From a design standpoint, the properties of titanium must be
kept in mind. Low modulus of elasticity, for instance, means greater
springback on forming. Shrinkage and distortion of welds may be
greater than is generally experienced with other metals. This,
coupled with low strength at elevated temperatures, may require
more careful attention to alignment during welding. Lower ductility
might require more generous radii on bending or preheating before
forming.
The welding of titanium requires special mention. Molten titanium
absorbs oxygen, nitrogen, and hydrogen readily on exposure to
air or moisture. To a lesser extent, solid titanium will also absorb
these elements, at least down to temperatures in the range 315
to 425°C (600 to 800°F). Inert gas shielding during welding is,
therefore, imperative down to temperatures in the range 315 to
425°C (600 to 800°F).
Good techniques for inert gas shielding of welds, which involve
use of trailing shields as well as back shields, have been developed
and are even being used in the field. These techniques, combined
with careful procedures to exclude all moisture, dirt, and other
foreign matter from the weld area, assure good welds.
The foregoing brief descriptions of fabrication details are well
recognized by the experienced titanium fabricator and present little
difficulty. Proper attention to these details results in weld properties
equivalent to those of the base metal. Contamination of welds may
mean loss of ductility, as well as degraded corrosion resistance.
BONDED TITANIUM
The joining of titanium to steel has always posed a problem. For

example, welding can only be accomplished successfully with transi-
tion welds. There has always been a considerable economic interest
in bonding titanium to steel. This is particularly true when, because
of corrosion resistance, it is necessary to use grade 2, which has
a relatively low allowable design stress. An examination of ASME
allowable design stresses shows that at 100°F the allowable design
stress of grade 2 is 12,500 psi, whereas that of grade 12 is 17,500
psi. At 500°F the allowable design stresses are 6600 psi and 11,400
psi, respectively. The differences in the design stresses is the
result of the addition of alloying ingredients that improve the mechan-
ical properties but at the expense of some corrosion resistance.
With a low design stress, relatively thick sections are required
for the fabrication of pressure vessels. By bonding a titanium layer
to a steel substrate, advantage is taken of steel1 s greater mechanical
properties and titanium1 s corrosion resistance, producing a less-
expensive final product.
Explosion Bonding
The explosion-bonding technique of applying a titanium-clad surface
to a steel substrate was originally developed by DuPont. In this
process, detonation of an explosive presses the plates together
with such force that the lowest elastic limit of the metals is exceeded,
and the unmelted surface metal is jetted through the rapidly closing
space between the plates, destroying interfering layers of metal,
and resulting in a metallurgical bond, with a relatively smooth sur-
face.
Explosive bonding has been used successfully for over 20 years
for cladding not only titanium, but other metals as well. There
are now several companies in the United States and abroad that
supply explosion-bonded materials.
Roll-Cladding
Roll-cladding of titanium has been under development for many
years. Attempts were made by Lukens Steel in the 1950s to produce
a roll-clad material without satisfactory results. The formation of
titanium carbide and decarbonized steel at the interface produced
a brittle bond.
A new product, developed by Nippon Kokan KK (Tokyo), will
be coming to market in 1987. This is a roll-clad titanium that is
produced by a technique that employs a metal interlayer between
10. Titanium 211
the steel and the titanium. Tests conducted have indicated that
the problem of the brittle bond has been overcome. It is expected
that this product will be approximately 20 to 30% lower in cost than
other clad materials.
Weld-Bonding
A weld-bonding method, known as Resista-Clad is available from
The Pfaudler Company. In this process an interlayer of copper
and a stainless steel net or metal screen is used as an intermediate
bonder. Pulses of electrical energy from electrode wheels are applied
to produce a series of overlapping bonds between the cladding and
substrate.
Material produced by this method has been in service in Japan
for over 12 years and in this country for over 4 years.
Economics
Whether it is more economical to use a clad material or a solid

titanium is dependent upon several factors. Grade 2 titanium (com-
mercially pure titanium) has the widest range of corrosion resistance
and the lowest mechanical properties of the various grades of titanium.
In general, if grade 2 titanium is required for a pressure vessel
that requires a wall thickness of 0.25 in. or greater, then explosive
bonding would be advantageous. Roll-clad material should fall between
these two ranges.
The development of various titanium alloys permits reduction
in wall thicknesses resulting from the improved mechanical properties.
For example, grade 12 titanium, which is an alloy containing 0.8%
nickel and 0.3% molybdenum, can reduce the required wall thicknesses
of grade 2 material by 30 to 40%. When these materials are suitable
they can prove to be less expensive than any of the clad materials.
REFERENCES
1. Cotton, J. B. and Downing, B. P. (1957). Corrosion resistance

of titanium to sea water. Trans. Inst. Mar. Eng. 69:311.
2. Danek, G. J . , J r . (1966). The effect of sea-water velocity
on the corrosion behavior of metals. Nav. Eng. J. 78:763.
3. Stough, D. W., Fink, F. W., and Peoples, R. S. The Corrosion
of Titanium. Titanium Metallurgical Laboratory, Rep. No. 57,
Battelle Memorial Institute, Columbus, Ohio, p . 60.
4. Davis, J. A. (1974). "The Effect of Velocity on the Seawater
Corrosion Behavior of High Performance Ship Material," Paper
No. 78, NACE Corrosion/74, Chicago, March 4-8.
5. Process Industries Corrosion. (1975). National Association of

Corrosion Engineers, Houston.
6. Oettinger, T. P. (1976). Austenitic stainless steels and titanium
for wet air oxidation of sewage sludge, Matr. Perf. 15(11):29.
7. Gegner, P. J. (1975). Corrosion resistance of materials in alkalies
and hypochlorites, Process Industries Corrosion, National Asso-
ciation of Corrosion Engineers, p . 296.
8. Millaway, E. E., and Klineman, M. H. (1967). Factors affecting
water content needed to passivate titanium in chlorine. Corrosion
23(4):88.
9. Godard, H. P . , Jepson, W. B . , Bothwell, M. R., and Kane,
R. L. (1967). The Corrosion of Light Metals, Wiley and Sons,
New York.
10. Milaway, E. E. (1965). Titanium: Its corrosion behavior and
passivation, Matr. Perf. 4:16.
11. Takamura, A., Arakawa, K., and Moriguchi, Y. (1970). Corro-
sion resistance of titanium and titanium-5% tantalum alloy in
hot concentrated nitric acid, The Science, Technology and Appli-
cations of Titanium (R. I. Jaffee and N. E. Promisel, e d s . ) .
Pergamon Press, Oxford.
12. Degnan, T. F. (1975). Materials for handling hydrofluoric,
nitric, and sulfuric acids, Process Corrosion Industries, National
Association of Corrosion Engineers, Houston, p . 229.
13. Blackburn, M. J . , Feeney, J. A . , and Beck, T. R. (1973).
Stress-corrosion-cracking of titanium alloys, Advances in Corro-
sion Science and Technology, Vol. 3 (M. G. Fontana and P. W.
Staehle, e d s . ) . Plenum Press, New York, p p . 67-292.
14. McMaster, J. A. (1977). "Titanium: Economical Corrosion Control
Tool for Petroleum Refineries." NACE, Corrosion/77, San Fran-
cisco.
11
TANTALUM
INTRODUCTION
Tantalum is not a new material. Its first commercial use at the turn
of the century was as filaments in light bulbs. Later, when it became
apparent that tantalum was practically inert to attack by most acids,
application in the laboratory and in the chemical and medical indus-
tries were developed. The rise of the electronics industry accelerated
the development of many nevi applications.
Much of this growth can be attributed to a broader range of
tantalum powders and mill products available from the producers:
high-melting-point ability to form a dielectric oxide film and chemical
inertness. Encouraging these applications, new reduction, melting,
and fabrication techniques have led to higher purities, higher relia-
bilities, and improved yields to finished products.
SOURCE OF TANTALUM
The earth1 s crust is made up of 92 naturally occurring elements,

but these elements are not all present in equal amounts. Eight ele-
ments, oxygen, silicon, aluminum, iron, calcium, sodium, potassium,
and magnesium make up 96.5% of the crust. The remaining 88 elements
make up only 3.5%, with tantalum amounting to only 0.0002%.
If the tantalum were equally distributed in the rocks of the
earth it would be uneconomical to recover, and there would be
no tantalum industry today. However, the tantalum is concentrated
213
214 Schweitzer
in a few unusual rocks in sufficient quantity to permit economical

mining and refining. The most important tantalum minerals, tantalite,
microlites, and wodginite, are found in rock formations known as
pegmatites.
Pegmatites are coarse-grained rocks formed when molten rock
material was cooled slowly. They range in size from 1 in. to many
feet in diameter. Also found in the pegmatites are many rare ele-
ments such as tantalum, niobium, tin, lithium, beryllium, and others.
The only operating mine in North America is located at Bernic
Lake in Manitoba, Canada. The other important mine in the Americas
is found in Brazil. In the humid tropics the rocks weather and
rot to great depths. Many times the rocks in which the tantalum
minerals were formed have completely weathered and have been
carried away by running water. The heavy tantalum minerals tend
to be concentrated in deposits called placers. These can be panned
or washed with machinery, much like gold was recovered during
the gold-rush days. One important placer type deposit is found
in Greenbushes in Western Australia.
Because tin and tantalum are often found together, tantalum
is a by-product of the tin industry. Because most of the tantalum
deposits are small, hard to find, and very expensive to mine, the
result is a high-priced ore and a correspondingly high-priced metal.
TANTALUM MANUFACTURE
Ingot Consolidations
The first production route for tantalum was by powder metallurgy.
Tantalum powder, produced by one of several reduction techniques,
is pressed into suitably sized bars and then sintered in vacuum
at temperatures in excess of 2100°C (3800°F). When completed,
the pressed and sintered bars are ready for processing into mill
shapes. Forging, rolling, swaging, and drawing of tantalum is per-
formed at room temperature on standard metalworking equipment
with relatively few modifications.
The powder metallurgy route, although still in use and adequate
for many applications, has two major limitations: (1) the size of
the bar capable of being pressed and sintered to a uniform density
limits the size of the finished shape available, and (2) the amount
of residual interstitial impurities, such as oxygen, carbon, and
nitrogen, remaining after sintering adversely affects weldability.
The use of vacuum melting, either by the consumable arc or
electron beam process, overcomes these limitations. Either melting
technique is capable of producing ingots that are big enough and
11. Tantalum 215
high enough in purity to meet most requirements of product size

and specifications adequately, provided that starting materials are
selected with care.
Quality Descriptions
The greatest volume of tantalum is supplied as powder for the manu-
facture of solid electolytic tantalum capacitors.
Because it is necessary to distinguish between capacitor-grade
powder and melting-grade powder, manufacturers of electronic com-
ponents tend to use the phrase capacitor grade when ordering forms
such as wire, foil, and sheet to identify end use and desired charac-
teristics .
The phrase capacitor grade means that the material should have
the ability to form an anodic oxide film of certain characteristics.
Capacitor grade in itself does not mean an inherently higher purity,
cleaner surface, or different type of tantalum. It does mean that
the material should be tested using carefully standardized procedures
for electrical properties. If certain objective standards, such as
formation voltage and leakage current, are not available against
which to test the material, the use of the phrase capacitor grade
is not definitive.
Metallurgical grade could be simply defined as noncapacitor
grade.
PROPERTIES OF TANTALUM
Alloys Available
Pure tantalum has a body-centered, cubic crystal lattice. There
is no allotropic transformation to the melting point, which means
that unalloyed tantalum cannot be hardened by heat treatment.
Additions of oxygen, carbon, or nitrogen above normal levels, either
purposefully or accidentally, are considered as alloying ingredients
no matter what the concentration.
Tantalum-niobium alloys containing more than about 5 to 10%
niobium are much less corrosion-resistant than tantalum itself.
Tantalum-tungsten alloys containing more than 18% tungsten
are inert to 20% hydrofluoric acid at room temperature. Few data
are available on the 90Ta-10W alloy. It is known to be somewhat
more oxidation resistant (e.g., to air at higher temperatures) than
tantalum. The indication is that it has about the same corrosion
resistance to acids as tantalum itself.
216 Schweitzer
The room-temperature mechanical properties of tantalum are depend-
ent on chemical purity, amount of reduction in cross-sectional area,
and temperature of final annealing. Annealing time apparently is
not critical. Close control over the many factors that affect mechani-
cal properties are mandatory to ensure reproducible mechanical
behavior. Typical mechanical properties for tantalum are shown
in Table 1.
Tantalum can be strengthened only by cold work, with a result-
ing loss in ductility. Because certain residual impurities have pro-
nounced effects on ductility levels and metallurgical behavior, the
purpose of most consolidation techniques is to make the material
as pure as possible. Cold-working methods are used almost without
exception to preclude the possibility of embrittlement by exposure
to oxygen, carbon, nitrogen, and hydrogen at even moderate tem-
peratures. Temperatures in excess of 425°C (800°F) should be
avoided.
There are basically three structures that can be ordered: (1)
unannealed, (2) stress relieved, and (3) annealed.
In the unannealed condition, the structure will be typically
wrought fibrous. Yield and tensile strength will be increased with
corresponding decreases in elongation, as shown in Table 2. The
amount of work-hardening will be dependent on the amount of cold
TABLE 1 Typical Mechanical Properties: Annealed Tantalum Sheet
Ultimate
0.2% yield tensile Elonga- Rockwell
strength strength tion hardness
Thickness (psi) (psi) (%) 15T B
0.005 29,000 41,000 22 — -

deep draw
0.005 44,000 55,000 18 — —
regular
0.010 40,000 52,000 32 — —
regular
0.030 35,000 45,000 40 75 -
regular
0.060 35,000 45,000 42 78 48
regular
11. Tantalum 217
TABLE 2 Typical Mechanical Properties: Tantalum Sheet with

Increasing Cold Work
0.2% Ultimate
Cold yield tensile Elonga-
work strength strength tion Hardness
(%) (psi) (psi) (%) (VHN)
30 70,600 74,200 18 189

50 82,200 86,000 9 192
80 100,500 109,200 4 235
90 117,800 123,400 2 239
95 127,000 135,500 1 265
98 — 135,500 1 280
reduction since the last anneal. The rate of work hardening is

rapid for the first 30% of reduction. The rate then diminishes so
that there will be no appreciable strengthening until reductions
of over 90% are taken. There is actually no limit to the amount
of cold work that the metal can take: there are only equipment
limitations or mechanical limitations, such as poor shape control
in rolling or excessive thinning when forming, which dictate periodic
heat treatment in vacuum to soften the metal.
Unannealed tantalum may be preferred for machinability. Corro-
sion behavior is not affected nor is the susceptibility to interstitial
contamination changed. Unalloyed sheet 0.030-in. thick, and less,
can make a 1-in. thickness bend, but the annealed condition is
preferred when bending because the metal is not as stiff or springy.
Stress relieving at 1010°C (1850°F) in vacuum reduces yield
and tensile strength and raises elongation levels. These properties
will be intermediate between annealed and unannealed. Stress-relieving
has been used more as a matter of expediency than design. Fabri-
cators need some ductility to allow them to roll tubes into tube
sheets. Until recently the only tubular heat-treating vacuum furnaces
were limited to 1010°C (1850°F) maximum. This equipment limitation
dictated the use of stress relieving. As newer furnaces allowing
full annealing in vacuum are now onstream, stress relieving may
gradually fall into disuse.
Tantalum specified in the annealed condition is in its softest,
most ductile condition. The usual objective of the procedure is
to choose an annealing temperature that will result in complete r e -
crystallization but avoid excessive grain growth. This temperature
will be about 1175 ± 32°C (2150 ± 75°F). The temperature for r e -
crystallization is, however, considerably affected by the purity
and amount of cold work before annealing.
218 Schweitzer
When the amount of reduction is limited, complete recrystalliza-

tion is very difficult unless the annealing temperature is substantially
increased. Purity is at the core of this problem. Unless sufficient
work (about 75% reduction) is put into the material, tantalum does
not have the impurities present to act as nucleation sites for grain
growth unless an inordinate amount of energy in the form of anneal-
ing heat is added. This will result in recrystallization, but to a
very large grain size. The larger the cross section, the more severe
is this problem. Recrystallization to a finer grain size becomes more
readily obtainable. The tensile test is normally used to determine
the state of anneal. American Society for Testing and Materials
(ASTM) specifications for annealed tantalum are shown in Table 3.
This test is backed by hardness tests, Olsen cups, and grain-
size determinations to ensure product quality. The Olsen test is
particularly effective for thin sheet because tensile test elongations
decrease as a function of material thickness. The Olsen cup has
the added advantage of detecting any strong directionality tendencies
or to show "orange peel," indicating a coarse grain (Table 4).
Tantalum sheet develops directionality if a producer does not
choose his rolling and annealing schedules with care. Directionality
is a term used to describe nonuniform sheet properties in the rolling
direction and transverse to the rolling direction. Sheet with direc-
tionality has reduced elongations in the transverse direction that
may affect performance in spinning and deep-drawing operations.
When these metalworking functions are to be performed, it is helpful
for the user to so specify when ordering the material.
TABLE 3 ASTM Specification Limits for Tensile Properties: Test

Procedure ASTM E8-61T
Mini-
Maxi- mum Maxi-
Ultimate psi mum elonga- mum
Mini- Maxi- yield tion hard-
mum mum (psi) (%) ness
Cold worked 75,000 2

Stress-relieved
any section >0 .021 in. 55,000 10
any section < 0.021 in. 55,000 7.5
Annealed
any section >0 .021 in. 55,000 45,000 25 80 + 5T
any section <0 .021 in. 55,000 45,000 15
to 0.005 in. min.
11. Tantalum 219
TABLE 4 Annealed Tantalum Sheet: Olsen Cup Data, 7/8-in. Ball
Minimum Typical
depth force
Typical specification (lb)
0.030 regular 0.450 — 3920

0.020 regular 0.425 — 3200
0.010 regular 0.350 0.320 1540
0.005 deep draw 0.380 0.320 820
0.005 regular 0.250 — 504
Physical Properties
Tantalum, the 73rd element in the periodic table is a member of
the group 5 elements. Physical properties for tantalum are shown
in Table 5.
TABLE 5 Physical Properties of Tantalum
Atomic weight 180.9

Density 16.6 g/cm 3 (0.601 lb/in. 3 )
Melting point 2996°C (5432°F)
Vapor pressure at 1727°C 9.525 x 10" 11 mmHg
Linear coefficient of expansion 1135 K; 5.76 x 10" 6 /°C
1641 K; 9.53 x 10" 6 /°C
2030 K; 12.9 x 10" 6 /°C
2495 K; 16.7 x 10" 6 /°C
Thermal conductivity 20°C; 0.130 cal/cm-sec °C
100°C; 0.131 cal/cm-sec °C
1430°C; 0.174 cal/cm-sec °C
1630°C; 0.186 cal/cm-sec °C
1830°C; 0.198 cal/cm-sec °C
Specific heat 100°C; 0.03364 cal/g
Electrical conductivity 13.9% IACS
Electrical resistivity -73°C; 9.0 pfi/cm
75°C; 12.4 ^ / c m
127°C; 18.0 uft/cm
1000°C; 54.0 vift/cm
1500°C; 71.0 yfi/cm
2000°C; 87.0 yJJ/cm
220 Schweitzer
Tantalum
Tantalum is inert to practically all organic and inorganic compounds
at temperatures under 150°C (302°F). The only exceptions to this
are hydrofluoric acid and fuming sulfuric acids. At temperatures
under 150°C (302°F), it is inert to all concentrations of hydrochloric
acid, to all concentrations of nitric acid (including fuming), to 98%
sulfuric acid, to 85% phosphoric acid, and to aqua regia (Table 6).
TABLE 6 Materials to Which Tantalum Is Completely Inert, up to

at Least 150°C (302°F)
Acetic acid Chlorine wet or dry

Acetic anhydride Chloroacetic acid
Acetone Chrome-plating solutions
Acids, mineral (except HF) Chromic acid
Acid salts Citric acid
Air Cleaning solutions
Alcohols Copper salts
Aluminum chloride Ethyl sulfate
Aluminum sulfate Ethylene dibromide
Amines Fatty acids
Ammonium chloride Ferric chloride
Ammonium hydroxide Ferrous sulfate
Ammonium phosphate Foodstuffs
Ammonium sulfate Formaldehyde
Amyl acetate Formic acid
Amyl chloride Fruit products
Aqua regia Hydriodic acid
Barium hydroxide Hydrobromic acid
Body fluids Hydrochloric acid
Bromine, wet or dry Hydrogen
Butyric acid Hydrogen chloride
Calcium bisulfate Hydrogen iodide
Calcium chloride Hydrogen peroxide
Calcium hydroxide Hydrogen sulfide
Calcium hypochlorite Iodine
Carbon tetrachloride Hypochlorous acid
Carbonic acid Lactic acid
Carbon dioxide Magnesium chloride
Chloric acid Magnesium sulfate
Chlorinated hydrocarbons Mercury salts
Chlorine oxides Methyl sulfuric acid
Chlorine water and brine Milk
11. Tantalum 221
Mineral oils Potassium dichromate

Motor fuels Potassium iodide, iodine
Nitric acid, industrial fuming Potassium nitrate
Nitric oxides Refrigerants
Nitrogen Silver nitrate
Nitrosyl chloride Sodium bisulfate, aqueous
Nitrous oxides Sodium bromide
Organic chlorides Sodium chlorate
Oxalic acid Sodium chloride
Oxygen Sodium hypochlorite
Perchloric acid Sodium nitrate
Petroleum products Sodium sulfate
Phenols Sodium sulfite
Phosphoric acid, < 4 ppm F Sugar
Phosphorus Sulfamic acid
Phosphorus chlorides Sulfur
Phosphorus oxychloride Sulfur dioxide
Phthalic anhydride Sulfuric acid, under 98%
Potassium chloride Water
Corrosion is first noticed at about 190°C (375°F) for 70% nitric

acid, at about 175°C (345°F) for 98% sulfuric acid, and at about
180°C (355°F) for 85% phosphoric acid. Fuming sulfuric acid attacks
tantalum even at room temperature. Similarly, hydrofluoric acid,
anhydrous HF, or any acid medium containing fluoride ion will
rapidly attack the metal. Commercial phosphoric acid may attack
tantalum because of the presence of small amounts of fluoride impurity.
One exception to fluoride attack appears to be in chromium-plating
baths. Hot oxalic acid is the only organic acid known to attack
tantalum. The corrosion rates of tantalum in various acid media
are given in Table 7.
Fused sodium and potassium hydroxides and pyrosulfates dissolve
tantalum. It is attacked by concentrated alkaline solutions at room
temperature; it is fairly resistant to dilute solutions. Tantalum
is completely inert to body fluids.
Tantalum1 s resistance to oxidation by various gases is very
good at low temperatures, but it reacts rapidly at high temperatures.
Only HF and SO3 attack the metal under 100°C (212°F); most gases
begin to react with it at 300 to 400°C (570 to 750°F). As the tem-
perature and concentration of such gases as oxygen, nitrogen,
chlorine, hydrogen chloride, and ammonia are increased, oxidation
becomes more rapid; the usual temperature for rapid failure is 500
to 700°C (930 to 1290°F). The conditions under which tantalum is
attacked are noted in Table 8.
222 Schweitzer
TABLE 7 Corrosion Rates of Tantalum in Selected Media
Temperature Corrosion rate

Medium (°C) (°F) (mpy)
Acetic acid 100 212 Nil

A1C13 (10% soln.) 100 212 Nil
NH4C1 (10% soln.) 100 212 Nil
HC1 20% 21 70 Nil
100 212 Nil
Cone. 21 70 Nil
HNO3 20% 100 212 Nil
70% 100 212 Nil
65% 170 338 1
H 3 PO if , 85% 25 76 Nil
100 212 Nil
10% 25 76 Nil
40% 25 76 Nil
98% 25 76 Nil
98% 50 122 Nil
100 212 Nil
200 392 3
250 482 Rapid
, fuming (15% SO 3 ) 23 73 0.5
70 158 Rapid
Aqua regia 25 78 Nil
Chlorine wet 75 167 Nil
H2O
Cl 2 s a t . 25 76 Nil
Sea 25 76 Nil
Oxalic acid 21 70 Nil
96 205 0.1
NaOH 5% 21 70 Nil
100 212 0.7
10% 100 212 1
40% 80 176 Rapid
HF, 40% 25 76 Rapid
11. Tantalum 223
TABLE 8 Temperatures at Which Various Media Attack Tantalum
Medium State Remarks
Air Gas At temperatures over 300°C (572°F)

Alkaline solutions Aqueous At pH > 9, moderate temperature,
some corrosion
Ammonia Gas Pits at high temperature and p r e s -
sures
Bromine Gas At temperatures over 300°C (572°F)
Chlorine, wet Gas At temperatures over 250°C (482°F)
Fluorides, acid Aqueous All temperatures and concentrations
media
Fluorine Gas At all temperatures
HBr, 25% Aqueous Begins to corrode at temperatures
over 190°C (374°F)
Hydrocarbons Gas React at temperatures around
1500°C (2732°F)
HC1 25% Aqueous Begins to corrode at temperatures
over 190°C (374°F)
HF Aqueous Corrodes at all temperatures and
pressures
Hydrogen Gas Causes embrittlement, especially at
temperatures over 400°C (752°F)
HBr Gas At temperatures over 400°C (752°F)
HC1 Gas At temperatures over 350°C (662°F)
HF Gas At all temperatures
Iodine Gas At temperatures over 300°C (572°F)
Nitrogen Gas At temperatures over 300°C (572°F)
Oxalic acid, s a t . Aqueous At temperatures of about 100°C
soln. (212°F)
Oxygen Gas At temperatures over 350°C (662°F)
H3PO1+, 85% Aqueous Corrodes at temperatures over
180°C (356°F), at higher tempera-
tures for lower concentrations
(continued)
224 Schweitzer
Medium State Remarks
Potassium carbonate Aqueous Corrodes at moderate temperatures

depending on concentration
Sodium carbonate Aqueous Corrodes at moderate temperatures
depending on concentration
NaOH, 10% Aqueous Corrodes at about 100°C (212°F)
NaOH Molten Dissolves metal rapidly (over
320°C) (608°F)
Sodium pyrosulfate Molten Dissolves metal rapidly (over
400°C) (752°F)
H2SOi+, 98% Aqueous Begins to corrode at temperatures
over 175°C (347°F); lower con-
centrations begin to corrode at
higher temperatures
H2SOi+ (oleum) Fuming Corrodes at all temperatures
(over 98% H2SOt+)
Sulfuric trioxide Gas At all temperatures
Water Aqueous Corrodes at pH > 9, reacts at
high temperatures
Tantalum-Based Alloys
The use of tantalum-based alloys provides certain advantages.
1. Alloying with a less-expensive metal reduces the cost of the

material although still retaining essentially all of the corrosion-
resistant properties.
2. The use of light material will reduce the overall weight.
3. Depending upon the alloying ingredient, the physical strength
of the tantalum may be improved.
The formation of these alloys is a relatively nevt development

and, consequently, there is limited data available on their properties.
Tantalum-Tungsten Alloys
The tantalum-tungsten alloys are probably the most common. The
addition of 2 to 3% tungsten will raise the strength of the tantalum
11. Tantalum 225
by 30 to 50%. By also adding 0.15% columbium, a marked increase

in the corrosion resistance to concentrated sulfuric acid at 200°C
is noted. In the lower temperature ranges (175°C or less) the
resistance of the alloy is equal to that of pure tantalum.
When the tungsten concentration is increased to 18% or higher,
the alloys exhibit essentially no corrosion rate in 20% hydrofluoric
acid. This is a definite advantage over pure tantalum.
Tantalum-Titanium Alloys
The tantalum-titanium alloys are receiving a great deal of study
because this series of alloys shows considerable promise of providing
a less-expensive, lower-weight alloy having a corrosion resistance
almost comparable with that of tantalum. Preliminary tests indicate
that tantalum-titanium alloys show excellent resistance in nitric
acid at 190°C and at the boiling point.
Tantalum-Molybdenum Alloys
When these alloys are exposed to concentrated sulfuric acid and
concentrated hydrochloric acid, they are extremely resistant, and
the properties of tantalum are retained, as long as the tantalum
concentration is higher than 50%.
FABRICATION
Welding
The weldability of tantalum is limited only by the ingenuity of the
welder in reducing the time and temperature at which the metal
may be exposed to moisture, carbon, oxygen, and nitrogen.
Tantalum is one of the reactive metals. Like titanium, zirconium,
and columbium, tantalum will react with contaminants when exposed
to them at temperatures as low as 315°C (600°F). It must be remem-
bered, however, that contamination is a time-temperature relationship.
Seconds at a high temperature, as in spot welding, or some minutes
at 315°C (600°F) when extruding may not be harmful. But there
is danger everywhere when heat is present. Once exposed to any
atmosphere except inert gases under closely controlled conditions,
the metal will, in all probability, become embrittled. Only hydrogen
contamination can be removed by outgassing by heating to 650°C
(1200°F) and cooling in vacuum.
Because of tantalumTs affinity for gettering, any fusion weld
must be performed in an atmosphere free of contamination. This
means not only the weld puddle, but all hot metal, must be pro-
tected. Four different procedures are used to achieve this protection.
226 Schweitzer
Although one method may be preferable to another, each has its

own limitations. Familiarity with each is necessary to achieve a
balance between specialization and flexibility.
Electron Beam Welding

Electron beam (EB) welding requires highly sophisticated expensive
equipment. Most welding is done in a vacuum chamber, although
efforts are being made to allow welding to be performed outside
a vacuum chamber using differential pumping. Unless this is done,
the size of the chamber limits the size of the work. Electron beam
welding produces good-quality welds that are characterized by narrow
weld zones and good penetration. It is useful for intricate, hard-to-
reach welds, particularly fillets and tees of different cross sections.
Equipment tooling and setup are all expensive.
Flow-Purged Chamber
A flow-purged chamber is used when the work is too large to fit
any available chamber and the joints are too complex to permit open-
air welding. The enclosure is constructed of polyethylene sheet
and masking tape. Argon flowing through the "bag" displaces or
mixes with the entrapped air to a level at which welding can be
performed. Argon must be allowed to flow until the work is cool.
Enclosure of all sides of the work is mandatory.
Dry-Box or Vacuum-Purge Chamber

The dry-box provides the best inert gas atmosphere possible. The
parts to be welded are placed in the box; the chamber is sealed,
and a vacuum is pulled on the box. Normal practice is to pump
down to approximately 50 ym. The box is then backfilled with high-
purity, tank argon to a slight positive pressure. Welding is done
from the outside by inserting the hands into rubber gloves through
the sides of the chamber.
The major limitations of the dry-box are the size of the box,
which predetermines the size of the work that can be handled,
and the skill of the operator necessary to manipulate the work.
This is not to mention the initial investment of the box itself. High-
quality butt welds joining 0.010-in. tantalum using 65 A at 5 in./min
with a 3/32 in. tungsten electrode are commonplace with use of this
technique.
Open-Air Welding
Open-air welding with tantalum is possible provided that the most
stringent precautions are observed. Only relatively simple joints
allowing adequate shielding are possible.
11. Tantalum 227
Protection must be given to the arc, to the heated metal in front,

to the sides, and to the cooling metal behind and underneath the
weld bead. The protective atmosphere is provided by using a gentle
but adequate gas flow from the maximum-sized cup feasible consistent
with good visibility. A blanket of inert gas must be supplied by
properly constructed trailing shields, which provide a flow of gas
until the metal is cooled below the critical temperature. Backup
shielding on the underside from the weld bead must also be used
to give protection until the material is cooled.
Absolute cleanliness is essential for good tantalum welding using
any of the foregoing techniques. A generally accepted procedure
to remove the naturally occurring oxide film is to use an emery
cloth to slightly abrade the surfaces to be joined. Then etch with
a nitric-hydrofluoric acid solution. Finally, rinse before welding
with a solvent, such as acetone, to be sure that all grease is re-
moved. Handle the work only with clean, lint-free nylon gloves.
Spot welding tantalum is fairly straightforward. Tip diameters,
typically 1/8 in., should be kept to a minimum. Tungsten-tipped
electrodes are used to prevent copper pickup. Typical settings
for welding 0.015-in. thick annealed stock that is used in the manu-
facture of furnace elements are 8-10 cycles/sec. Air pressure is
set at 25 psi, and the least amount of current possible for a good
nugget to form is permitted. The short cycle time helps preclude
contamination. Some discoloration on heavier gauges may result,
but this can be removed by acid cleaning.
Suggestions for good tantalum brazing are absolute cleanliness,
careful joint design and fit-up to assure complete brazing alloys,
and a brazing temperature well above the flow temperature [870°C
(1600°F) recommended].
Soldering is not used or recommended in tantalum fabrications.
Machining
Although tantalum cannot be classed as an easy material to machine,
it is not among the most difficult. The material is soft with low
strength and good ductility. Chips will not break cleanly. Instead,
the material is gummy and will tear rather than break clean unless
the machinist follows a few simple procedures.
Tools
High-speed tool steels are preferred because carbides are too brittle
for tantalum. Tools should be kept sharp. Breakdown will occur
rapidly after the first signs of dullness. Extreme cutting angles
are recommended to keep the tool and chip well clear of the work.
228 Schweitzer
Side rake 15°

Back rake 45°
Front rake 5°
Speeds and Feeds

Slow speeds and high feeds are the best procedure. Speeds should
not exceed 75 ft 2 /min, with the recommended speed 25 ft 2 /min.
Feed should be 0.015 in. per revolution for roughing and 0.005 in.
per revolution for finishing. Depth of cut can vary from 1/32 in.
to light finishing cuts, as desired. The tool should be well supported
with little overhang. Feed should be continued as long as tool and
work are in contact. Do not allow the tool to dwell on the work.
Lubrication
Single-point turning is generally d r y . For milling and drilling,
a generous amount of cutting fluid helps cool the work and carries
away chips. Chlorothane or 40% chlorothane in black oil is recom-
mended. Conventional cutting fluids are not satisfactory.
Forming
Tantalum in the annealed condition is an extremely ductile material.
Unusually high reductions without annealing are possible because
of its low rate of work-hardening characteristics. Tubing 1-1/16 in.
in diameter, with a 1/8-in. wall by 16-in. long has been drawn
from circular blanks, without annealing, in a series of seven draws.
It i s , nevertheless, recommended that the producer be advised
when spinning or drawing is planned.
Spinning
Successful tantalum spinning can be accomplished using conventional
spinning techniques. The slow work-hardening rate permits repeated
drafts without in-process anneals; unless unusually severe formations
are to be attempted. The spinning of thinner material, such as
0.110- or 0.020-in. thick, may have to be annealed more often.
Mandrels should be made of steel or aluminum bronze. Hardwood
and composition mandrels are usually too soft to permit sufficient
ironing for good surface finish. If steel mandrels are used, the
bottoms should be faced with aluminum bronze to prevent galling
of the blank. Steel roller wheels or yellow brass tools are used
with a generous amount of yellow soap. A commercial compound,
Warren1 s Spinning Compound 1, has been found to offer good lubri-
cating characteristics for tantalum.
11. Tantalum 229
Deep Drawing
Although tantalum is a soft, ductile metal, certain precautions are
suggested for optimum results. Conventional reductions are possible
provided that due allowance is made for tantalumTs galling character-
istics. The metal will have more of a tendency to seize on the punch
or on the draw ring. This friction may result in premature failure
unless lubrication is generous. Aluminum bronze is recommended
for the draw ring when justified.
The metal can be stretched, and ironing is feasible with aluminum
bronze dies. As in any depp-drawing operation, some experimentation
with hold-down, punch, and draw ring radii, and clearance may be
necessary to prevent wrinkling. Initial reductions of 50% are possible.
Drawing may be continued, although gradually decreasing the amount
of reduction per draw is recommended.
SUGGESTED APPLICATIONS
Because of its relatively high price, tantalum can be recommended

only for use in extremely corrosive media, in areas where no corro-
sion of the part can be tolerated, or where very high-purity materials
are being processed. Although some plastics, and even glass, fill
these requirements to a large extent, tantalum is a structurally
sound material of construction, can take considerable mechanical
abuse, and has a much higher heat transfer coefficient. Tantalum
should be used as a material of construction in locations and for
equipment where hot concentrated hydrochloric, sulfuric, or phos-
phoric acids will be present. Tantalum is used by the medical profes-
sion for instruments and for metal implants in the body. In the
manufacture of high-purity chemicals and Pharmaceuticals, tantalum
ensures that no impurities are introduced from the container or
reactor.
ACKNOWLEDGMENT
Data for this chapter were furnished by Zane B. Laycock of NRC,

Inc.
12
ZIRCONIUM
TE-LIN YAU Teledyne Wah Chang Albany, Albany, Oregon
INTRODUCTION
Zirconium, atomic number 40 and atomic weight 91.22, was identified

as an element by Klaproth in 1789. In 1824, Berzelius made the first
impure metal by reducing potassium fluorozirconate with potassium.
In 1925, Van Arkel and de Boer prepared the first high-purity
zirconium by using an iodide decomposition process. The commercial
Kroll process was developed in 1946 at the U.S. Bureau of Mines
in Albany, Oregon.
Zirconium's primary ore source is zircon (ZrSiO^), which occurs
in several regions throughout the world in the form of beach sand.
It is ranked 19th in abundance of the chemical elements occurring
in the earth1 s crust, and it is more abundant than several common
metals, such as nickel, chromium, and cobalt.
In 1940, Gillett detected the excellent corrosion resistance of
zirconium for a large number of acids and alkalies. This property
was confirmed by Kroll in 1946 when commercial-grade zirconium
became available. Kroll predicted that zirconium would find uses
in hydrochloric acid (HC1) applications. Hydrochloric acid is con-
sidered to be the most corrosive of the common acids. Indeed, one
of the earliest applications for zirconium was in processing HC1.
About the time of Kroll!s work, Kaufman and Utermeyer found
that the early measurements of the thermal neutron cross section
of zirconium were inaccurate, because the metal that was tested
contained hafnium. Hafnium occurs naturally in ores with zirconium.
When hafnium is separated from zirconium, zirconium has a very
231
232 Yau
low thermal neutron cross section. Because of the close chemical

properties of zirconium and hafnium, the separation of these two
metals is the most difficult step in extractive processing.
The high transparency to thermal neutrons, coupled with excellent
corrosion resistance and good mechanical properties, make zirconium
very useful in nuclear power application, especially as cladding
for uranium fuel and for other reactor components. Considerable
alloy development work has taken place over the past 30 years
to develop alloys with higher strength, improved corrosion resistance
in high-temperature water and steam, and heat resistance [1,2].
The most significant results are the zircaloys, a group of zirconium-
tin alloys developed in the United States, and zirconium alloys with
1 to 2.5% niobium, developed in Russia and Canada.
Nuclear applications account for a large portion of all the zirconium
consumed. The excellent corrosion resistance of zirconium to strong
acids and alkalies, salts, seawater, organics, and other agents
has attracted increasing attention for applications in chemical-
processing equipment. Zirconium is used as a getter in vacuum
devices, as an alloying element, and in the manufacture of such
items as surgical appliances, photoflash bulbs, and explosive primers.
Alloyed with niobium, zirconium is superconductive at low tempera-
tures and is used to make superconductive magnets.
PHYSICAL AND MECHANICAL PROPERTIES
A compilation of physical and mechanical properties for zirconium

is given in Table 1. A few comparisons can be made between the
properties of zirconium and those of other structural metals. First,
the density of zirconium is lower than that of iron or nickel. Second,
zirconium has a low coefficient of thermal expansion. The coefficient
of thermal expansion of zirconium is about two-thirds that of titanium,
about one-third that of type 316 stainless steel and about one-half
that of Monel. Third, zirconium has high thermal conductivity,
about 18% better than that of type 316 stainless steel.
Zirconium ores normally contain a small percentage of its sister
element, hafnium. Hafnium has chemical and metallurgical properties
similar to those of zirconium, although its nuclear properties are
remarkably different. Hafnium is a neutron absorber, but zirconium
is not. As a result, there are nuclear and nonnuclear grades of
zirconium and zirconium alloys. The nuclear grades are essentially
hafnium free, and the nonnuclear grades may contain up to 4.5% Hf.
Hafnium has no great effect on the corrosion resistance. Properly
speaking, the alloys named zircaloys, Zr-2.5Nb and Zr-lNb, apply
to nuclear-grade materials. The ASTM specifications for nonnuclear
TABLE 1 Typical Physical and Mechanical Properties of Zirconium Grade 702 and Grade 705
Physical properties Zr 702 Zr 705

O
Atomic number 40
lium
Atomic weight 91.22 —
Atomic radius
A (zero charge) 1.60-1.62 —
A (+4 charge) 0.80-0.90
Density
(g/m at 20°C) 6.510 6.640
(lb. /cubic in.) 0.235 0.240
Crystal structure
alpha-phase Hexagonal close-packed
(below 865°C)
beta-phase Body-centered cubic Body-centered cubic
(above 865°C) (above 854°C)
alpha + beta-phase Hexagonal-close-packed
+ body-centered cubic
(below 854°C)
Melting point 1852°C (3365°F) 1840°C (3344°F)
Boiling point 4377°C (7910°F) 4380°C (7916°F)
Coefficient of thermal expansion per °C 5.89 x 10" 6
6.3 x 10"6
25°C (73°F)
(continued)
233
Physical properties Zr 702 Zr 705
Thermal conductivity (300-800°K)

(BTU«ft/hr-ft 2 -°F) 13 10
(W/m-°K) 22 17.1
Specific heat [BTU/lb-°F (320-212°F)] 0.068 0.067
Vapor pressure (mraHg)
2000°C (3632°F) 0.01 -
3600°C (6512°F) 900.0 -
Electrical resistivity [yft-cm at 20°C, (68°F)] 39.7 55.0
Temperature coefficient of resistivity per °C
20°C (68°F) 0.0044 -
Latent heat of fusion (cal/g) 60.4 —
Latent heat of vaporization (cal/g) 1550 —•
Mechanical properties
Modulus of elasticity
106 psi (GPa) 14.4 (99) 14.0 (97)
Shear modulus
106 psi (GPa) 5.25 (36) 5.0 (34)
Poisson^ ratio (ambient temperature) 0.35 0.33

TABLE 2 Properties of Annealed Commercial Grades of Zirconium and Its Alloys
UNS n o . a R60702 R60704 R60705 R60706

3
Nominal 4.5 Hf max, 4.5 Hf max, 4.5 Hf max, 4.5 Hf max, £'
composition, %D 99.2 Zr + Hf min, 1.00 - 2.00 Sn, 2.0-3.0 Cb, 2.0-3.0 Cb
0.2 Fe + Cr max, 97.5 Zr + Hf min, 95.5 Zr + Hf min, 95.5 Zr + Hf min,
0.16 0 max 0.20-0.40 Fe + Cr, 0.2 Fe + Cr max, 0.2 Fe + Cr max,
0.18 O max 0.18 O max 0.16 O max
Average physical
properties
Modulus of 14.4 (99) 14.5 (100) 14.0 (97) 14.0 (97)
elasticity,
106 psi (GPa)
Modulus of 5.25 (36) 5.25 (36) 5.0 (34) 5.0 (34)
rigidity,
106 psi (GPa)
Pois son's ratio 0.34 0.35 0.33 0.33
3
Density, lb/in. 0.234 0.237 0.240 0.240
(kg/m 3 ) (6480) (6560) (6640) (6640)
Coefficient of 3.2 (5.8) at 60°F (15°C), 3.7 (6.7) from 3.5 (6.3) at 3.5 (6.3) at
thermal expansion, 60 to 750°F (15 to 400°C) 60°F 60°F
y i n . / i n . / ° F (ym/m/°C)
Average mechanical 70°F 600°F 70°F 600°F 70°F 600°F 70°F
properties (20°C) (315°C) (20°C) (315°C) (20°C) (315°C) (20°C)
(continued)
CO
OH
ISO
CO
UNS no. a R60702 R60704 R60705 R60706
Tensile strength, 65(450) 18(125) 70(485) 20(140) 85(585) 48(330) 80(550)

103 psi (MPa)
Yield strength, 45(310) 12(85) 55(380) 15(105) 65(450) 30(205) 65(450)
103 psi (MPa)
Elongation, % 25 35 20 32 20 30 25
Reduction in 50 65 42 60 45 65 50
area, %
Characteristics Good fabricability, Fair fabricability Excellent fabrica- Excellent fabrica-
and applications excellent corrosion good corrosion bility, good corro- bility for severe
resistance; chemical resistance; chemical sion resistance; forming applica-
equipment, heat equipment, heat chemical equipment, tions, good corro-
exchangers exchangers piping, heat ex- sion resistance;
changers plate-type heat
exchangers
Applicable specifications include ASTM B493 (forgings), B523 (seamless and welded tubing), B550 (bars),
B551 (flat rolled products), B653 (seamless and welded fittings), B658 (seamless and welded pipe), and
AWS A5.24-79 (welding rods and electrodes). Corresponding ASME specifications also apply for grades
R60702 and R60705.
b
0.05 C max, 0.005 H max, 0.025 N max.
Source: Teledyne Wan Chang Albany. (Reviewed February 1985).
3
o
£'
TABLE 3 Minimum ASTM Requirements for the Mechanical Properties of Zirconium at Room Tempera- 3
ture (Cold-Worked and Annealed)
Grade Zr 702 Zr 704 Zr 705 Zr 706

(ASTM designation) (R60702) (R60704) (R60705) (R60706)
Tensile strength, min. 55 (379) 60 (413) 80 (552) 74 (510)

ksi (MPa)
Yield strength, min. 30 (207) 35 (241) 55 (379) 50 (345)
ksi (MPa)
Elongation (0.2% offset) 16 14 16 20
min. (%)
Bend test radius a 5T 5T 3T 2.5T
a
Bend tests are not applicable to material over 0.187 in. (4.75 mm) in thickness. T equals the thick-
ness of the bend test sample.
O
CO
CO
00
TABLE 4 ASME Mechanical Requirements of Zirconium Grade 702 and Grade 705 for Unfired
Pressure Vessels
Specified Minimum Maximum allowable stress values in

Material tensile yield tension for metal temperature
form and strength strength not exceeding °F
spec. no. Grade Condition (Kips/in. 2 ) (Kips/in. 2 ) Notes 100 200 300 400 500 600 700
Flat rolled
products 702 52.0 30.0 13.0 11.0 9.3 7.0 6.1 6.0 4.8
SB 551 705 80.0 55.0 20.0 16.6 14.2 12.5 11.3 10.4 9.9
Tubing 702 Seamless 52.0 30.0 13.0 11.0 9.3 7.0 6.1 6.0 4.8
SB 523 705 Seamless 80.0 55.0 20.0 16.6 14.2 12.5 11.3 10.4 9.9
Tubing 702 Welded 52.0 30.0 a,b 11.1 9.4 7.9 6.0 5.2 5.1 4.1
SB 523 705 Welded 80.0 55.0 a,b 17.0 14.1 12.0 10.6 9.6 8.5 7.6
Forgings 702 52.0 30.0 13.0 11.0 9.3 7.0 6.1 6.0 4.8
SB 493 705 80.0 55.0 20.0 16.6 14.2 12.5 11.3 10.4 9.9
Bar 702 52.0 30.0 13.0 11.0 9.3 7.0 6.1 6.0 4.8
SB 550 705 80.0 55.0 20.0 16.6 14.2 12.5 11.3 10.4 9.9
a
85% joint efficiency has been used in determining the allowable stress value for welded tube.
^Filler metal shall not be used in the manufacture of welded tube.
12. Zirconium 239
grades list UNS R60704 as the alloy corresponding closely to zirca-

loys, and UNS R60705 and R60706 as the alloys corresponding closely
to Zr-2.5Nb.
Properties and design specifications for zirconium alloys are given
in Tables 2 to 4. Grade 704 has higher strength but has less duc-
tility than grade 702. The fabrication properties, however are very
similar. Grade 705 has greater strength than grade 704 and has
more ductility than grade 702. Grade 705 can be cold-bent around
a radius three times the metal!s thickness compared with five times
the thickness for grades 702 and 704. Grade 706 has less strength
than grade 705, but it has greater fabricability, especially in die
forming. Typical tensile properties of zirconium and its alloys,
relative to temperature, are illustrated graphically in Figures 1 to 3.
The most notable elements affecting mechanical properties are oxygen,
nitrogen, and iron.
0 100 200 300 400 500 600 700 800

Temperature (°F)
FIGURE 1 Typical tensile properties of zirconium grade 702.
240 Yau
0 100 200 300 400 500 600 700 800

Temperature ( F)
Zirconium and its alloys exhibit a fatigue-limit behavior similar

to most ferrous alloys. Grade 702 fatigue characteristics are illus-
trated in Figure 4. The fatigue limit is increased by most alloy
additions. Oxygen has a very strong effect on fatigue properties.
CORROSION PROPERTIES
Zirconium is a reactive metal, as evidenced by its redox potential

of -1.53 V versus the normal hydrogen electrode at 25°C. It has
a high affinity for oxygen. When zirconium is exposed to an oxygen-
containing environment, an adherent, protective oxide film forms
on its surface. This film is formed spontaneously in air or water
at ambient temperature and below. Moreover, this film is self-healing
and protects the base metal from chemical and mechanical attack
0 100 200 300 400 500 600 700 800
Temperature (°F)
30
H I M — M l ' Nil H I M
n i l , i i i l i ii I I i il I I i
104 10 5 10 6 107
CYCLES
FIGURE 4 Flexure fatigue curves for zirconium grade 702.

242 Yau
at temperatures up to 300°C. As a result, zirconium resists many

chemical solutions. These include mineral acids, alkaline solutions,
most organic and salt solutions, and molten alkalis [3-10]. It has
excellent oxidation resistance up to 400°C in air, steam, carbon
dioxide, sulfur dioxide, nitrogen, and oxygen [1,2,6]. It will not
be attacked by oxidizing media unless halides are also present.
It is attacked by hydrofluoric acid, wet chlorine, concentrated
sulfuric acid, aqua regia, ferric chloride, and cupric chloride
[7,11-16].
Water and Steam

Corrosion and oxidation of unalloyed zirconium in high-temperature
water and steam are found to be irregular [17,18]. This behavior
is probably caused by variations in the impurity content in the
metal. Nitrogen and carbon impurities are particularly harmful.
The oxidation rate of zirconium increases markedly when nitrogen
and carbon concentrations exceed 40 and 300 ppm, respectively
[17,18]. The irregular corrosion behavior of unalloyed zirconium
stimulated alloy development programs. Zircaloy-2, Zircaloy-4,
Zr-2.5Nb, and Zr-lNb are the most important alloys used in water-
cooled nuclear reactors because they have the most reliable corrosion
resistance in high-temperature water and steam. Zircaloy-2 is
superior to unalloyed zirconium in high-temperature water and steam.
A tightly adherent oxide film forms on this alloy at a rate that is
at first quasi-cubic but, after an initial period, undergoes a transi-
tion to linear behavior. Unlike the oxide film on unalloyed zirconium,
the oxide film on Zircaloy-2 remains dark and adherent throughout
transition and in the posttransition region.
Zircaloy-4 differs in composition from Zircaloy-2 in having no
nickel and a slightly higher iron content. Both variations are intended
to reduce hydrogen pickup in reactor operation. Zircaloy-4 and
Zircaloy-2 have close corrosion resistance. However, hydrogen pick-
up for Zircaloy-4 is significantly lower, particularly when the alloy
is exposed to water at 360°C. At this temperature, hydrogen pickup
for Zircaloy-4 is about 25% of theoretical, or less than half that
for Zircaloy-2. In addition, hydrogen pickup for Zircaloy-4 is less
sensitive to hydrogen overpressure than that for Zircaloy-2. For
both zircaloys, hydrogen pickup is markedly decreased when dissolved
oxygen is present in the corrosion medium [17],
Alloy Zr-2.5Nb is considered to be somewhat less resistant to
corrosion than the zircaloys. Nevertheless, Zr-2.5Nb is acceptable
for many applications. An example is the use of Zr-2.5Nb pressure
tubes in the primary loops of some reactors. The corrosion resistance
of Zr-2.5Nb can be substantially improved by heat treatments [19,20].
12. Zirconium 243
Also, Zr-2.5Nb is superior to zircaloys in steam at temperatures

above 400°C [21].
Salt Water
Zirconium has excellent corrosion resistance to seawater, brackish
water, and polluted water. The corrosion properties of zirconium
grades 702 and 704 in natural seawater can be found in Reference 22.
Specimens with or without crevice attachment of Zr 702 were placed
in the Pacific Ocean at Newport, Oregon, for up to 129 days. All
welded and nonwelded specimens exhibited negligible corrosion rates.
Marine biofouling was observed; however, no attack was found be-
neath the marine organisms or within the crevices. Laboratory tests
were performed on Zr 702 and Zr 704 in boiling seawater for 275
days and in 200°C seawater for 29 days. Both alloys were resistant
to general corrosion, pitting, and crevice corrosion. Tests of U-bend
specimens, with or without steel coupling, of Zr 702, nickel-containing
Zr 704, and nickel-free Zr 704 were conducted in boiling seawater
for 365 days. Results are given in Table 5. No cracking was ob-
served during the testing period. Overstressing of the tested
U-bends indicated that all specimens were still ductile except for
the welded nickel-containing Zr 704 with steel coupling. Steel-coupled
nickel-containing Zr 704 showed much higher hydrogen and oxygen
absorption and formed hydrides, particularly in the weld heat-
affected zone. Chemical analysis and metallographic examinations
on other U-bends did not show evidence of hydride formation.
TABLE 5 Chemical Analyses for Hydrogen and Oxygen of Tested

U-Bends in Boiling Seawater for 365 Days
Hydrogen Oxygen
Metal (ppm) (ppm)
Nonwelded Zr 702 U-bend with steel coupling 6 1350

Non welded Zr 704 (Ni-containing) U-bend with
steel coupling 8 1480
Nonwelded Zr 704 (Nl-free) U-bend with steel
coupling 9 1440
Welded Zr 702 U-bend with steel coupling 8 1250
Welded Zr 704 U-bend (Ni-containing) with steel 450 5000
Welded Zr 704 (Ni-free) U-bend with steel
coupling 5 1480
244 Yau
Halogen Acids
Zirconium is vigorously attacked by hydrofluoric acid (HF) at all
concentrations, even small amounts (>. 1 ppm) in an acidic solution
will cause accelerated corrosion [16]. Moreover, fluoride impurities
tend to form HF in pH < 3 solutions [23]. In the presence of HF,
corrosion of zirconium equipment can be prevented by adding an
inhibitor that forms strong fluoride complexes. Examples of using
zirconium sponge and phosphorus pentaoxide as inhibitors are given
in Table 6. There are other materials, such as zirconium nitrate
and thorium, that can also be considered as HF inhibitors. The
other halogen acids, e . g . , hydrochloric (HC1), hydrobromic (HBr),
and hydroiodic (HI) acids, do not attack zirconium [3,11,24],
Corrosion information for HBr and HI is based on test results
obtained at Teledyne Wah Chang Albany (TWCA). Corrosion rates
in boiling 20, 45, and 48% HBr were less than 5 mil per year (mpy),
in boiling 47% HI, and in 5% HI with 85% acetic acid at 80°C were
less than 1 mpy.
One of the most important corrosion-resistant properties of zir-
conium is its excellent resistance in HC1 at all concentrations and
temperatures even above boiling [11,12,24,25]. For metallic materials,
hydrochloric acid is the most difficult to handle of the common acids.
The presence of even a small amount of HC1 in a medium may cause
TABLE 6 Effect of Zr Sponge or P 2 O 5 on the Corrosion of Zirconium

in Fluoride-Containing Solutions
Temp. Corrosion
Medium Inhibitor (°C) rate (mpy)
7.2% A1F3 1H- 0,5% HF None 90 >1000

16% Zr sponge 90 < 1
0.2% CaCl2 + 0.1% MgCl2
+ 620 ppm CaF 2 ; pH 1 None 80 350
1200 ppm P 2 O 5 80 15
2% CaCl2 + 1% MgCl2
+ 620 ppm CaF 2 ; pH 1 None 80 150
1200 ppm P 2 O 5 80 <1
6.6% CaCl2 + 3.3% MgCl2
+ 620 ppm CaF 2 ; pH 1 None 80 40
1200 ppm P 2 O 5 80 <1
90% HNO3 + 200 ppm HF None 25 >1000
800 ppm Zr sponge 25 < 1
12. Zirconium 245
260-
220-
180-
Corrosion Rate
0-5 mpy
140-
Boiling Curve
60-
20
10 20 30 40
HCl Concentration (wt%)
FIGURE 5 Isocorrosion chart for zirconium in HCl.
pitting and stress-corrosion cracking (SCC) of common metals and

alloys.
The isocorrosion diagram for zirconium in HCl is shown in Figure
5. Zirconium is suitable for handling HCl at all concentrations.
Moreover, zirconium is not as susceptible to hydrogen embrittlement
in HCl as tantalum is [26,27]. As discussed in Reference 27, tantalum
lost 33% and 18% of its ductility after 1000 hr in 11 M HCl and 11 M
HCl + 7% GaCl 3 , respectively, at 70°C. Under the same testing
conditions, zirconium remained, unattacked and retained 100% of
its ductility.
Although HCl is highly reducing, the anodic polarization curves
of zirconium do not have the active region (Fig. 6). This corrosion
property explains the resistance of zirconium to crevice corrosion
in chloride solutions. However, Figure 6 shows that zirconium can
suffer pitting or SCC, or both, when it is anodically polarized to
a potential at or exceeding the pitting potentials. The same types
of corrosion problems can be developed in HCl when highly oxidizing
ions, such as Fe 3 + and Cu 2 + , are present. Figure 7 demonstrates
246 Yau
the detrimental effect of Fe 3 + in 20% HC1 at 100°C. It can be seen

that the presence of Fe 3 + polarizes the zirconium surface to a poten-
tial exceeding the pitting potential. Thus, local breakdown of the
passive surface at preferred sites occurs, and a condition develops
that favors both pitting and SCC. Maintaining zirconium at a poten-
tial in its passive region, which is arbitrarily set at 50 to 100 mV
below the corrosion potential, can counteract the detrimental effects
resulting from the presence of Fe 3 + [28].
Nitric Acid
Nitric acid (HNO 3 ), because of its passivating power, is not con-
sidered to be a difficult acid for passive metals to handle. Neverthe-
less, HNO3 becomes highly corrosive when its temperature is high
or when impurities, such as heavy-metal ions, are present.
The excellent corrosion resistance of zirconium in HNO3 has
been known for over 30 years [17,11,25]. Below the boiling point
and at 98% HNO3 and up to 250°C and at 70% HNO3, the corrosion
-0.4
Log(Current Density), jx
FIGURE 6 Anodic polarization curves for zirconium in HC1.

12, Zirconium 247
1
1 ' ' 1 '
^
0.24
0.14
A "
E(V,sce)
Z
HO + 500ppm F e - ^ \ . .
-<X16 —
-0L26 —
, i . , i , , 1 , , 1 ,
10" 10 10 2 103 104
K/ttA/cnf)
FIGURE 7 Polarization curves for zirconium in 20% HC1 with and

without 500 ppm Fe 3 + at 100°C.
rate of zirconium is less than 5 mpy (Fig. 8). Recent autoclave

tests showed that the corrosion rates of zirconium were less than
1 mpy in 80% HNO3 and 90% HNO3 at 120 and 150°C [29]. Moreover,
the corrosion rates were still under 1 mpy when zirconium was
tested in boiling 30 to 70% HNO3 with up to 1% FeCl 3 , 1% NaCl,
1% seawater, 1% iron or 1.45% type 304 stainless steel at 205°C
[29]. These results indicated that the presence of heavy-metal
ions and Cl" in HNO3 has little effect on the corrosion resistance
of zirconium.
Zirconium is normally susceptible to pitting in acidic oxidizing
chloride solutions. However, NO 3 " ion effectively inhibits the pitting
of zirconium [25,30,31]. The minimum [NO 3 "]/[C1"] molar ratio
required to inhibit pitting of zirconium was determined to be 1
[25,30] or 5 [31]. Nevertheless, the presence of an appreciable
amount of HC1 should be avoided because zirconium is not resistant
to aqua regia.
248 Yau
The anodic polarization curves of zirconium in HNO3 are shown

in Figure 9. Zirconium exhibits the passive-to-active behavior in
HNO3. It has very noble corrosion potentials because of the oxidizing
nature of HNO3. The transpassive potential decreases with increasing
acid concentration. Still, common oxidizing agents, such as oxygen
and Fe 3 + , will not affect the corrosion resistance of zirconium.
The polarization curves do suggest that, although corrosion rates
are low, zirconium may be sensitive to stress in concentrated HNO3.
This is consistent with the observation of SCC in U-bend specimens
in more than 70% HNO3 [32]. The slow strain-rate technique can
reveal zirconium's SCC susceptibility in less than 70% HNO3 [33],
The primary concern in the use of zirconium for HNO3 service
is SCC in concentrated HNO3. Results of C-ring tests indicate that
zirconium specimens will have a long life when they are stressed
below the yield point [32]. Cracking can be prevented by avoiding
• r
260-
-450
220-
i not tested
Corrosion Rate
Z, 1 8 0 - 350
O-5 mpy
3
Boiling Curve 250
0-5 mpy
-150
60-
20 I I
20 40 60 80 100
HNO3 Concentration (wt%)
FIGURE 8 Isocorrosion chart for zirconium in HNO3.

12. Zirconium 249
LogCCurrent Density),
FIGURE 9 Anodic polarization curves for zirconium in HNO3.
high, sustained tensile stresses or by applying other preventative

measures [34].
Other concerns include the accumulation of chlorine gas in the
vapor phase and the presence of noncomplexed F" ion [29], Chlorine
gas can be generated by the oxidation of chlorides in HNO3. Areas
that can trap chlorine gas should be avoided for zirconium equip-
ment when Cl~ is present in HNO3. In addition, the corrosion of
zirconium in HNO3-F~ solutions can be controlled by adding an
inhibitor, such as zirconium sponge and zirconium nitrate, to con-
vert F~ ion into noncorrosive complex ion.
Sulfuric Acid
Sulfuric acid (H^SO^) is a complicated corrosive. It has a wide
range of strengths, changing from the reducing character of dilute
solutions to the oxidizing character of concentrated solutions. The
250 Yau
resistance of most engineering metals and alloys depends greatly

on the acid concentration and temperature. The usefulness of many
materials is restricted to some specific conditions, such as low con-
centrations, high concentrations, or low temperatures.
The corrosion of zirconium in I^SO^ is rather straightforward
(Fig. 10). It can be seen that zirconium resists attack by I^SO^
at all concentrations up to 70% and at temperatures to boiling and
above. In 70 to 80% I^SO^, the corrosion resistance of zirconium
depends strongly on temperature. In highly concentrated I^SO^,
the corrosion rate of zirconium increases rapidly with concentration.
In the range in which zirconium shows corrosion resistance in
I^SO^, a passive film is formed on zirconium that is predominantly
cubic zirconium oxide (ZrO2) with only traces of the monoclinic
phase [35], Zirconium corrodes in highly concentrated f^SO^ (for
example, 80%) because loose films are formed that prove to be
200 mpy 500

260
450
220-
400
180 350 _
300 |
140 CD
Q.
250 a
100
Boiling Point Curve 200
150
60
100
\\\
20
0 20 40 60 80 100
Concentration (Wt%)
FIGURE 10 Isocorrosion chart for zirconium in

12. Zirconium 251
1.2 Zr vs. H2SO4 (wt. %)

Temp.: Near B.P.
Scan Rate: 10 mV/min
0.8
72.5
-0.4-
101 102
log i, pA/cm2
FIGURE 11 Anodic polarization curves for zirconium in
zirconium disulfate tetrahydrate [Zr(SOi t ) 2 «4H 2 O] [36]. Also, at

the higher acid concentrations, films that flake off are formed,
and are probably partly zirconium hydrides [36].
The anodic polarization curves of zirconium in 4.9 to 72.5%
K^SO^ at near-boiling temperatures are shown in Figure 11. As
indicated in Figure 11, zirconium experiences a passive-to-
transpassive transition in t^SO^ with an increasing potential.
Zirconium does not have the active region in I^SO^, as do common
metals and alloys. Figure 11 shows that the transpassive potential
of zirconium in K^SO^ decreases with increasing concentration.
As shown in Figure 12, in less than 65% K^SO^, zirconium can
tolerate some amounts of strong oxidizing agents, such as Fe 3 + ,
252 Yau
pure acid 200ppm Cu 2+

200ppm NO3" 200ppm Fe3+
>0.125 mm/y
Corrosion Rate
<0.125 mm/y
a 90-
70
50-
50 60 70 80
H2SO4 Concentration (wt%)
FIGURE 12 Isocorrosion chart for zirconium in with impurities.
Cu 2 + , and NO3 , without a reduction in corrosion resistance, as

confirmed by results of immersion tests [37]. Moreover, in 40%
or less I^SO^, zirconium can tolerate large amounts of strong oxi-
dizing agents. Consequently, zirconium equipment is often used
in steel pickling [38-41], In more than 65% J^SO^, zirconium be-
comes sensitive to the presence of oxidizing agents [42],
Zirconium weld metal may corrode preferentially when H2SO^
concentration is approximately 55% and higher. Heat treatment at
775 ± 15°C for 1 hr per 25.4 mm of thickness was found to restore
the corrosion resistance to the same high resistance of the parent
metal [43-45].
12. Zirconium 253
TABLE 7 Inhibiting Effect of Sulfate Ion on the General and Local

Corrosion of Zirconium in Boiling Sulfuric Acid and Containing FeCl 3
Temp. Corrosion
rate (mpy) a
40% H 2 SO 4 HH 2% FeCl 3 115 199 b

50% H2SOl+ Hh 2% FeCl 3 124 80
55% H2SOi+ HH 2% FeCl 3 131 83
60% H2SOlf HH 2% FeCl 3 141 26
70% H ^ O , Hi- 2% FeCl 3 166 33
a
Four 1-day cycles.
^Localized corrosion.
The acid concentration limit is very important when zirconium

equipment is used to process H ^ O ^ at elevated temperatures in
the marginal concentration region, such as 60% or more. When the
limit is exceeded, zirconium may corrode rapidly. In less than 65%
H 2 SO^, the vapor phase is almost entirely water vapor [46]. How-
ever, the concentration change is negligible when the system is
under a pressurized condition [47]. Consequently, acid concentration
can change significantly because of, for example, imperfect sealing
of a system. In a nonpressurized system, the acid concentration
can exceed the concentration limit. Acid concentration can easily
change when the system is under vacuum operation because the
water vapor is continuously taken away.
The results of the impurity effect study can be found in Refer-
ences 2, 13, 25, 37, and 42. Several general conclusions are given
as in the following:
1. Ferric, Cu 2 + , and NO 3 " impurities in H ^ O ^ significantly degrade

zirconiumTs corrosion resistance at acid concentrations above 65%.
2. Chloride ion alone does not change the corrosion resistance of
zirconium in H ^ O ^ .
3. When heavy-metal ions and halide ions coexist in H ^ O ^ (for
example, when FeCl3 is present), the optimum acid concentration
range for zirconium is 60 to 70% as demonstrated in Table 7.
4. Zirconium can tolerate only very small amounts of fluoride ions
in H 2 SO 4 , even at low acid concentrations. Fluoride ions must
be complexed using an inhibitor, such as zirconium sponge and
zirconium nitrate.
5. Chlorine gas-saturated 40 to 55% H2SOlf attacked and caused
pitting of zirconium. However, in higher acid concentrations
254 Yau
(55 to 70%), zirconium's corrosion resistance is not affected by

chlorine gas [13].
6. The addition of 1% bichromate or 0.0082 to 0.0548 M tetravalent
zirconium ions in 80% I^SO^ can reduce corrosion of zirconium
[2,25].
When the corrosion resistance limits of zirconium in K^SO^ are

exceeded, a pyrophoric surface layer may be formed on zirconium
under some specific conditions [4,48]. The pyrophoric surface layer
on zirconium formed in 77.5% I^SO^ + 200 ppm Fe 3 + at 80°C consisted
of y-hydride, ZrO 2 , Zr(SO t+ ) 2 , and fine metallic particles [48].
The combination of y-hydride and metallic particles is suggested
to be responsible for the pyrophoricity. Treating in hot air or
steam can eliminate this tendency [48].
Phosphoric Acid
Phosphoric acid (HgPO^) is less corrosive than other mineral acids.
Many materials demonstrate useful resistance in HgPO^ at low tem-
peratures. As usual, corrosion rates increase with temperature,
concentration, and impurities in the acid. Areas such as the liquid-
level line or the condensing zone are particularly vulnerable to
attack.
Zirconium resists attack in H3POi+ at concentrations up to 55%
and temperatures exceeding the boiling point. Above 55% HgPO^,
the corrosion rate could increase greatly with temperature (Fig. 13).
The most interesting area for zirconium would be dilute HgPO^ at
elevated temperatures. Zirconium outperforms common stainless alloys
in this area [49].
Figure 14 shows the anodic polarization curves of zirconium in
H3PO1+ at near-boiling temperatures. As the concentration increases,
the passive range diminishes gradually, and the passive current
increases progressively. It appears that zirconium passivates more
slowly in H3POi+ than in other mineral acids.
If H3POi+ contains more than a trace of F" ion, attack on zirconium
may occur. Because fluoride compounds are often present in H3POi+,
the use of zirconium has always been questioned. However, because
P 2 O 5 is an effective fluoride inhibitor for zirconium and a large
amount of P 2 O 5 is usually present in H3PO4 processes, tests should
be performed to determine the suitability of zirconium in the actual
H3POLf medium.
Other Acids
Zirconium has excellent corrosion resistance in up to 30% chromic
acid at temperatures to 100°C [6]. It cannot be used in chrome-
12, Zirconium 255
260-
-450
220-
180- -350
140-
-250
Boiling Curve
100
0-5 mpy
Corrosion Rate
-150
60-
20
20 40 60 80 100
H3PO4 Concentration (wt%)
FIGURE 13 Isocorrosion chart for zirconium in H3PO1+.
plating solutions because of the fluoride catalyst. In sulfurous acid,

zirconium has a corrosion rate of less than 0.2 mpy at 100°C.
Zirconium is also resistant to some mixed acid systems. It can
be used in acid mixtures of sulfuric-nitric, sulfuric-hydrochloric,
and phosphoric-nitric. The sulfuric acid concentration must be
below 70% [7,25]. Zirconium is aggressively attacked in 1:3 volume
mixtures of nitric acid and hydrochloric acid (aqua regia). In
1:1 volume mixtures, zirconium is attacked but much slower than
in the 1:3 mixture [25]. In mixtures greater than 3:1 nitric acid/
hydrochloric acid, zirconium is resistant. Some data for the mixed
acid systems are given in Table 8.
Alkalies
Zirconium resists attack in almost all alkalies, either fused or in
solution [6,13,50]. It is resistant in sodium hydroxide (NaOH) and
potassium hydroxide (KOH) solutions, even under anhydrous condi-
256 Yau
1.0 /
/730%
^50%
m 0.8 - / ^— ^ /60*
/
/
a6 / .70*
75
nti
/
0) / / /
-
/ /
Q. /
"D /
.2> 0.2 - /
/1 7/'
Q. /
a ;
i /
/
0.0 -
/
/
-0.2
6 1 2 3
Log(Current Density),
FIGURE 14 Anodic polarization curves for zirconium in H3POi+.
tions. It is also resistant to calcium hydroxide and ammonium hy-

droxide solutions at concentrations to 28% and temperatures to boiling.
This makes zirconium distinctly different from other highly corrosion-
resistant materials, such as tantalum and glass.
Zirconium U-bend specimens were tested in boiling, concentrated
NaOH at TWCA. During the test period, the concentration changed
from 50% to about 85%, and temperature increased from 150 to 300°C.
The polytetrafluoroethylene washers and tubes used to make the
U-bends dissolved. However, the zirconium U-bend specimens
remained ductile and did not show any cracks after 20 days.
Zirconium coupons were tested in a white-liquor, paper-pulping
solution, which contained NaOH and sodium sulfide, at 120, 175,
and 225°C at TWCA. All coupons had corrosion rates of less than
1 mpy. In the same solution, graphite and glass both corroded
badly at 100°C.
12. Zirconium 257
TABLE 8 Corrosion Rates of Zirconium in Some Mixed Acids
Test solution a Temperature Corrosion

(wt%) (°C) r a t e s (mpy)
1% H ^ O ^ 99% HNO3 R T , b 100 0.06

10% U2SO^ 90% HNO3 RT, 100 WGC
14% H^SO^ 14% HNO3 Boiling 0.1
25% H2SOLf 75% HNO3 100 150
50% H 2 SO If 50% HNO3 RT 0.63
68% H2SOi+ 5% HNO3 Boiling 2000
68% H2SOLf 1% HNO3 Boiling 11
75% H2SOl+ 25% HNO3 RT 260
88% HgPO^ 0.5% HNO3 RT 0.0
88% ^ P O ^ 5% HNO3 RT WGC
Aqua Regia RT Dissolved
20% HCl 20% HNO3 RT Dissolved
10% HCl 10% HNO3 RT Dissolved
7.5% H ^ O , , 19% HCl Boiling 0.5
34% H ^ O ^ 17% HCl Boiling 0.3
40% H 2 SO 4 14% HCl Boiling 0.2
56% H2SOLf 10% HCl Boiling 2.0
60% H 2 SO 4 1.5% HCl Boiling 1.0
69% H 2 SO 4 1.5% HCl Boiling 5.0
69% H2SOi+ 4% HCl Boiling 15.0
72% H2SOl+ 1.5% HCl Boiling 20.0
a
Corrosion test with HC1/H2SOI+ and HC1/HNO3 solutions were con-
ducted at TWCA.
^ R T , room t e m p e r a t u r e .
C
WG, weight gain.
Source: Refs. 7,25.
Salt Solutions
Zirconium is resistant to most salt solutions [7]. These include
halogen, nitrate, carbonate, and sulfate salts. Corrosion rates are
usually very low at all temperatures up to the boiling point. Solutions
of FeCl3 and CuCl 2 are examples of the few exceptions. Although
zirconium has good corrosion resistance in sodium fluoride (NaF)
and potassium fluoride (KF) at low temperatures, resistance de-
creased rapidly with increasing temperature. Consequently, zirconium
is not recommended for handling any fluoride-containing solutions
unless F" ions are complexed. Zirconium is considerably more resist-
258 Yau
ant to chloride SCC than stainless steels are. No failure was ob-
served in U-bend tests conducted in boiling 42% magnesium chloride
(MgCl2) at TWCA. The other attractive corrosion property of zir-
conium is its high crevice corrosion resistance. Zirconium is not
subject to crevice corrosion even in acidic chloride solutions at
elevated temperatures. No attack was observed on zirconium in
salt spray environment [51].
Unlike many common metals, zirconium has very little affinity
for sulfur. Zirconium-sulfur compounds were found to form only
at temperatures above 500°C [52]. Furthermore, there is no instance
of zirconium-sulfur bonds forming in aqueous systems [53]. Conse-
quently, hydrogen sulfide (H 2 S) is not expected to participate
in the corrosion reactions of zirconium in sulfide-containing solutions.
Zirconium coupons and U-bends were tested in numerous NaCl-H2S
solutions at temperatures to 232°C [22,54-56]. No pitting, crevice
corrosion or cracking was observed.
Organic Solutions
The corrosion resistance of zirconium in organic solutions is excellent
[1,57], as indicated in Table 9. It has been tested extensively in
organic-cooled reactors where the coolant consisted of mixtures
of high-boiling aromatic hydrocarbons ( e . g . , terphenyls) [1]. These
coolants are noncorrosive to zirconium. Early experiments in the
organic coolants indicated that hydriding could be a major problem.
It was found that chlorine impurity in the organic was the major
cause of gross hydriding. Elimination of the chlorine and maintenance
of a good surface oxide film by ensuring the presence of adequate
water (> 50 ppm) alleviates the hydriding problem. Zirconium is
susceptible to SCC in alcohol solutions with halide impurities present.
In some chlorine-containing carbon compounds, e . g . , carbon tetra-
chloride and dichlorobenzene, zirconium has excellent corrosion
resistance at temperatures up to 200°C.
Gases
Zirconium is not attacked by most gases (CO, CO 2 , SO 2 , C 3 H 8 ,
N 2 , steam, and air) until temperatures exceed 300 to 400°C [1,6].
Zirconium reacts with hydrogen at 300°C to form hydrides. The
metal oxidizes readily in air when temperatures exceed 500°C.
Zirconium1 s resistance to air, hot water, and steam is of special
interest to nuclear power applications. The metal can be exposed
for prolonged periods without pronounced attack at temperatures of
425° C. In hot water and steam applications at 360°C, zirconium
can tolerate up to 350 ppm chloride and iodide ions, 100 ppm fluoride
12. Zirconium 259
TABLE 9 Corrosion Rates for Zirconium in Organic Solutions
Concentration Temperature Corrosion

Environment (wt%) (°C) rate (mpy)
Acetic acid 5-99.5 35-boiling < 0.07

Acetic anhydride 99.5 Boiling 0.03
Aniline hydrochloride 5, 20 35-100 < 0.01
Chloroacetic acid 100 Boiling <0.01
Citric acid 10-50 35-100 <0.2
Dichloroacetic acid 100 Boiling <20
Formic acid 10-90 35-boiling <0.2
Lactic acid 10-85 35-boiling <0.1
Oxalic acid 0.5-25 35-100 < 0.5
Tartaric acid 10-50 35-100 <0.05
Tannic acid 25 35-100 < 0.1
Trichloroacetic acid 100 Boiling >50
Urea reactor 58% urea 193 < 0.1
17% NH3
15% CO2
10% H2O
Source: Excerpted by special permission from Chemical Engineering,

June 2, 1980. Copyright 1980 by McGraw-Hill, I n c . , New York.
ions, and 10^ ppm sulfate ions without influencing the corrosion
resistance. Zirconium is stable in NH3 up to about 1000°C. It reacts
readily with all halogens at moderate temperatures (200 to 400°C)
to form volatile halides. Zirconium is resistant to attack in dry
Cl 2 gas at 50°C but is attacked at a rate of 200 mpy in wet chlorine
gas [13]. In chlorine-saturated water zirconium corrodes at less
than 1 mpy. Zirconium hydrates in hot (400°C) gas halide acid
environments [58].
Molten Salts
Zirconium is resistant to attack in many molten eutectic salts [1,6].
An excellent set of references is found in an article by Janz and
Tamkins [59]. Zirconium is very resistant to corrosion by molten
sodium hydroxide, up to temperatures exceeding 1000°C [50], Other
investigators find that in hot sodium hydroxide the resistance lasts
only until the white oxide forms [60]. It is somewhat less resistant
in potassium hydroxide although not enough to prohibit use for
reasonable periods [6,13]. In nitrate salts and eutectic mixtures
260 Yau
TABLE 10 Corrosion of Zirconium in Some Liquid Metals
Melting
temperature Temperature I(°O
Liquid metal <°C) 300 600 800
Bi 271.3 Unknown Poor Poor

Bi-In-Sn 60 Unknown Poor Unknown
Bi-Pb 125 Good Limited Unknown
Bi-Pb-In 70 Unknown Poor Unknown
Bi-Pb-Sn 97 Good Limited Unknown
Ga 298 Limited Poor Poor
Hg -38.4 Poor Poor Unknown
Li 180.5 Good Limited Limited
Mg 650 — Poor a Unknown
Na, K, or NaK 12.3-97.9 Good Good Unknown
Pb 327.4 Gooda Limited Limited
Sn 231.9 Good Unknown Unknown
a
At its melting point.
Source: Ref. 61.
of sodium nitrate, and potassium nitrate zirconiumTs oxidation proper-

ties are similar to that in air [1J.
Molten Metals
Corrosion results for zirconium in molten metals should be considered
carefully because corrosion rates are very sensitive to trace impuri-
ties, e . g . , oxygen, hydrogen, or nitrogen, in the liquid metal.
Table 10 illustrates zirconium1 s corrosion resistance in several liquid
metal systems [61]. It has corrosion rates of less than 1 mpy in
liquid lead at temperatures up to 600°C, lithium up to 800°C, mercury
up to 100°C, and sodium up to 600°C [6]. Zirconium is rapidly
attacked in molten zinc, bismuth, and magnesium.
SPECIAL CORROSION TOPICS

Pitting
Zirconium has the susceptibility to pitting in all halide solutions
except fluoride [62]. This susceptibility is greatest in chloride
solutions and decreases as the halide ion becomes heavier, i . e . ,
the pitting potentials in IN solutions of Cl~, Br~, and I" are 380,
12. Zirconium 261
660, and 910 H I V ^ E , respectively. However, zirconium does not

pit in most halide environments because the corrosion potential
is lower than the pitting potential. The presence of oxidizing ions,
such as Fe 3+ and Cu 2+ , in acidic halide solutions increases the
corrosion potential, and pitting can occur when the corrosion poten-
tial exceeds the pitting potential. Zirconium can also pit in per-
chlorate solutions if oxidizing impurities are present. Nitrate and
SOJ;~ ions can inhibit the pitting of zirconium in certain conditions
[63].
Stress-Corrosion Cracking
Zirconium and its alloys resist SCC in many environments, such
as NaCl, HC1, MgCl2, NaOH, and H2S, that would induce SCC in
other alloys. Zirconium service failures resulting from SCC are
few in chemical applications. The high SCC resistance of zirconium
can probably be attributed to its high repassivation rate. Any break
in the surface film will be quickly healed if sufficient oxygen is
present. Even in dehydrated systems, sufficient oxygen is generally
present for repassivation.
The environments known to cause SCC of zirconium alloys include
FeCl3 or CuCl2 solutions, mixtures of methanol (CH3OH) and HC1
or methanol and iodine, concentrated HNO3, and liquid mercury
or cesium. Stress-corrosion cracking in zirconium alloys can be
prevented by
Avoiding high sustained tensile stress

Modifying the environment, e.g., changing concentration or adding
an inhibitor
Achieving a crystallographic texture with the hexagonal basal planes
perpendicular to the cracking path
Maintaining a high-quality surface film, i . e . , one low in impurities,
defects, and mechanical damage
Using electrochemical protection techniques
Fretting Corrosion
Fretting corrosion takes place when vibrational contact is made
at the interface of tight-fitting, highly loaded surfaces, such as
between the leaves of a spring or the parts of ball and roller bear-
ings. Fretting of zirconium occurs when its protective oxide coating
is damaged or removed. The best way to overcome this type of
corrosion (if it cannot be eliminated mechanically) is to apply a
heavy oxide coating on the zirconium. This coating reduces friction
drastically and prevents the removal of the passive protection oxide.
262 Yau
TABLE 11 Galvanic Series in Seawater
Cathodic
(most noble) Platinum
Gold
Graphite
Titanium
Silver
Zirconium
Type 316, 317 stainless steel (passive)
Type 304 stainless steel (passive)
Type 410 stainless steel (passive)
Nickel (passive)
Silver solder
Cupronickels (70-30)
Bronzes
Copper
Brasses
Nickel (active)
Naval brass
Tin
Lead
Type 316, 317 stainless steels (active)
Type 304 stainless steel (active)
Cast iron
Steel or iron
Aluminum 2024
Cadmium
Aluminum (commercially pure)
Anodic Zinc
(active) Magnesium and magnesium alloys
Galvanic Corrosion
Because of the protective oxide film that forms on zirconium in
air, zirconium assumes a noble potential similar to that of silver.
When this protective film is damaged, zirconium can become activated
and can, therefore, corrode when in contact with other more noble
metals (Table 11).
Other less noble metals will corrode when in contact with zirconium
when its oxide film is intact. For example, in seawater or acid solu-
tions, corrosion of steels, aluminum, and zinc is accelerated in
electrical contact with zirconium. Therefore, care should be taken
to keep them electrically insulated.
12. Zirconium 263
Crevice Corrosion
Of all the corrosion-resistant structural metals, zirconium and
tantalum are the most resistant to crevice corrosion. In low-pH
chloride solutions or chlorine gas, for example, zirconium is not
subject to crevice attack.
CORROSION PROTECTION
Oxide Film Formation
One of the unique properties of zirconium that makes it attractive
for chemical use is the protective nature of its oxide film. This
film gives excellent corrosion resistance, in spite of the reactive
nature of the metal. If it is mechanically destroyed, this impervious
oxide barrier will regenerate itself in many environments. Aluminum
and titanium exhibit similar characteristics, but the film on zirconium
is considerably more corrosion-resistant.
Several methods of oxide formation are possible, depending on
the properties desired. Normal methods include anodizing, autoclaving
in high-temperature water or steam, and formation in air.
Anodizing
Anodizing forms a very thin film, but it may be useful in some
applications. Because it is formed near room temperature, the film
does not have the adhesion to the underlying metal of thermally
produced coatings.
Autoclave Film Formation

Autoclave film formation is a practice common to the nuclear reactor
industry. In this process, the uniform film of high integrity that
is formed is superior to the films formed at lower temperatures.
In addition to the slower corrosion rate, the rate of hydrogen
absorption is drastically reduced. Films can be formed in 14 days
in pressurized (19 MPa) deionized water at 360°C or in 1 to 3 days
at 400°C and 10 MPa in high-purity steam.
Film Formation in Air

Film formation in air is the most common method used in the chemical
industry. This film is often formed during the final stress relief
of a component (30 min to 4 hr at 550°C). This film will range
from a straw yellow, to an iridescent blue or purple, to a powdery
tan or light grey. Such films need not be taken as a sign of metal
contamination. This low-temperature stress relief does not cause
264 Yau
significant penetration of oxygen into the metal, but it does form

an oxide layer that is diffusion bonded to the base metal.
In addition to the corrosion resistance provided by the oxide
film, a properly formed film serves as an excellent bearing surface
against a variety of materials in several environments and over
a broad temperature range [64]. This treatment consists of cleaning
the surface, followed by 4 to 6 hr in air at 550°C. The resultant
oxide layer, approximately 5 ym thick, is equivalent to sapphire
in hardness and is diffusion bonded to the base metal. The oxide
layer can be damaged by a striking action, but it serves as an
excellent bearing surface for sliding contacts. Oxidized zirconium
pump shafts are an example of a common application.
Electrochemical Protection
Zirconium experiences a passive-to-transpassive transition with
increasing potential in all mineral acids except HF [65]. The com-
monly observed active node in many metal-acid systems is not ob-
served for zirconium. Consequently, zirconium prefers a more
reducing condition, which produces more stable passive films. In
fact, zirconium is one of the best metals for handling reducing
acids.
By impressing a potential that is arbitrarily 50 to 100 mV below
its corrosion potential, zirconium can be used to handle oxidizing
HC1 solutions [28]. Tables 12 and 13 demonstrate the benefits of
electrochemical protection in greatly reducing pitting and SCC.
The uniform corrosion rates of unprotected coupons are usually
low. However, the penetration rates are much greater than the
uniform corrosion rates and increase with immersion time. Electro-
chemical protection eliminates this local attack. Similarly, unprotected
TABLE 12 Corrosion Rate of Zirconium in 500 ppm F e + 3 Solution

After 32 Days
Temp. Penetration rate (mpy)

Environment Acidity °C) Unprotected Protected
10% HC1 3N 60 7,.1 < 0.1
120 51 < 0.1
Spent acid 5N 65 36 < 0.1

(15% Cl) 80 36 < 0.1
20% HC1 6N 60 3.,6 < 0.1

107 59 < 0.1
12. Zirconium 265
TABLE 13 Time to Failure of Welded Zirconium U-Bends in 500 ppm

Fe + 3 Solution After 32 Days
Temp. Time to failure (days)

Environment Acidity (°C) Unprotected Protected
10% HC1 3N 60 <0.1 NF a

120 <0.1 NF
Spent acid 5N 65 <0.3 NF
(15% Cl)
60 NF NF
20% HC1 6N 107 <0.1 NF
60 2 NF
28% HC1 9N 94 < 0.1 NF
53 1 32
32% HC1 ION 77 <0.1 20
30 0.3 NF
37% HC1 12N 53 1 NF
a
NF, no failure.
welded U-bends cracked in all but one case shortly after exposure,
whereas protected U-bends resisted cracking for the 32-day test
interval in all but one acid concentration. Thus, electrochemical
protection offers a very definite improvement to the corrosion proper-
ties of zirconium in oxidizing acid chlorides.
This electrochemical protection technique can also be used to
combat the SCC of zirconium in concentrated HNO3 [34], In HNO3,
because of the difference between the corrosion potential and the
critical potential that can cause SCC, it is desirable to control the
potential of zirconium a few hundred millivolts below the corrosion
potential, or at 740 m V ^ E .
Others
Zirconium is susceptible to pitting in acidic oxidizing chloride solu-
tions. Cupric ion is more detrimental than Fe 3+ ion in promoting
the pitting and general corrosion of zirconium in acidic chloride
solutions. The test results of zirconium in NaCl + CuCl2 given in
Tables 14 and 15 demonstrate the effects of pH, surface condition,
and heat treatment. The pitting and general corrosion of zirconium
in NaCl + CuCl2 can be controlled by adjusting the pH to 6 or
266 Yau
TABLE 14 Test Results of Zirconium (As-Received Condition) in

Boiling 500 ppm Cu +2 Containing NaCl Solutions After Seven
1-Day Runs
Average corrosion rate (mpy)

Nonwelded Welded
No. % NaCl PH coupons coupons
1. 3.5 1 2.1a 23.6 a

2. 25 1 1.6 21.7 a
3. 3.5 4.8 0.38 a 23.8 a
4. 25 4.0 1.0 21.9 a
5. 3.5 5.0 0.7 25.3 a
6. 25 5.0 Nil Nil
7. 3.5 6.0 Nil Nil
8. 25 6.0 Nil Nil
9. 3.5 7.5 Nil Nil
10. 25 7.5 Nil Nil
a
Pitting.
TABLE 15 Effects of Heat Treatment on the Corrosion of Zirconium

(Sand-Blasted and Pickled) in Boiling NaCl + CuCl2 Solutions After
Seven 1-Day Runs
Average corrosion rate (mpy)

3.5% NaCl 25% NaCl
No. Metal Condition + 500 ppm Cu +2 + 500 ppm Cu +2
1. Nonwelded As conditioned 0.27 a 0.98 a

2. Welded IAS conditioned 0.45 a 1.30 a
3. gelded 760°C/AC <0.1a 0.23 a
4. Welded 760°C/WQ <0.1a 0.17 a
5. Welded 871°C/AC 0.13 0.23 a
6. ( Welded 871°C/WQ 0.13 0.17 a
7. Welded 982°C/AC 0.20 0.27
8. Welded 982°C/WQ 0.20 0.27
a
Pitting.
AC, air cooled; WQ, waterquenched.
12. Zirconium 267
higher (see Table 14) or by heat treatments (see Table 15). Also,
resistance to pitting and general corrosion can be improved by
surface conditioning. As usual, the weld metal is more susceptible
to pitting than the base metal.
TYPICAL APPLICATIONS
Nuclear Industry
The development of water-cooled nuclear power reactors brought
about the use of zirconium for uranium fuel cladding and for struc-
tural components. As a result of these developments in the nuclear
industry, the cost of zirconium and its alloys decreased considerably.
Zirconium and its alloys have emerged as engineering materials
rather than laboratory curiosities. Materials for fuel cladding and
structural components in nuclear reactors are restricted because
of the following crucial requirements:
Low-absorption cross section for thermal neutrons

Adequate strength, creep resistance, and ductility after prolonged
irradiation in the reactor coolant
Excellent corrosion and oxidation resistance
Absence of interactions with the fuel material and fission products
Zirconium alloys, such as the zircaloys and Zr-2.5Nb, have been

developed to meet these requirements. In water-cooled reactors,
zirconium alloys have found extensive use for fuel cladding and
as pressure tubes. In systems in which the first requirement of
those listed is of overriding importance for reasons of neutron
physics, the choice is virtually restricted to zirconium or one of
its alloys.
Zirconium and its alloys also find application in other nuclear
reactor systems, such as gas-cooled or organic coolant-cooled re-
actors.
Chemical-Processing Industry
The earliest application for zirconium was in the production of hydro-
gen peroxide (H 2 O 2 ) using E^SO^. Zirconium shell and tube heat
exchangers replaced graphite exchangers at one plant where they
were used to condense a 75% concentrated K^SO^ medium. The aver-
age maintenance-free life of the heat exchanger was 12 years. The
tubes were thinned at the liquid/gas interface area because of
bubble collapse, but no other corrosion occurred.
268 Yau
Because of this experience, the company replaced the graphite

heat exchangers with zirconium shell and tube exchangers used
in the manufacturing of acrylic films and fibers. In this application,
the I^SO^ concentration was as high as 60% at 150°C.
Another major application in I^SO^ concerns the manufacture
of methyl methacrylate. The system at one company includes pressure
vessels, columns, heat exchangers, piping systems, pumps, and
valves made from zirconium.
Zirconium is also widely used for column internals and reboilers
in the manufacture of butyl alcohol. The operating conditions are
60 to 65% I^SO^ at temperatures to boiling and slightly above.
Zirconium is also used in steel pickling, I^SO^ recovery and recycle
systems in which fluorides are not present and the acid concentration
does not exceed 65%.
Zirconium has many applications relative to HC1, such as the
production of concentrated HC1 and polymers. Zirconium heat ex-
changers, pumps, and agitators have been used for over 15 years
in an azo dye-coupling reaction. In addition to being very corrosion
resistant in this environment, zirconium does not plate out undesirable
salts that would change the color and stability of the dyes. Other
applications with HC1 include the breaking down of cellulose in the
food industry and the polymerization of ethylene chloride, which
is carried out in HC1 and chlorinated solvents.
Zirconium and its alloys were identified as offering the best
prospects from a cost standpoint as materials for an HI decomposer
in hydrogen production [66]. Tantalum, molybdenum, Nb-lZr, and
zirconium alloys showed good corrosion resistance in Hi-media (as
liquid or gas) from room temperature to 300°C, but most nickel-
and iron-based alloys and some nonmetallic materials show corrosion
resistance only at low temperatures.
There is an increasing interest in the use of zirconium for HNO3
service. For example, because of the high degree of concern over
safety-zirconium is chosen as a major structural material for the
critical equipment used to reprocess spent nuclear fuels. Another
application is the production of HNO3.
Zirconium columns and reboilers are being used at one company
to produce 67% HNO3 from 57% HNO3. Previously, such materials
as AISI type 304L stainless steel, titanium, and glass-lined steel
were used. Titanium and 304L stainless steel had relatively short
service lives, while glass-lined steel presented maintenance problems.
A 27-ton zirconium heat exchanger is being used by one company
to produce 65% HNO3 at 205°C. Before the use of zirconium, the
company was faced with such problems as frequent replacement
costs and downtime. In service since October 1984, the zirconium
heat exchanger has already outperformed its stainless steel prede-
cessor.
12. Zirconium 269
With proper design, zirconium can be used to handle a highly

concentrated HNO3. For example, an Israeli chemical plant uses
zirconium tubes in a U-tube cooler that processes bleached HNO3
at concentrations between 98.5 and 99%. The unit cools the acid
from 70 to 75°C to 35 to 40°C. Previously, U-tube coolers were
made from aluminum, which failed in 2 to 12 weeks. The zirconium
has been in service for about 2 years, operating 24 hr a day, 6
days a week.
Another important application for zirconium is in processes that
cycle between HC1 or H2SOlf and alkaline solutions. One company
replaced a lead and brick-lined carbon steel reactor vessel with
zirconium because the reaction alternated between hot F^SO^ and
caustic. The vessel has been in use for several years with no corro-
sion problems.
Zirconium reactor vessels and heat exchangers have been used
in urea production for over 30 years. The use of zirconium equip-
ment allows the reaction to take place at higher temperatures and
pressures, permitting greater conversion of CO2 to urea.
Zirconium is commonly used in the production of acetic acid and
acetic anhydride. Its corrosion rate is less than 2 mpy in all con-
centrations and temperatures.
A zirconium distillation column proved to be safe and economical
in a chlorinated hydrocarbon environment at more than 150°C. The
column was built as a replacement for an old brick-lined column.
Corrosion of the old column necessitated frequent renovations, with
resultant high maintenance costs and plant downtime.
In the zirconium extraction process, several corrosive chemicals
are used, including methyl isobutyl ketone, HC1, ammonium thio-
cyanate, I^SO^, and zirconyl chloride. Zirconium has been found
to withstand the rigors of this manufacturing process, as in the
following five examples.
First, the pumps used to transport the process chemicals are
primary candidates for failure. Various materials, including stainless
alloys, plastics, and high-silicon cast iron had been tried, but
each had some limitation in this severe service. All wetted pump
parts were converted to zirconium. The oldest one has been operating
for more than 5 years and shows no sign of corrosion.
Second, for heat exchanger service in the same process chemicals,
zirconium tubes replaced impervious graphite tubes that were prone
to failure. The oldest zirconium heat exchanger has been in service
more than 7 years and shows no signs of corrosion.
Third, steam stripper columns were converted from a furan resin
to zirconium. At the 105°C operating temperature of the columns,
the plastic would embrittle and crack. Failure of these columns
often resulted in expensive spills. By contrast, zirconium columns
require no maintenance for material failure.
270 Yau
Fourth, zirconium was selected for use in an electrostatic pre-

cipitator installed to scrub corrosive gases emitted from rotary
kilns. The emitting electrodes and all fixtures exposed to the
ammonium sulfate and chloride gas process stream were constructed
from zirconium. The emitting electrodes are charged with 45,000 V.
Fifth, several parts of a crude chlorination scrubber were con-
verted from plastic to zirconium. The plastic parts were replaced
approximately every 6 months. The zirconium replacement is expected
to last at least 25 years.
Zirconium is not toxic and has very low corrosion rates in many
media. It is an excellent material for equipment used in food proc-
essing, the manufacture of electronic-grade chemicals, and pharma-
ceutical preparations.
Potential applications also include heat exchangers exposed to
seawater, cladding for high-strength or lightweight alloys, parts
subjected to thermal and mechanical stresses in a marine environ-
ment, and nuclear waste packages.
Finally, zirconium is an excellent material for laboratory equip-
ment, such as crucibles and autoclaves. Preoxidized zirconium can
be used as insulating washers and measuring devices exposed to
high-temperature corrosives.
FABRICATION PRACTICES
Zirconium and its alloys are ductile and workable. They can be
fabricated using standard shop equipment with a few modifications
and special techniques. Of primary concerns are the tendency of
zirconium to react with gases in air at elevated temperatures and
to gall and seize under sliding contact with other metals. Fabrica-
bility depends on the oxygen content of the metal. The lower the
oxygen content the easier the metal is to form.
Proper fabrication practices are fully described in reference 67.
Forming
In forming operations, a thin oxide layer on zirconium acts as a
lubricant against galling. If additional lubricant is required, use
any oil or grease that does not contain halogen or sulfur, except
that molydisulfide may be used. Be sure to clean off all traces
of oil and dirt before heat treating.
Zirconium can be easily bent and formed using standard shop
equipment. Zirconium grade 702 sheet and strip can be bent on
conventional press brake or roll-forming equipment to a 5T bend
12. Zirconium 271
radius at room temperature and to 3T at approximately 200° C.

Zirconium grade 705 can be bent to 3T bend radius at room tempera-
ture and to 1.5T at approximately 200°C.
Punching
Pure zirconium and zirconium alloys act differently during punching
operations. Pure zirconium requires high-pressure plate pressures
or excessive side flow occurs. Very close punch and die tolerances
(1 to 2% of the metal thickness) provides the best results. Somewhat
larger punch and die clearances are satisfactory with the zirconium
alloys.
Tube Bending
The same techniques and equipment used to cold-form stainless
steels are also used on zirconium tube. Because of work-hardening
behavior, spring back may be encountered and provisions for this
should be made for any bending operation. For cold forming, a
minimum bend radius of approximately three times the OD dimension
is recommended. Hot forming at 200 to 425°C or the use of special
bending techniques are required for smaller-radius bends. To pre-
vent buckling and wall thinning, both the inside and outside tube
surfaces at the bend area must be in tension during any bending
operation.
Machining
Zirconium alloys can be machined by conventional methods. However,
the following three basic conditions should be used:
1. Slow speeds
2. Heavy feeds
3. A flood coolant system using a water-soluble oil lubricant
Zirconium exhibits a marked tendency to gall and work-harden.

This indicates that higher than normal clearance angles on tools
are needed to penetrate the previously work-hardened surface and
cut a clean coarse chip. Satisfactory results can be obtained with
both cemented carbide and high-speed tools; however, the carbide
usually gives better finishes and higher productivity. Polishing
or honing the cutting edges will give the tool added life. Zirconium
alloys machine to an excellent finish, requiring relatively light horse-
power compared with alloy steel. The tool forces are relatively low.
272 Yau
Welding
As with other reactive metals, welding zirconium requires proper
shielding of the weld puddle and hot bead from air. The shielding
must be made with highly pure argon, helium, or a mixture of these
two. Any oxygen, hydrogen, nitrogen, or carbon dioxide in the
shielding gas mixture will be absorbed by the molten metal and
results in the weld embrittlement.
Zirconium is most commonly welded by the gas tungsten arc
welding (GTAW) technique. Other welding methods include metal
arc gas welding (MAGW), plasma arc welding, electron beam welding,
and resistance welding.
Zirconium has a low coefficient of thermal expansion, which con-
tributes to a low distortion during welding. Inclusions are not usually
a problem in zirconium welds because the metal has a high solubility
of its own oxide and, because no fluxes are used in welding, flux
entrapment is eliminated. Because of the low modulus of elasticity
of zirconium, residual stresses are low in a finished weld. However,
stress relief of welds has been found to be beneficial. Because
zirconium grades 705 and 706 are heat-treatable alloys, all welding
variables and postweld heat treatments should be carefully reviewed
to ensure weld ductility.
Equipment
The most common techniques used for welding zirconium are the
inert gas welding methods of GTAW and MGAW welding. This equip-
ment can be set up and used in the manual or automatic welding
of zirconium. Either AC or DC current can be used in an arc weld-
ing. However, DC straight polarity is preferred for welding with
a consumable electrode such as zirconium wire, because it results
in a more stable arc. High-frequency arc starting is desirable to
reduce the possibility of contamination by a nonconsumable electrode
but is not required for most applications.
Weld Preparation
In preparation for welding zirconium, the edges to be joined should
be draw filed or wire brushed with a stainless steel brush immediately
before welding. This should be followed by a thorough cleaning
with alcohol or acetone to ensure a clean area for welding. Avoid
chlorinated solvents when preparing the area for welding.
Shielding
Zirconium is subject to severe embrittlement by relatively minute
amounts of impurities, especially nitrogen, oxygen, carbon, and
12. Zirconium 273
hydrogen. Zirconium has a high affinity for these elements at weld-

ing temperatures. Because of this high affinity for gaseous elements,
zirconium must be welded with gas-shielded, arc-welding processes
with inert shielding gases, such as argon or helium, or both.
Arc welding in ah inert blanket with use of either a tungsten
electrode or a consumable electrode of zirconium gives the best
results. The weld puddle, the bead just behind the weld puddle,
and the backside of the weld must all be protected from the atmos-
phere in some manner. The weld puddle and the bead just behind
the weld puddle can be protected by secondary shielding, such
as a trailing shield. This trailing shield is a device attached to
the torch head that provides protection (inert gas convering) to
the weld area while it cools.
Other protection may include side shields that pass protective
gas over the area being welded or by covering the weld area with
a plastic or cardboard enclosure purged with argon. The size and
configuration of the work being welded determine the means of
shielding the weld. When the backside of the weld is inside an
enclosed area, the entire enclosure can be sealed and purged with
inert gas.
Circumferential and longitudinal seam welds are commonly made
using a fixture positioner which both chills and shields. Rapid
cooling of the weld and heat-affected zone is promoted by the use
of copper backup plates and holddown clamps. Holddown bars,
backing blocks, and trailing shields are necessary to protect the
weld and weld zone from contamination until the metal has cooled
to below 250 to 300°C.
Shielding lines should permit uniform movement of the inert gas,
and care should be taken to prevent any pockets in the system
that would bleed contamination into the shielding gas during welding.
The shielding system should be thoroughly cleaned and purged
before use. Welding-grade shielding gases will produce the best
results.
In consumable electrode welding, the torch should have provision
for purging at the point of the wire entry to prevent drag of air
into the torch with the wire.
When desired, a flow purge or vacuum purge chamber may be
used. The same precautions against contamination apply in the use
of these chambers.
Welding Process
Welding techniques normally used to weld stainless steels, aluminum,
and titanium apply to the welding of zirconium. After purging the
torch, the weld should be made using a smooth, continuous motion
along the weld joint. When welding with zirconium wire as a filler,
274 Yau
the wire should be fed continuously into the puddle to prevent

contamination from the air. After the welding has stopped, the
contaminated end of the weld wire should either have the black
oxide removed or be cut off before beginning the next weld. This
measure prevents the contamination of the next weld from the wire
end. Sample welds should be made before production welding to
check the process. The sample welds can be checked easily by
bend testing. The welds should withstand a 90° bend, without crack-
ing, around a rod with a diameter of six times the thickness of
the weld sample.
Weld Inspection
A clean, bright weld is obtained through the use of a proper shield-
ing system, but discoloration of a weld is not necessarily an indica-
tion of its acceptability. White deposits or a black color in the weld
area are not acceptable. A bend test is probably the best test to
determine weld acceptability.
Welding of Dissimilar Metals

Zirconium cannot be welded directly to most other structural metals,
the exceptions are titanium, vanadium, and niobium. Because it
is difficult to weld zirconium directly to most metals, it is necessary
to fabricate all-zirconium equipment or line other materials with
zirconium. In the latter, the liner can be fastened to the shell
by mechanical means. Proper design of the vessel provides the
combination of excellent corrosion resistance and heat transfer in
the use of lined systems.
If the equipment is going to be subject to vacuum, high tempera-
ture, or high internal pressures that require 25.4-mm, or more,
wall thickness, it may be desirable to use thin plates of zirconium
explosively clad to low-cost carbon steel. The metallurgically bonded
cladding will utilize the corrosion resistance and excellent heat
transfer characteristics of zirconium, with the steel contributing
the mechanical strength needed for the equipment. Another cladding
process suitable for vacuum service is a special resistance welding
process. Very thin zirconium layers (0.76 to 2.0 mm) combined
with a variety of basement metals can be used in this process.
Welding Clad Plate

Explosively clad zirconium provides a metallurgically bonded lining
on steel or other structural metals. Butt welding of clad plate can
be accomplished by two methods. A single V or U joint is used
for welding steel plate by any conventional steel-welding process.
The joint is then back-chipped to clean metal and back-welded with
12. Zirconium 275
compatible filler wire. The zirconium cladding should be machined

back from the weld joint to prevent dilution from the molten steel.
The zirconium clad can then be joined with a zirconium cover strip.
The other technique is to overlay the steel weld with silver
or vanadium and then weld the zirconium cladding with zirconium
filler wire. A zirconium coverstrip should then be welded over the
previous weld.
Health and Safety

Zirconium is nontoxic and consequently does not require serious
limitations on its use because of health hazards.
Zirconium is pyrophoric because of its heat-producing reaction
with oxidizing elements such as oxygen. Large pieces of sheet,
plate, bar, tube, and ingot can be heated to high temperatures
without excessive oxidation /mass ratio; smaller pieces, such as
machine chips and turnings, are easily ignited and burn at extremely
high temperatures. Large accumulations of chips and other finely
divided materials should be avoided. When storing the chips and
turnings, care should be taken to place the material in nonflammable
containers and remove to isolated storage areas.
One effective storage method is to keep the material covered
with water in the containers and in turn, use oil on the water to
keep it from evaporating. If a fire accidentally starts in zirconium,
do not attempt to put it out with water or ordinary fire extinguishers.
Use dry sand, powdered graphite, or commercially available Metal-X
powder (produced by Ansul Manufacturing, Marinette, Wisconsin).
Large quantities of water can be used to control and extinguish
fires in other flammables in the vicinity of a zirconium fire.
ZIRCONIUM PRODUCTS
The variety of mill products available are comparable with those

of stainless steels. This includes sheet, plate, billet, wire, foil,
tubing (both seamless and welded), fasteners, and the like. Zir-
conium can also be obtained as cladding on steel plates and as cast-
ings. Figure 15 shows a zirconium casting.
Zirconium can be fabricated into tanks, liners, strainers, agitators,
exhausters, hubs, fans, valves, pipe fittings, nozzles, and pump
parts, to name a few. Figure 16 illustrates some components made
from zirconium for industrial use. Figure 16a is a heating coil made
for use in a hydrochloric acid application. Figure 16b is a zirconium
stripper column made for use in a hydrochloric acid application.
276 Yau
FIGURE 15 Zirconium 16-in. enclosed impeller for use in acetic

acid production. This impeller is cast and machined by Oremet.
(Courtesy of Oremet, Albany, Oregon.)
12. Zirconium 277
(a)
(b)
FIGURE 16 (a) Zirconium heating coil for use in hydrochloric acid.

Fabricated by Saffran Engineering. (Courtesy of Saffran Engineering,
St. Clair Shores, Mich.); (b) Zirconium stripper column for use
in hydrochloric acid. Fabricated by Futura. (Courtesy of Futura
Metal Technology.)
278 Yau
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280 Yau
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46. Fasullo, O. T. (1965). Sulfuric Acid. McGraw-Hill, p . 290.
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Tests and Standards, STP 866, ASTM, p. 36.
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BMI-706, Battelle Memorial Institute.
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Containing Environments," to be presented at the 5th Asian-
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"The Static Corrosion of Nickel and Other Materials in Molten
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12. Zirconium 281
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Chang, Albany.
13
CAST ALLOYS
GLENN W. GEORGE and PATRICIA G. BREIG The Duriron Company,

Inc., Dayton, Ohio
INTRODUCTION
The purpose of this chapter is to make the reader aware of the

broad range of cast alloys that are available for use in corrosive
services. The degree of emphasis placed on each group is in propor-
tion to its level of use and importance in corrosive applications.
Therefore, the iron-carbon materials and the stainless steels receive
the most emphasis because these alloys account for the major share
of use.
For practically every wrought alloy composition, there is an
equivalent grade available as a casting. In addition, there are many
alloy compositions available only as castings because of the design
freedom associated with the various casting processes. Wrought
products are subject to many rolling and forming operations that
require alloys with reduced strength and considerable hot- and
cold-working ductility. The compositions of many of the cast grades
are modified relative to their wrought equivalents to take advantage
of the casting processes because little or no mechanical working
of the cast component will be necessary. By being able to modify
the alloy compositions of the cast grades, unique and improved
properties can be imparted to some cast alloys compared with their
wrought equivalents. Because there are variations in compositions
and the resulting physical and mechanical properties of the cast
alloys versus the recognized wrought equivalents, various alloy
designation systems have been adopted to separate the two. For
example, the Alloy Casting Institute (ACI) Division of the Steel
283
284 George and Breig
Founders1 Society of America (SFSA) developed a system for high-

alloy stainless steels. Under this system, CF-8M is the alloy designa-
tion for the cast equivalent of 316 stainless steel. Similar designations
exist for cast carbon steel, nickel, copper, aluminum, and other
alloy systems.
References will be made throughout this chapter to American
Society for Testing and Materials (ASTM) standards. It is felt that
these standards offer the best and most recognized basis for under-
standing between casting purchaser and supplier. There are certainly
other standards used, but it would be impossible to list all of them,
and many of the other standards are referenced in the ASTM docu-
ments. Also, the cast-grade designations will be cross-referenced
to their wrought equivalents because the wrought designations are
more readily recognized by many individuals. There are many modifi-
cations of the standard cast alloy grades available under various
trade names. Because these modifications are quite numerous and
to avoid offending any producer through exclusion, only generic
alloy designations will be used when available.
Before presenting the specific alloy groups and their applications,
a few words concerning castings and recent developments relating
to casting processes and alloys seem appropriate. Castings offer
the designer several distinct advantages in producing a component,
and this certainly applies to the design of components for corrosive
services. Of course, castings are not the answer to all design prob-
lems, and the limitations of the casting processes and cast components
should be realized. Some of the advantages of castings include
literally unlimited freedom in design configuration, minimization
or elimination of machining and material waste, broad range of alloy
choice, mechanical property isotropy, and production economies.
The most serious limitation is variations in quality from casting
to casting and foundry to foundry. Possible quality shortcomings
involve surface finish, internal integrity, compositional purity,
and dimensional control. All these limitations can be overcome through
judicious application of sound foundry principles.
Producers of quality castings are constantly striving to provide
an improved product at an economical price. Two recent developments
in ferrous and high-alloy-casting production serve to illustrate
this point. The first deals with melt refining and involves the intro-
duction of the argon-oxygen decarburization (AOD) process into
foundries. This process has been used for some time in the produc-
tion of wrought stainless steels, but it is just beginning to find
use in casting production. The AOD refining will have a significant
influence on the foundry processing and alloy properties of not
only high-alloy materials but also carbon and low-alloy steels. The
second development deals with the binders used in mold and core
13. Cast Alloys 285
making. It has been recognized for some time that these binders
could lead to deleterious contamination of cast alloys. Most of these
binders are organic materials and, when contacted by molten metal,
the binders break down, and certain elements, the most notable
being carbon, are picked up by the alloy. New binders that are
inorganic and form a ceramic-type bond have been developed, thus,
alleviating the pickup problem. This is obviously important to pro-
ducers of low carbon alloys, but these ceramic systems offer advan-
tages to carbon and low-alloy steel producers because they prevent
the pickup of elements such as phosphorus and sulfur. These
systems also provide improved dimensional stability, better surface
finish, cleaner castings, and enhanced working environments.
IRON-CARBON ALLOYS
The iron-carbon alloys are the most widely used group of cast
materials. Included in this group of alloys are the cast irons, the
carbon and low-alloy steels, and some specialty alloys. Many of
these alloys find use in corrosion-type applications and perform
quite satisfactorily; however, the primary reason for choosing from
this group is generally not corrosion resistance, but low cost, good
mechanical properties, and occasionally, ease of production. It would
be impossible to list and discuss all the various compositions belong-
ing to the iron-carbon alloy group. Instead, the more common and
widely used materials are presented.
Carbon and Low-Alloy Steels

There are many cast grades of carbon and low-alloy steels available.
Table 1 lists a representative group of ASTM alloys that find use
in many applications where mild corrosives are handled. ASTM A148
deals primarily with tensile properties and, in fact, leaves the choice
of composition up to the casting producer. ASTM A216 is much
more specific about composition so that uniform welding character-
istics can be expected. ASTM A352 introduces alloying, but again
the major concern is mechanical properties, specifically low tempera-
ture impact toughness.
At the levels of alloying present in carbon and low-alloy steels,
no element or combination of elements can substantially influence
the corrosion rate of iron under immersed conditions [1]. For this
reason it is not necessary to distinguish among the many grades
of carbon and low-alloy steels when considering corrosion resistance
under immersed conditions; rather, they will be assembled together
and discussed as one group. Carbon and low-alloy steels find
TABLE 1 Carbon and Low Alloy Steels
tio
Sto Tensile Yield
Strength Strenigth Si S-g J
P b
S b MPa c
ksic MPac ksi c as (So Jc ft-lb c
0.05 0.06 Balance e 552 80 276 40 18 30 180

A148 80-40
A148 80-50 0.05 0.06 Balance e 552 80 345 50 22 35 180
A148 90-60 0.05 0.06 Balance e 621 90 414 60 20 40 190
A148 105-85 0.05 0.06 Balance e 724 105 586 85 17 35 230
A148 120-95 0.05 0.06 Balance e 827 120 655 95 14 30 260
0.06 Balance e 1034 135 826 125 9 22 330
A148 160-145 0.05 0.06 Balance e 1207 160 1000 145 6 12 —
A216 WCA
1.00 0.60
0.04
0.04
0.045
0.045
0.50b
0.50 b
0.50 b
0.50 b
Balance
Balance
C .30
C .20
c .03 ?
( .30 Cu b
C .20
415
485
60
70
205
250
30
36
24
22
35
35
140
150
c .03
b b
0.25 1.20 0.60 0.04 0.045 0.50 0.50 Balance f .10 r.ub 485 70 275 40 22 35 160
b b
0.25 0.70 0.60 0.04 0.045 0.50 0.50 1.30 Cu° 415 60 205 30 24 35 150
.20 M o b
.03 V*
1.00 0.60 0.04 0.045 0.50b 0.50 b
0.25 1.20 0.60 0.04 0.045 0.50b 0.50 b Balance 0.30 Cu" 485 70 275 40 -50
0.20 M o b
0.03 V 8
0.25 0.50/ 0.60 0.04 0.045 — Balance 0.45-0.60 Mo 450 65 240 35 18 13 -59 -75
A352 LCI
0.80
A352 LC2 0.25 2.00-3. Balance 485 70 275 40 20 15 -73 **-100
A352 LC2-1 0.22 0.55/ 0.60 0.04 0.045 1.35-1.85 2.50-3. Balance 0 . 3 0 - 0 . 6 0 Mo 725 105 550 80 41 30 -73 -100
0.75
A352 LC3 0.15 0.50/ 0.60 0.04 0.045 — 3.00-4. Balance 485 70
0.80
A352 LC4 0.15 4.00-5. Balance 485 70
a
Wrought grade most closely corresponding to cast alloy. Composition and properties may vary
between wrought and cast.
b
Maximum unless otherwise noted.
c
Mlnlmum unless otherwise noted.
d
Typlcal.
Composition shall be selected by manufacturer to achieve desired mechanical properties. to
f
g
Castlngs may be annealed, normalized, normalized and tempered, or quenched and tempered.
Castings may be annealed, normalized, or normalized and tempered.
3
h
Castings will be normalized and tempered or quenched and tempered.
13. Cast Alloys 287
application in many mildly corrosive media, such as neutral to alkaline

waters and brines, alkalies at ambient temperatures, neutral organics,
and concentrated sulfuric acid. This group of materials is used
extensively for handling concentrated sulfuric acid under ambient-
temperature conditions, but there are a few precautions that should
be taken. First, concentrated sulfuric acid is hygroscopic. It is
possible for the acid to pick up sufficient moisture from the atmos-
phere to dilute the surface layer to the point that the steel will
be rapidly attacked. Second, velocity conditions can remove the
protective ferrous sulfate film that is formed, and serious corrosion
will result. Finally, hydrogen grooving can occur, particularly
in pipelines and storage tanks, making catastrophic failure a possi-
bility. Small additions of copper will make steels more resistant
to hydrogen grooving.
Although small additions of alloying elements to steels do not
appreciably affect the corrosion resistance under immersed conditions,
the resistance to atmospheric corrosion is significantly improved.
Small additions of elements such as copper, phosphorus, chromium,
nickel, and molybdenum can improve atmospheric corrosion resistance
as much as five to eight times over unalloyed steels [ 1 ]. This factor
could be important when purchasing steel castings for structural
applications for which improved resistance to atmospheric corrosion
is a factor.
In addition to general immersion corrosion and atmospheric corro-
sion, carbon and alloy steels are susceptible to stress-corrosion
cracking (SCC) and hydrogen stress-corrosion cracking (HSCC).
This form of corrosion occurs when an internal or external stress
combined with chemical attack initiate and propagate cracking in
a metal part. The stress applied can be well below the design stress
of the metal. Carbon steels are susceptible to SCC in caustic environ-
ments when the temperature exceeds 120°F. The high-strength,
low-alloy steels that have tensile strengths in excess of 180 ksi
are particularly susceptible to SCC and HSCC when exposed to
a stress and a gaseous environment of chlorine, hydrogen chloride,
hydrogen bromide, hydrogen sulfide, and hydrogen.
Even though Table 1 presents a representative group of carbon
and low-alloy steel cast grades, it is by no means exhaustive.
Generally, other ASTM standards deal with alloys to meet specific
mechanical property needs or are written around various casting
processes. To make tfcfe reader aware of the various materials avail-
able, Table 2 presents a fairly complete list of ASTM standards
dealing with cast carbon and low-alloy steels.
Cast Irons
The general term cast iron encompasses a great number of materials.
Included in this group of materials are gray iron, white iron, malle-
TABLE 2 ASTM Carbon and Low Alloy Steel Casting Standards
A27 Steel Castings, Carbon, for General Application

A148 Steel Castings, High Strength, for Structural Purposes
A216 Steel Castings, Carbon, Suitable for Fusion Welding, for
High Temperature Service
A352 Steel Castings, Ferritic and Martensitic, for Pressure Con-
taining Parts, Suitable for Low Temperature Service
A356 Heavy-Walled, Carbon, Low Alloy, and Stainless Steel
Castings for Steam Turbines
A389 Steel Castings, Alloy, Specially Heat-Treated, for Pressure-
Containing Parts, Suitable for High-Temperature Service
A487 Steel Castings Suitable for Pressure Service
A732 Castings, Investment, Carbon and Low Alloy Steel for
General Application, and Cobalt Alloy for High Strength
at Elevated Temperatures
able iron, nodular or ductile iron, and many grades of specialty

irons. The major factor distinguishing cast irons from steel is the
amount of carbon present. Generally, in cast irons there is more
carbon present than can be held in solution in austenite at the
eutectic temperature. This excess carbon precipitates and, at room
temperature, the microstructure of these alloys will show free carbon
or graphite present as flakes or nodules. The presence of this
free graphite has a very crucial effect on the mechanical properties
compared with steel, and it also affects the corrosion resistance.
The most common of the cast irons is gray iron. This is a material
containing from 1.7 to 4.5% carbon and 1 to 3% silicon [2]. The
carbon is present as graphite flakes, and when the material is frac-
tured, it has a gray appearance; thus, the name gray iron. Gray
iron is the least expensive of all cast metals, and this factor,
together with its properties, has lead to it being the most widely
used cast material on a weight basis. As with steels, minor alloying
additions have little influence on the corrosion resistance of gray
iron; therefore, gray iron would find use in the same environments
as carbon and low-alloy steels. Note that gray iron is not suitable
for oleum, because it has been known to rupture in this service
13. Cast Alloys 289
with explosive violence. In certain environments, gray iron may

show an apparent advantage over carbon steel because of the nature
of the porous graphite-iron corrosion product film that forms on
its surface. This film gives a particular advantage under velocity
conditions, and this is evident in the widespread use of underground
gray iron water pipes. Gray iron is subject to a form of corrosion
known as graphitization [3], This involves a selective leaching
of the iron matrix, leaving only a graphite network. Even though
no apparent dimensional changes occur, there can be sufficient
loss of section and strength to lead to failure. Gray iron usually
performs adequately under atmospheric corrosion conditions because
of the heavy sections used. With these heavy sections, the degree
of corrosion that occurs is not sufficient to present a problem.
There are a number of ASTM standards dealing with gray iron
castings, but A48 is probably the one referred to most commonly.
This standard classifies the alloy on the basis of tensile strength,
with values ranging from 138 MPa (20,000 psi) to 414 MPa (60,000
psi). No limits are placed on composition. Other ASTM standards
dealing with gray iron include A126, A278, and A319.
Mechanical properties are a major drawback to more widespread
use of gray iron. Presence of the graphite flakes in the microstruc-
ture results in a brittle alloy with very poor shock resistance,
particularly at low temperatures. Through carefully controlled manu-
facturing procedures, it is possible to cause the graphite to be
present in a nodular form, thus creating fewer discontinuities in
the metal structure, resulting in a stronger and much more ductile
material [4], If the graphite is caused to nodularize by treating
the alloy with small additions of magnesium or cerium while it is
liquid, the resulting material is called ductile or nodular cast iron.
If the graphite is caused to nodularize by an appropriate heat treat-
ment, the material is called malleable iron. The corrosion resistance
of these alloys is comparable with that of gray iron, except that
under velocity conditions they may be slightly less resistant because
they do not form the same sort of film that is present on gray iron.
The major ASTM standards covering ductile iron are A395 and A536
and, for malleable iron, they are A47 and A220. Table 3 presents
the mechanical properties for these alloys.
There are two groups of highly alloyed cast irons. One group
is found in ASTM A436 and is referred to as the Ni-resist alloys.
This group consists of high nickel austenitic cast irons used primarily
for their corrosion resistance [2]. The Ni-resist alloys find use
in mildly oxidizing acids, alkalies, salts, seawater, foods, plastics,
and synthetic fiber manufacturing. These alloys tend to maintain
their corrosion resistance under high-velocity conditions and show
TABLE 3 Malleable and Ductile Iron Properties
Tensile Yield Elongation Brinell

ASTM Alloy strength strength in 50 mm hardness
standard grade MPa ksi MPa ksi (2 in.) number
A47 22010 340 49 220 32 10 156 max.

A47 24018 360 52 240 35 18 156 max.
A220 40010 414 60 276 40 10 149-197
A220 45008 448 65 310 45 8 156-197
A220 45006 448 65 310 45 6 156-197
A220 50005 483 70 345 50 5 179-229
A220 60004 552 80 414 60 4 197-241
A220 70003 586 85 483 70 3 217-269
A220 80002 655 95 552 80 2 241-285
A220 90001 724 105 621 90 1 269-321
A395 — 414 60 276 40 18 143-187
A536 60-40-18 414 60 276 40 18 —
A536 65-45-12 448 65 310 45 12 —
A536 80-55-06 552 80 379 55 6 —
A536 100-70-03 689 100 483 70 3 —
A536 120-90-02 827 120 621 90 2 —
good wear resistance. Although the alloys show relatively low tensile
strengths in the range 138 to 207 MPa (20,000 to 30,000 psi), they
have much improved toughness over unalloyed gray iron. It is possi-
ble to obtain ductile or nodular Ni-resist alloys. The corrosion
resistance is essentially the same as that for conventional flake
graphite Ni-resist alloys, but the mechanical properties, particularly
the low-temperature impact toughness, are much improved. ASTM
A571 covers ductile Ni-resist. Table 4 presents the composition
and properties of the Ni-resist alloys.
The second group of highly alloyed cast irons is the white irons.
The carbon in these alloys is essentially all in solution and the
fracture surface appears white. There are two major subgroups
of the white irons; the Ni-hards and the high chromium irons.
Nickel in the range 4 to 5% and chromium in the range 1.5 to 3.5%
are the major alloying elements in the Ni-hards [2]. Chromium levels
up to 25% are found in the high chromium irons [2]. This group
of alloys is intended primarily for abrasive-wear applications. Some
of these alloys are capable of Brinell hardness levels in excess
of 700, with 600 being fairly typical. Areas where these alloys find
use include mining, power generation, cement manufacture, pulp
and paper, and similar industries in which severe abrasive services
o
TABLE 4 Ni-Resist Irons

CO
50 mm (2 in.T
c
Elongation in.
Heat-treated
Designation
Cast Alloy
Condition
(J Charpy Impact
Hardness
Brine11
Composition Tensile Yield CO
Number
Strength Strength Test Tem P C
Other
AST
Spe
C Mn Si Sa Cr Nl Fe Elements MPab ksi b MPa b ksi b J ft-lb °F °C
A436 Type 1 3.00 0.5/1.5 1.00/2.80 0.12 1.5-2 .5 13.5-17.5 Balance 5.5-7.5 Cu — 172 25 — - 131-183 136d 100d RT RT
A436 Type lb 3.00 0.5/1.5 1.00/2.80 0.12 2.5-3 .5 13.5-17.5 Balance 5.5-7.5 Cu - 207 30 - 149-212 109d 80 d RT RT
A436 Type 2 3.00 0.5/1.5 1.00/2.80 0.12 1.5-2 .5 18.0-22.0 Balance 0.5 Cu a - 172 25 „ - 118-174 136d 100d RT RT
A436 Type 2b 3.00 0.5/1.5 1.00/2.80 0.12 3.0-6 .0 18.0-22.0 Balance 0.5 Cu a - 207 30 .. -- 171-248 82 d 60 d RT RT
A436 Type 3 2.60 0.5/1.5 1.00/2.00 0.12 2.5-3 .5 28.0-32.0 Balance 0.5 Cu a
- 172 25 .. - 118-159 204d 150d RT RT
A436 Type 4 2.60 0.5/1.5 5.00/6.00 0.12 4.5-5 .5 29.0-32.0 Balance 0.5 Cu a - 172 25 .. - 149-212 109d 80 d RT RT
A436 Type 5 2.40 0.5/1.5 1.00/2.00 0.12 0.10a 34.0-36.0 Balance 0.5 Cu a - 138 20 .. - 99-124 204d 150d RT RT
A436 Type 6 3.00 0.5/1.5 1.50/2.50 0.12 1.0-2 .0 18.0-22.0 Balance 3.5-5.5 Cu — 172 25 124-174
1.00 Mo a
A571 — 2.2/ 3.75/4.5 1.50/2.5 -- 0.20a 21.0-24.0 Balance 0.08 P a e 448 65 207 30 30 121-171 21 b 15 b -195 -320
2.7
a
b
Minimum unless otherwise noted.
C
RT, room temperature.
Typical, unnotched.
e
Annealed.
to
CO
are encountered. The composition and properties of these alloys

can be found in ASTM A532.
The final cast iron to be discussed is high silicon cast iron.
This alloy contains nominally 14.5% silicon, 1% carbon, and the
balance iron [ 2 ] . This alloy has unexcelled corrosion resistance
to a wide range of chemicals and, in fact, it is probably the most
universally corrosion-resistant alloy that is commercially available.
One of the major uses for the alloy is in handling sulfuric acid.
It is resistant to all concentrations of sulfuric acid, up to and
including the normal boiling point. The alloy will handle nitric acid
above 30% to the boiling point. Below 30%, the temperature is limited
to about 180°F. By adding 4.5% chromium to the alloy, it becomes
resistant to environments such as severe chloride-containing solutions
and other strongly oxidizing services. The chromium-bearing grade
will handle hydrochloric acid up to a temperature of 80°F, and
the presence of ferric chloride, which wreaks havoc on many alloys,
actually inhibits corrosion with this alloy when the acid is present
at less than 20%. Unfortunately, the high silicon irons are particu-
larly susceptible to thermal and mechanical shock. The alloys cannot
withstand any substantial stressing or impact, and they cannot
be subjected to sudden fluctuations in temperature. With proper
precautions, it is possible to obtain outstanding performance with
these materials under some very severe corrosion conditions. High
silicon cast irons are covered by ASTM A518.
STAINLESS STEELS
Stainless steels are iron-based alloys containing at least 11.5%

chromium. This level of chromium is required to produce passivity.
The term stainless steels covers a very complex and extensive series
of alloys that have been developed and tailored for many specific
corrosive services. Cast stainless steels are available in all the
grades comparable with the wrought grades plus many additional
grades for special end-use applications [5]. The standard wrought
stainless steels are generally identified by a three-digit American
Iron and Steel Institute (AISI) designation and the alloys are usually
grouped for discussion by their microstructure. The largest group
comprises the 300 series nickel-chromium austenitic grades. The
400 series alloys, which contain primarily chromium as an alloying
element, are identified as either martensitic or ferritic. The cast
alloys are identified by a system developed by the Alloy Casting
Institute (ACI). Designations that begin with the initial letter C
indicate alloys generally used to resist corrosive attack at tempera-
tures less than 1200°F. The second letter represents the nominal
13. Cast Alloys 293
chromium-nickel type; the nickel content increasing in amount from

A to Z. For example, F stands for the 19% Cr-9% Ni, K for the 25%
Cr-20% Ni, and W for the 12% Cr-60% Ni alloy types. Numerals follow-
ing the letters indicate the maximum carbon content of the corrosion-
resistant alloys. If special elements are included in the composition
they are indicated by the addition of a letter to the symbol. To
illustrate, CF-8M is an alloy for corrosion-resistant service containing
19% Cr-9% Ni, 0.08% maximum carbon, and a molybdenum addition.
Even though the cast and wrought grades are discussed as being
equivalent, it should be noted that significant compositional and
property differences exist for some of the grades that result in
their not being truly equivalent. Some of these differences will
be presented when the specific alloys are discussed. It is desirable
for users of stainless castings to reference the ACI designations
when specifying alloys because substantial differences can exist
relative to the wrought grades. Grouping the cast alloys by micro-
structure is a convenient method for presenting these materials,
and this procedure is used in the following discussion. Table 5
and Table 6 contain the alloys that will be discussed.
Martensitic Alloys
The martensitic alloys found in Table 5 are CA-6NM, CA-15, CA-15M,
CA-40, and CB-7Cu. The chromium in CA-15 is the minimum required
to make a rustproof alloy. Its resistance to atmospheric corrosion
is good, and it finds use in mildly corrosive organic services. Be-
cause the alloy is martensitic, it is used in some abrasive applications.
Some specific areas for which the alloy has been used include alkaline
liquors, ammonia water, boiler feedwater, pulp, steam, and food
products [6]. CA-15M contains molybdenum which provides improved
elevated-temperature mechanical properties. CA-40 is a higher carbon
version of CA-15. The higher carbon content permits heat treatment
to higher strength and hardness levels. Corrosion resistance is
comparable with CA-15, and this alloy finds use in similar applica-
tions. CA-6NM is an iron-chromium-nickel-molybdenum alloy that
is hardenable by heat treatment. Its corrosion resistance is compara-
ble with CA-15, although the addition of molybdenum does make
CA-6NM more resistant to corrosion in seawater. The major advan-
tages of CA-6NM over CA-15 are its much improved foundry charac-
teristics and increased toughness. Some specific applications for
CA-6NM include boiler feedwater, seawater, and other waters to
a temperature of 400°F. This alloy has found particular use in very
large turbine runners for power generation. CB-7Cu is a precipitation-
hardened alloy, equivalent to the wrought alloy type 17-4 PH. The
alloy is martensitic with minor amounts of retained austenite present
TABLE 5 Stainless Steel Compositions and Properties
Applicaible CO
ASTM
Standard Impact Toughne ss
° tfl" r-< W O
Hardne
Brlnel
Number
Test Temp.
3 <
£ 3
Desl
Cast
J ft-lb °Ce
3 5
MARTENS;ITIC
• CA-6NM 0.06 1.00 1.00 0.04 0.40-1.0 Mo 35 240 95 70 RT RT
• CA-15 0.15 1.00 1.50 0.04 0.04 11.5-14.0 1.00a Balance 0.50 M o a NT 620 '450 30 210 27 20 RT RT
a 30 220
* CA-15M 0.15 1.00 0.65 0.040 0.040 11.5-14.0 1.0 Balance 0.15-1.0 Mo NT 620 450 "" "" ""
a 240
m CA-40 1.00 1.50 0.04 0.04 11.5-14.0 1.0 Balance 0.5 Mo a NT 690 485 25
1.00 1.00 0.04 0.04 5 Cu SA AH 892
CB-30 0.30 1.00 1.50 0.04 0.04 18.0-21.0 2.00a Balance 450 65 205 30
CC-50 0.50 1.00 1.50 0.04 0.04 26.0-30.0 4.00a Balance 380 55
1.00 1.00 690 100 485 70
CE-30 190 10
CF-3 0.03 1.50 2.00 0.04 0.04 17.0-21.0 8.0-12.0 Balance 0.5 Moe 150 149
CF-3A 0.03 1.50 2.00 0.040 0.040 17.0-21.0 8.0-12.0 Balance 0.5 Moa 160 136
CF-8 0.08 1.50 2.00 0.04 0.04 18.0-21.0 8.0-11.0 Balance 0.5 Moe 150 100
a
CF-8A 0.08 1.50 2.00 0.040 0.040 18.0-21.0 8.0-11.0 Balance 0.5 Mo 530
CF-20 0.20 1.50 2.00 0.04 0.04 18.0-21.0 8.0-11.0 Balance 485
CF-3M 0.03 1.50 1.50 0.04 0.04 17.0-21.0 9.0-13.0 Balance 2.0-3.0 Mo 485 205
CF-3MA 0.03 •1.50 1.50 0.040 0.040 17.0-21.0 9.0-13.0 Balance 2.0-3.0 Mo 550 255
CF-8M 0.08 •1.50 2.00 0.04 0.04 18.0-21.0 9.0-12.0 Balance 2.0-3.0 Mo 485
CF-8C 1.50 2.00 0.04 0.04 18.0-21.0 9.0-12.0 Balance 485
1.50 1.50 0.040 0.040 15.0-18.0 13.0-16.0 Balar 1.75-2.25 Mo

10 x C CbC
1.20 Cba
CF-16F 18.0-21.0 9.0-12.0
CG-8M 0.08 1.50 1.50 0.04 0.04 18.0-21.0 9.0-13.0 Balance

CG-12 0.12 1.50 2.00 0.04 0.04 20.0-23.0 10.0-13.0 Balance
CH-20
CK-20 0.04 0.04 23.0-27.0 19.0-22.0 Balance 0.5 Mo
19.0-22.0 27.5-30.5 Balance
to
b
NT, normalize and temper; A, anneal; SA solution anneal; AH, age harden
c
Mlniroura unless otherwise noted.
Splcal.
e
Only specified In ASTM A351 as a maximum.
13. Cast Alloys 295
in the microstructure. By aging the alloy at 496°C (925°F) after

solution annealing, submicroscopic copper particles precipitate and
effectively strengthen the alloy. In the age-hardened condition,
the alloy possesses corrosion resistance superior to the straight
martensitic and ferritic grades, but inferior to the CF and higher-
alloy grades. This alloy finds use where moderate corrosion resistance
and high strength are required. Typical application areas include
aircraft parts, food-processing equipment, and pump shafting.
Similar to the high-strength, low-alloy steels, the higher-strength
martensitic stainless steels are subject to SCC and HSCC. Increasing
the yield strength of these martensitic stainless steels increases
the probability of cracking. The environments that cause failure
are not specific; almost any corrosive environment capable of causing
hydrogen evolution can cause SCC and HSCC failures in these alloys.
Ferritic Alloys
Included in Table 5 in this group of alloys are CB-30 and CC-50.
CB-30 is essentially all ferritic and, as such, is nonhardenable.
Chromium is present at a sufficient level to give this alloy much
better corrosion resistance in oxidizing environments. Areas in
which this alloy has been used include food products, nitric acid,
steam, sulfur atmospheres, and other oxidizing atmospheres at
temperatures up to 760°C (1400°F) [6]. A major drawback to this
alloy is its poor impact toughness, and for this reason CB-30 has
been replaced in many applications by the CF grades. CC-50 has
a higher chromium content than CB-30, resulting in improved corro-
sion resistance in oxidizing media. Also, at least 2% nickel and
0.15% nitrogen are usually added to CC-50, resulting in improved
toughness. This alloy has found use in acid mine waters, sulfuric
and nitric acid mixtures, alkaline liquors, and sulfurous liquors [6].
Duplex Alloys
The alloy in Table 5 that comprises these alloys is CD-4MCu. Al-
though not included in Table 5, there are additional duplex alloys
not currently recognized in an ASTM specification such as Ferralium
and Uranus 50. Ferralium is similar to the composition of CD-4MCu
except a 0.10-minimum nitrogen level is required and the molybdenum
runs about 0.5% higher. Uranus 50 has 20 to 22% chromium, 5 to 9%
nickel, 2 to 3% molybdenum, 1 to 2% copper, and 0.07 maximum
carbon. These chromium-nickel-molybdenum-copper stainless steels
were developed to meet the demand for a high-strength alloy possess-
ing good ductility and hardness together with corrosion resistance
equal or superior to the popular 19% chromium-9% nickel stainless
steels [6]. The alloys are two-phased, having a microstructure

of ferrite containing large austenite pools. Typically, these alloys
contain approximately 40 to 60% ferrite, with the balance being
austenite. Because the alloys contain such a high percentage of
ferrite, they are strongly magnetic. The alloys develop yield strength
and hardness levels about twice that of the cast 304 and 316 equiva-
lents. This increased hardness has led to greatly improved resistance
to erosion and velocity conditions. Also, owing to the duplex micro-
structure, the alloys show exceptional resistance to chloride stress
cracking.
The high ferrite level in these duplex alloys limits their continuous-
operating temperature to below 600°F. Above 600°F, the ferrite
becomes embrittled by the "885°F embrittlement" that occurs in
ferritic stainless steels [7]. Continuous operation above 600°F could
result in catastrophic brittle failure of the cast components.
CD-4MCu has found application in a wide variety of services.
Because of its high chromium level, it is outstanding in oxidizing
environments, such as nitric acid, and the low concentrations of
solids in these environments present little problem because the
alloy possesses good hardness. Reducing environments are also
well handled. CD-4MCu is widely used in dilute sulfuric acid services
up to fairly high temperatures. The alloy has excelled in fertilizer
production and the wet-process method for producing phosphoric
acid in which phosphate rock containing fluorides is encountered.
Even though the alloy is low in nickel, it has outstanding resistance
to sodium hydroxide—in fact, almost as good as the much higher
alloyed CN-7M. Other services that have been successfully handled
by CD-4MCu include seawater, concentrated brines, fatty acids,
pulp liquors, hot oils, scrubber solutions containing alumina and
hydrofluoric acid, and dye slurries [6]. Many of these duplex grades
are alloyed with nitrogen, which gives these alloys excellent resist-
ance to pitting and crevice corrosion.
Austenitic Alloys
Of the alloys listed in Table 5, the austenitic alloys are the largest
group, both in terms of the number of compositions and the quantity
of material produced. This group of alloys also illustrates most
vividly the differences that can exist between so-called equivalent
cast and wrought grades. Included in this group are CE-30, CF-3,
CF-3A, CF-8, CF-8A, CF-20, CF-3M, CF-3MA, CF-8M, CF-8C,
Cf-IOMC, CF-16F, CG-8M, CH-20, and CK-20.
The austenitic alloys are the cast equivalents of the wrought
300 series stainless steels. In the wrought form, the 300 series
alloys are fully austenitic. This structure is required to permit
13. Cast Alloys 297
1.600
1.500
1 4 0 0
a, -
z
0)
o
? 1.300
|jj 1.200
o
Q.
o
o
1.100 Cre - (%Cr) + 1.5(%Si) + (%Mo) + (%Cb)-4.99
Nie = (%Ni) + 30(%C) + 0.5(%Mn) +
26(%N-0.02) + 2.77
1.000
0.900
10 15 20 25 30 35 40 45 50
FERRITE NUMBER
FIGURE 1 Diagram for estimating ferrite content in cast stainless

steels. (Adapted from Ref. 23.)
the necessary hot- and cold-forming operations that are needed

to produce the various wrought shapes. Because castings are pro-
duced essentially to finished shape, it is not necessary for the
alloys to be fully austenitic. Although these alloys are commonly
referred to as the cast austenitic alloys, the cast compositions can
be balanced such that the microstructure contains from 5 to 40%
ferrite. The amount of ferrite present can be estimated from the
composition using Figure 1 or from the magnetic response achieved
with calibrated measuring instruments. It is important to note that
the cast equivalents of the 300 series alloys can display a magnetic
response ranging from none to quite strong. The wrought 300 series
700
Tensile strength
600
500
a. 400
CO
CO
UJ
cc Yield strength
fe 300
200
100
10 20 30 40
FERRITE BY VOLUME, %
FIGURE 2 Relationship of yield strength and tensile strength to

ferrite content for CF-8 and CF-8M. (Adapted from Ref. 23.)
alloys contain no ferrite and, in the annealed condition, they are

nonmagnetic.
The presence of ferrite in the cast alloys offers a number of
advantages. Weldability is substantially enhanced, particularly for
resistance to fissuring. The mechanical strength increases, and
this increase is proportional to the amount of ferrite present (Fig. 2).
Finally, the presence of ferrite raises the resistance of these alloys
to stress-corrosion cracking compared with the fully austenitic
wrought equivalents. It is possible to specify castings with specific
ferrite levels and, in fact, some of the alloys discussed later are
designated as controlled ferrite grades.
13. Cast Alloys 299
The presence of a continuous phase of ferrite in the cast austen-

itic alloys will limit their high-temperature service. Above 600°F,
chromium precipitates in the ferrite phase, which embrittles the
ferrite. The presence of a continuous ferrite phase in a cast struc-
ture that has been embrittled will drastically reduce the impact
properties (ductility) of the casting. To provide a noncontinuous
ferrite phase, the ferrite number should be maintained below 10%.
CE-30 is a high carbon cast stainless steel. The alloy has a
duplex microstructure of ferrite in austenite, and carbide precipitates
are present as-cast. There is sufficient chromium present so that
resistance in the as-cast condition to intergranular corrosion is
not seriously impaired. Because the alloy does retain good corrosion
resistance as-cast, it is useful where heat treatment is not possible
or where heat treatment following welding cannot be performed.
Of course, corrosion resistance and ductility can be significantly
enhanced by solution annealing. The alloy is resistant to sulfurous
acid, sulfites, mixtures of sulfurous and sulfuric acids, and sulfuric
and nitric acids [6]. Also, the controlled ferrite grade CE-30A
is resistant to stress-corrosion cracking in polythionic acid and
chlorides. Other major uses include pulp and paper manufacture,
acid mine water, caustic soda, and organic acids.
The CF alloys constitute the major segment of the corrosion-
resistant casting alloys. These are the 19% chromium-9% nickel
materials that possess particularly good processing characteristics
and mechanical properties and are resistant to a wide range of
corrosive environments. Microstructurally, the alloys are generally
ferrite in austenite, with the composition balanced to provide 5
to 25% ferrite. For applications for which nonmagnetic castings are
required, a fully austenitic structure can be provided; however,
because of the many desirable benefits derived from the presence
of ferrite, it is usually present in the structure. To provide optimum
corrosion resistance, these alloys are provided in the solution-
annealed condition. The CF alloys are not hardenable by heat treat-
ment. The corrosion resistance of the cast alloy is at least equal
to its wrought equivalent. For many applications, the CF alloys
are over specified; that is, they are applied where a lesser alloy
would be adequate from a corrosion standpoint. This happens be-
cause the CF alloys have such outstanding foundry characteristics
compared with the 12% chromium materials that the total cost to
produce a casting can be less with the CF grades. This factor
should be kept in mind when selecting an alloy for moderately cor-
rosive services.
CF-8 is the base composition for the CF alloy group. Its wrought
equivalent is 304. It contains nominally 19% chromium-9% nickel-0.08%
maximum carbon. The alloy has good strength and ductility and its
impact toughness is maintained to below -240°C (-400°F). CF-8

is particularly good in strongly oxidizing media, such as boiling
nitric acid. Other typical applications include adipic acid, copper
sulfate, fatty acids, organic liquids and acids, sewage, sodium
carbonate, sodium sulfite, vinegar, and white liquor [6]. CF-3
is the low carbon (0.03% maximum) version of CF-8. It is generally
specified where welding will be performed and postweld heat treat-
ment is not possible. Because the carbon content is so low, castings
have been used in the as-cast condition for some applications. How-
ever, to achieve the best corrosion resistance and mechanical proper-
ties, solution annealing is performed. The overall corrosion resistance
of CF-3 is somewhat better than CF-8, but in general, they find
use in the same applications. CF-8C is the stabilized grade of the
CF-8 alloy. Controlled amounts of columbium (niobium) or columbium
plus tantalum are added to the alloy to tie up the carbon to prevent
the formation of chromium carbides. This alloy finds use where
field welding without subsequent heat treatment will be performed.
CF-8C provides essentially equivalent corrosion resistance to CF-8.
CF-8A and CF-3A are the controlled ferrite grades of the 19%
chromium-9% nickel alloys. By controlling the composition and, thus,
the percentage ferrite present (see Fig. 1), it is possible to achieve
a 35-MPa (5-ksi) increase in the minimum yield strength and a 45-
MPa (7-ksi) increase in the tensile strength. This also results in
increased resistance to stress-corrosion cracking, with no sacrifice
in overall corrosion resistance. CF-3 A has found extensive use
in nuclear power plant construction. Because of the thermal instability
of the higher ferrite microstructures, CF-3 A has an upper tempera-
ture limit of 340°C (650°F) and CF-8A an upper limit of 425°C (800°F).
CF-20 is a high carbon version of CF-8. It somewhat fills the gap
between CA-15 and CF-8. This alloy performs satisfactorily in
moderately oxidizing environments. Microstructurally, the alloy
is fully austenitic and is nonmagnetic. Typical services include
caustic salts, food products, sulfite liquor, and sulfurous acid [6].
CF-8M is the cast equivalent of 316 stainless steel. This is a
19% chromium-9% nickel-2% molybdenum-0.08%-maximum carbon alloy.
The nickel level in this alloy is usually a little higher than CF-8
to offset the ferritizing influence of the molybdenum and, thus,
maintain a comparable ferrite level in the microstructure. The alloy
can be made fully austenitic and, thus, nonmagnetic. Addition of
molybdenum improves the general corrosion resistance, provides
greater elevated temperature strength and, particularly, improves
pitting resistance in chloride environments. Some resistance to
strongly oxidizing environments, such as boiling nitric acid, is
sacrificed by adding molybdenum, but passivity is enhanced under
weakly oxidizing conditions compared with CF-8. This alloy has
13. Cast Alloys 301
good resistance to reducing media. Overall corrosion resistance

is equal to or better than 316 stainless steel. Because of the versa-
tility of this alloy, it is used mainly for pumps and valves in corro-
sive services. Some typical services for CF-^M include acetone,
acetic acid, black liquor, chloride solutions, hot dyes, fatty acids,
phosphoric acid, sulfate and sulfite liquors, dilute and concentrated
sulfuric acid, sulfurous acid, and vinyl alcohol [6]. The alloy is
supplied in the solution-annealed condition. CF-3M is the low carbon
grade intended for use where postweld heat treatment is not possible.
The areas of application for CF-3M are essentially the same as for
CF-8M. CF-3MA is the controlled ferrite grade. Increases in minimum
yield strength of 50 MPa (7 ksi) and tensile strength of 65 MPa
(10 ksi) can be achieved. There is an upper temperature limit of
425°C (800°F) for use of CF-3MA. CF-10MC is the stabilized grade
of CF-8M for field-welding applications.
CF-16F is a free-machining 19% chromium-9% nickel stainless
steel. Small additions of selenium and phosphorus form inclusions
that act as chip breakers during machining. The microstructure,
in addition to the selenium inclusions, contains about 15% ferrite.
Corrosion resistance is slightly inferior to CF-20. This alloy and
CF-20 find use in similar applications.
CG-8M is a higher molybdenum version of CF-8M. It is particu-
larly resistant to reducing media and performs very well in sulfuric
and sulfurous acids; in addition, it resists the pitting action of
halogen compounds. The alloy is not suitable for strongly oxidizing
environments. Microstructurally, the alloy usually displays a high
ferrite content, and this results in very good stress-corrosion crack-
ing resistance. However, because of its high ferrite level, the alloy
has an upper temperature limit of 425°C (800°F).
CH-20 is similar to CE-30 but has higher nickel and lower chromium
levels. This alloy is more ductile than CE-30 and stronger than
CF-8. CH-20 is considerably more corrosion resistant than CF-8
and is less susceptible than CF-8 to intergranular corrosion after
exposure to sensitization temperatures. Solution annealing is required
to achieve maximum corrosion resistance and mechanical properties.
CK-20 finds use in many of the same services as CH-20 but at
higher temperatures [6].
Highly Alloyed
The CN-7M alloy is included in the high-alloy group in Table 5.
As with the duplex alloys, several of the high-alloy stainless steels
are fairly new and not currently recognized in an ASTM Specification,
with the exception of CN-7M alloy which can be found in A351,
A743, and A744. The nominal composition of several of these high-
TABLE 6 Nominal Composition of High-Alloy Stainless Steels
Trade
name C Mn Si Cr Ni Mo Fe Other
254 SMO 0.02 0.50 1.00 20.0 18.0 6.1 Balance 0.20 N
904L 0.02 1.70 1.00 20.0 25.0 4.5 Balance 1.5 (ZJu
A1-6X 0.025 1.50 1.00 20.25 24.50 6.25 Balance —
JS700 0.04 2.00 1.00 21.0 25.0 4.50 Balance .30 Cb
.40 Cu
alloy stainless steels is shown in Table 6. These alloys are completely

austenitic as a result of their high nickel content and must be solu-
tion annealed for maximum corrosion resistance. The high nickel
content, along with other alloying elements, gives these alloys the
best corrosion resistance of any of the stainless steels. CN-7M,
also known as Alloy 20 or Capenter 20, is the oldest of the high-
alloy stainless steels. It finds widespread use in sulfuric acid services
and is suitable for all concentrations at temperatures up to 65°C
(150°F), and even higher, for most concentrations. Because of
its high nickel content, CN-7M has excellent resistance to alkaline
environments. It can be used in sodium hydroxide up to 73% and
temperatures to 149°C (300°F). This good resistance in caustic
environments plus good chloride resistance makes this alloy an
excellent choice for the hot alkaline brines found in caustic chlorine
plants. Because the alloy contains appreciable chromium, it is
superior to the CF grades in nitric acid—even better than CF-3,
which is generally considered the best alloy for this service. Hydro-
chloric acid, certain chlorides, and strong reducing agents, such
as hydrogen sulfide, carbon disulfide, and sulfur dioxide, will
accelerate corrosion as will deaeration of the solution. Additional
services where CN-7M is used include hot acetic acid, dilute hydro-
fluoric and hydrofluosilicic acids, nitric-hydrofluoric pickling solutions,
phosphoric acid, and some plating solutions [6].
The 254 SMO, 904L, A1-6X, and JS700, are newer variations
of CN-7M developed for better resistance to pitting and crevice
corrosion in environments like seawater, wet phosphoric acid, and
acid chloride services. These alloys contain 4 to 6% molybdenum
to obtain this additional corrosion resistance in pitting-type services
[8]. Table 7 contains a list of several highly alloyed, duplexed,
and austenitic alloys ranked by their critical crevice and pitting
temperature. The higher the temperature, the better the pitting
and crevice resistance.
13. Cast Alloys 303
TABLE 7 Casting Alloys and Corrosion Resistance
Critical crevice Critical pitting

Alloy temperature (°C) corrosion temperature (°C)
CN-7M 0 and below 12.5

CF-8M 10 17.5
CD-4MCU 10 15
CD-4MCU + N 20 27.5
Uranus 50 20 25
904L 28.3 45.8
Ferralium 255 32.0 —
A1-6X 40 50
254 SMO 45 62.5
A1-6XN 20 —
Source: Ref. 24.
NICKEL-BASED ALLOYS
Table 8 lists the major cast nickel-based alloys that find use in
corrosive environments. These alloys generally are used only in
specialty areas and very severe service because of their high cost
compared with stainless steels. ACI designations have been adopted
for these alloys because, like the stainless steels, their compositions
and properties do in many instances vary significantly from the
wrought equivalents. The cast nickel-based alloys are found in
ASTM standard A494.
Cast nickel, CZ-100, is the equivalent of commercially pure
wrought nickel [ 9 ] . The carbon and silicon levels are necessarily
higher in the cast grade to provide adequate castability. By treating
the alloy with magnesium in the molten state, the carbon in the
cast alloy is caused to nodularize, and this leads to enhancement
of the mechanical properties, much as with ductile cast iron. The
properties of CZ-100 are not improved by heat treatment; therefore,
the alloy is generally provided in the as-cast condition. CZ-100
finds its widest use in alkaline services. It has unsurpassed resist-
ance to all bases except ammonium hydroxide [10]. Above 1%,
ammonium hydroxide causes rapid attack. In sodium and potassium
hydroxide, CZ-100 is resistant to all concentrations and temperatures.
The presence of chlorates and oxidizable sulfur compounds will
accelerate the corrosion rate in caustic. Food processing, for which
product purity is important, is an area where CZ-100 is used. Also,
the alloy is used in synthetic fiber manufacture.
CO
o
Spec ific at ion TABLE 8 Nickel-Base Alloys Composition and Properties
•v
Designation "*"' d Impact Toughnes gc
8. Tn
Cast Alloy
Alloy Ty
Heat-tre
Conditio
50 mm (2
Hardness
Elongati
Composition Tensile Yield Test
Wrought
Brinell
Number3
Strength Strength Temp
ASTM
a a Other
Mn a
Si a
P s Cr Ni Fe Elements MPa c
ksi c
MPa c
ksi c
J ft-lb °C °F
C a a
A494 CZ-100 Nickel 200 1.00 1.50 2.00 0.03 0.030 95.00 3.00 1.25 Cu AC 345 50 125 •18 10 120
A494 CY-40 Inconelf 600 0.40 1.50 3.00 0.03 0.030 14.0-17.0 30 140
A494 M-35-1 Monelf 400 0.35 1.50 1.25 0.03 0.030 Balance 3.50a 26.0-33.0 Cu AC 450 65 170 25 25 130 ._ -_ --
A494 M-35-2 Monelf 400 0.35 1.50 2.00 0.03 0.030 - Balance 3.50a 26.0-33.0 Cu AC 450 65 205 30 25 130 --
A494 M-30H Monelf 400 0.30 1.50 2.7-3.7 0.03 0.030 - Balance 3.5 27.0-33.0 Cu AC 690 100 415 60 10 243-294 -
M-25S Monelf 400 1.50 3.5-4.5 0.03 0.030
A494 M-30C Monelf 400 0.30 1.50 1.0-2.0 0.03 0.030 -- Balance 3.5 26.0-33.0 Cu AC 450 65 225 32.5 25 125-150
1.0-3.0 Cb
a
A494 N-12MV Hastelloy B 8
0.12 1.00 1.00 0.040 0.030 i.oo Balance 4.0-6.0 26.0-30.0 Mo SA 520 76 315 46 6 190
0.20-0.60 V
A494 N-7M — 0.07 1.00 1.00 0.040 0.030 1.0a Balance 3.0a 30.0-33.0 Mo SA 520 76 315 46 20 190 27 20 RT RT
A494 CW-12MW Hastelloy8 C 0.12 1.00 1.00 0.040 0.030 15.5-17.5 Balance 4.50-7.50 16.0-18.0 Mo SA 495 72 275 40 4 200 "-
0.20-0.60 V
3.75-5.25 W
A494 CW-6M - 0.07 1.00 1.00 0.040 0.030 17.0-20.0 Balance 3.0a 17.0-20.0 Mo SA 495 72 275 40 25 200 27 20 RT RT
A494 CW-2M Hastelloy8 C-4 0.02 1.00 0.80 0.03 0.030 15.0-17.5 Balance 2.0 15.0-17.5 Mo SA 495 72 275 40 20
1.0 W a
A494 CW-6MC Inconel£ 625 0.06 1.00 1.00 0.015 0.015 20.0-23.0 Balance 5.0 8.0-10.0 Mo SA 485 70 275 40 25
3.15-4.50 Cb
a
c
SA, solution annealed; AC, as cast. o
d
Typical.
e
RT, room temperature.
Trademark of the International Nickel Company, Inc. o
8
Trademark of Cabot Corporation.
to
3
13. Cast Alloys 305
Cast Inconel, CY-40, is the equivalent of wrought Inconel alloy

600. Again, the carbon and silicon in the cast grade are higher
than the wrought material to provide adequate castability. CY-40
is solution annealed to maximize corrosion resistance and mechanical
properties. The alloy is used primarily for oxidation resistance
and strength retention at high temperatures [10]. In chloride en-
vironments, the alloy resists stress-corrosion cracking, and it is
frequently substituted for CZ-100 in caustic soda-containing halogens.
Because it resists chloride stress cracking and corrosion by high-
purity water, CY-40 is widely used in nuclear reactor services.
Also, some CY-40 is used in food processing.
The cast 70 Ni-30 Cu alloys (Monels) are the equivalent of
wrought Monel 400. The compositional variations between the wrought
and cast grades are again a result of foundry characteristics. Be-
cause nickel and copper are mutually soluble in each other at all
concentrations, there is no need to heat treat the 70 Ni-30 Cu alloys
and, therefore, they are used in the as-cast condition. These alloys
find widespread use in water handling, particularly in seawater
and brackish water [9]. They handle water services extremely well
under high-velocity conditions, and many pump and marine compo-
nents are cast in the Monel grades. Air-free hydrofluoric acid is
commonly handled by the M-35-1 grade because of the lower silicon
level. The lower silicon content also makes the M-35-1 grade of
Monel the preferred alloy for welding. Because M-35-1 possesses
good resistance to fluorides, it is finding widespread use in uranium
enrichment. The higher silicon grade alloy M-30H is used for rotating
parts and wear rings because it combines corrosion resistance with
high strength and wear resistance. M-25S is employed where excep-
tional resistance to galling is needed. The ductility will decrease
sharply with the higher silicon levels and the tensile and yield
strengths will increase. Because the strength and ductility cannot
be controlled readily, the only mechanical property recorded for
M-25S is hardness. The high silicon grades M-30H and M-25S are
considered nonweldable. The M-30C grade of Monel obtains its high
strength from an addition of columbium rather than higher silicon.
Because of the lower silicon level good weldability is maintained,
but the columbium carbide phase that forms will decrease the corro-
sion resistance of this alloy in services like hydrofluoric acid. The
70 Ni-30 Cu alloys have excellent resistance to reducing mineral
acids, organic acids, and salt solutions. These alloys have found
some use in sulfuric acid services where reducing conditions exist
and in chlorinated solvents. However, oxidizing conditions or con-
taminants accelerate the corrosion rate of Monel in all services.
The final alloys in the nickel-based group are the cast equivalents
or modifications of the nickel-molybdenum and nickel-chromium-
molybdenum alloys. The N-12MV and N-7M alloys in this group

comprise the nickel-molybdenum materials. The solution-anneal heat
treatment, together with alloy purity of these alloys, are critical
to producing a microstructure that will provide maximum corrosion
resistance. If impurities, such as carbon and silicon, are not con-
trolled to as low levels as possible, a secondary phase will be
present in the microstructure that will adversely affect corrosion
resistance. It should be noted that the N-7M alloy is much more
ductile than N-12MV. These alloys are particularly recommended
for handling hydrochloric acid at all concentrations and temperatures,
including boiling [11]. Oxidizing contaminants or conditions can
lead to rapid failure. Cupric or ferric chloride, hypochlorites, nitric
acid, and even aeration are common causes of accelerated corrosion
with these alloys. At 26°C (78°F), the tolerable ferric ion concen-
tration in 10% hydrochloric acid is 5000 ppm, at 66°C (150°F) it
is less than 1000 ppm, and at boiling it is less than 75 ppm [12].
This illustrates the importance not only of the contaminant level
but also of temperature. The Ni-Mo alloys also perform well in hot
sulfuric acid, again without the presence of oxidizing contaminants.
Phosphoric acid in all concentrations can be handled up to 140°C
(300°F) by these alloys.
The CW-12MW, CW-6M, CW-2M, and CW-6MC alloys make up the
nickel-chromium-molybdenum group. CW-12MW and CW-2M are actually
dual-purpose alloys intended for both corrosion and high-temperature
services. Tungsten and vanadium are specifically added for high-
temperature oxidation resistance. CW-2M is essentially a low carbon
version of CW-12MW with improved ductility and high-temperature
service. The alloy resists the formation of grain-boundary precipi-
tates in the as-welded condition allowing its use in corrosive environ-
ments without postweld heat treatment. CW-6M is intended primarily
for corrosive services. By so limiting the intended use of this alloy,
the tungsten and vanadium are removed and the chromium, molyb-
denum, and nickel levels are raised. This provides improved corro-
sion resistance and enhanced mechanical properties, particularly
for ductility. CW-6MC is the cast equivalent of wrought Inconel 625.
The alloy is solution annealed to maximize corrosion resistance and
mechanical properties. CW-6MC is primarily used for oxidation resist-
ance and strength retention at high temperatures. The alloy has
improved corrosion resistance compared with CY-40. Heat treatment
and compositional purity are again important, for the same reasons
as those mentioned earlier for the Ni-Mo alloys. The essential differ-
ence between the Ni-Mo and Ni-Cr-Mo alloys is that approximately
one-half of the molybdenum in the Ni-Mo group has been replaced
with chromium. The addition of chromium gives these alloys oxidation
resistance while maintaining good resistance to reducing acids. For
13. Cast Alloys 307
example, these alloys can handle hydrochloric acid contaminated

with ferric chloride at all concentrations at temperatures up to
50°C (120°F). At lower concentrations, higher temperatures can
be tolerated. CW-12MW and CW-6M are quite useful for acid brine
solutions. Other typical applications include hot, contaminated mineral
acids, solvents, chlorine- and chloride-contaminated solutions, hot
organic acids, hypochlorites, acetic anhydride, and seawater.
COPPER-BASED ALLOYS
The copper-based alloys comprise a very large group of materials.

Included are relatively pure copper, many different grades of brasses
and bronzes, the copper-nickel alloys, and various special alloys.
It would be impossible to present and discuss each cast alloy here,
so a broad listing of the various cast copper alloy families is pre-
sented in Table 9, and a few selected alloys will be discussed in
some detail. There are a number of ASTM standards dealing with
cast copper alloys. The major ones are listed in Table 10.
Copper and its alloys are generally not chosen for their corrosion
resistance alone but, rather, for that characteristic plus one or
more other properties [13]. In fact, for many applications, some
other characteristic, such as thermal conductivity, may be the over-
riding consideration. Copper castings have some advantages over
wrought materials, much the same as was found with other alloy
systems, in that the casting process permits greater latitude in
alloying because hot- and cold-working properties are not important.
This is particularly true relative to the use of lead as an alloying
element.
Before getting to specific alloys and applications, it is appropriate
to point out a few precautions that are pertinent when considering
copper alloys for corrosive applications [14]. Copper alloys contain-
ing 20 to 40% zinc are susceptible to a form of corrosion known
as dezincification [3]. This form of corrosion is like the graphitiza-
tion of cast iron in that overall component dimensions do not change
but strength is seriously impaired. Therefore, these alloys should
not be used in dilute or concentrated acids, organic and inorganic
acid salts, dilute or concentrated alkalies, neutral solutions of
chlorides and sulfates, and mild oxidizing agents such as calcium
hypochlorite, hydrogen peroxide, and sodium nitrate. Copper alloys
containing less than 15% zinc can withstand a wide range of environ-
ments, including acids, alkalies, and salt solutions, as long as
the services do not contain dissolved air, oxidizing materials such
as nitric acid, ferric salts, dichromates, and chlorine; compounds
such as ammonia and cyanide that form soluble complex ions with
Co
o
00
TABLE 9 Cast Copper Alloy Families
UNS n o . a Description Major constituents
C80100-C81100 Coppers Cu
C81300-C82800 High copper alloys Cu
Cu + Cr
Cr,, Be,
Be, Co,
Co Ni, Si
C83300-C83800 Red brasses, leaded red brasses Cu , Sn, Zn, Pb
C84200-C84800 Semired brasses, leaded semired brasses Cu , Sn, Zn, Pb
C85200-C85800 Yellow brasses, leaded yellow brasses Cu , Sn, Zn, Pb
C86100-C86800 Manganese bronzes, leaded manganese bronzes Cu, Zn, Al,
Cu , Zn, Al, Mn,
Mn, Pb
C87200-C87900 Silicon bronzes and brasses Cu , Zn, Si
C90200-C91700 Tin bronzes Cu , Sn
C92200-C92900 Leaded tin bronzes Cu , Sn, Pb
C93200-C94500 High-leaded tin bronzes Cu , Sn, Pb
C94700-C94900 Nickel-tin bronzes Cu , Sn, Ni
C95200-C95800 Aluminum bronzes Cu , Al,Fe, Ni
C96200-C96600 Copper-nickels Cu , Ni,Fe
C97300-C97800 Nickel-silvers Cu , Ni,Zn
C98200-C98800 Leaded coppers Cu , Pb
C99300-C99700 Special aUoys Cu,
Cu , Ni,
Ni,Fe,
Fe, Al,
Al, Zn §
a
Unified numbering system. ^
to
13. Cast Alloys 309
TABLE 10 ASTM Copper and Copper Alloy Casting Specifications
ASTM
standard Title
B61 Steam or Valve Bronze Castings

B148 Aluminum-Bronze Sand Castings
B271 Copper-Base Alloy Centrifugal Castings
B369 Copper-Nickel Alloy Castings
B505 Copper-Base Alloy Continuous Castings
B584 Copper Alloy Sand Castings for General Applications
copper; and compounds that react directly with copper, such as

sulfur, hydrogen sulfide, silver salts, mercury and mercury com-
pounds, and acetylene.
Relatively pure copper (99+ %) finds use in many applications.
Because of its resistance to industrial, marine, and rural atmos-
pheres, this material finds use in many architectural applications
[15]. It also is used in freshwater applications and some seawater
services, although certain copper alloys are more desirable here.
No ASTM standard exists for cast copper.
The brasses are probably the most useful of all the copper alloys.
Table 11 lists some of the more common cast brass compositions
and properties. Red brass is much superior to copper for handling
hard water. The brasses also find use in seawater with the higher-
strength, higher-hardness materials used under high-velocity and
turbulent conditions. Other services for which the brasses might
be used include boric acid; neutral salts, such as magnesium chloride
and barium chloride; organics, such as ethylene glycol and formalde-
hyde; and organic acids.
The bronzes are the next major group of copper alloys. Table 11
lists some of the more common cast bronze compositions and proper-
ties. From a corrosion standpoint, the bronzes are quite similar
to the brasses. The addition of aluminum to the bronzes does im-
prove resistance to high-temperature oxidation and also raises the
tensile properties. The bronzes do find use in sulfate environments
where brasses might not be used. Silicon bronzes can handle cold,
dilute hydrochloric acid, cold and hot, dilute sulfuric acid, and
cold, concentrated sulfuric acid.
The copper-nickels are the final major group of cast copper
alloys. Table 11 shows the composition and properties of the two
most common cast copper-nickel alloys. These materials have the
highest corrosion resistance of all the copper alloys. The copper-
nickels have outstanding resistance to seawater and probably find
GO
O
TABLE 11 Copper-Based Alloys Compositions and Properties
Cast
ASTM alloy Nominal composition Tensile Yield Elongation
stand- desig- Other strength strength in 50 mm
ard nation Zn Sn Pb Mn Al Cu Fe Si elements MPaa ksi a MPaa ksi a (2 i n . ) a
B584 C83600 5 5 5 — — 85 — — 207 30 97 14 20

B584 C85200 24 1 3 — — 72 — — — 241 35 83 12 25
B584 C86200 27 — — 3 4 63 3 — 621 90 310 45 18
B584 C86300 27 — — 3 6 61 3 — — 758 110 414 60 12
B584 C90500 2 10 - — — 88 — — — 276 40 124 18 20
B584 C87200 5 1 - 1.5 1.5 89 2.5 3 — 310 45 124 18 20
B369 C96200 — _ — 0.9 — 87.5 1.5 0.1 10 Ni 310 45 170 25 20
B369 C96400 — — — 0.8 — 67 0.7 0.5 30 Ni 415 60 220 32 20
1 Nb
a
Minimum co'
o
to
13. Cast Alloys 311
their most widespread use in the area of sea- and brackish-water

handling. Dilute hydrochloric, phosphoric, and sulfuric acids cause
no attack. The copper-nickels are almost as resistant as Monel to
caustic soda.
ALUMINUM ALLOYS
As with the other systems, there are many different aluminum alloys.
There is a major difference with aluminum cast alloys for corrosive
applications in that, in general, adding alloying elements to aluminum
tends to decrease corrosion resistance, but pure aluminum castings
are rarely made owing to poor casting quality and low mechanical
properties [15]. Most aluminum-casting applications can be handled
by three alloys: 356, 443, and 514. These alloys can be found in
ASTM B26 and B108 for sand castings and permanent mold castings,
respectively. Aluminum die castings also find some use, particularly
for atmospheric corrosion resistance, and the die-cast alloys can
be found in ASTM B85.
Table 12 shows the compositions and properties for the preceding
three alloys. The 356 alloy is used where a combination of good
strength characteristics and atmospheric corrosion resistance is
required. This alloy also finds use in some water applications. Alloy
443 possesses excellent resistance to domestic and marine atmospheric
conditions. It is also very resistant to the mildly acidic solutions
encountered in the textile industry and finds widespread use there.
Alloy 514 possesses very good stress-corrosion resistance even
at very high stress levels. It has high resistance to general corro-
sion and pitting. Applications include seawater, salt spray, mild
alkalies, and high-octane gasolines. In addition to these services,
aluminum castings find use in nitrogen fertilizer solutions, ammonium
nitrate, urea, 98% nitric acid, concentrated sulfuric acid to avoid
iron contamination, sulfite solutions, synthetic fiber manufacture,
and sewage disposal.
TITANIUM
Titanium castings have found increasing use in corrosive services

because of their resistance to some particularly severe environments.
Titanium is much like aluminum, in that alloying generally decreases
the corrosion resistance. Therefore, only two cast titanium materials
are generally used for corrosive services, the commercially pure
grade and a grade stabilized with a small addition of palladium.
Cast titanium alloys are covered by ASTM B367.
TABLE 12 Aluminum Alloys Compositions and Properties
Cast Heat-
alloy treated Tensile Elongation
desig- Composition a condi- strength in 50 mm
nation Mn Si Zn Ti Cu Mg Fe tion MPab ksib (2 i n . ) b
A356 0.,20 6. 5/7. 5 0.,10 0 .20 0.,20 .20-0.40 0.20 T6 C 254 37 5.0
O
B443 0.,35 4. 5/6. 0 0.,35 0 .25 0..15 .05 0.8 Fd 117 17 3.0
O
514 0.,35 0. 35 0,,15 0 .25 0.,15 .5-4.5 0.50 Fd 151 22 6.0
CO
a
^Minimum unless otherwise noted.
C
T6, solution heat treated, artificially aged.
°^F, sand cast, no heat treatment.
CO
o
to
2
13. Cast Alloys 313
Before discussing the applications in which titanium excels, it

seems appropriate to enumerate some precautions relative to its
use [16]. Titanium is particularly prone to hydrogen pickup even
at room temperature. This pickup causes the protective film to
become embrittled, and it can then be eroded away, particularly
under high-velocity conditions. This can lead to rapid wastage
of the titanium surface. Titanium can exhibit pyrophoric reactions
in certain environments, such as red fuming nitric acid, high-
pressure oxygen, and dry chlorine. Stress-corrosion cracking can
be a problem in certain environments, including nitrogen tetroxide,
fuming nitric acid, methyl alcohol, chlorinated solvents, hot dry
salt, and hydrogen chloride. Finally, titanium is extremely susceptible
to crevice corrosion in some environments, although the addition
of palladium overcomes this problem to a great degree. Titanium
does have some shortcomings, and castings are costly, but for
certain severe services this can prove to be a wise and economical
alloy choice.
The compositions and properties of two of the commonly used
corrosion-resisting grades found in B367 are shown in Table 13.
One of the outstanding characteristics of titanium is its resistance
to inorganic chlorides that destroy stainless steels and other common
materials of construction. Titanium can easily handle hot or cold
chlorinated brines and marine environments. In fact, titanium handles
these services so well that it has replaced the copper-nickel alloys
in many seawater applications. Titanium is widely used in the manu-
facture of ferric and cupric chlorides, corrosives that play particular
havoc on stainless steels. Services containing wet chlorine gas and
bleaching solutions containing chlorites, hypochlorites, and chlorine
dioxide are very successfully handled by titanium. As little as 50
ppm water is required to avoid vigorous attack by the chlorine.
Titanium is used in strong nitric acid at temperatures up to 200°C
(392°F), but other mineral acids tend to attack it. The presence
of oxidizing species such as ferric or cupric ions sufficiently inhibit
attack to permit use in acidic services. Also, the palladium-stabilized
grade shows much improved behavior in acidic services. Because
titanium tends to be nontoxic, it is being used more frequently
in food service applications.
ZIRCONIUM
The major use of zirconium is in nuclear applications, but it is

coming into more widespread use for some very severe corrosive
services. The cast zirconium-based alloys are covered by ASTM
B752. The composition and properties for the grade of zirconium
TABLE 13 Titanium Compositions and Properties
Brinell
Cast Heat- Elonga- hard-
ASTM alloy Compositiona treated Tensile Yield tion in ness
stand- desig- Other condi- strength strength 50 mm num-
ard nation Pd Ti Fe elements tion13 MPac ksi c MPac ksi c (2 i n . ) c bera
B367 C-3 0.10 0.015 0.05 0.40 - Bal- 0.25 0.10 each AC 450 65 380 55 12 235
ance 0.40 total
B367 Ti- 0.10 0.015 0.05 0.40 0.12+ Bal- 0.25 0.10 each AC 450 65 380 55 12 235
Pd8A ance 0.40 total
a
b
AC, as-cast.
c
13. Cast Alloys 315
TABLE 14 Zirconium Composition and Properties
ASTM standard B752

Cast alloy designation 702C
a
Composition
Hf 4.5
Fe + Cr 0.30
H 0.005
N 0.03
C 0.01
O 0.25
P 0.01
Zr Balance
Other elements 0.40
Heat-treated condition 0 AC
Tensile strength
MPac 380
ksic 55
Yield strength
MPac 276
ksi c 40
Elongation in 50 mm (2 i n . ) c 12
Reduction of area, %c 20
Brinell hardness number 200
a
ÂC, as cast.
c
used mostly in corrosive applications are given in Table 14. One

of zirconium1 s outstanding properties is its resistance to hydrochloric
acid [5]. It can handle boiling hydrochloric acid up to 20% and
can handle higher concentrations at somewhat lower temperatures.
The presence of oxidizing species such as cupric or ferric chloride
and wet chlorine render zirconium unacceptable. Sulfuric acid to
70% can be handled up to the boiling point. Zirconium can handle
all concentrations of nitric acid at temperatures up to boiling. It
is superior to stainless steels, nickel alloys, and titanium for organic
acids and is particularly useful at high temperatures. Severe caustic
services can be handled very successfully. Zirconium can also handle
all inorganic salts except ferric and cupric chloride.
MAGNESIUM ALLOYS
There are a number of cast magnesium alloy grades produced, and

these can be found in ASTM specifications B80, B94, B199, and
B403 for sand castings, die castings, permanent mold castings,
and investment castings, respectively. Magnesium is not generally
chosen for its corrosion resistance. In fact, because magnesium
is anodic in comparison with most metals, it is frequently used
as a sacrificial anode to protect other alloys. Magnesium alloys find
widespread use in aircraft and related applications where weight
savings are important. Magnesium alloys do resist attack by most
alkalies, many organic chemicals, concentrated hydrofluoric acid,
pure fluorides, chromates, and dichromate. These alloys are generally
attacked by other acids and aqueous salt solutions. The addition
of alloying elements to magnesium does not appreciably influence
corrosion resistance.
CASTING PRODUCTION
Casting Design
If a component is to be made as a casting, it should be designed
as a casting. This statement may seem redundant, but there are
too many instances where it is not adhered to. Casting design is
certainly much too broad a topic to cover in detail here, and there
are many references [17-20] that cover the topic quite well. There
are a few general points concerning casting design that are worthy
of mention.
Casting design and casting process go hand in hand, and the
inherent advantages and disadvantages of each process must be
considered starting with the design step. There are a number of
processes in use today for manufacturing castings for corrosive
services. The major processes include sand casting, plaster casting,
investment casting, die or permanent mold casting, and centrifugal
casting. Sand casting is by far the most common of the processes.
This process provides design flexibility and low cost. The largest
castings are made by this process, but through proper design and
good foundry practices, small pieces can also be produced. Surface
finish is not generally as good as with other processes, but with
proper controls it can be quite adequate. Available molding equip-
ment is capable of producing consistent molds at very good produc-
tion rates. Pattern equipment cost can vary depending on production
quantities and molding systems, but it is generally the lowest of
all the casting processes. Because relatively inexpensive patterns
can be obtained, it makes sand casting attractive for low-volume
and prototype work.
13. Cast Alloys 317
There are many variations of the basic sand casting process.

The most prevalent are green sand and chemical or air-setting
sand casting. Green sand derives its name from the molds (consisting
of a sand-clay water mixture) that are poured soon after they are
made or before any appreciable drying has occurred; thus, they
are in the green condition. The chemical or air-setting process
involves mixing a chemically bonded air-setting resin with sand.
The air-setting resin hardens and bonds the sand. Dry sand molds
are those from which moisture is removed before pouring. Shell
molding is a relatively new variation, whereby a very thin mold
is produced on a heated pattern with use of a resinous or organic
binder. This procedure finds particular use for making cores that
are placed in green sand molds. The shell-molding process lends
itself to higher production rates, better surface finish, and improved
dimensional control, but it has the drawbacks of leading to contami-
nation of low carbon alloys and presenting some environmental
problems. Progress has been made in reducing the alloy contamination
through the use of additives to the molding sands, and inorganic
binder systems have been developed to totally eliminate problems
encountered with resin systems. Practically all nonreactive metals
and alloys are produced in some form of sand-casting process.
Plaster casting involves making a mold by pouring a plaster
slurry around a contained pattern or into a core box. It is particu-
larly suited for the lower-melting-point alloys and finds widespread
application in producing aluminum- and copper-based castings.
Dimensional control and surface finish are good, and relatively
thin sections can be poured. There is some limitation on casting
size.
Investment casting involves producing an expendable pattern,
usually of wax or plastic, then forming a shell or solid mold around
this pattern. The pattern is removed by melting, burning, or dis-
solution, leaving a cavity that is an exact replica of the pattern.
Surface finish and dimensional control are excellent, and the process
produces a ceramic mold that does not contaminate the alloy or
present environmental problems. Because the molds can be poured
hot, very thin sections can be produced. Cost of production dies
to produce the patterns is relatively high, although lower-cost
prototype tooling can be made. Production rates vary depending
on the degree of mechanization. Casting size is definitely limited.
Because dimensional control is so effective, it is possible to produce
castings that require very little or no machining. Castings in all
alloys are produced by this process.
Die or permanent mold casting involves introducing a molten
alloy into a metal mold, either through gravity pouring or under
pressure. Dimensional tolerances and surface finish are excellent.
This is a high-production rate process with a very high initial

cost for dies and casting machines. Casting size is limited. Some
ferrous die casting is being performed, but on a restricted basis.
Generally, the lower-melting-point alloys are cast by this process.
Centrifugal casting, as generally performed, can be considered
a special form of permanent mold casting. A metal mold coated with
a ceramic wash or sand mixture is spun on its central axis while
the molten metal is introduced. The centrifugal force produces a
dense casting requiring no risering and no central core. This process
is widely used with many different alloys to produce tubes and
cylindrical configurations for corrosive services.
Production of castings for reactive metals such as titanium and
zirconium requires special melting and casting techniques. Because
the alloys are reactive, it is necessary to melt and pour under
vacuum. Some sort of centrifugal assist is commonly used to produce
a sound casting. The molds are made from either a graphitic-bonded
or ceramic-type system. The necessity of vacuum melting and pouring
is an obvious contributor to the high cost of cast titanium and zir-
conium components.
Because design is so critical to the final cost and quality of
cast components, and because there are a number of casting proc-
esses available, the final choice of which process to use is highly
dependent on design, it is imperative that casting expertise be
input into the design function at an early stage. Most good-quality
casting producers can provide this input and will be of valuable
assistance in producing a design that will provide the needed per-
formance at a reasonable cost.
Casting Quality
Cast components find use in many unusually critical corrosive appli-
cations. As operating conditions become more severe, as maintenance
costs and the costs of shutdowns continue to rise, as product con-
tamination and product losses attract increasing interest, and as
safety and reliability assume more importance, the matter of compo-
nent integrity becomes even more important. There are certain
defects inherent in castings, and control of these defects is critical
to the production of a quality part. The important quality aspects
of any casting intended for a corrosive service can be assigned
to one of three areas: surface integrity, internal integrity, and
alloy purity.
Surface integrity deals with surface finish, surface defects,
and dimensional accuracy. Surface finish has importance for many
reasons. There is an aesthetic consideration that cannot be over-
looked. Equipment manufacturers do not want unsightly castings
13. Cast Alloys 319
representing their product, which is understandable. For velocity

applications, rough surfaces can disrupt flow patterns and reduce
efficiency. Included in the area of surface defects are cracks, dirt
and slag inclusions, and porosity. Again, the aesthetic value of
a casting is reduced by surface defects. More important, surface
defects can be serious enough to lead to component failure. This
is particularly true of cracks, and these defects are often not dis-
cernible through visual inspection. A more searching technique,
such as dye penetrant or magnetic particle inspection, is required
to detect many linear-type defects. Finally, dimensional accuracy
can influence machining operations, assembly, and final component
performance. Factors influencing surface integrity include casting
design and process, foundry practices, and alloy selection. Casting
performance and cost are influenced by surface integrity require-
ments, and these must be given adequate consideration and be
carefully defined for inclusion in the final purchasing specification.
Internal integrity deals with the internal soundness of a casting.
Common defects leading to unsound castings include shrinkage,
porosity, and inclusions. The presence of these defects can be
determined only through such techniques as radiographic or ultra-
sonic inspection. These defects can certainly lead to component
failure, and their effect can be very insidious. Internal quality
levels can be defined relative to ASTM reference standards. For
example, ASTM E446 contains reference radiographs for steel casting
section thicknesses up to 51 mm (2 in.), and ASTM E155 contains
reference radiographs for aluminum and magnesium castings. Good
casting design and extremely careful control of all foundry practices
are required to produce sound castings. Required internal integrity
must be defined in casting specifications.
Surface and internal integrity are certainly important for accept-
able performance of cast components. However, in corrosive service,
the casting alloy is of the utmost importance. Proper alloy selection
must receive careful consideration. It is essential that a sufficiently
resistant alloy be chosen, but the selection should also include
economical considerations. Metallurgical expertise in alloy selection
is as vital as with wrought alloys. Selection of the proper alloy
for a service does not, however, ensure acceptable service, because
there is the matter of alloy purity. The same basic alloy grade can
display variations in performance in the same service, and this
variation is commonly due to differences in alloy purity. The two
major factors determining alloy purity are melting practices and
mold environment.
Many factors are included under the broad topic of melting prac-
tices. Those having the most influence on alloy purity are raw
materials, melting method, and melt additives. Raw materials are
obviously critical, but they have particular significance for those

alloys made without benefit of melt refining. Here, to achieve a
high-purity alloy necessitates using high-purity raw materials.
The melting method is also crucial. Most high-melting-point metals
are melted in electric furnaces: the two major types are arc and
induction. Induction melting is commonly found in foundries and
is used to melt ferrous and nickel-based alloys, in particular. Arc
melting is generally used in the larger foundries and has the advan-
tage of being able to refine alloys to some degree. Most of the
lower-melting-point materials, such as aluminum, copper, and mag-
nesium, are melted in fuel-fired furnaces, although induction melting
is also used. Melt additives include such materials as degasers and
inoculants. These materials are generally added to correct a problem
introduced during melting, such as deoxidizing steels. The additives
generally perform their intended purpose remarkably effectively,
but by making these additions the overall alloy purity is frequently
reduced. There has been a major development in the past few years
that will have an important influence on melting practices and result-
ing alloy purity. This is the refining process called argon-oxygen
decarburization (AOD).
Argon-oxygen decarburization refining is a duplex operation
[21] used to improve the compositional purity and properties of
alloys. The process offers several distinct advantages, including
raw material cost savings, high-purity alloys, improved casting
cleanliness, and enhanced corrosion resistance and mechanical proper-
ties. Stainless steels can be routinely produced to low carbon speci-
fications, thus, eliminating the problem of sensitization during welding.
Desirable effects can also be achieved with low-alloy steels [22].
Reduction of the sulfur levels in these alloys substantially enhances
their ductility and impact toughness. Lower hydrogen and nitrogen
levels reduce the susceptibility to embrittlement. Nickel-based alloys
can also benefit from AOD refining. Major improvements in the duc-
tility of some nickel alloys have been reported [22]. Sufficient field
experience has not been achieved to define adequately the influence
of AOD refining on the corrosion resistance of cast alloys.
REFERENCES
1. Leckie, H. (1975). Iron, carbon steel, and low alloy steels in

the process industries. Process Industries Corrosion. National
Association of Corrosion Engineers, Houston, p p . 90-102.
2. Cast iron. (1961). Metals Handbook, Vol. 1. American Society
for Metals, Metals Park, Ohio, p p . 349-406.
3. Fontana, M., and Greene, N. (1978). Corrosion Engineering,
2nd ed. McGraw-Hill, New York.
13. Cast Alloys 321
4. LaQue, F. (1958). The corrosion resistance of ductile iron,

Corrosion 14:485t-492t.
5. Shoefer, E. (1977). The cast stainless steels, Handbook of
Stainless Steels (D. Peckner and I. Bernstein, e d s . ) , McGraw-
Hill, New York, p p . 2/1-2/18.
6. Shoefer, E. (1973). High alloy data sheets, Corrosion Series.
Alloy Casting Institute Division of Steel Founders 1 Society of
America, Rocky River, Ohio.
7. Fisher, Dulis, and Carroll (1953). Trans. AIME 197:690-695.
8. Spence, T. (1986). Corrosion resistant cast alloys, Process
Industries Corrosion (B. Moniz, W. Pollock, e d s . ) , National
Association of Corrosion Engineers, Houston, Texas, p p . 557-565.
9. Huntington Alloys Handbook, 5th ed. (1970). International Nickel
Company, Toronto.
10. Graver, D. (1975). Nickel and high nickel alloys, Process Indus-
tries Corrosion, National Association of Corrosion Engineers,
Houston, p p . 109-113.
11. Hughson, R. (1976). High nickel alloys for corrosion resistance,
Chem. Eng. 83(24) : 125-152.
12. Lee, T . , Ill, and Hodge, F. (1976). Resistance of "Hastelloy"
alloys to corrosion by inorganic acids, Matr. Perf. 15(9,) :29-36.
13. Lyman, W., and Cohen, A. (1978). Engineering with copper
alloys-I, Chem. Eng. £5(6; :99-102.
14. Lyman, W., and Cohen, A. (1978). Engineering with copper
alloys-II, Chem. Eng. 85(9) : 147-150.
15. Gackenbach, R. (1960). Material Selection for Process Plants,
Reinhold, New York.
16. Boyd, W. (1975). The use of titanium, zirconium, tantalum,
and columbium in chemical environments, Process Industries
Corrosion, National Association of Corrosion Engineers, Houston,
p p . 207-212.
17. Metals Handbook, Vol. 5 (1970). American Society for Metals,
Metals Park, Ohio.
18. Taylor, H., Flemings, M., and Wulff, J. (1959). Foundry
Engineering, Wiley and Sons, New York.
19. Steel Casting Design, Engineering Data File No. 1, Steel
Founders' Society of America, Rocky River, Ohio.
20. Briggs, C. W. (ed.) (1970). Steel Castings Handbook, 4th ed.
Steel Founders 1 Society of America, Rocky River, Ohio.
21. Hilty, D . , and Kaveny, T. (1977). Melting of stainless steels,
Handbook of Stainless Steels (D. Peckner and I. Bernstein,
e d s . ) , McGraw-Hill, New York, p p . 3/1-3/35.
22. Venne, L., and Oldfather, C. (1978). Enhancement of physical
properties by argon oxygen decarburization, Mod. Cast. 68(8):
70-71.
23. Herrnstein, W. (1977). Cast iron-nickel-chromium alloys, Hand-

book of Stainless Steels (D. Peckner and I. Bernstein, e d s . ) ,
McGraw-Hill, New York, p p . 10/1-10/18.
24. Information presented at INCO Chemical and Petrochemical Indus-
tries Materials Conference, held by International Nickel Co.
at Wrightsville Beach, North Carolina, September 19-21, 1983.
14
DEVELOPMENT AND APPLICATION
OF PLASTIC MATERIALS
JOHN H. MALLINSON J. H. Mallinson PE & Associates, I n c . ,
Front Royal, Virginia
INTRODUCTION AND HISTORY [1-3]
One of the great steps in human development was the discovery

that we could change the nature of materials. Slowly at first, we
adapted materials to our use and, then, as the Industrial Revolution
produced a much more complex civilization, the problems of material
preservation changed together with the emphasis. Economic competi-
tion is the driving force that compels engineers to provide the
lowest-cost unit over the service life of equipment. Practically all
engineering materials are composites of some sort. Cannons made
of wood were bound with brass. Steel is painted to withstand corro-
sion. Today, the corrosion engineer is constantly looking for mate-
rials that are lighter, stiffer, stronger, and more corrosion-resistant
than their predecessors.
Practically every engineering design is a balance of economic
choices, but economic factors act as the independent variable.
Design is for expected life, and reliability is an important part
of the picture. The performance demands of a vessel or process
system generally involve a combination of many different materials.
Each part is the engineer's optimum choice for the local function.
Rarely, if ever, does a single material become a blanket prescription
for success.
Nature has natural polymers in abundance but, at our level
of technical learning, we were unable to grasp the idea that trial
and error were not the keys to the great materials of the future.
Only with new instrumentation, such as the electron microscope,
323
324 Mallinson
ultracentrifuge, infrared analyzer, and gas chromatograph, has

polymer development really pushed forward. With advanced computers,
by which molecular design can be accomplished and properties pre-
dicted, many doors are being opened for further advances.
The plastics industries began about 1868 when Hyatt discovered
celluloid. This was followed by Baekeland and his phenol-formaldehyde
resins (including Bakelite) in 1907 and nylon in 1938, the polyesters
and polyethylene in 1942, and the epoxies and acrylonitrile-butadiene-
styrene (ABS) in 1947. In the first half of the century use of the
thermoset resins were at the center of the corrosion battle—at first
on a small scale and then on a much larger scale in the early 1950s.
Some plastic and lined pipe were available in the 1940s, and the
first phenolics were being used for the chemical industry1 s corrosion
problems.
During the last several decades, poly vinyl chloride (PVC) and
ABS have become widely used in process equipment. The polyolefins
are now moving into the forefront where low cost and chemical inert-
ness are required. They are available in many forms, such as duct,
piping, and packing for scrubbers and columns. Polypropylene is
applied increasingly in process equipment.
Fluorinated thermoplastic resins have found special uses in the
chemical process industries because of their heat stability and inert-
ness. For example, heat exchangers built of Teflon have carved
out a unique position in many areas, particularly in crystallization,
for which fibrillation techniques require their use over rigid struc-
tures.
There are special reasons that make the use of other thermoplastic
resins desirable. Nylons and acetals are excellent materials for small
parts and gears; phenylene oxides provide high strength and have
been made into bolts and nuts for corrosive service; and the ure-
thanes provided a complete breakthrough in the insulation area.
Some elastomers are used for lining process equipment when particu-
lar properties are desired, even for large earthen pits running
into multimillion-gallon capacities. Great quantities of polyethylene
and polypropylene tubing are used in process instrument applications
because of their chemical inertness.
The basic push for other materials has constantly been prodded
by economic consideration. Alkaline materials at moderate temperature
have never represented a troublesome corrosion area. The tough
corrosion problems are found in oxidizing or reducing atmospheres
or combinations. Steel pipe may last only a few days. Type 304
stainless steel may do little better. Type 316 stainless steel might
last several months, and frequently, only the highest-grade Cr-Ni-Mo
is successful. The engineerTs first attempt to get around this was
to use lined steel equipment; sometimes, ceramic ware, lead, rubber,
14. Plastic Materials 325
glass, a few elastomers, and some phenolic linings were used, but
engineers were faced with high-priced solutions. They have continu-
ally looked for a material as strong as steel, as light as aluminum,
and with high chemical resistance to the service conditions at hand.
When engineers found that they could tailor-make a material to
suit particular corrosion problems, the field of possibilities broadened
explosively.
In the chemical industry, much has been achieved with the use
of plastics to perform difficult assignments. Many times the perform-
ance of 316 SS or high nickel alloys can be equaled or exceeded
at a greatly reduced cost with the thermoplasts or thermosets
(Table 1). But, sometimes problems occur. Quite often the problem
lies in improper selection of the plastic to be used or in not follow-
ing recommended installation procedures. Lack of knowledge plus
lack of application of proper engineering techniques are the most
general causes of problems.
Poly vinyl chloride is widely applied in piping, such as drain,
waste, vent, and rural irrigation systems, as well as electrical
conduit, telephone duct, and wire and cable insulation. Filled
phenolics are inherently flame-retardant with low smoke evolvement
and, as such, have potential use in corrosive fume systems, particu-
larly in ducts.
High-density polyethylene and cross-linked, high-density poly-
ethylene are becoming widely used. Applications in sewers and
chemical pipelines, with sizes up to 48 in. in diameter, are particu-
larly noteworthy. The use of these polymers is expected to increase
in the next decade because the chemical- and abrasion-resistant
properties of plastics are significantly better than those of steel.
Chemical process pumps of all descriptions are built from poly-
propylene cast epoxies, reinforced epoxies, Teflon, reinforced
polyesters, and vinyl esters. These include magnetic pumps of
polypropylene construction and vinyl or Tygon peristaltic pumps.
The entire field of valves has been invaded by both thermoplastic
and thermoset resins—ball valves, in particular. Applications include
diaphragm valves, gate valves, butterflies, multiport valves, globe
valves, check valves, foot valves, diverters, pressure regulators,
solenoid valves, and needle valves.
Material blends combine some of the unique properties of each
component. For example, ABS measurably improves the impact
strength of PVC. Inorganic additives such as fiberglass or graphite
provide considerably increased strength, and other additives produce
fire retardancy, increase abrasion resistance, or reduce permeability.
Process manufacturing innovations are continuing, such as rotary
molding, spray mold fluid-bed molding systems, and resin transfer
molding (RTM).
TABLE 1 Comparative Physical Properties of Metals and Reinforced Plastics (Room Temperature) a Co
ISO
O
Composite Glass-
Glass- structure reinforced
Carbon Stainless mat glass-mat epoxy,
steel steel Hastelloy Alumi- laminate woven roving filament-
1020 316 C num (1/8 i n . ) (3/8 in.) wound*5
Density, lb/in. 3 0.284 0.286 0.324 0.098 0.050 0.055 0.065

Coefficient of thermal ex- 6.5 9.2 6.3 13.2 17 13 9-12
pansion, i n . / i n . °F x 10"6
Modulus of elasticity, 30.0 28.0 26.0 10.0 0.7-1.0 1.0-1.5 3.0
psi x i o 6 , in tension
(Young's modulus)
Tensile strength, psi x 103 66 85 80 12 9-12 12-20 60-100
Yield strength, psi x io 3 33 35 50.6 4 9-12 12-20 60-100
Thermal conductivity, 28.0 9.4 6.5 135 1.5 1.5 1.5-2.0
BTU/hr-ft 2 *°F-ft
Strength/weight ratio, IO3 230 300 250 122 240 363 1500
a
The physical strength figures used here for the glass-reinforced plastic laminates are conservative. For
example, some filament-wound epoxy tensiles run to 300,000 lb, giving them phenomenal strength/weight
ratios of 4500 x IO 3 .
^The data on glass-reinforced filament-wound epoxy have been drawn from a variety of sources. Filament
winding, in general, polyester or epoxy, will result in much higher physical strengths.
Source: From Ref. 6. 03
O
3
During the 1930s, seven basic families of plastics were introduced,

but only four were introduced in the 1950s, and three in the 1960s.
During the 1970s only three new specialty materials were discovered:
thermoplastic polyester in 1970; polybutylene in 1973; and nitrile
barrier resins for bottles in 1975.
Other hybrid reinforcements are on the horizon, such as blends
of carbon fiber, polyether sulfone, and polyether ketone. These
hybrids have a tensile modulus of 21 psi x io 6 and tensile strength
of 267,000 psi. Polyphenylene oxide capacities are being expanded
greatly to meet demands. Polyphenylene oxides, their base resins,
and their blends are among the fastest-growing families of engineer-
ing materials. Some thermoplastic resins have higher-impact strength
than any of the thermosets. The field of filament winding with
thermoplastic filaments promises many new applications. Reinforced
polysulfone has higher heat resistance than most of the thermosets
and is being used to replace carbon fiber-reinforced epoxies on
jet engines. Polypropylene, polybutylene, nylon, and polyphenylene
sulfide may be reinforced with any type of continuous reinforcement,
including hybrids. Previously, all reinforcements of this type have
been short-cut reinforcements. In 1986 some 400 million pounds
of reinforced thermoplasts were used. All of these fall in the category
of engineered materials.
FORMS AND PRODUCTS COMMERCIALLY AVAILABLE
Most thermoplasts are available in various forms of molded products

in almost every conceivable shape and size within the practical
limits of the material. Poly vinyl chloride, ABS, polyethylene, and
polypropylene are available in piping, ductwork, and small tanks.
The thermoplasts can also be combined with the thermosets to
form composite structures and provide the best properties of each
to meet some specific need. As such, they serve as linings for
piping and duct systems, stacks, scrubbers, and tanks plus process
vessels. Much work has gone into this field and it provides a unique
area of reference.
The thermosets have been developed widely into piping and duct
systems and into small, to very large, stacks, tanks, process vessels,
reactors, mixing chambers, scrubbers, and hoods. These predomi-
nantly cover use of the families of polyesters, epoxies, furans,
vinyl esters, and some phenolics, in applications for which the
performance of high nickel alloy is available for less than the cost
of stainless steel. Much work has been done to develop minimum
fire-spread ratings (i.e., less than 25) and low smoke ratings (i.e.,
less than 50).
328 Mallinson
The development of very high strength reinforcing materials,

such as graphite, carbon, and aramid fibers, has provided laminates
of superior stiffness that have come into extensive use by the military
as ablative shields on the nose cones of reentry missiles, and they
have provided unique stiffness in special areas in the automotive
and aerospace industries. Prices of carbon yarns which were 200
dollars/lb in 1970 are now 18-20 dollars/lb (1987). Because this
reinforcement is inert, the areas of application are limited only
by the resin. Scrubbers that are 30 ft in diameter and 100-ft high
have been built of plastic. Stacks have been built up to 800-ft
high. Large chimney liners up to 1200-ft high have been constructed
using unique construction techniques. These fiberglass liners are
built inside concrete stacks and are probably the largest fiberglass
structures ever built. Many are 18 to 25 ft in diameter and consist
of a stack within a stack; they are used widely in flue gas desul-
furization systems and in smelters. Piping that is 9 to 12 ft in
diameter is commonplace, ducts of the same size have been success-
fully installed, and tanks of up to 750,000-gal capacity also have
been built for use in chemical service.
Successful case histories of crystallization vessels of 10,000-gal
capacity have been in continuous service for as long as 20 years.
Plastic piping has made large inroads into the field of lined piping
because it is lighter and less expensive, more easily installed, and
carries a reduced downtime liability.
The entire field of household water supply and drain piping
has been invaded by PVC, ABS, and polybutylene.
The new process of resin transfer molding (RTM) has greatly
advanced the methods for manufacturing large (11 ft x 11 ft) flat
surfaces and is used to produce electrostatic precipitator plates
that have wide use in air purification exhaust systems in the chemi-
cal industry.
SPECIFIC PLASTIC FAMILIES

Thermoplasts [3,4]
Polyethylene
One of the most interesting of all the thermoplasts is polyethylene.
Molecular weights of 120,000 to 220,000 are common. High-density
polyethylene (HDPE) has a wide range of chemical resistance to
oxidizing chemicals and salts and is useful in continuous service
up to temperatures of 82°C (180°F). Ultraviolet stabilizers are widely
used, particularly carbon black. It also enjoys good lubricity and
has been used for bearings in heavy machinery. That some 600
different polyethylene compounds are offered commercially indicates
its wide acceptability. Although polyethylene has exceptional abrasion

resistance, it is outranked by the more recently developed poly-
butylene, which will handle coal or ores and chemical and abrasive
aggressive slurries, and is used as liners for hopper cars and
discharge gates. One-step higher is ultrahigh molecular weight
polyethylene, commonly called UHMWPE, for which the molecular
weights may be as high as 5 million. To illustrate the wide applica-
tions of the various grades of polyethylene the following partial
listing of uses is given:
Polyethylene (PE)
Consumer packaging Shrink wrap
Potable water Agricultural use
Cable insulation Pharmaceutical use
Linear low-density PE
Pipe and tubing Food packaging
Wire and cable insulation Trash bags
Garment bags
Very low-density PE
Industrial hose and tubing
Squeeze bottles
HMW, high-density PE (average molecular weight 200,000-500,000;
density > 0.941)
Pressure pipe
Large blow-molded articles
T-shirt grocery bags
Large-diameter pipe for sewer relining
55-gal, liquid shipping containers for chemicals
Pond and tank liners (20 to 100-mil thick in 18-20-ft widths)
This grade is widely used in industry for industrial piping—

particularly for large-diameter sewer lines where its wide corrosion
resistance makes it adaptable. It is also has a large use for relining
failed terra cotta or clay sewer piping when infiltration has become
a problem—either through overloading a waste-treatment facility
or contaminating a storm drain with unwanted chemicals. One of
the problems observed in some sewer-lining projects has been the
continued infiltration between the old pipe and the liner leaking
out through the seal at the next manhole.
Industrial tubing, particularly instrumentation tubing, made
from various grades of polyethylene is an important use.
High-density polyethylene is used extensively in small plastic
tanks up to 12 ft in diameter. These tanks are molded with heavy
walls and are used for the gravity storage of chemicals and agri-
cultural products where service conditions are suitable. Polyethylene
330 Mallinson
has a wide range of chemical resistance, particularly to many acids,

alkalies, and fertilizer solutions. These molded polyethylene tanks
have a cost advantage over their fiber-reinforced plastic (FRP)
counterpart, costing about 80% of an FRP tank with the same volume.
Polybutylene
Polybutylene is the newest member of the polyolefin family. It has
the highest pressure ratings for any of the polyolefin group, and
some designs are capable of supporting 1000 psi at 73°F and 500
psi at 180°F.
The combination of stress-cracking resistance, chemical resistance,
and abrasion resistance makes it particularly useful. It is resistant
to acids, bases, soaps, and detergents at temperatures up to 200°F.
It is not completely resistant to aliphatic solvents at room temperature
and is partially soluble in aromatic and chlorinated hydrocarbons
above 140°F.
It has reached substantial use in abrasive slurry pipelines and
high-temperature and effluent lines, where it may be used at tem-
peratures up to 200°F. It is excellent in fly ash and bottom ash
service. It is also used in trash liners, industrial sheeting, shipping
containers, hot-water plumbing, transport covers, and in agriculture
and is competitive with copper tubing and lined steel pipe.
Polypropylene
Polypropylene is a relatively young plastic, created in the mid-
1950s. It is unique in that it is used in all four primary fabrication
processes: molding, extrusion, fibers, and film. It also competes
with metals and natural fibers. It is the lightest of the major plastics.
Furthermore, it can be reinforced with glass fibers to materially
increase its physical properties, and polypropylene fibers can be
used to reinforce polyesters. In the chemical industry, polypropylene
compares favorably with rubber in use as a liner. It is also being
used as a composite with a fiberglass overlay in many items of duct-
work, mixing chambers, and other chemical equipment. If exposed
to sunlight, an ultraviolet (UV) absorber or screening agent should
be used to protect it from degradation. Thermal oxidative degradation
is also a major enemy, particularly where copper is involved. Here,
copper inhibitives should be added to prevent catalyzation. Fortu-
nately, polypropylene is not affected by most inorganic chemicals,
except the halogens and severe oxidizing environments. Chlorinated
hydrocarbons can cause swelling and softening at elevated tempera-
tures. With a fiberglass overlay, temperature resistance up to 150°C
(300°F) is possible. Fillers are often used to improve impact resistance
for increased stiffness. Impact properties may also be improved by
blending in up to 25% EP rubber or by blending in 8 to 10% rubber
compounds. Rubber blending enhances impact resistance. This is

accomplished at a sacrifice of some stiffness.
Polypropylene is widely used in engineering fabrics such as
bale wraps, filter cloths, bags, ropes, and strapping. Piping and
small tanks of polypropylene are widely used in industry; 90% of
all battery casings are made of polypropylene. Ignition-resistant
grades became available through the addition of halogenated organic
compounds. With this development, polypropylene was used in duct
systems in the chemical industry. Because polypropylene exhibits
good flex life, it is useful in the construction of integral hinges.
There are many textile applications for polypropylene, such as
carpet face and backing yarn, upholstery fabrics, and diaper cover-
stock. It is singularly useful in outdoor clothing and sports clothes
that are worn next to the body because its unique wicking qualities
absorb body moisture and still leave the wearer dry. Furthermore,
it is used widely in automotive applications such as interior trim
and under-the-hood components. In the appliance area, it is used
in washer agitators and dishwasher components. In consumer goods,
it goes into straws, housewares, luggage, syringes, toys, and
recreational items. Polypropylene has captured the food-packaging
market by supplanting cellophane. All in all, this is an unusually
versatile plastic.
Polyphenylene Sulfide
Polyphenylene sulfide (PPS) is one of the most economical thermo-
plasts. Although initially expensive, it is useful up to temperatures
as high as 230°C (450°F). Strangely enough, as temperature in-
creases, there is a corresponding increase in toughness. Polyphenyl-
ene sulfide can provide outstanding performance for use with aqueous
inorganic salts and bases, and it is inert to many organic solvents.
The use of a glass filler enhances its physical properties. Fasteners
have been made of this remarkable material for use under highly
oxidizing conditions, and coatings exhibit good hardness and chemical
inertness. Polyphenylene sulfide is also widely used in processing
equipment, such as centrifugal and gear-type pumps, that are ex-
posed to extremely aggressive environments. Relatively few materials
react with PPS, even at high temperatures. Flame resistance is
inherent in its stable chemistry. It is also used in injection and
compression molding and has been used to build perforated plates
where, acting as a screen, it outlasted the high nickel alloys many
times over.
Polyvinyl Polymers
Polyvinyl chloride is by far the largest family in this group and
can be found in many products, from rigid pipe to film and relatively
332 Mallinson
heavy sheets. In general, high-molecular-weight PVC has better

physical properties. Like other plastics, additives are used to further
specific end uses such as thermal stabilizers, lubricity, impact
modifiers, and pigmentation. It can be either rigid or flexible;
both plastisols and organosols can be produced with PVC. Hard
films can be produced as thin as 1 mil. The largest use for PVC
is piping systems for water supply, irrigation, and chemical process-
ing. It is used extensively in chemical piping with a temperature
service range of -18 to 60°C (0 to 140°F). Above 60°C, the use
of PVC is not recommended. However, poly vinyl dichloride (PVDC)
is used extensively in chemical piping systems up to a temperature
of 82°C (180°F); PVDC is also used in residential hot-water systems.
One of the problems with the PVC formula is that with fluctuating
temperatures there is a tendency for the material to "grow" and
not return to its original length when the temperature subsides.
This produces a growth in pipelines that can be troublesome. Another
disadvantage is that under sudden shock the resistance to impact
is limited. It has found extensive use in venting systems, gravity
lines in corrosive chemical service, electrical conduits, and telephone
ducts. It has a wide range of chemical stability and has been success-
fully overlaid with fiberglass to provide external reinforcing. In
prolonged high-temperature use, thermal degradation is evident.
Even with a fiberglass backing, PVC, PVDC, and chlorinated PVC
(CPVC) are subject to checking, crazing, and cracking that ultimately
destroy the structure. In terms of use, however, it is a particularly
important plastic and is widely used in the building and allied indus-
tries, including household appliances.
Polycarbonate
Polycarbonate is yet another of the new cost-effective resins that

have been introduced since the early 1950s. Because of its extremely
high impact resistance and good clarity, it is widely used for windows
in chemical equipment and glazing in chemical plants. The addition
of glass fiber reinforcement improves strength and stability at tem-
peratures as high as 210°F (99°C). This also reduces mold shrinkage
so that closer tolerances can be met for molded parts. It has wide
application in the food service industry for beverage pitchers,
bowls, and even microwave cookware if clarity is required. It also
is used in frozen food trays, retort jars, and bottles. Coated thin-
gauge sheet is used for protective eyewear appliances and business
machines. The exceptional weather ability, corrosion resistance,
and high impact strength of polycarbonate give it wide use in out-
door energy management devices, network interfaces, electrical
wiring blocks, and telephone equipment, also in lighting diffusers,
globes, and housings in industry. Polycarbonate foam has wide
application in machine housings.
Polycarbonate blends with other polymers have pushed its upper

temperature limit to 270°F (132°C), in the autoclave sterilization
range, where it is used in medical applications.
Thermoplastic Alloys
The alloying of several thermoplastic systems often produces better
physical qualities than any system can produce by itself. These
include impact resistance, flame retardancy, and thermal stability.
Alloying is generally done with intensive mixing or screw extruders.
Poly vinyl chloride and ABS are frequently blended to provide rigidity,
toughness, flame retardancy, and chemical resistance. Polycarbonate
can be blended with ABS to provide better heat resistance and
toughness. Polyurethane improves the abrasion resistance and tough-
ness of ABS, while retaining the advantage of reduced cost. The
impact strength of polypropylene is increased by alloying with poly-
isobutylene. Alloying is generally done on a relatively small scale,
varying from as low as 0.01% up to as high as 9%.
Fluoroplastics
The fluoroplastics are a unique class of paraffinic polymers that
have some or all of the hydrogen replaced by fluorine. These poly-
mers are of major interest to chemical engineers because they perform
well in aggressive chemical environments* They are unaffected by
hot, concentrated acids and bases and are totally insoluble in organic
solvents. Their useful temperatures range from -200°C (-360°F) to
250°C (500°F). They are difficult to ignite and have virtually zero
fuel contribution and flame spread.
The fluoroplastics are used extensively for coatings and linings
of process equipment, and offer a solution for difficult heat ex-
changer and crystallization applications in which their nonadhesive
and self-lubricating properties can eliminate surface buildup.
Liquid/liquid heat exchangers typically give heat transfer coefficients
of 60 to 80 BTU/hr-ft 2 -°F.
These polymers are also used in filter housings, pump casings,
and impellers in corrosive applications. With a knitted backing of
glass or polyester, they are used as fluoroplastic liners in steel
and FRP tanks and vessels. They are also used in small-diameter
tubing and pipe and in valve diaphragms. However, the use of
thin fluoroplastic liners in highly alkaline condition pH > 10 should
be approached with caution. Some are not suitable. Check the
applicator.
Thermoplastic Fibers
Nylon and polyester fibers have been specifically developed for
use in plastic composites. They are sized to enhance wet-out and
334 Mallinson
dispersion. These fibers are available as-cut to the desired length

or as a roving or fabric. They also have been combined with glass
as a hybrid fiber. They are used in high-impact housings for power
tools to provide shatter-resistant products and in urethane systems
to improve thermodimensional stability and abrasion resistance.
The polyester fibers have been used extensively as a surfacing
veil for which, in many applications, it outperforms C glass. Poly-
propylene fibers are used in thermoset applications, where they
can provide enhanced chemical resistance in alkaline areas. The
laminate, however, is not as strong as a glass-reinforced laminate.
The thermoplastic reinforcements produce a lighter laminate than
that of a glass reinforcement.
RECOMMENDED DESIGN P R A C T I C E S [ 2 , 3 ]
The Popular Thermosets
The successful application of any corrosion-resistant material begins

with a complete and accurate definition of the problem to be solved.
To consider any material as a potential solution to the problem,
engineers must be thoroughly familiar with the material to be applied.
They need to know its strong points and its weaknesses and, above
all, the limits placed on its successful application* For the general
classes of reinforced plastic material available we, therefore, must
first determine when each can be used successfully and when it
should be avoided. Many different types of polyester and epoxy
chemical-resistant resins (and furans and vinyl esters) are being
manufactured today, both in the United States and abroad.
Generally, we are dealing with families of resins that have the
following characteristics:
An upper-wet-temperature limit of about the boiling point of water

or perhaps a little higher [120°C (250°F)].
A dry limit of perhaps 175°C (350°F).
Remarkable resistance to many of the oxidizing acids, up to fairly
strong concentrations.
Potentially, superior alkaline resistance.
Good solvent resistance in some areas but limited resistance in others.
In variegated shapes, most useful in the areas of low-pressure or
vacuum services.
Can provide complete piping systems at relatively high operating
pressures and in most of the common sizes at pressures up to
250 psig.
Can be tailor-made for ablative conditions for which service under
extended temperatures for short periods is desired.
Low thermal and electrical conductivity, so that use can be made

of these properties.
The reinforcement, which is generally glass or a synthetic fiber,
may be furnished by other suppliers.
Epoxies
The family of epoxy resins can provide outstanding service in chemi-
cal process equipment under severe conditions. Most formulations
used in the chemical industry require postcuring. These resins
dominated the high-pressure pipe market for many years until the
vinyl esters came along, and the epoxies are still a major factor;
the choice of hardner has a pronounced effect on the properties
of the end-product. Their exothermic temperature is low, with no
by-products involved. Aliphatic amines and polyamides are used
in room-temperature-curing systems, and aromatic amines and acid
anhydrides are used for heat-cured resin processes. Virtually all
pipe is heat cured to attain the best physical properties.
For small-diameter, high-pressure pipe up through 12 in. in
diameter, the epoxy resins predominate, although the vinyl esters
are used by some producers. Excellent high-strength adhesive
systems formulated from epoxy resins are used to assemble adhesive
joint systems, and some producers use epoxy resins exclusively
in the pipe shop, thereby eliminating the styrene emission problem
of the polyesters and vinyl esters. The use of asbestos reinforce-
ment, which prevailed in the early and mid-1960s in the corrosion
barrier of epoxy pipe, has been eliminated for health reasons.
Corrosion barriers in epoxy pipe range from 10 mil upward. In
chemical service the minimum should be 50 to 60 mil.
The epoxy resins have good resistance to alkalies, nonoxidizing
acids, and many solvents. Piping systems in reinforced epoxy have
been well engineered and their use is prevalent. Flanged and ad-
hesive systems are used, as are rapid O-ring assemblies. The
following services are applicable at temperatures up to 200°F (93°C),
unless otherwise stated.
Acid(s)
Acetic, 10% (to 150°F) Hydrochloric, 10%
Benzoic Sulfuric, 20% (180°F)
Butyric Rayon spin bath
Fatty Oxalic
Bases
Sodium hydroxide, 50% Calcium hydroxide
(to 180°F) Trisodium phosphate
Sodium sulfide, 10% Magnesium hydroxide
336 Mallinson
Salts
Metallic salts, aluminum, Most ammoni
barium, calcium, iron,
magnesium, potassium,
sodium
Solvents
Alcohol: methyl, ethyl, Naphtha
isopropyl (to 150°F) Toluene
Benzene (to 150°F) Xylene
Ethyl acetate (to 150°F)
Miscellaneous
Distilled water Jet fuel
Seawater Gasoline
White liquor Diesel fuel
Sour crude oil Black liquor
The epoxies have been found to be unsatisfactory in the following

service:
Bromine water Hydrogen peroxide

Chromic acid Sulfuric acid above 70%
Bleaches Wet chlorine gas
Methylene chloride Wet sulfur dioxide
Furans
The furans occupy a special place in the field of thermoset resins.

They carry a premium cost of perhaps 30% over other thermosets,
such as the polyesters but, many times, they are the most economical
choice under conditions where
1. The presence of solvents exists in a combination with acid and

bases.
2. The need exists for a low flame spread (< 25), low smoke develop-
ment (< 50), corrosion-resistant material in ducts, stacks, and
scrubbers.
3. As an alternative to high nickel alloys and high-cost linings.
4. Process changes may occur that result in exposure to solvents
in oxidizing atmospheres. This can be a most important considera-
tion. The engineer needs to look into the future and attempt to
anticipate changes in exposure or temperature.
The furan polymer is a derivative of furfuryl alcohol and furfural.

With use of an acid catalyst, polymerization occurs by condensation,
which generates heat with the formation of water. The exotherm
must be controlled to prevent the water vapor from blistering and
cracking the laminate. Furan resin catalysts should always be above

65°F (18°C) and not over 85°F (29°C).
For optimum properties, all furan laminates must be postcured
to drive out the reaction "condensate." Fresh laminates should be
cured at an initial temperature of 150°F (65°C) for 4 hr, then
slowly raised to 180°F (82°C) and cured 8 hr. Too fast a cure
can result in a blistered or cracked laminate. A final Barcol of
40 to 45 is necessary to develop optimum laminate properties, and
Barcols as high as 55 are achieved. Cellophane- and PVA-release
film should not be used with the furan laminates. Mylar is preferred
or a wax with a high carnauba content. Tensile elongations of 1.9-
2.0% exist with the furan laminates, and they show excellent physical
property retention at high temperatures (Table 2).
Fabrication is by hand-laidup and filament-wound methods. The
physical properties meet those established by the U.S. Department
of Commerce NBS Voluntary Product Standard PS 15-69 (Table 3).
Postcuring of the furan laminate results in minimum flame-spread
ratings and minimum smoke-development ratings. To achieve this,
a cure at 180°F (82°C) for 4 hr minimum is necessary.
The strong point of the furans is their excellent resistance to
solvents in combination with acid or alkalies. The following listing
incorporates corrodants against which the furans can be safely used:
1. Solvents: Acetone, benzene, carbon disulfide, chlorobenzene,

ethanol, ethyl acetate, methanol, methyl ethyl ketone, perchloro-
ethylene, styrene, toluene, trichloroethylene, xylene
2. Acids: Acetic, hydrochloric, 5% nitric, phosphoric, 60% sulfuric
(up to temp, of 150°F)
3. Bases: Diethyl amine, sodium carbonate, sodium sulfide, 50%
sodium hydroxide
4. Water: Demineralized, distilled
5. Miscellaneous: Pulp mill liquor
Note: The furans are not resistant to bleaches such as peroxides

and hypochlorites, concentrated sulfuric acid, phenol, free chlorine,
and higher concentrations of chromic or nitric acid.
Phenolics
As one of the oldest thermoplasts, the phenolic compounds have
been widely used in the chemical industry because of their relative
inertness to acids and good temperature stability. As such, they
have been used for many machine-processing parts and, particularly
in Europe, they have been developed into various trade-named
applications on ducts, pumps, scrubbers, heaters, and the like.
They are one of the two compounds that will pass the NFPA regula-
338 Mallinson
TABLE 2 Furan Laminates Versus PS15-69 Physical Properties at

Elevated Temperaturesa
% of PS15-69 physical properties

Temperature Tensile Flexural Flexural
°F strength strength modulus
50 93 92 92
100 88 85 83
150 82 76 73
200 76 68 65
250 70 61 57
300 68 55 53
350 66 54 52
400 65 53 51
a
Refer to Table 3 for NBS psl5-69 Physical Properties
Source: From Ref. 5.
tions for ducts and fans, having a fire-spread and smoke-spread

rating of 50 or less. These compounds are used widely in molded
products in the United States, but they have not met with the
general acceptance of the polyesters, epoxies, furans, and vinyl
esters for use in the chemical industries. This is because, in general,
they do not have the impact resistance possessed by the polyesters
and the epoxies, even when glass-filled. They possess little alkaline
and bleach resistance and, hence, their use should be avoided in
these areas.
General-Purpose Polyester Resins

General-purpose polyester resins normally are not recommended
for use in chemical process equipment. Their use in the finished
fabrication represents a potential savings of 10 to 20%. Only the
purchaser can make the ultimate decision about the premium to
be paid for chemical resistance. These resins are generally adequate
for use with nonoxidizing mineral acids and corrodants that are
relatively mild. This is the type of resin that is primarily used
in boat building so that, obviously, its resistance to water of all
types, including seawater, is more than adequate. Test work has
indicated satisfactory application in the following areas for tempera-
tures up to 125°F:
Acids
Acetic (10%) Oleic
Citric Benzoic
Fatty Boric
Salts
Aluminum sulfate Ferrous chloride
Ammonium chloride Magnesium sulfate
Ammonium sulfate (10%) Magnesium chloride
Calcium chloride (saturated) Nickel chloride
Calcium sulfate Nickel sulfate
Copper sulfate Potassium chloride
Ferric chloride Potassium sulfate
Ferric nitrate Sodium chloride, 10%
Ferric sulfate
Solvents
Amyl alcohol Kerosene
Glycerin Naphtha
The general-purpose resins have been found to be unsatisfactory

in oxidizing acids; alkaline solutions, such as calcium hydroxide,
sodium hydroxide, and sodium carbonate; bleach solutions, such
as 5% sodium hypochlorite; solvents, such as carbon disulfide,
carbon tetrachloride, and gasoline.
To be competitive, some fabricators have used a high-performance
resin in the corrosion barrier and a general-purpose resin for the
structural layup. This is a hazardous practice because many of
the orthophthalic resins have heat distortion points of 125°F, although
some are as high as 150°F. A break in the corrosion barrier spells
potential catastrophic failure with all but the most mild solutions.
These resins have their place in building panels, boats, pultrusions,
radomes, and television satellite dishes, for example, where exposure
is confined to ambient conditions.
TABLE 3 Requirements for Properties of Reinforced Polyester Laminates
Thickness (in.)
1/8 to 3/16 1/4 5/16 3/8 and up
Property at 23°C (73°F) PSI PSI PSI PSI
Ultimate tensile strength 9,000 12,000 13,500 15,000

(min.)
Flexural strength 16,000 19,000 20,000 22,000
(min.)
Flexural modulus of 700,000 800,000 900,000 1,000,000
elasticity (tangent)
(min.)
Source: From Ref. 6, Table 1.

340 Mallinson
When the use of a general-purpose resin is contemplated, an

environmental test program should be inaugurated to determine
if the resin will be satisfactory. All contemplated applications above
temperatures of 125°F (49°C) should receive rigorous testing.
Isophthalic Polyesters
The isophthalic polyesters offer better chemical resistance than
the general-purpose resins in certain specific areas, at a slightly
higher cost. They definitely show much better resistance to attack
in the solvent areas, and they are used extensively in the manufac-
ture of underground gasoline tanks, for which a satisfactory service
life in the storage of gasoline under the varied conditions of ground-
soil corrosion are successfully met.
Isophthalic resins have been used widely as liners in the bottom
of sour crude storage tanks to prevent corrosion where they have
been very successful.
Their use as a structural resin in the backup laminate for the
high-performance corrosion barrier is fairly widespread. Here,
again, they are used for competitive reasons, because the isophthalic
resin costs about 70 to 75% of the high-performance resin. This may
represent a final savings of perhaps 10% in the vessel1 s construction
cost to the customer. Surprisingly, orthophthalic/isophthalic/bisphenol
resin cost ratios have maintained a fairly constant relationship. Pre-
sumably, this is because they all originate from an oil base.
Engineers should be certain they understand the implications
of not using a high-performance resin throughout the laminate.
The service conditions should always be such that a break in the
corrosion barrier will not produce rapid structural failure of the
vessel.
The general use areas for isophthalic resins at temperatures
up to 150°F are as follows:
Acids
Acetic (10%) Oleic
Benzoic Phosphoric (25%)
Boric Tartaric
Citric Sulfuric (10%)
Fatty Sulfuric (25%)
Salts
Aluminum sulfate Iron salts
Ammonium carbonate (10%) Hydrogen peroxide (5%)
Ammonium chloride Magnesium salts
Ammonium nitrate Nickel salts
Ammonium sulfate Sodium and potassium salts
that do not have a strong
alkaline reaction
Barium chloride
Calcium chloride (saturated)
Copper chloride Dilute bleach solutions
Copper sulfate
Solvents
Amyl alcohol Gasoline
Ethylene glycol Kerosene
Formaldehyde Naphtha
Isophthalic resins have been found to be unsatisfactory in acetone,

amyl acetate, benzene, carbon disulfide, solutions of alkaline salts
of potassium and sodium, hot distilled water, and higher concentra-
tions of oxidizing acids.
High-Performance Polyester Resins
If most failures in glass-reinforced plastic equipment are physical

or mechanical, but not too often chemical, then it can be concluded
that they are preventable and that successful application is an
attainable objective. Most failures in FRP field are generally due
to "sins of omission," compounded by lack of knowledge, usually
on the part of the purchaser but, sometimes, on the part of the
fabricator or the sales staff.
The original resin producer has accumulated a vast reservoir
of laboratory tests plus field service tests, often spanning 10 to
20 years of successful service. A good background exists defining
the successful limits of application in terms of both chemical service
conditions and temperature exposure. These data, available from
any of the fabricators for their particular series of resins, are
the basic source of information. The engineer can also broaden
the scope of applications: the union of thermoplasts and thermosets
permits a wider range of acceptable service conditions. Thermosets
combined with other thermosets may permit greater economy by
using a premium resin in the corrosion barrier and a less expensive
resin in the structural wall. The engineer needs to be very specific
about this. Some of the prices quoted do not make it clear that
the corrosion barrier is a premium resin and the structural wall
is an isophthalic resin. This thermoset-thermoset combination is
prevalent in the FRP industry.
For the successful application of reinforced plastics to corrosion-
resistant process equipment, the following summaries have been
prepared, covering a variety of common chemical environments.
Remarks about the application under specific environmental conditions
are meant only to serve as a guide for the engineer. For details
to meet specific corrosion conditions, the designer should consult
either the fabricator or the original resin producer; also refer to
Table 4.
TABLE 4 Seven Generic Types of Resins
Resin type Basic organic formula Comments End uses CO
ISO
General Generally not used for wet Tote boxes, baptistries,

polyester chemical service boats, fishing poles,
building materials, car and
truck bodies
Isophthalic Good chemical resistance Gasoline tanks, composite
polyester in many environments; less chemical tanks, refinery
expensive than those below tank linings
Bisphenol Excellent overall chemical resistance; Chemical piping, tanks,
polyester one of the major workhorses of the structures, linings
industry
Halogenated Chlorinated or Excellent chemical resistance in Chemical piping, tanks and
brominated molecu- many severe services, particularly structures; with small
lar structure chlorine quantities of Sb2O3 added
provides high fire retard-
ancy for ductwork and
stacks
Vinyl ester Excellent chemical resistance to Chemical piping, tanks,
bleach, alkaline and chlorine compounds structures, linings
Epoxy Bisphenol group Provides good chemical resistance Chemical piping, superior
when heat-cured; more expensive alkaline resistance; good
than polyesters. solvent resistance in some
areas
Furans Furfuryl alcohol- Superior chemical resistance to sol- Chemical piping, tanks,
based resin system vents; particularly useful when com- ducts; premium cost resin
bined with acids and bases; poor system 3
resistance to bleaches; low flame and CO
O
3
smoke rating
Bisphenol Polyesters. One of the earliest high-performance poly-

esters was the bisphenol polyester. For some installations, manufac-
turers can quote 25 to 30 years of performance. For many years
bisphenol polyesters were the workhorse of the industry.
The bisphenol polyesters have an exceptionally high degree of
chemical resistance, superior to both the general-purpose and
isophthalic classes of polyester resin. Depending upon the particu-
larly severe chemical environment, the bisphenol, the chlorinated
or brominated chemical-resistant polyesters, and the vinyl esters
represent the current ultimate in resins available for severe chemical
service. These three classes of resins cost approximately twice as
much as a general-purpose resin and one-third more than an iso-
phthalic resin. Only a fraction of this premium, however, carries
over into the final fabricated cost of the equipment. These high-
class, chemical-resistant resins are much easier to fabricate than
epoxies or furans. They show acid resistance superior to the epoxies.
The bisphenol resins show good performance with moderate alkaline
solutions and excellent resistance to the various categories of bleach-
ing agents. All of the polyesters and the epoxies break down under
highly concentrated acids or alkalies, such as 93% I^SO^ and 73%
NaOH. Failure with the concentrated acid is by dehydration and
pyrolysis.
Recommended areas of application are as follows:
Acids (to 200°F)

Acetic (25%) Maleic
Benzoic Oleic
Boric Oxalic
Butyric Phosphoric (80%)
Chloroacetic (15%) Stearic
Chromic (5%) Sulfuric (50%)
Citric Tannic
Fatty acids Tartaric
Hydrochloric (10%) Trichloroacetic (50%)
Lactic Rayon spin bath
Salts (Solutions to 200°F)
All aluminum salts Low sodium and low potassium
salts, except the high
alkaline salts
Most ammonium salts Zinc salts
Calcium salts Most plating solutions
Copper salts
Iron salts
Solvents
All the solvents shown Alcohols at ambient tempera-
under the isophthalic resins ture
Sour crude oil Glycerin
Linseed oil
344 Mallinson
Alkalies (to 160°F)

Ammonium hydroxide (5%) Potassium hydroxide (25%)
Calcium hydroxide (25%) Sodium hydroxide (25%)
Bleaches (to 200°F)
Calcium hypochlorite (20%) Sodium hypochlorite (up to
stable temperature)
Chlorine dioxide (15%) Textone
Chlorite
Hydrosulfite
Gases (up to 200°F)
Carbon dioxide Sulfur dioxide, dry
Carbon monoxide Sulfur dioxide, wet
Chlorine, dry Sulfur trioxide
Chlorine, wet Rayon waste gases at 150°F
This type of resin has been found to be unsatisfactory for solvents.

Test any organic solvent other than those just listed. Such solvents
as benzene, carbon disulfide, ether, methyl ethyl ketone, toluene,
xylene, trichloroethylene, and trichloroethane are not satisfactory
nor are 93% sulfuric acid, 73% NaOH, and 30% chromic acid. The
upper limit for sulfuric acid is about 70%.
Chlorinated or Brominated Polyesters. Although it is a generalization,
and generalizations have many exceptions, it can be said that halo-
genated chemical-resistant polyesters cured at room temperature
and reinforced with fiberglass possess unique chemical-resistant
characteristics. However, these polyesters are not resistant to highly
alkaline solutions of sodium hydroxide, which the bisphenols handle
well. (Check supplier for exact service recommendations.)
The chlorinated polyesters merit the engineer's consideration
for several reasons.
1. They have a high heat-distortion point, and the laminates show

a high retention of physical strength at elevated temperatures
(see Table 5). This permits them to survive high-temperature
upsets in flue gas desulfurization scrubbers, some of which
may reach temperatures as high as 400°F.
2. They are routinely used in chimney liners at temperatures of
240 to 280°F.
3. They are very forgiving resins that are easy to lay up.
4. They are widely used in the pulp and paper industry in bleach
atmospheres where they outperform the stainless steel and high
nickel alloys.
Ashland Chemical Hetron 197 series and Koppers Atlac 797, Dion
6693 are examples of this group and will be used here as a basis
TABLE 5 Elevated Temperature Performance of Hetron 197 Laminates

Temperature Retention tensile Retention flexural
(°F) strength (%) modulusa (%)
75 100
125 96
175 100 88
225 98 77
275 92 65
325 84 46
375 73 25
425 60
Particularly important for high-temperature performance under

vacuum conditions.
for discussion. Outlined below are findings based on almost 25 years

of highly successful applications throughout the industry and on
extensive laboratory and field investigations. Resistance, in many
instances, can be improved by elevated temperature postcures.
Additionally, these resins possess the highest heat resistance of
any chemical-resistant polyester and are inherently fire retardant.
Their use in the field of solvents should be approached with
great care. Even a small amount of a solvent may be insoluble in
water so the laminate is confronted with a 100% concentration.
Straight-chain hydrocarbons of the aliphatic group represent no
problem, but many of the ring compounds must be evaluated on
a case-by-case basis.
These polyesters are uniquely resistant to many oxidizing
acids and solutions such as 35% HNO3 to 140°F, 70% HNO3 at room
temperature, 40% chromic at 140°F, chlorine water to 200°F, wet
Cl2 to 220°F, 15% hypochlorites to 110°F, 6% hypochlorites to 140°F.
Concentrated H2SO4 is severely destructive (pyrolysis).
They are resistant to gases (wet and dry) up to temperatures
of about 350°F, with intermittent exposure to as high as 425°F,
with the exception of SO3, which can cause severe attack.
Vinyl Ester Resins
An important addition to the thermoset family became commercially

available in the mid 1960s. Now, virtually all of the large resin
producers offer vinyl esters. This family of resins, manufactured
with the same catalyst system and styrene solvent system as poly-
346 Mallinson
esters and fabricated by the same techniques, speedily found a

place in the corrosion-resistant thermoset resin field. The resins
are also available in halogenated modifications for duct work and
stack construction where fire retardancy and ignition resistance
is a major concern. There are a number of basic advantages to
the vinyl esters.
1. Because of their molecular structure they cure rapidly and give

early strength and superior creep resistance.
2. They provide excellent fiber wet out and good adhesion to the
glass fiber, usually similar to that of the amine-cured epoxies
but less than that of the heat-cured epoxies.
3. Laminate tests show somewhat higher strength with vinyl ester
resins over the polyesters, but this is not equal to that of the
heat-cured epoxies.
4. The chlorendic and bisphenol resins have low elongation (1.5
to 2.0%) and are essentially brittle resins, whereas the vinyl
esters run 4 to 6%, and sometimes higher. This translates into
better impact resistance and greater tolerance to cyclic tempera-
tures, pressure fluctuations, and mechanical shocks. The end
result is a tough laminate that is resistant to cracking and crazing.
5. The basic structure of the vinyl ester molecule is such that
it is more resistant to some types of chemical attack such as
hydrolysis and oxidation or halogenation. These are relative
comparisons because some of the bisphenol resins and chlorendic
polyesters have compiled very enviable service records over
long periods.
6. The vinyl esters excel in alkaline and bleach environments and
are used extensively in the very corrosive conditions found
in the pulp and paper industry.
The vinyl esters should be limited to an upper temperature of

about 225°F for maximum retention of physical properties. A modifi-
cation of this is the novalac backbone which extends the high-
temperature performance to 325 to 350°F (Derakane 470) and also
increases solvent resistance. As is generally found, the important
flexural modulus must be closely examined for all elevated temperature
considerations because by 225°F the vinyl esters have lost up to
half of their flexural strength. This is an important consideration
for use under vacuum conditions.
Some formulations have been modified to provide elongation as
high as 20%. With that, however, goes a low heat-distortion tempera-
ture of 145°F. These high-elongation resins can be blended with
other vinyl esters to achieve practically any desired elongation in
the 5 to 20% range. Where abrasion is a problem, a high-elongation
resin with an ABR additive provides superior performance. The

higher-elongation blend can be used in the corrosion barrier (100
mil), with the structural backup construction of a lower elongation
and a higher heat-distortion point. The elevated performance of
a vinyl ester resin laminate (Derakane 411), is shown in Table 6.
Polyurethane
Polyurethane is used principally as an insulating foam, with a low
K factor [(0.11-0.14) BTU/hr«ft2-°F] for 2 lb/ft foam. This is
used as a building insulator between studs and in process vessels
where it is laid between the vessel and an outer skin. It is also
used in panel and tank cover construction with fiberglass skins,
and widely used as an insulator in transportation and shipping.
It is in use in boat and ship compartments for flotation. As an
elastomer, polyurethane is also used for large ship fenders when
reinforced with glass roving.
This resin has extremely good abrasion resistance and toughness
and is used as a coating and lining where service conditions permit.
Overlaid with fiberglass pipe it has been used for bottom ash and
slurry applications. Reinforcement with short glass fibers improves
its strength and flexural modulus. The major problems found with
its use are low resistance to steam, some fuel solvents, strong
acids, and bases. Polyurethane is resistant to aliphatic hydrocarbons
and dilute acids and bases.
PLASTICS-THEIR SERVICE AND USE
Table 7 is not intended to cover all of the plastics presently in

use in the chemical industry, but it does cover the most prevalent
TABLE 6 Elevated Temperature Performance of A Vinyl Ester

Resin Laminate (Derakane 411)
Temperature Retention physical Retention flexural
(°F) strength (%) modulus (%)
70 100 100
150 121 98
200 105 83
225 88 48
250 57 22
300 37 22

348 Mallinson
TABLE 7 Plastics: Their Service and Use
Normal upper
service limit
Type of plastic °C °F Typical areas for use
Poly vinyl chloride 60 140 Piping: water, gas, drain,

vent, conduit, oxidizing acids,
bases, salts; ducts: (breaks
down into HC1 at high tempera-
tures); windows plus accessory
parts and machine equipment
in chemical plants; liners with
FRP overlay
Chlorinated PVC 82 180 Similar to PVC, but upper-
temperature limit is increased
Polyethylene 60 140 Tubing, instrumentation
(laboratory): air, gases,
potable water, utilities, irriga-
tion pipe, natural gas; tanks
to 12-ft diameter
High-density 82 180-220 Chemical plant sewers, sewer
polyethylene liners, resistant to wide variety
of acids, bases, and salts;
generally carbon filled; highly
abrasion-resistant; can be
overlaid with FRP for further
strengthening
ABS 60 140 Pipe and fittings; transporta-
tion, appliances, recreation;
pipe and fittings is mostly
drain, waste, vent; also elec-
trical conduit; resistant to
aliphatic hydrocarbons but not
resistant to aromatic and
chlorinated hydrocarbons;
formulations with higher heat
resistance have been intro-
duced
Polypropylene 82-104 180-220 Piping and as a composite
material overlaid with FRP in
duct systems; useful in most
inorganic acids other than
Normal upper
service limit
halogens; fuming nitric and

other highly oxidizing environ-
ments; chlorinated hydrocarbons
cause softening at high tem-
peratures; resistant to stress
cracking and excellent with
detergents; flame-retardant
formulations make it useful in
duct systems; further rein-
forced with glass fibers for
stiffening, increases the flex
modulus to 106 and deformation
up to 148°C (300°F)
Polybutylene 104 220 Possesses excellent abrasion
and corrosion resistance; use-
ful for fly ash and bottom ash
lines or any lines containing
abrasive slurries; can be over-
laid with fiberglass for further
strengthening when required
General-purpose 50 120 Made in a wide variety of
polyesters formulations to suit the end-
product requirements; used
in the boat industry, tub-
showers, automobiles, aircraft,
building panels
Isophthalic 70 150 Increased chemical resistance;
polyesters used extensively in chemical
plant waste and cooling tower
systems plus gasoline tanks;
also liners for sour crude
tanks
Chemical-resistant 120-150 250-300 Includes the families of bisphe-
polyesters nol, hydrogenated bisphenols,
brominated, and chlorendic
types; a wide range of chemical
resistance, predominantly to
(continued)
350 Mallinson
(Table 7 , continued)
Normal upper
service limit
oxidizing environments; not

resistant to HÔ^ above 78%;
can operate continually in gas
streams at 148°C (300°F); end
uses include scrubbers, ducts,
stacks, tanks, and hoods
Epoxies 150 300 More difficult to formulate than
(wet) the polyesters; more alkaline-
resistant than the polyesters,
with less oxidizing resistance;
highly resistant to solvents,
especially when postcured;
often used in filament-wound
structures for piping; not
commonly used in ducts; more
expensive than polyesters
Vinyl esters 93-140 200-280 Especially resistant to bleaching
(wet) (dry) compounds in chlorine-plus-
alkaline environments; wide
range of resistance to chemi-
cals, similar to the polyesters;
used extensively in piping,
tanks, and scrubbers; modifi-
cations developed to operate
continuously up to 140° C
(280°F)
Furans (wet) 150-200 300-400 Excel in solvent resistance and
combinations of solvents with
oxidizing chemicals; one of the
two resins to pass the 50 smoke
rating and 25 fire-spread
rating; carries about a 30-50%
cost premium over the poly-
esters; excellent for piping,
tanks, and special chemical
equipment; does not possess
the impact resistance of poly-
esters or epoxies
Source: From Refs. 2-4.

ones. Exceptions are the polycarbonates where very high-impact

resistance is required. Nylon and the acetals are also used exten-
sively for small gears.
The temperatures shown for the upper service limits are a function
of service conditions, so they vary with the chemical environment.
Many of the thermoplasts have a poor memory; hence, with tempera-
ture changes they tend to "grow" and not return to their original
state. This is not true of the thermosets, which appear to have
an excellent memory.
REINFORCEMENT [2,9,10]
Early History
The field of manufactured synthetic composite materials dates back
to the early 1900s. Laminates were principally molded parts, rods,
or tubes and were made of phenolic, epoxy, or melamine resins.
Reinforcements were paper, cotton, linen, or glass cloth.
The type of reinforcement has changed so that it is now predomi-
nately glass, although other fibers, such as carbon, aramid, poly-
ester, polypropylene, and acrylic, are used for special purposes.
Each has a useful niche (Table 8). The use of asbestos reinforce-
ment, widely practiced in the 1960s and 1970s, particularly for
liners, has been eliminated. As in the field of radiation exposure,
the asbestos exposure limits were progressively tightened. The
dangers of asbestosis and mesothelioma have made its use hazardous.
Present Grades of Reinforcement

Glass fiber reinforcements predominate in the field of composite
materials in corrosive environments. There are several grades of
glass.
E Glass
E glass is an electrical grade glass with excellent water resistance,
strength, low elongation, and reasonable cost. This boroalumino-
silicate glass is a leader in the 45 years it has been in existence.
Virtually all glass mat, continuous filaments, and woven rovings
come from this source.
C Glass
C glass is a calcium aluminosilicate glass widely used for surfacing
mats, glass flakes or flake glass linings, and for acid-resistant
cloths. Unfortunately, it has poor water resistance and carries a
premium cost. At one time, consideration was given to trying to
TABLE 8 Chemical-resistant Laminate Surfacing Systems
Type of
surface layer Thickness range Description Specific uses
Gel coat 10-20 mil common, Unreinforced layer of Commonly used in many epoxy piping systems;
but may go to 60 resin little used in other corrosion composite con-
mil with some struction
vendors
Type C-glass 10-20 mil 10-mil type C mat Most commonly used for reinforcement, for
surface mat commonly employed chemical plant applications; particularly neces-
adding strength and sary on tanks, ductwork, etc.; commonly used
stability to the re sin- in composite piping; about 10% glass/90% resin
rich surface
Organic veil 10-20 mil Dacron, acrylic, Good weathering characteristics; improves
polypropylene, orlon abrasion resistance and impact strength in
many cases; some provide complete trans-
parency; Standard specification in HFa work
or caustic applications
Carbon mat 3 mil 0.2 oz/yd 2 Provides high surface electrical conductivity in
antistatic applications; normally used with a
backup surfacing system such as C glass or
polyester
a
Hydrogen fluoride.
3
o
03
develop this in the form of an R glass for filament-win ding applica-

tions. The economics, however, were against it, and R glass passed
away in the developmental stage.
The role of C veil as a surfacing mat has a long-established
history. The standard specification for corrosion-resistant equipment
for years was 10-mil C veil. The use of 20-mil C veil with brittle
resins, such as the bisphenols, should be avoided because they
are easily subject to impact and handling damage. Until the develop-
ment of synthetic veils, 10-mil C glass was nearly universally used.
It is available in 10, 15, 20, and 30 mil thicknesses.
S Class
S glass is used widely in the aerospace industry because of its
exceptional strength. It is several times more expensive than E
glass but has excellent resistance to acids and water. It is not
used in the corrosion industry because of its cost. It is comparable
in strength to Kevlar (duPontTs aramid fiber).
Polyester
Polyester is used principally for surfacing mat for the resin-rich
inner surface of filament-wound or custom contact-molded structures.
It may also be used in conjunction with C-glass surfacing mats.
By overwinding a C-glass surfacing mat with a polyester mat
under tension, the tendency of C glass to bridge and form voids
is reduced or eliminated. Nexus surfacing veil is also used on interior
and exterior surfaces of pultruded products. The Nexus surfacing
veil possesses a relatively high degree of elongation that makes
it particularly compatible with the higher-elongation resin and
reduces the risk of checking, crazing, and cracking in temperature-
cycling applications. Nexus surfacing veil shows excellent resistance
to alcohols, bleaching agents, water, hydrocarbons, and aqueous
solutions of most weak acids at boiling. As expected for the poly-
ester derivatives, it is not resistant to strong acids, such as 93%
sulfuric acid. Surface examination indicates improved surface finish
over C glass, better impact strength, and increased resistance
to flexural fatigue before cracking. This is particularly pronounced
when used with filament-wound pipe and higher-elongation resins,
such as vinyl esters.
In a study of 30 synthetic veils, Bautista [10] showed that,
next to the aramid group, the nexus surfacing veil and acrylic
surfacing mats showed the best abrasion resistance of the synthetic
nonwovens. This study also reinforced the observation that post-
curing is a definite advantage to increasing the abrasion resistance
of any laminate. The role of multiple layers of Nexus surfacing veil
354 Mallinson
has been investigated and it has been used in field service for
severe conditions, particularly in the paper industry, where it is
used with high-elongation vinyl esters in four to ten layers. With
brittle resins, Nexus surfacing veil should be limited to one or
two plies. In electrostatic precipitators, two to five plies of Nexus
surfacing veil are used to combat the presence of fluorides from
the gas stream. It is also used in the resin transfer-molding process.
The use of synthetic veiling depresses the Barcol hardness of
the cured laminate about 5 points below that of a C-glass veil.
However, acetone-testing reveals no sensitivity, which indicates
a full cure has occurred.
Other reinforcement materials are available, but they are in
limited use in the corrosion industry, chiefly because of their cost.
Carbon Fiber
Carbon fiber is available in mat form, typically in 0.2, 0.5, 1,
and 2 oz/yd 2 . It is very useful in imparting surface conductivity
to FRP laminates. The 0.2-oz/yd2 form provides a translucent and
fully inspectable laminate. Heavier weights impair the translucent
feature. The carbon fiber mat, either alone or supplemented with
a ground carbon or graphite filler, provides in-depth grounding
systems and static control in hazardous areas where static sparks
may result in fires or explosions. The use of a carbon fiber mat
on a pipe or vessel outside diameter accompanied by an impressed
voltage results in complete thermal tracing and may be considered
an alternative to tracing with piping or electrical tape. Increased
resistance to microchecking or cracking when used as a surface
mat has been reported.
The carbon fibers are also available in continuous roving and
in chopped fibers in sizes 1/8 to 2 in. In continuous roving they
are an essential part of the space program, and with their high
strength, produce very light high-strength laminates. Their high
cost precludes their present use in the corrosion industry, although
the cost has decreased markedly from about 200 dollars a pound
in the early stages to 18 dollars a pound in 1985. The use of carbon
veiling, however, is fairly widespread in antistatic applications.
Its use in large chimney liners is widely practiced.
Carbon fiber is also available in a 0.5-oz/yd2 mat as a blend
with 33% glass fiber. Other blends are becoming available, such
as 25% carbon fiber/75% glass fiber. Carbon fiber is also available
in 50:50 blends with aluminized glass for electromagnetic interferance
(EMI) shielding. Precursors of carbon fiber have some effect on
the final properties. Carbon fibers are inert to most chemicals.
In 1988 carbon fiber from a pitch precursor became available at
$7.50 per pound.
Aramid Fibers
A high-strength popular fiber, Kevlar, is widely used in bullet-
proof vests, canoe and boat manufacturing, and other selected
areas where its high strength produces a cost-effective laminate.
It is available as both surfacing mat and in cloth form. Typically,
surfacing mats are available in 0.4 and 1 oz/yd 2 . In tests, Bautista
[10] reported the Kevlar surfacing mat had the highest abrasion
resistance. Kevlar cloth is used occasionally as reinforcement for
high-stress areas in the corrosion industry, such as the vertical
corners of rectangular tanks.
Dynel
Dynel was originally used as surfacing mat instead of C glass where
exposure to HF was probable. Dynel was manufactured by Union
Carbide, which discontinued its manufacture in 1974. Other synthetic
veils have taken its place, such as modacrylic, polyester, and poly-
acrylic .
NONFIBROUS ENHANCERS [ 2 , 3 ]
The nonfibrous additives are used single or in blends to enhance

specific properties of plastics or composites. Some of the more
common ones are listed below with the properties they improve.
Sand Sand is used extensively in composite piping to reduce cost;

it adds to compressive and flexural strength and also improves
abrasion resistance; it performs well at 35% loading in laminate,
but decreases the tensile strength.
Carbon, metal powder, graphite-silver, aluminium, nickel-coated
glass spheres Those are cost-effective conductive fillers used
to carry off static electricity in hospital operating rooms; they
are also used to line ducts, tanks, and stacks where static elec-
tricity may be hazardous, and to provide electromagnetic inter-
ference (EMI) shielding.
Alumina, silicon carbide, tungsten carbide, basalt These materials
are used at the 10 to 30% level to enhance abrasion resistance
of composites; in a platelet shape, they reduce permeability as
well.
Glass flake Glass flake is used as a filler in corrosion-resistant
coatings and linings. Glass is oriented in multiple planes to reduce
lining permeability by a factor of 10; it also increases upper
working-temperature limit; and it is also an important reinforce-
ment for resin injection molded (RIM) auto parts.
356 Mallinson
Talc Talc is a hydrated magnesium silicate that is used as platelets

with its good aspect ratio it becomes a filler plus reinforcement;
it increases flexural modulus in polypropylene, polyethylene,
and rigid PVC plus high impact polystyrene; and it also increases
tensile strength.
Fire retardent agents (Tables 9 and 10)
1. Antimony trioxide (Sb2O3) and antimony pentoxide (Sb2O5)
when used at a 3 to 5% level react with halogen to produce
Sb2OCl3 or SbOBr3, which are snuffing agents; these agents
are used extensively in the chemical industries to provide
fire retardancy in ducts, stack, scrubbers; they are also
used in adhesives and foams.
2. Alumina trihydrate (A12O3-3H2O) is the most used flame retard-
ant in the United States; it releases water of hydration which
cools the combustion reaction; high loadings (50%) are neces-
sary; it is used in panels and tub-showers. This also acts
as a smoke suppressant. The alumina trihydrate releases
34.5% of its weight in water vapor beginning at 230°C (446°F).
It is not used in the chemical industry because of high loading.
3. Halogen compounds such as brominated aromatic compounds
are used widely in the bulk of thermoplastic resins. Chlorinated
cycloaliphatic compounds are also used.
Smoke suppressant Oxides of boron and molybdenum are used
in combination with zinc and antimony oxides to lower smoke
involvement. Other agents are alumina trihydrate, magnesium
hydroxides, and zinc compounds. Zinc borate acts synergetically
with antimony compounds and may reduce smoke levels as much
as 50%.
Fillers Here the addition is covered by economic incentives. Sand
at 4 cents a pound is obviously a good filler to replace resin
at 1.25 dollars a pound. Common fillers are silica, woodflour,
TABLE 9 Flame Spread Classification8 (To be used in conjunction

with Table 10)
Flame spread Classification
0-25 Noncombustible
25-50 Fire retardant
50-75 Slow burning
75-200 Combustible
Over 200 Highly combustible
a
Based upon common tests as outlined by the Underwriters1 Labora-
tories .
TABLE 10 Flame-Spread Rating Table, Reinforced Polyesters, Vinyl Ester, and Furan Resins (with other
reference material)
Flame- a » c CO
spread
Trade name Generic type rating Comments
Asbestos 0 Cement asbestos board (control)

Hetron 800 Furane 10 Smoke rating, <50
Derakane 510 A/5% Sb 2 O 3 Brominated vinyl ester 10 Oxygen index, 40.8
Atlac 711/5% Sb 2 O 3 Brominated polyester 15
Hetron 197 AT/3% Sb 2 O 3 Chlorinated polyester 15
Interplastic VE 8400 75% Sb 2 O 3 Brominated vinyl ester 15
Dion Cor-Res 6695 FR 15 Good to 300°F; high chemical
resistance
Dion Cor-Res 6693 FR/5% Sb 2 O 3 15 Good to 250°F
Hetron 92 AT Chlorinated polyester 15-20 Oxygen index, 42.5 b ; good to
250°F; class 1
Hetron 92 FR, unfilled Chlorinated polyester 20 Oxygen index, 40.8
Dion Cor-Res 6604T/5% Sb 2 O 3 Fire-retardant iso 20 Good to 275°F
Quacorr 1200 FR Furan <25 Smoke rating, <50
Atlac 797 /5% Sb 2 O 3 Chlorinated polyester 30
(continued) Co
Ox
•si
CO
(Table 10, continued) <in

00
Flame-a>c
spread
Trade name Generic type rating Comments
Derakane 510A, unfilled Brominated vinyl ester 30 Oxygen index 29.7

Hetron 197 or Hetron 72/5% Sb2O3 Chlorinated polyester 30
Hetron 197, unfilled Chlorinated polyester > 75 Smoke rating, > 750; good to
350°F
Red Oak 100 Control
Masonite 130
Atlac 797, unfilled Chlorinated polyester 150
Plywood 200
General-purpose, isophthalic, 350-400 High smoke rating; not fire-
bisphenol, hydrogenated retardant
bisphenol, or vinyl esters,
unfilled
a
By ASTM E 84 Tunnel Test.
b
Limiting Oxygen Index Test ASTM D 2863.
c
Current industry practice requires materials of construction for ducts, hoods, stacks, and fume-handling
equipment to exhibit a flame-spread rating of 25 or less and a class 1 fire rating. A class 1 fire rating
means the fire will go out when the source of ignition is removed.
I
kaolin, calcium carbonate, alumina trihydrate, talc, mica, glass

spheres, and wollastonite• Glass spheres cost about 40% of the
cost of the resin they replace and have many beneficial effects.
Mica These are high-aspect ratio plates and are true reinforcing
fillers. Mica reinforces in two directions plus lowering the permea-
bility of a resin. They have been widely used in the thermosets
but are now also used in the thermoplasts.
Wollastonite is a naturally occurring high-aspect ratio calcium silicate
that, when added to a plastic, improves rigidity and dimensional
stability.
COMPOSITE LAMINATES [2]
It is quite common to use a lined polypropylene, furan, Armalon,

ABS, or PVC, backed with a knitted fiberglass overlay. This permits
the handling of a wide variety of materials that alone would not be
satisfactory in a plastic composite resin system. Where we are able
to tailor-make chemical resistance by a combination of thermoplast
and reinforced thermoset materials, considerable equipment economies
have been achieved. Dimensional stability and abrasion resistance
can be increased similarly. By using techniques such as these it
is possible to handle solvents, 93% sulfuric acid, hydrofluoric acid,
brominated compounds, and similar materials.
If the tank is of all-thermoset construction, it is customary to
provide a 100-mil corrosion barrier (25% glass plus 75% resin) before
the high-strength filament winding (60% glass) begins.
The evaluation of plastic construction material together with
various reinforcements can produce some intriguing results that
combine the optimum properties of filament winding with the corrosion
resistance of hand-laidup structure. Typically, the corrosion barrier
would be followed by alternating layers of 55% wind, followed by
a chopped mat, followed by a hoop wind, followed by a chopped
mat, after which the 55% wind, chopped layup, hoop wind, and
so on, are repeated. This will produce a laminate that runs about
50% resin and 50% glass. A simple graph illustrates that at approxi-
mately this point the optimum combination of chemical and physical
properties is obtained. A variation of this is a 0 to 90° wind, with
chopped strand interspersed, that is used in flue gas desulfurization
chimney liners.
Many different kinds of dual laminates are available, including
ABS and polyester; bisphenol and isophthalic fibrous glass systems;
vinyl ester, epoxy, and polyester; glass, and reinforced polyester;
Teflon and reinforced polyester; polypropylene-lined reinforced
polyester; and PVC and polyester composite. With these dual laminates
we are able to combat many of the most difficult corrosive systems.
360 Mallinson
In addition, they offer additional strength and improved dimensional

stability and abrasion resistance.
Considerable equipment economies can be achieved by using
an expensive corrosion barrier (polyester, vinyl ester, or furan)
and then a structural backup of an isophthalic polyester system.
The use of general-purpose resins as structural backups is not
recommended because they have relatively low heat distortion points
and lose their physical properties above 120°F.
CHEMICAL ATTACK OF PLASTICS-THE COUNTERPART

OF METALLIC CORROSION [2,11-13]
If and when reinforced plastic composites are misapplied, chemical

attack, which is a relatively complicated phenomenon for these
materials, may occur in several ways. These may be broadly classi-
fied as follows:
1. Disintegration or degradation of a physical nature because of

absorption, permeation, solvent action, or other factors
2. Oxidation, by which chemical bonds are attacked
3. Hydrolysis, by which ester linkages are attacked
4. Dehydration (rather uncommon)
6. Thermal degradation, involving depolymerization and possibly
repolymerization
7. Combinations of these mechanisms and possibly others
As a result of such attacks, the material itself may be affected

in one or more ways: for example, it may be embrittled, softened,
charred, crazed, delaminated, discolored, dissolved, blistered,
or swelled.
Although all plastics are attacked in essentially the same manner,
certain chemically resistant types suffer negligible attack, or exhibit
significantly lower rates of attack, under a wide variety of severely
corrosive conditions, primarily because of the unique molecular
structure of the resin, including builtin steric protection of the
ester groups. However, because of the complicated way in which
attack occurs, knowledge of the chemical structure of the resin
does not preclude actual testing in most environments to determine
resistance.
Cure, of course, plays an important part in the chemical resistance
developed by a thermoset, as does the construction of the laminate
itself and the type of glass or reinforcing used. The degree and
nature of the bond between the resin and the glass or other rein-
forcement also play an important role.
All of these modes of attack affect the strength of the laminate

in different ways, depending on the environment and other service
conditions and the mechanism or combinations of mechanisms that
are at work. For example, in certain instances, absorption can
weaken the polymer network by relieving internal strains or stresses.
Certain environments may weaken primary or secondary polymer
linkages, or both, with resultant depolymerization; others may cause
swelling or microcracking, and still others may hydrolyze ester
groupings or linkage. Extraction can occur in certain environments
and, still other environments, repolymerization can occur with a
resultant change in structure. Chain scission and a decrease in
molecular weight can occur under certain conditions. Simple solvent
action may also occur. Absorption or attack at the interface between
the glass and the resin will result in weakening. All in all, the
mechanisms involved are rather complicated and certainly not well
understood. In addition to the combinations of mechanisms that
can occur at the same time, it is believed that synergism probably
enters the picture in many instances.
Fortunately, chemical attack on plastics is a "go/no go" proposi-
tion. Attack on reinforced plastics by many of the ways described
previously may occur within a relatively short time in an improper
environment. In reaching the extreme upper limit of its temperature
range, the phenomenon known as "blistering" may take up to a
year to become evident. However, this is a physical rather than
a chemical phenomenon. Experience has indicated that if an installa-
tion has been soundly engineered and has operated satisfactorily
for a year, the probability is good that the operation will continue
in a completely satisfactory manner for a substantial period. Fortu-
nately, all this can be determined in advance with a well-conceived
test program, so that the engineer's liability at any time can be
suitably limited. Here, we are dealing with only the high-grade
chemically resistant plastics. In severe chemical service, these highly
resistant resins will normally be the material of choice as opposed
to either a general-purpose polyester or an isophthalic polyester.
Oxidation
One of the more common types o£ degenerative processes in fiber-
glass laminates is an oxidative atmosphere combined with high-
temperature exposure and perhaps variable-cycling temperatures.
Examples of this are
1. Crystallization batch processes during which temperatures may

cycle from 140°F to 32°F six or eight times a day.
2. Thermocompressors of FRP where temperatures cycle from room
temperature to 215°F and back to 32°F six to eight times daily.
362 Mallinson
3. Exothermic reaction processes in an FRP vessel during which

the temperature may cycle from ambient to 225°F three to four
times daily.
4. Chimney liners operating continually in the bypass mode and
subject to temperature ranges of 240 to 280°F in the liner and
subfreezing to 90°F in the annulus, meanwhile being bathed
in hot sulfuric acid condensation of varying strengths, some
of which may be quite high. Acoustic emission tests show that
these liners are undergoing continual changes in stress.
In the long term, these oxidative processes can produce checking

and cracking of varying degrees of severity. Flexibilized corrosion
barriers may be helpful.
Duct systems, even exhausting from very corrosive solutions,
are generally exposed to a much less severe environment and can
handle exposures very well. Some that the author has inspected
that have been in service for 15 to 20 years show practically no
degradation and appear ideal for the service, even though the
exhaust gas was from a highly oxidative medium with temperature
cycling.
Pyrolysis
The simple word for pyrolysis is charring. The molecule of all plastic
materials is an organic molecule that can be destroyed by severe
oxidation. This can occur by fire or it can occur, for example,
with very strong sulfuric acid ( e . g . , 93%). This completely destroys
the molecule, and severe oxidation takes place. The resin turns
black and loses all physical strength, so that the structure is
destroyed. Service life is measured in a matter of hours. The poly-
esters, for example, can withstand up to 78% K^SO^ for short periods
and 70% H2SO4 almost indefinitely at room temperature, but above
that oxidation becomes so severe that the molecule is destroyed.
This applies to many of the organic compounds, with exceptions
such as some of the thermoplasts—polyethylene, polypropylene,
and PVC—for which higher concentrations are acceptable.
Solvent Attack on Reinforced Plastics [12,13]

The attack of aqueous solutions on reinforced plastics occurs through
hydrolysis by the water that degrades bonds in the backbone of
the resin molecule. The ester linkage is the most susceptible. The
attack by solvents is different because the solvent penetrates the
resin matrix of the polymer through spaces in the polymer chains.
The penetration of the polymer chain causes the laminate surface
to swell, soften, and crack. In the first stages of solvent attack
we have
1. Softening: decrease in Barcol hardness by a substantial amount.

2. Swelling: the specimen swells considerably.
3. Weight: pronounced weight gain. Anything over 2% is cause for
concern.
Quite naturally, there are all degrees of the preceding stages.
1. If there is little weight gain (less than 2%) and considerable

retention in hardness over a 12-month period, plus little or no
swelling, the laminate will do very well.
2. If the Barcol hardness is retained at a high level, the weight
gain has stabilized, and the swelling has stabilized at the 12-
month level, then the resin may be acceptable for limited service.
3. If, for example, there is a 10% weight gain in 1 month, a swelling
of 19%, and hardness has dropped from 43 to zero, bisphenol
performance with toluene would be a total failure.
The degrees of solvent attack are
1. Softening: Barcols drop to zero

2. Swelling: the absorption of the molecule continues, producing
mechanical stresses that cause fractures in the laminate. This
may occur in either the liquid or vapor zones.
Conchoidal fragments may be seen in the vapor area and are

caused by a severe swelling-solvent condensing on the upper surface.
They appear to break away from the substrate at the boundary
interface. It is really the C-glass layer (20 mil; 10% glass) that
is mechanically weakest, breaking away from the mat layer (80 mil;
25% glass). This conchoidal flaking is believed to be a function
of the swelling factor, the shear modulus, and the shear strength
of the two strata. Strong swelling-solvents, such as acetone and
toluene, produce this phenomenon.
Organic contaminants in waste waters may have low solubility
and tend to form a separate phase. Even in very weak solutions,
these contaminants coalesce and settle on the surfaces of tanks
and piping in which the waste or process water is being handled.
This settling produces a concentrated exposure to the chemical
being handled, even when the contaminants may exist only in dilute
amounts in the waste water or process.
Organic materials, such as carbon disulfide, with carbon-to-carbon,
unsaturated double bonds are powerful swelling-solvents and show
greater swelling action than their saturated counterparts. An illus-
tration of this is an acid wash solution of 5% sulfuric acid that
contains trace contaminants of carbon disulfide, at a temperature
364 Mallinson
of 90°C. Tanks and troughs of bisphenol polyester have run well

for years under these tough conditions. The process conditions
changed and the unit became a recovery effort at 20 to 25°C.
Within a very short period the bisphenol system failed. The reason:
condensation of the carbon disulfide caused coalescence of the trace
contaminant. The bisphenol laminate was exposed to 100% carbon
disulfide. Failure was quick in coming, with softening, swelling,
cracking, and leakage of the system. Troughs, piping, and tanks
totally failed within a few months. A cold 5% sulfuric acid solution
with carbon disulfide traces was infinitely more destructive than
the same solution at 90°C because the solvent action was prevented
at 90°C.
Smaller solvent molecules can penetrate a polymer matrix more
effectively than larger molecules. The degree of similarity between
solvent and resin is important. Slightly polar resins, such as the
polyesters and the vinyl esters, are attacked by mildly polar solvents.
Generally, saturated long-chain organic molecules, such as the
straight-chain hydrocarbons are handled well by the polyesters.
That is what makes gasoline tanks so successful. The polymer1 s
ability to resist attack is improved by
The cross-linked density of the resin

The ability of the resin to pack into a tight structure
The heat-distortion temperature of the resin is strongly related

to its solvent resistance. The higher the heat-distortion temperature,
the better the solvent resistance, with some exceptions. The more
resilient resins can withstand a greater degree of solvent absorption.
Brittle resins are notoriously poor in this respect.
Generally speaking, resistance to solvents, such as acetone,
carbon disulfide, toluene, trichloroethylene, trichloroethane, and
methyl ethyl ketone, is poor for orthophthalic and isophthalic poly-
esters, as well as for bisphenol polyester and the chlorinated or
brominated polyesters. The vinyl esters, such as Derakane 470
and Interplastics 8770, show much-improved solvent resistance.
Heat-cured epoxies such as Shell's Epon 828 and Dow's Derakane
also have better solvent resistance. The best solvent resistance
of all, however, is found in the furan resins, such as Quacorr
1001, Quacorr 1200 FR, and Hetron 800, which excel in this area.
The ability of furan equipment to handle solvents in combination
with acids and bases may circumvent the need for new equipment
if process changes occur. The illustration previously given of a
process change involving a 5% I^SO^ solution at 90°C and the dis-
astrous effects of changing to 20°C, which provoked the CS2 attack,
is a prime example of this. Subsequently, all of this system equipment
was replaced with a furan resin composite with complete success.

The furans are resistant to mixtures of very aggressive solvents
coupled with acids and bases and have an excellent temperature
range that covers high-temperature performance.
Gasoline and mineral spirits have minimal effect on the polyesters.
Xylene has little effect, but toluene has a severe effect. Gasohol,
whether methyl or ethyl, does well with the vinyl esters. Even
though some loss in Barcols is seen, the vinyl esters still retain
75% of the original flexural modulus in gasohol service. This is
a better judgment criteria for evaluating performance.
Extensive studies on the effects of solvents on thermoset laminates
have been made, and the data have been confirmed many times by
field observations. The work by McClellan et al. [12] covered four
families of resins in over 150 organic chemical environments during
a 12-month period. The work of Burrell and Ohearn [13], although
it covered only 120 days, generally confirmed previous findings
and provided many useful theoretical advances in the field of solvent
attack. Heavier materials, such as the trichloroethylene, trichloro-
methane, and carbon disulfide sink to the bottom, coalesce, and
attack the bottom of the tank, trough, or vessel.
OTHER CAUSES OF FAILURE

Checking, Crazing, and Cracking
Often, when one observes a thermoset resin in performance over
long periods, such as 5 to 10 years, at elevated temperatures,
one observes checking, cracking, and crazing that may occur to
a depth of 50 to 70 mil and be profusely abundant. However, the
core of the structure shows that the action has essentially stopped
at this depth. This action is particularly prevalent with high tem-
peratures, above 80°C (175°F), and in oxidizing atmospheres.
Depending on service conditions, one frequently observes this type
of corrosion and it is often seen to a mild degree in service conditions
that are not particularly severe. In general, it does not affect the
performance of the vessel or system, except with electrically conduc-
tive liners, for which the conductivity will literally be destroyed
if the conductivity of the surface has become a series of islands
such that a satisfactory ground cannot be established to the ground-
ing points.
In general, submerged conditions pose more difficult service
than ducts with gas flow. However, some gas conditions can be
particularly severe. Flue gas chimney liners operating on bypass
conditions may run at 240 to 280°F under extremely acid conditions
caused by condensation. These present extremes in heat and oxida-
tion.
366 Mallinson
Delamination
The general cause of delamination is faulty fabrication, and it is
seen especially in vessels that operate under a vacuum. Generally,
the delamination occurs at the interface of the mat and roving.
Roving is extremely difficult to wet out. Studies with an electron
microscope have shown the difficulty of resin penetration in the
roving bundle. Occasionally, however, it is seen between layers
of mat where a secondary bond has been made. Bond intensifiers,
whose sole purpose is to increase the strength of the secondary
bond, appear to have been successful. It should be realized that
secondary bonds are essentially mechanical unless bond intensifiers
are used, at which time the secondary bond becomes a chemical bond.
Heat Resistance
A rough measure of the high-temperature performance of the various
resin systems lies in the heat-distortion point (HDP) of the resin.
This is published for virtually all resins and is a vital physical
property to consider when high-temperature performance is desired.
The HDP is measured on a clear unreinforced casting of the resin
as outlined by ASTM 648 (264 psi). It is not measured on a glass-
reinforced laminate. But, if we examine a laminate1 s physical prop-
erties and compare them with the HDP of the resin, there is a
pronounced decrease in tensile strength as the HDP is reached,
and a severe reduction is evidenced as it is exceeded. Even more
pronounced is the effect on flexural modulus, which may lose up
to 75% by the time the HDP is reached. This is particularly important
in vacuum or buried pipe service. To objectively assess this, we
need to determine a profile of the temperature across the laminate
wall. If the vessel or structure is insulated, the laminate average
temperature is close to the inner gas or liquid temperature. If it
is not insulated, there can be a substantial temperature drop through
the laminate wall. The mean wall temperature may be substantially
lower and, with that, the physical properties much higher. This
is particularly true of heavy walls.
The general-purpose (orthophthalic) resins have low HDPs of
100 to 150°F; those of the isophthalic resins are about 185 to 195°F.
This can vary widely with the degree of elongation. In the high-
performance; chemical-resistant families of resins the vinyl esters
average 210 to 220°F HDP, the bisphenol polyesters 260 to 285°F.
High-temperature chlorinated polyesters have HDPs of about 285°F;
the novalac epoxies 295 to 305°F; and the furans over 450°F. These
are only general guides. The exact HDP for each resin is available
from the manufacturer's published literature.
Flexibilizing a resin lowers its HDP. The greater the percentage

of elongation, the lower the HDP. Although there are different
opinions on the subject, a widely held view is to limit laminate
exposure to 30°F below the HDP of the resin. When considering
this, the mean laminate temperature should be used. The HDP is
also apparently related to the property of solvent resistance.
Thermal Stresses
In extremely large structures, such as chimney liners, the tempera-
ture difference across the wall is substantial and, at times, can
amount to 350°F. This produces thermal stresses across the wall
that must be factored into the overall liner design. If a vessel
or pipe is insulated, the wall temperature is about the same as
the temperature of the contents. This virtually eliminates the stress
produced by the thermal gradient across the wall, but it forces
the laminate to face a higher mean operating temperature, which
can mean a reduced stress operating capability.
Mechanical Failure in Buried Fiber Reinforced Polymer

Of tremendous importance is the realization that mechanical failure
plays a large role in the failure of FRP equipment, which in some
areas equals or exceeds the rate of chemical attack. For example,
the 1986 EPA study on 111 buried FRP tanks showed failure from
the following causes:
Structural failure 50%

Corrosion 10%
Fittings 10%
Improper installation 22%
Natural phenomena 8%
Total 100%
One can draw the conclusions that structural failures and improper
installations are largely preventable; that the basis for buried tank
design should be further evaluated; and that a better educational
process is needed on buried tank design and installation. The
industry is in need of a buried tank design, construction, and
installation standard.
PLASTICS: MECHANISMS OF FAILURE FROM ABRASION
Failures by abrasion are more prone to occur from particles in a

gaseous medium that in a liquid medium. This is because in the
368 Mallinson
gaseous environment a particle can be easily hurtled along at speeds

of 5500-6100 m/min (18,000-20,000 ft/min), whereas in the liquid
environment velocities may be 90-120 m/min (300-400 ft/min). The
gaseous medium produces a sand-blasted effect and failures are
much more common in this area.
Among other variables, failure by abrasion is a function of kinetic
energy, which is made up of mass and velocity squared and is
particularly pronounced in particles whose diameters are larger
than 100 mesh. It is also related to the shape and hardness of
the particle. In fact, as a rule of thumb, in liquid streams, particles
smaller than 100 mesh in diameter present no problem; however,
when they are above 100 mesh, they may present a problem. For
example, fly ash per se does not represent a conveying problem
in a liquid stream, but fly ash mixed with bottom ash, which repre-
sents a very large particle, can easily generate erosion. Polyethylene
and polybutalene have shown exceptional resistance to erosive attack
within the temperature limitations of their capabilities. Also, special
formulations have been made of epoxies, polyesters, and polypropylene
plastics that serve unique purposes in many chemical process forms.
In general terms, one realizes that a "corrosion" as it relates
to metallic materials does not exist in plastics. Plastics do fail,
but they fail for a variety of reasons. Because plastics do not belong
in the electromotive table, it generally is not possible to develop
an electromotive force unless the particular plastic has been made
properly conductive.
Combined particles carried in a gas stream at high velocities,
operating at the uppermost temperature limits of the plastic's range,
represent the worst possible conditions. For example, a highly
corrosion-resistant fiberglass line carrying a gaseous stream at
11,000 m/min (36,000 ft/min) can fail in less than 1 day when gas
temperatures are 270°F, but the same line carrying the same veloci-
ties operating at 70°C (150°F) can easily last for 4 years. This
is particularly true of the polyesters, epoxies, furans, and vinyl
esters.
Table 11 is an abrasion league table of common materials, ranked
by abrasion resistance, that are found in the chemical industries.
Table 12 summarizes some of the variables relative to abrasion-
resistant laminates with comments on process evaluation.
E L E C T R I C A L L Y GROUNDING P L A S T I C SYSTEMS [2]
Inherently, plastics are nonconductors of electricity with a volume

resistivity of 1012-1019 ohm-cm3. They can, however, act as con-
densers and store substantial electrical charges on this surface.
TABLE 11 League Table Taber Tests (Relative Abrasion Resistance)
Material Taber abrasion number
High-molecular-weight polyethylene 0.3 (best)

Heavily filled high ceramic laminate,
inside a filament-wound pipe 1-2
Polyurethane (depending on formulation) 1-20
Soft rubber 3
Toughened matrix vinyl ester with
alumina filler 4a
Polyester resin laminate with small-
particle high alumina filler 10-20b
Steel pipe 15b
Polyester resin with 10-30% silicon carbide 16-25
Polypropylene 18
PVC 19-22
Clay sewer pipe 19-22
Polyester resin with 10-30% tungsten
carbide 22-25
Lexan, unfilled 20-30
Good parent polyester resin (no additive) 53-142
a
A number of toughened matrix vinyl ester resins have been devel-
oped. These have tensile elongations of 12-20% but lower heat distor-
tion points. Resin blends can often produce the most desirable
properties. Toughened matrix resins combined with abrasion fillers
generally provide the most improvement in the abrasion-resistant
field for custom contact-molded requipment or filament-wound equip-
ment.
^This is borne out by inservice tests that gave the same service
life in abrasive-noncorrosive areas.
TABLE 12 Abrasion Resistant Laminate and Process Evaluation
Variable Evaluation comment Recommendation
Resin The resin itself has a wide influence on the Evaluate the resin selection for
laminate's total resistance to abrasion. A the total "corbrasion" process
variation of 270% can exist. under your conditions; particu-
larly look at the toughened
matrix resins.
Type of cure Best resin performance is always obtained Postcure, if possible; make sure
with a postcure. desired Barcols are met.
Veiling system Important in parallel flow; less important in Use a mix of C glass-synthetic
impingement type. veiling; if in doubt, polyester
veiling has better abrasion
resistance than C
Abrasive particle Fly ash and particles 100 mesh and smaller Look at particle size closely; the
are no problem; salts generally are no prob- guidelines here spell the kind of
lem because most salts have a Moh hardness system you may need.
of about 2; bottom ash and larger particles
of 1/4-1/2 in. spell problems.
Velocity of Salt crystals are all right in piping systems
abrading stream at velocities up to 10-12 ft/sec; trouble
occurs at 30 ft/sec (watch for localized
problems).
Fly ash (100 mesh) up to 10 ft/sec is satis-
factory.
Vapor velocities with wet entrained salts at
250-1100 ft/sec, if parallel to wall, are no
problem. The same vapors at 250 ft/sec, but 03
O
impinging directly, present a real problem.
If the same impinging vapor velocities are
reduced to 50 ft/sec, the problem disappears.
Temperature of Within the normal operating limits of the resin Keep well within the recommended
system no substantial change occurs. As tem- temperature performance range of
perature increases to 270-300°F and physical the resin. Stay 30°F below the
properties drop off, the ability to resist abra- HDT of the resin.
sion falls rapidly. Failure can be in a day or
two. 03
Additive type The addition of an additive to the resin used This can be a real plus and
in laminate layup can improve any resin's should be considered as a method
performance. Take a look at it. Make sure it to provide substantial improve- 8.
does not affect corrosion performance. It must ment in laminate performance.
be compatible. ST
Additive The shape of the particle is beneficial. A flake- Evaluate the shape as part of
particle shape like particle is preferred to other types in the total picture.
light loadings; a round-type particle in heavy
loadings.
Additive loading Do not add to the point that physical proper- Evaluate loading versus overall
ties suffer. If you do, then heavy-up the performance. If we are dealing
wall. with increasing abrasion resist-
ance only, then it is difficult to
justify going beyond a 10-30%
loading in small particles (much
higher in large particles 0.050-
0.070 m.).
Design steps Analyze type of flow, particle size hardness. In heavily abrading systems a
Keep velocity reasonable. service life of 6-7 years may be
Build the abrasion resistance into the lami- a practical limit. Recognize this
nate. Do not make it an add-on! as part of your material evalua-
Keep within the performance capabilities of tion.
the resin.
Incorporate into your system design a corro-
sion allowance.
372 Mallinson
Because the plastics possess a finite capability, they will discharge

in the form of static electricity. If they have been incorporated
into a potentially explosive system, they present the real hazard
of causing a fire, an explosion, or a high-voltage shock to personnel.
The following types of conditions merit close review where plastics
are involved:
1. A potentially explosive area such as an acidic reaction generating

hydrogen.
2. A fire hazard area in which, under some conditions, the ductwork
may be ignited by a flammable gas.
3. The conveying of an organic or inorganic dust in a plastic duct.
(An organic dust can result in an explosion such as occurs in
grain elevators.)
4. The static electricity hazard to personnel. Chimney liners, for
example, can give a substantial electrical shock to operating
maintenance personnel.
The use of fiberglass composites in ducts, stacks, scrubbers, and

chimney liners is common. These materials have volume resistivities
of 1013-1015 ohm-cm3.
Where static grounding is deemed necessary by the engineer,
the following guidelines are suggested:
1. Where explosive atmospheres can exist, try to maintain the

gas concentration at 2 to 5% of the lower explosive limit. This
is done by an air sweep through the vessel.
2. Fiberglass composites can be made conductive by creating a
network of electrical pathways within the surface of the composite
as a result of fiber-to-fiber contact or particle-to-particle con-
tact. This is done at the inner surface to a depth of 5 to 60 mil.
3. Where severe oxidizing conditions exist, the conductivity should
be 30 to 60 mil deep. In duct systems 5 mil may be sufficient.
4. A 5-mil conductive surface may be established by using a 0.2-
oz/yd 2 carbon fiber mat or a 0.5-oz/yd 2 (33% carbon/66% glass)
mat. These laminates are translucent and fully inspectable.
5. NFPA 77-77 recommends that for static grounding a resistance
to ground of not more than 106 ohm be achieved. This is from
any point in the system. Use this as a guideline.
6. A carbon fiber mat may be used with a graphite carbon particle
filler to achieve conductivity in depth. This is recommended
for severe oxidizing conditions or high and variable temperatures
at which surface checking and cracking may occur.
7. If corrosive conditions do not exist, other types of filler may
be used, e.g., metalized glass fibers such as those coated with
aluminum or nickel. Also available are 8% silver-coated glass

spheres. These can produce excellent conductivity and are
used widely in electromagnetic interference (EMI) shielding.
8. A surface conductivity of 100-500 ohm ft and a volume conduc-
tivity of 10-1000 ohm cm are readily achieved with carbon
mat and carbon mat/carbon black.
9. Always make a sample layup (12 in. x 12 in.) with the proposed
layup before beginning the project. Test the resistance with
a multitester.
10. Do not let contact resistance ruin your test work. Use clamped
copper pennies on the laminate face to measure the resistance.
11. A good electrical ground (at the ground) is 25 ohm. This can
be a copper pipe driven 8 ft into the earth, or it can be building
steel or a nearby water pipe.
12. Use a No. 4-6 copper ground wire. Use a double-grounded
system.
13. Perform maintenance checks on your system every 4 to 6 months
to make sure that everything is functioning as it should be.
DUCTS, SCRUBBERS, FANS, AND STACKS [2]

The problems engineers must solve when dealing with scrubbers,
fans, exhaust systems, and stacks are
1. Good corrosion resistance

2. Low fire-spread rating
3. Low smoke evolvement; good fire protection
5. Economic cost
Corrosion in ducts is generally an order of magnitude lower than

that from a submerged solution.
Sometimes a compromise must be made to meet the hazard en-
gendered by chemicals traveling at high speed. The engineer then
chooses the appropriate material of construction, such as fiber-
reinforced plastic, stainless steel or brick; or ceramic-lined concrete,
PVC, fluoropolymer; or rubber-lined steel, stainless steel, lead,
or Plastisol-lined systems. It is easy to conceive of a system built
completely of fire-proof material such as stainless steel or brick-
lined concrete.
Actually, in view of the hard reality of past experience, no
system is really fireproof because deposits on the system may burn
and cripple the exhaust system by knocking out the fans.
374 Mallinson
SOME COMMENTS ON OTHER TYPES OF MATERIALS USED

IN DUCT, SCRUBBER, FAN, AND STACK CONSTRUCTION
Ducts, Scrubbers, Stacks
Fluoropolymer-Lined Steel
A 30- to 40-mil liner with zero flame spread is good for acid-laden
and solvent exhaust systems. This type of liner is not suitable where
alkaline systems above pH 10 exist. It has zero fuel contribution
and is suggested for use in flue gas stacks where high-temperature
performance is desired. It is expensive.
Polyvinyl Chloride
Poly vinyl chloride is used in many small duct systems. It shows
a good all-around chemical performance, but it is not satisfactory
above 140°F; PVDC or CVPC may be used up to 180°F. Polyvinyl
chloride can break down and liberate hydrochloric acid in duct
fires. Interrupters made of PVC are sometimes used in fiberglass
ducts. Koroseal is a flexible PVC and is also used as a duct liner
on steel.
316 L Stainless Steel

This alloy allows zero flame spread and has zero fuel contribution.
It is used widely in flue gas desulfurization duct systems. At low
pH it is subject to chloride attack causing pitting, crevice corrosion,
and stress-corrosion cracking; however, it is excellent in alkaline
areas.
Foam Glass-Lined Steel

Foam glass-lined steel seems to be doing well in some areas. It
has been tried in flue gas desulfurization ducts. This material is
generally applied over a flake-glass lining. It is very inert to most
chemicals and allows zero flame spread with zero fuel contribution.
Phenolic Epoxy Systems

The phenolic epoxy systems are generally coatings on steel; quite
often baked to a hard finish. They are low-cost systems that have
a very low fuel contribution and flame spread. Their disadvantages
include the lack of abrasion resistance, and they are prone to chip-
ping. The systems have widespread chemical resistance.
Flake-Glass-Lined Steel
Flake-glass-lined steel is used at 30 to 40 mil in light-duty systems
and at 60 to 80 mil for heavy-duty and submerged systems. Bisphenol
polyesters and vinyl esters predominate. They are widely used

because of their good performance and their economy. The upper
temperature limit in gas applications is less than 220°F and about
160°F if the system is submerged.
Fans
Rubber, Neoprene, Other Elastomers
Fans constructed of these materials are sometimes used in ducts
and stacks. These elastomers are widely used on fans and housings
where abrasion is a problem. The construction should always be
sprinkler protected. The upper temperature limit depends on the
elastomer used.
Warning: In flue gas desulfurization systems, always place the
fans before the scrubbers: before the scrubbers, corrosion is minor;
after the scrubbers, corrosion plus erosion can be severe.
DESIGN CHECKPOINTS FOR SUCCESSFUL

PLASTIC PIPING SYSTEMS
1. Do not use a metal expansion joint with plastic pipe or wire-

reinforced rubber expansion joints. Stick to a bellows type,
where action forces are low.
2. A Teflon bellows joint will also serve as a vibration isolator
and flexible connector.
3. Try to use the natural changes in direction of the pipe to allow
for expansion, without creating additional expansion loops.
4. Do not use a U bolt as an anchor; it violates the principle
of point loading.
5. Loose-fitting U bolts used in pairs can serve as a guide.
6. Guides and supports are not synonymous. Use each for its
own intended purpose.
7. When heat-tracing a line, take care to prevent it from freezing.
Spiral wrapping of the trace material should be covered with
light insulation to contain the heat. Watch carefully the upper-
temperature limitations of the plastic pipe.
8. The operating bending moment should not exceed 25% of the
allowable moment.
9. When plastic piping passes through wall openings, protect it
from hammering against the wall, thus reducing abrasion.
10. Be careful of rotational moments in plastic piping. Do not wring
it out like a dishrag.
11. Support all valves independently.
12. The handling of plastic piping is extremely important. Do not
ruin it before you get it installed.
376 Mallinson
13. Most plastic-piping system failures are physical, a result of

violations of good design principles.
14. There are many kinds of piping systems available in today f s
market. Make sure the one you purchase will provide a long,
reliable life. Corrosion barriers range from 10 mil for very
light duty service, to 40 mil for medium service, to 100 mil
for heavy-duty corrosion services. This is all reflected in the
price of the finished product. Do not buy pipe on the basis
of price alone.
15. If the pipe is to be buried, make sure the design conforms to
AWWA C 950-81 and reflects the revisions made in 1983. This
is basic standard for buried pipe.
16. All gravity and pumped systems must be suitably vented. The
penalty for not venting gravity systems is an air lock that
restricts system flow. The penalty for not venting pumped
systems can be serious, e . g . , complete system separation by
blowing off fittings. The compressed gas becomes a loaded gun.
17. If abrasion is a problem, use long sweep elbows (3 R preferred).
Keep velocities in pumped lines to 6 ft/sec. Large particles,
such as bottom ash, present problems (rotate pipe 90° every
6 months). Small particles, such as fly ash, are not troublesome.
If salts are being conveyed, check the Moh hardness. Many
salts have a Moh hardness of about 2 and can be conveyed
successfully in plastic piping.
DESIGN CHECKPOINTS FOR PLASTIC TANKS
1. Be absolutely certain of the pressure specifications. Except

for pressure vessels, most plastic tanks are used for gravity
storage. Make sure that venting arrangements are provided
such that negative pressure will not collapse the tank.
2. Select the plastic carefully. Review the service conditions,
and tailor the selection to meet these conditions.
3. If valves are used with tank outlets, make sure that the valves
are supported independently throughout the system.
4. Proper drainage is essential. Make sure that the tank will drain
completely and that the drain size is adequate to empty the
tank within a reasonable period.
5. Eliminate vibration and hammering. The worst enemy of a plastic
tank is vibration. It can reduce the life of a tank by as much
as 80%, particularly from internal heating with a steam sparger.
6. Strengthen the knuckle area. Too often overlooked, the point
at which the bottom of the tank joins the side wall can develop
flexing stress as the tank is rapidly filled and emptied. As a
minimum, the knuckle thickness should be
t 8 + t b = tk
where t s = thickness of side, in inches
t^ = thickness of bottom, in inches
tk = thickness of knuckle, in inches
This is particularly true of batch vessels. For example, a tank

processing 10 batches a day will have processed over 36,500
batches in 10 years.
7. Design for a minimum life expectancy of 15 years. Many plastic
tanks have been in service for at least this long.
8. Look closely at the bottom support. For a plastic tank, a con-
tinuous support is generally used, but intermittent supports
can be used if the bottom of the tank is made sufficiently strong.
9. Make tank lids strong. If there is any possibility that personnel
will walk on top of the vessel, the lid should be capable of
supporting four or five 200-lb persons. If this is not intended,
a notice to this effect should be posted on the tank. Serious
accidents have occurred in which workers have fallen into shallow
tanks of hot acid, purely because the lid was not designed to
support personnel. As a minimum, the lidding system should
be capable of supporting 1000 lb evenly distributed or a 250-lb
load concentrated in a 4-in. diameter circle.
10. Establish good communications between yourself and the tank
vendor. Write exact specifications: do not, for example, confuse
vacuum with positive pressure.
11. Look at agitators and platforms. The evolution of design in
this area has progressed markedly in the past 10 years, so
that agitators can now be mounted on tanks with suitable sup-
port. Design the tank for the agitator. The consequence of
ignoring this can be a reduction in service life by 50 to 70%.
Further accessories, such as platforms, ladders, and level
gauges, can be purchased from any reputable vendor.
12. Watch the freezing conditions in plastic tanks. Expansion forces
in freezing are large, and some tanks can be severely damaged
if freezing occurs.
13. Take care of the inner surface. Often the life of a plastic tank
is determined by its inner corrosion barrier. Treat it with care;
do not damage it mechanically. Wear rubbers or rubber-soled
shoes inside a plastic tank.
14. Be careful in heat tracing a tank. The heat input in the traced
area can result in greatly accelerated deterioration. This is
particularly marked in ferric chloride solutions.
15. The permeation of a solution through the tank wall can be seen
when the solution crystals appear on the outer laminate. If this
378 Mallinson
is pronounced, the laminate has been compromised. Sometimes

a remedy is attempted through laying a new corrosion barrier.
This has met with mixed success because of the basic underlying
contamination. The problem arises most often in hot, strong
solutions of salts and is seen more often in chop/hoop construc-
tion than in custom contact-molded layup.
16. Buried tanks are designed on the basis of no earth support
and full flotation. Because of problems associated with all buried
tanks, state and federal laws have insisted on a secondary
impoundment below the tank plus a monitoring system to deter-
mine if leaks are occurring. This adds substantially to buried
tank costs.
LININGS
Many plastics—PVC, the polyesters, epoxies, furans, polypropylene,

and the fluoroplastics—are used as lining materials for pipe, tanks,
and vessels in a manner similar to rubber lining. It is difficult to
generalize about liners, but some items are noteworthy concerning
the less exotic variety commonly employed in the chemical industry.
1. The liners, in themselves, generally are about 60- to 150-mil

thick, depending on service, whereas a rubber liner would be
125- to 375-mil.
2. Often liners are filled or reinforced to enhance physical properties
such as strength, conductivity, and permeability.
3. Permeability is largely a function of temperature (the driving
force), hence, with the polyesters and vinyl esters, the addition
of flake glass can reduce lining permeability by a factor of 10.
Large steel vessels 30 to 50 ft in diameter and 60- to 100-ft
high, serving as scrubbers, are often built with formulated flake
glass polyester or vinyl ester liners of 60 to 80 mil, with operating
temperatures up to 160°F wet, 220°F dry.
4. Lining failures generally occur by a number of mechanisms.
a. Inadequate surface preparation A blast with 3- to 5-mil
profile is essential.
b. Inadequate priming coat Always measure thickness from the
peak of the valley.
c. Poor ambient conditions Do not line in wet weather or when
the ambient temperature is within 5° of the dewpoint.
d. Pinholes, improper coverage This would show up in a defective
spark test. The solution is to grind out the area and begin
again.
e. Temperature excursions Each lining has its own temperature
limitations both under wet and dry conditions. Flake glass
TABLE 13 Thermal Excursions on Flake Glass and Silica-Filled Linings Based on Flue Gas
Desulfurization Service Conditions
Continuous Excursion Duration of Heavy-duty
operation temperature excursion (60-80 mil) Roving-reinforced Comments on p
Wet Dry Dry polyester silica-filled lining damage CO
flake glass polyester, 1/8 in. and reason o*

160°F < 220°F No damage No damage p
Above 220°F Several minutes No damage Probably minor cracking Thermal s t r e s s 1

300-310°F Rapid excursion No damage High probability of
damage; cracks
350°F max. Several hours No damage Cracks; possible
shearing from substrate
Above 350°F Rapid Blister damage Substantial damage Surface blistering;
substrate may still
be protected
400°F Very rapid Extensive Substantial damage
2-3 min. blister damage
650°F Very extensive Very extensive damage
damage
1. Recommended safe program

Limit temperature excursions to less than 220°F to no more than 2-3 min.
Design system of damper operations, quench s p r a y s , and demister sprays to accomplish t h i s .
Install multiple temperature sensors and recorders to provide a good record.
2. Damage to lining with temperature excursion is principally due to thermal stresses which cause cracking and
shearing from substrate on roving-reinforced silica-filled polyester.
Surface blistering is a resin degradation phenomena.
At very high temperatures lining chars and is destroyed.
3. Limitations on epoxy silica-filled linings are similar.
4. Temperature excursions are cumulative
380 Mallinson
and fiberglass linings have a good wet limit of 71°C (160°F).

In the range 76 to 82°C (160 to 180°F), the lining may or
may not be successful. Above 82°C (180°F) many linings
are not suitable, except the fluorocarbons, which may go
to 115°C (240°F) wet, but this varies widely with chemicals;
thus, it should be checked in each case. With temperature,
the driving force failure occurs by migration of the water
molecule in the solution through the lining to the substrate
and ultimate debonding. The same phenomena occur in all
plastic vessels, but because the water molecule rapidly evapo-
rates from the surface of the solid plastic vessel, it is not
a problem. With gases, successful lining applications go to
220°F. Excursions above that, depending on temperature,
produce lining failure by thermal stress and surface blistering.
f. Debonding The most prevalent form of failure observed in
linings, debonding, can be caused by permeation, poor prepa-
ration, or temperature excursions above the useful upper
limit of the plastic.
g. Solvent action Softening of the lining with a pronounced
decrease in hardness is often the result of solvent action,
which can be fairly rapid.
Adhesion tests are normally performed with an Elcometer, which

pulls off small circular areas in tension. The mode of failure is
important. A mat lining on concrete should fail in the concrete,
not at the mat-concrete interface. Mat linings on steel will fail at
the mat-steel interface. Flake-glass or epoxy-rove-reinforced linings
fail within the lining. This is a "cohesial" failure.
A concise overview of the effect of thermal excursions on flake
glass and silica-filled bisphenol polyester linings is presented in
Table 13. Mat linings, which were widely used 20 years ago, are
being used much less now and are being replaced with silica-filled
roving linings and flake glass linings.
Linings are attractive because of their low capital cost. A 150,000
gal flake glass-lined steel tank costs about 75% of the same-sized
fiberglass vessel.
Commonly, the fluoroplastics, polypropylene, and PVC are fitted
with knitted reinforcing backs that provide a positive lock when
used as a lining with fiberglass vessels. When they are used with
steel vessels, adhesives are used.
NONDESTRUCTIVE TESTING
Acoustic Emission Testing [14]
Perhaps the most far-reaching advance in nondestructive testing
of composite equipment is in acoustic emission (AE) technology.
Acoustic emission is an excellent test for monitoring the structural

integrity of equipment and for inservice performance testing. This
testing of FRP equipment on stream is currently the largest end
use. An important and substantial area is also served by the use
of AE as an acceptance test for new products. The widespread
use of this tool has resulted in a sharp decrease in the failure
rate of structural composite components.
Briefly, an acoustic emission test is run by attaching piezoelectric
transducers to the surface of the material. A load is applied to the
equipment by structural means, by raising the pressure or liquid
levels, by applying vacuum, or by other methods. Under this appli-
cation of stress, a defect will grow and release energy in the form
of stress waves. These are picked up by the transducer. Generally,
multiple sensors are used, with each sensor covering a local area
of the vessel. Sensors should be located so that impulses overlap.
If we take a simple example and test a wrapped joint to destruc-
tion by increasing the hydraulic load on the joint, the joint is
designed to burst at approximately 1000 psi. A piezoelectric trans-
ducer is mounted on the joint. The transducer is connected to a
counter, an oscillograph, a continuous chart showing activity break,
and an audible output. As the pressure is increased, we go through
three levels of activity: matrix cracking, fiber debonding and pull-
out, and fiber rupture on a massive scale with failure of the part.
Each level of activity is accompanied by an increase in the number
of events recorded.
Important areas of application cover inservice testing in the
chemical process, utility, and aerospace industries. These include
such specific items as tanks, chimney liners, pipe, rocket casings,
and man-lift booms.
Prices are steadily decreasing such that in 1985 a 16-channel
AE instrument that cost 75,000 dollars 10 years ago is now 14,000
dollars. The tests, which once required a scientist or specialist
at 3500 dollars a day, is now done by a technician at 1000 dollars
a day. About 10 companies are offering testing services in the
United States at 16 different locations. Mobile laboratories are now
available to run tests on the job site.
Probably, 7000 tank and vessel tests have been run and 10,000
pipe tests. At least 50,000 man-lift boom tests have been carried
out, with 20,000 being performed by one company alone. Codes
and standards, which cover piping, pressure vessels, tanks, and
man-lift booms, have been, and are being, developed by the SPI,
STM, and ASTM. In addition, as a laboratory tool, better fiber-
resin bonding can be developed. This alone is an event of major
importance because through studies in this area we can most effec-
tively use the materials at hand.
Acoustic emission does not replace the many current tests, but
it is intended to supplement them and allow a better understanding
382 Mallinson
and increased reliability of composite materials. The damage mecha-

nisms detected in FRP by acoustic emission testing are resin cracking,
debonding, fiber pull-out, fiber breakage, delamination, and bond
failure at assembled joints, such as nozzles, man-ways, and knuckles.
Obviously, unstressed areas will not generate AE.
Thickness Measurement [15,16]
Digital thickness sensors are available to measure the thickness

of linings and FRP-fabricated parts. Magnetic thickness sensors
require a magnet or metal wall on one side of the material to be
tested.
Linings
The conventional instrument (the Polygage CL; 15) measures non-

magnetic lining thicknesses up to 0.05 in., with an accuracy of
±0.01 in. This is particularly useful for tank-lining inspection to
make sure the applicator has met specifications. It can be used
for FRP, glass, lead, and rubber. The power supply is two 9-V
batteries, the weight is 14 oz, and the instrument is completely
portable.
Thickness of Fabricated Laminates [15,16]
In fabrication and inspection it is desirable to establish vessel or

pipe wall thickness to make sure specifications are met. One way
to do this is to examine cutouts, which should always be done
because this procedure permits direct observation of laminate thick-
ness and quality.
Digital Magnetic Thickness Sensors. The polygage CL [15] enables
observation of laminate thickness before removal from the mold to
make sure specifications have been met. Because it is applicable
to a rotating mold, the opportunity for a proper quality control
check is apparent. The instrument is not influenced by the density
of the material, by voids, or by delaminations. The standard capacity
is a solid-state model that measures thicknesses up to 1-1/4 in.
to an accuracy of ±0.01 in. and is powered by two 9-V batteries.
It will nondestructively measure the thickness for any nonmagnetic
material, such as FRP, other plastics, rubber, paper, nonferrous
metals, wood, and concrete. A magnetic backup must always be
present. A ceramic magnet is furnished when off-mold measurements
are desirable.
Ultrasonic Thickness Gauges in FRP Work. Another class of instru-
ment, which has wide use, depends upon ultrasonic waves to measure
the thickness of FRP laminates. One of these is the Kraut-Kramer-
Bronson Model CL 202 F [16] which has had a long history of

successful use. Briefly, it has a measuring range of 0.1 to 3.5 in.,
with an attainable precision of 0.01 in. and a resolution of 0.001 in.
Battery operated, portable, and hand-held, it can be used in the
temperature range of 40 to 120°F. The instrument measures the
time for the ultrasonic wave to make a round-trip from probe to
the opposite material surface and back. Because temperatures can
affect sound velocity, the temperature of the test should be the
same as the temperature of the laminate to be measured. A liquid
or paste couplant is used to exclude air between the transducer
and the clean surface.
The instrument is also useful in detecting voids and delaminations
in composite material. The velocity of sound in fiber resin composite
materials is a function of layup and may vary from 60,000-110,000
in./sec.
SANDWICH C O N S T R U C T I O N [2]
The use of fiberglass sandwich construction is common. Experience

that was initially gained in the boat industry spread into the chemical
industry. A typical sandwich is an end-grain Ecuadorian balsa with
fiberglass skins. The advantage is a tremendous increase in strength
at a relatively low cost. With such construction, economies of 20%
over solid FRP laminates are easily obtained in vessel construction.
Very large tanks, vapor heads, and rectangular vessels have been
built by using this construction technique. Other sandwiches consist
of honeycomb or foam cores and metallic or FRP skins. The use
of urethane as a sandwich material with FRP skins on both sides
is a real advance in building an FRP process vessel or tank that
operates at very low temperatures. In addition, the vessel—if suitably
specified—is literally corrosion-proof inside and out, because it is
immune to fumes, drippage, spillage, and accidental overflows that
would wreak havoc on a conventional insulation.
Examples of successful installations follows.
1. One such typical agitated vessel, serving as a crystallizer, has

been in service 15 years. It is 12 ft in diameter and 12-ft high,
holds 9500 gal, and cycles from 50°C (122°F) to 0°C (32°F) as
each batch is processed. A 10-mm (3/8-in.) inner shell is covered
with 25 mm (1 in.) of 2-lb/ft3 density urethane insulation. This,
in turn, is overlaid with 3 mm (1/8 in.) of FRP fire-retardant
resin.
2. Large duct systems, at slightly negative pressures of 4 in. H2O
and running 11 to 12 ft on a side, have been running 12 years.
These produced a savings of 30% over solid FRP construction.
384 Mallinson
3. Rectangular tanks are ideal for this construction because they

produce excellent stiffness in long walls. Many process vessels
have been built with this design.
4. Large-diameter, horizontal, cylindrical tanks of sandwich construc-
tion can achieve substantial economies over solid FRP because of
the high beam strength achieved.
5. The use of sandwich construction for tank lids is widely practiced,
particularly on large vessels. The lids are light, very stiff, and
very economical.
The use of sandwich laminates under high-vacuum conditions (2 to 4

in. Hg absolute) should be approached with caution. The key to
superior performance under these conditions is a perfect bond of
inner laminate to the core. Calculations, such as those performed
by Roark calculates maximum stress at bubble peak [17] case 1 and
indicate the size of debonding that can occur before trouble ensues.
At or near a complete vacuum, and with 9.5-mm (3/8-in.) skins
and a 38-mm (1.5-in.) balsa core laminate, the critical diameter
of unbonded surface is about 254 mm (12 i n . ) . Isolated spots of
25 to 50 mm (1 to 2 i n . ) at that thickness are of no concern. Such
construction is particularly adaptable to computer calculations, for
which a whole range of choices for any set of service conditions
permit the engineer the optimum choice. Debonding in thin skins
is easily seen as a white spot, or area, in an otherwise clear laminate.
Tap testing with a mallet or with a key to detect voids (hollow
versus solid) are present methods for detection of debonding. Sonic
testing in the hands of a skilled operator is also feasible. As the
laminate becomes heavier, physical inspection is more difficult.
Although most fabricators do not have the capability, a 48-hr test
at 50-mm (2-in. Hg absolute) pressure would be ideal to detect
the loss of a bond of sufficient size to cause trouble (this is for
full-vacuum service). The use of acoustic emission testing in conjunc-
tion with the vacuum test would be ideal because any debonding
occurring at the laminate-core interface would produce audible
signals.
Vacuum Service Failures

The observed mode of failure is debonding of the inner laminate
from the core, which forms a bubble. Often a crack will appear
in the laminate at the bubble, or at its base. This permits the
liquor to penetrate the core material. Depending on the core material,
various sequences may ensue. Balsa-cored material is highly vulnera-
ble to wicking, closed-cell urethane much less so. The repair consists
of removing all damaged core and replacement of the core and interior
laminate. An adhesive intensifier may be used to obtain a good

bond with the repair. Make sure that the core surface is thoroughly
saturated with resin. Layup on the wet resin core with a chopped
strand mat (at least four layers of 1.50-oz material). Make sure
that a good bond exists before proceeding with the layup.
Damage Control
In any sandwich construction, whether subject to positive or negative
pressure, damage control should be incorporated into the original
design. One method, which has been used extensively, has been
to isolate the core into square sections by tying together the interior
and outer skins with two to three layers of 1-1/2 oz. mat on a
3- to 4-ft grid. This would limit damaged areas to small sections
and prevent wicking, which can destroy a sandwich structure and
eventually result in catastrophic failure.
It is absolutely essential that every care be taken to obtain
a perfect bond of the sandwich material to the laminate; therefore,
the sandwich material should be rolled into the laminate in a very
thorough fashion. Patting it down with the hand is not adequate.
The outer limit of visually cured laminates is about 0.63-cm (1/4-in.)
skins: above that, acoustic emission procedures must be followed.
It is essential that the vendor guarantees the fabrication for 1 year
against defects, and in the event that they do occur, be prepared
to repair them promptly.
Cored construction has great cushioning properties, which can
be felt as well as heard; audible reactions in a vessel continue in
a very muted atmosphere.
ILLUSTRATED CASE HISTORIES
Figure 1 shows a marriage of the best plastics; each designed to

fulfill its purpose at an economical price.
1. A 12-ft diameter x 12-ft high FRP agitated vessel. Side walls

are:
100-mil corrosion barrier of a bisphenol resin

375 mil modular wound wall of an isophthalic polyester resin
1.0 in. of 2 lb/ft3 urethane foam for insulation
125-mil isophthalic protective covering over the insulation
2. 16 Teflon tube bundles. Calcium chloride brine at 15°F in the

tubes 10,000-gal rayon spin bath at 120 to 32°F outside the tubes.
386 Mallinson
Flat-Bottom Tanks
34
52
54
FIGURE 1 A marriage of the best plastics. A 10,000-gal FRP

crystallizer with 16 Teflon tube bundles to crystallize Glauber salts
from a rayon spin bath. (From Ref. 2, with permission.)
;" bolts-12" long ss.
washers ss.
f Gosket *
Neoprene hex nut s
Polyester duct
Nozzle-polyester
Pyroxylin cover
FIGURE 2 A sprinkler head protected against corrosion in an FRP

duct. (From Ref. 2, with permission.)
FIGURE 3 An 8-ft diameter FRP hydroelectric penstock in the Nova

Scotia Power Corporation Plant. (Courtesy ABCO Plastics, Mahone
Bay, Nova Scotia, Canada; from Ref. 2, with permission.)
388 Mallinson
FIGURE 4 A 180-ft high x 8.5-ft diameter FRP stack that handles

mill exhaust gas in Quebec. (Courtesy ABCO Plastics, Mahone Bay,
Nova Scotia, Canada; from Ref. 2, with permission.)
FIGURE 5 A 760,000-gallon Kabe-O-Wrap tank built to hold dilute

sulfuric acid. (Courtesy Metal Cladding, North Tonawanda, New
York; from Ref. 2, with permission.
3. Crystallization time for 7800-lb Na2SO4 batch was 2-1/2 to 3 hr

versus 5 to 6 hr for a vacuum crystallizer.
4. Service life 15 years.
Figure 2 illustrates a protected sprinkler head in an FRP duct.

The head is protected from corrosive fumes at 70 to 120°F by a
Pyroxylin (cellulose nitrate) cover. An alternate construction would
be to wrap the head with two 4-mil polyethylene bags. The head
is designed to be changed from outside the duct. The FRP duct
would be a chlorinated or brominated polyester, or a furan with
a flame spread of < 25.
Figure 3 is a 8-ft diameter hydroelectric penstock installed in
1980 by the Nova Scotia Power Corporation. It was fabricated by
ABCO Plastics of Vibrin F-106.5 isophthalic resin (Fiberglas Canada).
Many power companies and industrial concerns have taken advan-
tage of the corrosion-resistant properties of fiberglass and of its
immunity from tuberculation to install water lines and condensing
water systems. The backfill is being tamped to 70% of the pipe
diameter to ensure a good bedding for the pipe.
390 Mallinson
FIGURE 6 A helicopter acts as a sky derrick in lifting a 40-in.

diameter by 40-ft long plastic ductwork onto a plant roof. (From
Ref. 2, with permission.)
i i
392 Mallinson
Figure 4 pictures an 8.5-ft diameter stack 180-ft high that

handles mill exhaust gas. It is being installed at the CIP La Tuque,
P.Q. Canada mill in 1985.
Figure 5 shows a 760,000-gal tank, 60-ft diameter x 30-ft high,
that used a Kabe-O-Wrap design. It was built by Metal Cladding,
North Tonawanda, New York, to hold a dilute sulfuric acid solution.
The suspension bridge technique is used to support a panel-
assembled tank. A corrosion barrier seals each seam internally.
This technique has been particularly successful with large field-
erected tanks.
Figure 6 shows a sky derrick rigging. A 40-ft section of 40-in.
diameter ductwork is being lifted to previously prepared cradles.
The light weight of fiberglass makes rapid lifting and easy placement
a cost-effective method.
REFERENCES
1. Mallinson, J. H. (1972). Plastics: Trends in CPI Materials,

Chem. Eng. , Deskbook Issue, December 4.
2. Mallinson, J. H. (1987). Corrosion Resistant Plastic Composites
in Chemical Plant Design, Marcel Dekker, New York.
3. Modern Plastics Encyclopedia (1985). McGraw-Hill, New York.
4. Modern Plastics Encyclopedia (1977). Vol. 54, No. 10A, McGraw-
Hill, New York.
5. R. L. Industries, Inc. (1980). Miamitown, Ohio.
6. U.S. Dept. of Commerce (1969). NBS Voluntary Product Stand-
ard, PS 15-69 Custom Contact Molded Reinforced Polyester
Chemical Resistant Process Equipment.
7. Ashland Chemical Co. Columbus, Ohio, Hetron 197 R e s i n s -
product literature.
8. Dow Chemical Co. (1979). Corrosion Resistance Guide—Derakane
Resins, Midland, Michigan.
9. Rolston, J. A. (1980). Fiberglass, composites, and fabrication,
Chem. Eng. Jan. 28.
10. Bautista, T. O. (1980). "The Role of Synthetic Veil in the
Wear Factor of Corrosion Resistant Laminates," 35th Annual
Technical Conference, Society of the Plastics Industry.
11. Syzmanski, W. Ashland Chemical Co. Columbus, Ohio.
12. McClellan, W. W., Anderson, T. F . , and Stavrinola, R. F.
(1975). "Solvent Resistance of Reinforced Plastics," 30th Annual
Technical Conference Society of the Plastics Industry.
13. Burrell, P. P . , and Hearn, T. P. Solvent Resistance of Selected
Polyesters and Vinyl Esters, Interplastics Corp. Minneapolis,
Minn.
14. Fowler, T. J. (1986). "Acoustic Emission Comes of Age," 41st

Annual Conference, Society of the Plastic Industry.
15. R. C. Maybee Ltd. (1984). Polygage Literature, Oaksville,
Ontario, Canada.
16. Krautkrammer and Bronson Inc., Stratford, Conn.
17. Roark, R. J. Formulas for Stress and Strain Table X, p . 216.
Case 1, 4th Ed. 1965. McGraw Hill, N.Y., N.Y.
15
OF CERAMIC MATERIALS
RONALD A. McCAULEY Department of Ceramic Engineering,
Rutgers, The State University, New Brunswick, New Jersey
FUNDAMENTALS OF CORROSION
Introduction
Throughout the history of the materials industries, various material
types or compositions have been used because of some particular
advantageous intrinsic property. High strength, low electrical con-
ductivity, or some other property may be the primary concern for
a particular application. However, excellent resistance to attack
by the environment (corrosion) always plays a role and, sometimes,
may be the prime reason for the selection of a particular material.
This is especially true for those materials selected for furnace con-
struction in the metals and glass industries. Almost all environments
are corrosive to some extent. For practical applications it comes
down to a matter of kinetics—how long will a material last in a par-
ticular environment? Occasionally, corrosion may be beneficial, such
as in the preparation of samples by etching for microscopic evaluation.
The proper selection of materials and good design practices can
greatly reduce the cost caused by corrosion. To make the proper
selection, engineers must be knowledgeable in the fields of thermo-
dynamics, physical chemistry, and electrochemistry.
The corrosion of ceramic materials has not been as well categorized
as it has been for metals. Similar terms do, however, appear in
the literature. The more common types referred to in the literature
are diffusion corrosion, which is very similar to concentration cell
corrosion in metals; galvanic cell corrosion; grain boundary corrosion;
and stress corrosion. A more common trend in ceramic materials is
395
396 McCauley
to group corrosion under a more general mechanism, such as dis-

solution corrosion (i.e., corrosion of a solid by a liquid). In this
type of corrosion, diffusion, galvanic cell, grain boundary, and
stress corrosion all may be present.
Thermodynamics and Kinetics

In the selection of materials, an engineer wishes to select those
materials that are thermodynamically stable in the service environ-
ment. Because this is a particularly difficult task, a knowledge
of thermodynamics and kinetics is required so that materials can
be selected that have slow reaction rates or have harmless reactions.
Thermodynamics provides a means for the engineer to understand
and predict the chemical reactions that take place. The reader is
referred to any of the numerous books on thermodynamics for a
more detailed discussion of the topic. Only a brief summary will
be given here.
The driving force for corrosion is the reduction in free energy
of the system. In general, a reaction can occur if the free energy
of the reaction is negative. The free energy of the reaction is given
by
AF = AH - TAS
where
AF = Gibbs free energy

AH = heat of formation
T = absolute temperature
A S = entropy of reaction
The quantities necessary to calculate AF are available for most

pure compounds. These published values are for standard states,
and any changes from standard states require calculation using
AF = AF° + RT In k
where
AF° = free-energy change at standard state

R = gas constant
k = concentration constant
At equilibrium the change in free energy must be zero; therefore,

15. Ceramic Materials 397
AF° = -RT In k
Thus, the value of k can be calculated at any temperature.

The importance of the entropy term increases with temperature.
The reactions of concern involving ceramic materials are predominantly
those at temperatures at which the entropy term may have consider-
able effect on the reactions. In particular, species with high entropy
values have a greater effect at higher temperatures.
The real problem with predicting whether or not a reaction may
take place is in selecting the proper reaction to evaluate. Care
must be taken not to overlook some possible reactions.
Because the corrosion of ceramics in service may never reach
an equilibrium state, thermodynamic calculations cannot be strictly
applied because these calculations are for systems in equilibrium.
Many reactions, however, closely approach equilibrium and, thus,
the condition of equilibrium should be considered only as a limitation,
not as a barrier.
It is normally expected that materials will corrode and, thus,
it is important to know the kinetics of the reaction so that predictions
of service life can be made. Reaction rates for condensed-phase
processes normally involve the transport of products away from
the boundary. Thus, the rate of the overall process is determined
by the rate of each individual step and on the reaction rate constant
and concentration of reactants for that step. The reaction with the
lowest rate determines the overall rate of the corrosion process.
Some of the more important factors that may influence the rate
of reaction are diffusion rates, viscosity, particle size, and the
degree of contact or mixing.
The Arrhenius equation
k =
where
k = reaction rate constant

A = constant
Q = experimental activation energy
R = gas constant
describes the effect of temperature on the rate process.

For corrosion rates to be useful to practicing engineers, it is
best that they be expressed in a meaningful manner. Usually, the
engineer is involved with the amount of material corroded away
during a specified time or with the depth of penetration per unit
398 McCauley
time. In the literature, corrosion rates are often given in the weight
of material reacted per unit area for a unit time. These can easily
be converted to the depth of penetration per unit time by dividing
by the density of the material. Another useful rule for the engineer
to remember is that the temperature at which diffusion-controlled
reactions first become observable is at about one-half the melting
point in degrees Kelvin.
Polycrystalline Ceramic Materials

General
Most, if not all polycrystalline materials can be looked on as com-
prising several components. The minor components may make up
as much as 50% of the total or as little as a fraction of 1%. See
Figure 1 for a typical microstructure. It is the combination of
FIGURE 1 Microstructure of an alumina-zirconia-silica refractory.

Reflected oblique illumination (magnification 200X). Brightest areas
are ZrO 2» next darker areas are A12O3, next darker areas are
silicate glass (diagonal area across middle) and the few darkest
spots are pores.
properties of these various components and how they are bonded

together that gives a material its unique properties.
If one were to group together all the secondary additives or
components of a particular composition that are used for any number
of reasons (bonding agents, mineralizers, grain-growth inhibitors,
and so on, a material would consist of two groups of components:
the major components or phases that exhibit the desired properties
for a certain application, and the minor components or phases that
have been added to enhance or modify the desired properties. It
is these minor components that are, usually, of primary concern
to corrosion resistance. Porosity should be included as one of these
components and, in general, would be a minor component. The
corrosive attack of a ceramic polycrystalline material starts with
the least corrosion-resistant component, which is normally that
component used for bonding or, more generally, the minor components
of the material.
The effects of these minor components have presented the indus-
tries that manufacture and consume these materials with a constant
struggle to optimize material properties for a particular application.
The trend has been toward purer starting materials and higher
firing temperatures. In this way, less modification of the desired
final properties is caused by the secondary components. More
recently, efforts have been expanded to include the development
of newer processes such as hotpressing, reaction bonding, and
chemical vapor deposition. See Table I for a comparison of manufac-
turing techniques.
The corrosion of polycrystalline materials will be discussed in
a general fashion taking into account the state of the environment:
vapor, liquid, or solid. Occasionally, the environment may not pro-
vide any real corrosion effects of its own but may function only
in relation to temperature. Any corrosion that does take place will
occur at a faster rate at higher temperatures. It is generally accepted
that many reactions double their rate for every 10° rise in tempera-
ture. There may be a situation, however, in which corrosion does
not take place unless the temperature somehow alters the polycrystal-
line material to the point that it is susceptible to corrosion.
A good source of information on the effects of temperature are
equilibrium phase diagrams. Thousands of these diagrams have
been published by the American Ceramic Society [1], The most
obvious effect of temperature is that of melting. A more subtle
effect in real materials is the partial melting of the secondary,
or bonding, phases. One should, however, have an understanding
of how the properties are affected by temperature. Polymorphic
transformations play an important role in the design of high-quality
materials. Thermal expansion mismatch of various components is
400 McCauley
TABLE 1 Comparison of Manufacturing Techniques
Process Reaction Result
Vitrification Partial melting of Very dense;

powders impervious; low high
temp, strength; cheap
Sintering Solid state diffusion High density; requires
(pressureless or with small amount more additives than
sintering) of liquid hot pressing; 20%
shrinkage; cheap
Reaction bonding/ Chemical reaction Low density; 10-20%
reaction sintering forms new phases in porosity; 0% shrinkage;
already shaped moderate strengths;
compact inexpensive
Hot pressing Pressure applied Maximum density but
with liquid phase limited high-temperature
sintering strength; very expen-
sive
Chemical vapor Chemical reaction Maximum density and
deposition purity; high strength;
expensive
also important. High thermal expansion anisotropy of individual

crystals can cause severe cracking, allowing a corrosive medium
to enter into a material.
To understand how corrosion takes place, one must have a
thorough understanding of how the material is constructed. The
distribution of phases is particularly important in describing bonding
mechanisms and corrosion. In a system with a secondary liquid
phase, the degree of solid-solid contact is extremely important and
desirable for high-temperature strength. A small amount of liquid,
if it completely wets the solid phase, can produce a weak material,
as opposed to one that may contain a larger amount of solid contact.
This fact was brought out by Van Vlack [2], who reported that
a higher liquid content silica refractory did not deform during heat-
ing, whereas a magnesiowustite refractory slumped during heating,
although it contained a lower liquid content. Van Vlack stated:
"Less energy is required to form two interfaces between two peri-
clase grains." This energy requirement, however, is removed in
the silica example. Van Vlack reported that even though a silicate
liquid will penetrate between two periclase or magnesiowustite grains,
it will not penetrate to as great an extent between a magnesiowustite

and a spinel grain.
The distribution of phases, which is obviously important, is
determined by a balance of surface tension forces between the inter-
faces or boundaries of the various phases. According to White [3],
for a phase 3 to surround completely a second phase a, we need
y a a £. 2 ya$ where y a a is the interfacial surface tension between
two a grains and ya3 * s the interfacial surface tension between
an a and a 3 grain. If y a a < ^â3» complete penetration will not
occur. When y a a = 2ya$ cos 0/2, a balance of forces is obtained.
The angle e is the equilibrium dihedral angle between intersecting
a and 3 interfaces. As 6 increases from 0 to 60°, penetration of
3-phase between the a grains will decrease. When 0 > 60°, however,
the 3-phase will occur as discrete inclusions. Thus, the obvious
step to take to increase solid-solid contact would be to change those
variables that yield 0 > 60°; however, the 3-phase will occur as
discrete inclusions. It has been found by White [3] in MgO systems
that by lowering the density and the mean grain size, 0 will increase.
This, in turn, will decrease the grain surface curvature. White
also found that the introduction of chromic oxide will increase 0,
whereas iron oxide will decrease 0 and, at a given composition,
0 will decrease with increasing temperature.
It may not always be desirable to keep the secondary 3-phase
as discrete inclusions, as pointed out by Rigby [4]. He described
a thin-film theory whereby a silicate phase becomes molten at high
temperature and coats the individual grains and, thus, upon cooling,
acts as a strong-bonding thin film. As long as service temperatures
are below the point where the thin film remains solid, materials of
this type will retain their strength. The strength of the material
will then depend on the ability of silicate to coat the individual
grains.
Attack by Vapor
The corrosion of a polycrystalline ceramic by vapor attack can be
exceedingly serious, much more so than attack by either liquids
or solids. One of the most important material properties related
to vapor attack is that of porosity or permeability. If the vapor
can penetrate the material, the surface area exposed to attack is
greatly increased and corrosion proceeds rapidly. It is the total
surface area exposed to attack that is important. Thus, not only
is the volume of porosity important, but so is the pore size distribu-
tion.
Vapor attack can proceed by producing a reaction product that
may be either solid, liquid, or gas, as in the equation
402 McCauley
As + B g - CS)1>g
As an example, the attack of SiO2 by Na2O vapors can produce
a liquid sodium silicate.
In another type of vapor attack, the vapor may penetrate a
material under thermal gradient to a lower temperature, condense,
and then dissolve material by liquid solution. The liquid solution
can then penetrate further along temperature gradients until it
freezes. If the thermal gradient of the material is changed, it is
possible for the solid reaction products to melt, causing excessive
corrosion and spalling at the point of melting.
A possible rate-controlling step in vapor attack is the rate of
arrival of a gaseous reactant and, possibly, also the rate of removal
of a gaseous product. It is obvious that a reaction cannot proceed
any faster than the rate at which reactants are added, but it may
proceed much more slowly. The maximum rate of arrival of a gas
can be calculated from the Hertz-Langmuir equation
Z =
1IZ
( 2 7T M R T )
where
Z = moles of gas that arrive at surface in unit time and over

a unit area
P = partial pressure of reactant gas
M = molecular weight of gas
R = gas constant
Using P and M of the product gas, the rate of removal of gas
product can be calculated using the same equation. To determine
if service life is acceptable, these rates may be all that are needed.
Actual observed rates of removal may not agree with those calculated
if some surface reaction must take place to produce the species
that vaporizes. The actual difference between observed and calculated
rates depends on the activation energy of the surface reaction.
If the gaseous reactant is at a lower temperature than the solid
material, an additional factor of heat transfer to the gas must also
be considered and may limit the overall reaction.
Pilling and Bedworth [5] have reported the importance of knowing
the relative volumes occupied by the reaction products and reactants.
Knowing these volumes can aid in determining the mechanism of
the reaction. When the corrosion of a solid by a gas produces another
solid, the reaction proceeds only by diffusion of a reactant through
the boundary layer when the volume of the solid reactant is less
than the volume of the solid reaction product. Here, the reaction
rate decreases with time. If the volume of the reactant is greater
than the product, the reaction rate is usually linear with time.
These rates are only guidelines because other factors can keep
a tight layer from forming (e.g., thermal expansion mismatch).
Atack by Liquid
The basic theory of corrosion by liquids in ceramic systems has
been described in detail by Cooper and Kingery [6]. The basic
equation describing the rate of solution under free convection with
density being the driving force is
- fl wzl £AP \ D-3/^ r* pxn 6

]
" ° - 5 ° 5 V ViX ) D
l ° eXP
VR + 6*/i)
where
g = acceleration resulting from gravity
P i ~ Poo
Ap = (p^ = saturated liquid density and pOT = original
liquid density)
VJ = kinematic viscosity
x = distance from surface of liquid
Dj = interface diffusion coefficient
C* = a concentration parameter
6* = effective boundary layer thickness
R = solute radius
The exponential term was introduced as a correction for cylindrical

surfaces. Because experimental tests often involve cylindrical speci-
mens, these equations have been developed for that geometry. In
practical applications, the condition relating to the corrosion of
slabs is the most predominant. However, if the sample diameter
is large compared with the boundary layer thickness, the two geome-
tries give almost identical results.
After a short induction period (which is of no consequence in
practical applications) in which molecular diffusion predominates,
the rate of corrosion becomes nearly independent of time. As a
surface corrodes the interface, if denser than the corroding medium,
will be eroded away owing to free convection caused by density
variation. Many corrosive environments involving ceramic materials
involve diffusion in the corroding medium and, thus, increased
velocity of the medium increases corrosion. Therefore, if transport
404 McCauley
in the liquid is important the corrosion rate must be evaluated under

forced convection conditions. Here, the rate will depend on the
velocity of forced convection.
j= <
The terms D* and v* were introduced because diffusivity and vis-
cosity may be composition-dependent. The important point of this
equation is that the rate of corrosion depends on the square root
of the angular velocity w.
Hrma [9] has used the work of Cooper and Kingery [6] to dis-
cuss further the rates of corrosion of refractories in contact with
glass. The following equation given by Hrma describes the corrosion
under the condition of free convection resulting from density differ-
ence:
D3APS
where
jc = rate of corrosion
Ac = solubility of material in liquid
D= coefficient of binary diffusion
g = acceleration resulting from gravity
v = kinematic viscosity
L = distance from surface of liquid
Ap = relative variation of density
k = constant
This is essentially the same equation as that of Cooper and Kingery,

without the exponential term.
In most practical cases, the solubility of the material in the
liquid and the density of the liquid change much slower than the
viscosity of the liquid. Under isothermal conditions the viscosity
change is due to compositional changes. Thus, the predominant
factor in the corrosion of a material by a liquid is the viscosity
of the liquid. This relationship holds quite well for the corrosion
of a solid below the liquid surface. At the surface where three
states of matter are present, the corrosion mechanism is different
and much more severe.
At the liquid surface a sharp cut normally develops in the verti-
cal face of the solid material being corroded. This region has been
called flux line, metal line, or glass line corrosion. Pons and Parent
[10] reported that the flux line corrosion rate was a nonlinear func-
tion of the oxygen potential difference between the surface and

the interior of a molten sodium silicate. Cooper and Kingery [6]
reported that flux line corrosion was the result of natural convection
in the liquid caused by surface forces. Hrma [9] reported that
the additional corrosion at the flux line depended only on the varia-
tion in surface tension and density, with surface tension being
the more important factor.
Downward-facing horizontal surfaces also exhibit greater corrosion
than does a vertical or upward-facing horizontal surface. A downward-
facing surface can exhibit excessive corrosion if bubbles are trapped
beneath the horizontal surface. This is known as upward drilling
because it results in vertically corroded shafts. Surface tension
changes around the bubble cause circulatory currents in the liquid
that cause excessive corrosion very similar to flux line corrosion.
The chemical species present in the liquid will determine whether
it is of an acidic or a basic character. Ceramics with an acidic/basic
character similar to the liquid will tend to resist corrosion the best.
The solubility of materials in liquids can be obtained from phase
diagrams that give the saturation composition at a given temperature.
Unfortunately, for many practical systems, phase diagrams are
either very complex or nonexistent. Many data are available, however,
for two- and three-component systems, and these should be consulted
before attempting to evaluate the corrosion of a specific material.
A good discussion on the use of phase diagrams in dissolution studies
is that by Cooper [11],
The corrosion of multicomponent materials proceeds through the
path of least resistance. Thus, those components with the lowest
resistance are corroded first. The corrosion of a fusion cast alumina-
zirconia-silica refractory will be used as an example. This particular
material is manufactured by fusing the oxides, casting into a mold,
and then allowing crystallization to occur under controlled conditions.
The final microstructure is composed of primary zirconia, alumina,
alumina with included zirconia, and a glassy phase that surrounds
all the other phases (see Fig. 1). The glassy phase (about 15%
by volume) is necessary for this material to provide a cushion for
the polymorphic transformation of zirconia during cooling and subse-
quent use. This material is widely used as a basin-wall material
in the soda-lime silica glass furnace. The corrosion proceeds by
the diffusion of Na+ ions from the bulk glass into the glassy phase
of the refractory. As Na+ is added to the glass, its viscosity is
lowered, and it becomes corrosive toward the refractory. The corro-
sion next proceeds by solution of the alumina and finally by partial
solution of the zirconia. Under stagnant conditions, an interface
of zirconia embedded in a high-viscosity glass is formed. In actual
service conditions, however, the convective flow of the bulk glass
406 McCauley
erodes this interface, allowing continuous corrosion to take place

until the refractory is consumed. This type of corrosion can take
place in any multicomponent material in which the corroding liquid
diffuses into a material that contains several phases of varying
corrosion resistance.
Much work has been done over the past 30 years on the galvanic
corrosion of refractories by glasses. Godrin [12] has published
a review of the literature on electrochemical corrosion of refractories
by glasses. It has been shown that a potential difference does exist
in such systems; however, the application of a bias potential has
been unsuccessful in eliminating corrosion. Even though not totally
foolproof, Godrin concluded that refractories that have an electrical
potential relative to glass that is positive 0.4 to 0.7 V are fairly
resistant to corrosion, that refractories with a potential greater
than 1.0 V have rather, poor resistance, and that refractories that
have a negative potential relative to glass should not be used.
Attack by Solids
Many applications of materials involve two dissimilar solid materials
in contact. Corrosion can occur if these materials react with one
another. Common types of reactions involve the formation of a third
phase at the boundary, which can be a solid, a liquid, or a gas.
Occasionally, the boundary phase may be a solid solution of the
original two phases. Again, phase diagrams will give an indication
of the type of reaction and the temperature at which it occurs.
When the reaction that takes place is one of diffusion, such
as a movement of atoms within a chemically uniform material, it
is called self-diffusion. When a permanent displacement of chemical
species occurs, causing local composition change, it is called inter-
diffusion or chemical diffusion.
The driving force for chemical diffusion is a chemical potential
gradient (concentration gradient). When two dissimilar materials
are in contact, chemical diffusion of the two materials in opposite
directions forms an interface reaction layer. Once this layer has
been formed, additional reaction can take place only by the diffusion
of chemical species through this layer.
Solid-solid reactions are predominantly reactions involving diffu-
sion. Diffusion reactions are really a special case of the general
theory of kinetics discussed previously. Thus, diffusion can be
represented by an equation of the Arrhenius form
D =D
where
D = diffusion coefficient
Do = constant
Q = activation energy
R = gas constant
The larger the value of Q, the activation energy, the more strongly
the diffusion coefficient depends on temperature.
The diffusion in polycrystalline materials can be divided into
bulk diffusion, grain boundary diffusion, and surface diffusion.
Diffusion along grain boundaries is greater than bulk diffusion
because of the greater degree of disorder along grain boundaries.
Similarly, surface diffusion is greater than bulk diffusion. When
grain boundary diffusion predominates, the log concentration de-
creases linearly with the distance from the surface. When bulk
diffusion predominates, however, the log concentration of the diffu-
sion species decreases with the square of the distance from the
surface. Thus, by determining the concentration gradient from
the surface (at constant surface concentration) one can determine
which type of diffusion predominates.
Because grain boundary diffusion is greater than bulk diffusion,
it would be expected that the activation energy for boundary diffu-
sion would be lower than that for bulk diffusion. The boundary
diffusion is more important at lower temperatures, and bulk diffusion
is more important at high temperatures.
Chemical reactions wholly within the solid state are less abundant
than those that involve a gas or liquid, primarily owing to the
limitation of reaction rates imposed by slower material transport.
The solid-solid contact of two different bulk materials also imposes
a limitation on the intimacy of contact—much less than that between
a solid and a liquid or gas.
Applications of ceramic materials commonly involve thermal gradi-
ents. Under such conditions it is possible for one component of
a multicomponent material to diffuse selectively along the thermal
gradient. This phenomenon is called thermal diffusion or the Soret
effect. This diffusion along thermal gradients is not well understood,
especially for ceramic materials.
The stability of various materials to graphite is a good example
of a solid-solid reaction. Here, however, at least one of the products
is a gas. The stability of a few selected refractory oxides in contact
with graphite increases in the order TiO 2 , A12O3, ThO 2 , MgO,
MgAÔ^, SiO 2 , and BeO, as reported by Klinger et al. [13].
Miller et al. [14] have shown that carbon reacts with SiO2 to
form the intermediate phase SiC, which then reacts with silica to
form the gaseous phase SiO. The following equations were given
to represent the reaction:
408 McCauley
SiO2 + 3C + SiC + 2CO

2SiO2 + SiC + 3SiO + CO
They stated that these reactions were sufficiently rapid at 1000°C

(1830°F) and in the presence of iron, which acts as a catalyst for
the reduction of silica by SiC, to cause failure of silicate refractories
in coal gasification atmospheres.
Because of the prevalence of platinum metal in various research
and manufacturing operations, the reactions of various refractory
oxides with platinum is of considerable importance. Ott and Raub
[15] reported that platinum acts as a catalyst for the reduction
of refractory oxides by hydrogen, carbon, CO, and organic vapors.
These reactions can occur as low as 600°C (1110°F) and result
from the affinity of platinum for the metal of the oxide by forming
intermetallic compounds and crystalline solutions.
Glassy Materials
General
This discussion will be concerned only with those materials that
fall under the conventional definition of a glass: specifically, amor-
phous materials produced by the fusion of inorganic materials and
then cooled at a rate that prevents crystallization. A complete dis-
cussion of all noncrystalline ceramic materials could very easily
occupy an entire book; thus, those materials that do not fall under
the definition of a glass as just given are excluded here.
Clark et al. [16] have recently published a book on the corrosion
of glass in which they not only describe the mechanisms of corrosion
but also discuss various techniques for analyzing the type and
degree of corrosion. However, their discussion is limited to silicate
glasses.
Attack by Vapor
The corrosion of glasses by atmospheric conditions, referred to
as weathering, is essentially an attack by water vapor. Weathering
occurs by means of one of two mechanisms. In both types, condensa-
tion occurs on the glass surface; however, in one type it evaporates,
whereas in the other it collects to the point that it flows from the
surface, carrying any reaction products with it. The latter type
is very similar to corrosion by aqueous solutions. The former type
is characterized by the formation of soda-rich films, according to
Tichane and Carrier [17]. This soda-rich film has been shown to
react with atmospheric gases such as CO2 to form Na2CO3, according
to the work of Simpson [18] and Tichane [19].
Metcalfe and Schmitz [20] studied the stress corrosion of E-glass

(borosilicate) fibers in moist ambient atmospheres and proposed
that ion exchange of alkali by hydrogen ions led to the development
of surface tensile stresses that could be sufficient to cause failure.
In soda-lime-silica glasses, atmospheric corrosion by water vapor
has been reported to halve the breaking strength [21].
Attack by Liquid
Probably the most abundant examples of glass corrosion are those

caused by a liquid. Release of toxic species (such as PbO) from
various glass compositions has received worldwide interest during
the past 15 to 20 years. Although glass is assumed by many to
be inert to most liquids, it does slowly dissolve. Usually, however,
the species released are not harmful.
The corrosion resistance of glasses is primarily a function of
composition. Glasses can be soluble under a wide range of pH values
from acids to bases, including water. Water-soluble sodium silicates
form the basis of the soluble silicate industry which supplies products
for the manufacture of cements, adhesives, cleansers, and flocculants.
At the other extreme are glasses designed for maximum resistance
to corrosion. In general, very high silica (>96% SiO2), aluminosilicate,
and borosilicate compositions have excellent corrosion resistance to
a variety of environments. Silicate glasses, in general, are less
resistant to alkali solution than they are to acid solution. A list
of about 30 glass compositions with their resistance to weathering,
water, and acid has been published by Hutchins and Harrington [22].
The attack of silica or silicate glasses by aqueous hydrofluoric
acid provides a good example of how the mechanism of corrosion
proceeds. Ernsberger [23] has described this attack in detail and
related it to the structure of silica glasses. The silicon-oxygen
tetrahedra are exposed at the surface in a random arrangement
of four possible orientations. Protons from the water solution will
bond with the exposed oxygens, forming a surface layer of hydroxyl
groups. The hydroxyl groups can be replaced by fluoride ions in
aqueous hydrofluoric solutions. Thus, the silicon atoms may be
bonded to an OH" or and F~ ion. The replacement of exposed oxygens
of the tetrahedron by 2F" causes a deficiency in the silicon atom
coordination, which is 6 relative to fluorine. This causes the addi-
tional bonding of fluoride ions, with a particular preference for
bifluoride. Thus, the four fluoride ions near the surface provide
an additional four-coordinated site for the silicon. A shift of the
silicon to form SiF^ can take place by a small amount of thermal
energy. The ready availability of additional fluoride ions will then
cause the (SiF6)2~ ion to form. This mechanism is supported by
data that show a maximum in corrosion rate with bifluoride ion con-
centration .
410 McCauley
The rate of corrosion of a glass that contains a cation that can

increase its coordination will be greater than one that contains a
cation that cannot increase its coordination. This coordination in-
crease was discussed earlier for SiO2 attacked by aqueous hydro-
fluoric acid.
According to Charles [21], the corrosion of an alkali-silicate
glass by water proceeds through three steps.
1. H+ from the water penetrates the glass structure. This H+

replaces an alkali ion, which goes into solution. A nonbridging
oxygen is attached to the H+.
2. The OH" produced in the water destroys the Si-O-Si bonds,
forming nonbridging oxygens.
3. The nonbridging oxygens react with an H2O molecule, forming
another nonbridging oxygen -H+ bond and another OH" ion.
This OH" repeats step 2. The silicic acid thus formed is soluble
in water under the correct conditions of pH, temperature, ion
concentration, and time.
The development of films on the glass surface has been described

by Sanders and Hench [24]. The nonbridging oxygen -H+ groups
may form surface films or go into solution. The thickness of this
film and its adherence greatly affect the corrosion rate. In Na2O-
SiO2 glasses, Schmidt [25] found that films formed only on glasses
containing more than 80 mol% SiO2 at 100°C (212°F) for 1 hr.
Budd [26] has described the corrosion of glass by either an
electrophilic or a nucleophilic mechanism, or both. The surface
of the glass has electron-rich and electron-deficient regions exposed.
Various agents attack these regions at different rates. Exposed
negatively charged nonbridging oxygens are attacked by H+ (or
H3O+), whereas exposed network silicon atoms are attacked by
02", OH", and F".
Budd and Frackiewicz [27] found that by crushing glass under
various solutions, an equilibrium pH value was reached after suffi-
cient surface area was exposed. The value of this equilibrium pH
was a function of the glass composition, and it was suggested that
it was related to the oxygen ion activity of the glass. When foreign
ions were present, the amount of surface required to reach an
equilibrium pH was greater.
The rate of hydrolysis of a glass surface is one of the major
factors that delineates the field of commercial glasses. The rate
of hydrolysis is of great importance because it determines the service
life of a glass relative to weathering or corrosion and, also, because
it influences the mechanical properties. Glass fracture is aided by
hydrolysis. The rate of hydrolysis of alkali-silicate glasses of the
same molar ratios proceeds in the order Cs > K > Na > Li.
Sanders and Hench [24] showed that a 33 mol% Li2O glass

corroded more slowly than a 31 mol% Na2O glass by two orders
of magnitude. This difference was caused by the formation of a
film on the Li2O glass with a high silica content. Scratching the
glass surface produced an unusually high release of silica.
In borosilicate glasses that require a heat treatment step after
initial melting and cooling to produce phase separation, a surface
layer is formed by selective evaporation of Na2O and B 2 O 3 . These
surface layers have been observed by several workers. This silica-
rich surface layer can influence the subsequent leaching process
that would be needed to produce Vycor-type glass [28]. If the
hydrated surface layer is removed before heat treatment, the silica-
rich layer is almost entirely eliminated.
Yoon [29] found that lead release was a linear function of pH
when testing lead-containing glasses in contact with various bever-
ages. Low pH beverages, such as orange juice or colas, leached
lead more slowly than did natural pH beverages, such as milk.
This dependence on pH was also reported by Das and Douglas [30]
and by Pohlman [31]. Later, Yoon [32] reported that if the ratio
of moles of lead plus moles of alkali per moles of silica were kept
below 0.7, release in 1 hr was minimized. If this ratio is exceeded,
lead release increased linearly with increasing PbO content. Lehman
et al. [33] reported a slightly higher threshold for more complex
compositions containing cations of Ca2+ and Al3+ or B 3 + in addition
to the base Na2O-PbO-SiO2 composition. The lead release in these
complex compositions was not linear but increased upward with
increased moles of modifiers. Lehman et al. related the mechanism
of release or corrosion to the concentration of nonbridging oxygens.
A threshold concentration was necessary for easy diffusion of the
modifier cations. This threshold was reported to be where the num-
ber of nonbridging oxygens per mole of glass-forming cations
equaled 1.4.
In general, mixed alkalies lower the release of lead by attack
from acetic acid below that of a single alkali-PbO-silicate glass;
lead release increases with increasing ionic radius of the alkaline
earths; however, combinations of two or more alkaline earths exhibit
lower lead release; A12O3 and ZrO2 both lowered the lead release,
and B2O3 increased it. Thinner glaze coatings on clay-based ceramic
bodies decreased lead release owing to interaction of the glaze and
the body, providing higher concentration of A12O3 and SiO2 at
the glaze surface [34].
The mechanism of release or corrosion for these glasses containing
lead is similar to those proposed by Charles [21] for alkali-silicate
glasses. The rate of this reaction depends on the concentration
gradient between the bulk glass and the acid solution and the
412 McCauley
diffusion coefficient through the reacted layer. In general, maximum

durability can be related to compact strongly bonded glass struc-
tures that, in turn, exhibit low thermal expansion coefficients and
high softening points [35].
Several workers have investigated the concentration profiles
of glass surfaces after leaching by water. Boksay et al. [36] postu-
slated a theory to explain the profiles in K2O-SiO2 glass, Doremus
[37] developed a theory to explain the profiles in Li2O-SiO2 glass,
and Das [38] attempted to explain the profiles in Na2O-SiO2 glasses.
Douglas and coworkers [39-42] found that alkali removal was
a linear function of the square root of time in alkali-silicate glass
attacked by water. At longer times the alkali removal was linear
with time. Wood and Blachere [43] investigated a 65SiO2-10K2O-
25PbO (mol%) glass and did not find a square root of time dependence
for removal of K or Pb, but they found a dependence that was
linear with time. This behavior has also been reported by Eppler
and Schweikert [44] and by Douglas and coworkers. Wood and
Blachere [43] proposed that an initial square root of time dependence
occurred, but that the corrosion rate was so great that it was missed
experimentally.
During the study of the corrosion by water of soda-lime-silica
glasses containing P 2 O 5 , Clark et al. [45] found that a double
reaction layer was formed consisting of a silica-rich region next
to the glass and a Ca-P-rich reaction next to the water solution.
This Ca-P film eventually crystallizes into an apatite structure and
provides a good mechanism to bond the glass to bone in implant
applications.
Katayama et al. [46] determined that the corrosion of a barium
borosilicate glass decreased in the order acetic, citric, nitric, tar-
taric, and oxalic acid, all at a pH of 4 at 50°C (122°F).
A discussion of glass would not be complete if some mention
of glass fibers was not made. The corrosion of fibers is inherently
greater than bulk glass simply because of the larger surface/volume
ratio. Because one of the major applications of fibers is as a rein-
forcement to some other material, the main property of interest is
that of strength. Thus, any corrosion reactions that would lower
the strength are of interest. This effect is important both when
the fiber is being manufactured and after it has been embedded
in another material. The strength of E-glass fibers in dry and
humid environments was studied by Thomas [47], with the observa-
tion that humid environments lower strength.
The study of phosphate glass corrosion has shown that the glass
structure plays a very important role in the rate of dissolution.
Phosphate glasses are characterized by chains of PO^ tetrahedra.
As the modifier (alkalies or alkaline earths) content of these glasses
increased, there is increased cross-linking between the chains.

When very little cross-linkage exists, corrosion is high. When the
amount of cross-linkage is high, corrosion is low. Similar phenomena
should exist for other glass-forming cations that form chain struc-
tures (B 3+ and V 5 + ).
Carbon and Carbon- and Nitrogen-Containing

Ceramic Materials
General
The corrosion of carbon and carbon and nitrogen-containing materials
is synonymous with oxidation. Sometimes (e.g., SiC), initial oxidation
forms a protective layer that prevents further oxidation. This is
called passive corrosion. The rate of oxidation depends on the
stability and texture of the oxide layer formed and is low when
a coherent film forms and high when a porous film forms or one
that is highly volatile or melts. In nonoxidizing environments the
corrosion is one of dissociation. The mechanisms of oxidation vary
among these materials and are still not fully understood for many
of them.
Carbon Materials
The predominant corrosion "mechanism of carbon-type materials is
one of oxidation. The oxidation of pyrolytic graphite has been
separated into two regions with increasing temperature [48]. Oxida-
tion is reaction rate controlled at low temperatures and diffusion
controlled at high temperatures, with the changeover slightly above
840°C (1545°F). Above 2500°C (4530°F) sublimation rates exceed
oxidation rates.
The oxidation of pitch-coke graphite is much greater than that
of pyrolytic graphite in the low-temperature region because of the
greater ease of oxidation of the binders used in pitch-coke graphite
and the greater inherent porosity.
Diefendorf [49] studied the effect of atmosphere on the strength
of graphite and concluded that it was a stress corrosion phenomenon.
Tests conducted in vacuum or in argon, or a combination, gave
higher strengths than in air.
Some aspects of the corrosion of carbon brushes have been dis-
cussed by Millet [50]. He concluded that humid air produced oxidation
of the surface between the carbon brush and the metal ring and
that a surface layer of water molecules formed. His data showed
that wear rates were also greater for humid air than for dry air
at 80 to 120°C (175 to 250°F) but lower for temperatures between
40 and 70°C (105 and 160°F). Moberly and Johnson [51] reported
414 McCauley
a critical humidity level of 0.12 g H2O/ft3 to avoid excessive electro-

graphitic brush-wear rates on copper rings. The critical level was
0.8 g/ft3 for graphite collector brushes on steel rings. The ideal
level was stated to be 2 g/ft 3 .
Robinson et al. [52] studied the alkali attack of carbon refrac-
tories and found that the primary mechanism of attack by alkali
was as a catalyst for oxidation. They also found that CO2 vapors
oxidize carbon at 1000°C (1830°F) with a rate that increases as
the CO2/CO ratio increases. It was indicated that a 100% CO environ-
ment caused zero attack. Alkali impurities (as carbonates, chlorides,
or hydroxide) within the carbon refractory acted to lower the initia-
tion temperature of reaction. Robinson et al. also investigated the
attack of molten alkali hydroxides and carbonates on carbon. The
molten hydroxide penetrated the porosity, reacted with the carbon
to form a carbonate, and caused cracking because of the expansion
on conversion from hydroxide to carbonate. Several authors [53-55]
have studied the corrosion of carbon by various alkali compounds,
but Robinson et al. [52] apparently were the most definitive, espe-
cially for reactions that occur in a blast furnace.
Carbides and Nitrides
None of the carbides and nitrides are stable in oxygen-containing

environments. Silicon carbide exhibits the greatest resistance by
forming a protective layer of silica on the surface. Some other
carbides and nitrides also form a protective metal oxide layer that
allows them to exhibit moderately good oxygen resistance (e.g.,
Si3Al303N5 forms a protective layer of mullite).
The oxidation of Si3Nlf has been described as occurring by either
an active or a passive mechanism [56]. The active mechanism is one
in which the fugitive SiO forms in environments with low partial
pressures of oxygen by the reaction
2 8 ^ ( 8 ) + 302(g) + 6SiO(g) + 4N2(g)
Passive corrosion occurs in environments with high partial pressures

of oxygen by the reaction
Si 3 lVs) + 302(g) + 3SiO2(s) + 2N2(g)
The SiO2 that is produced forms a protective coating and further

oxidation is limited. The pressure of N2 formed at the interface
can be large enough to form cracks or pores in the protective coat-
ing, which subsequently allows additional oxidation.
The rate-determining step in Si3Ni+ that contains MgO impurities
was reported by Cubicciotti and Lau [57] to be the diffusion of
TABLE 2 ASTM Test Methods Related to Corrosion of Ceramics
ASTM
designation Title
C-225 Resistance of Glass Containers to Chemical Attack

C-282 Acid Resistance of Porcelain Enamels
C-283 Resistance of Porcelain Enameled Utensils to Boiling Acid
C-288 Disintegration of Refractories in an Atmosphere of Carbon
Monoxide
C-454 Disintegration of Carbon Refractories by Alkali
C-456 Hydration Resistance of Basic Brick
C-556 Resistance of Overglaze Decorations to Attack by Detergents
C-614 Alkali Resistance of Porcelain Enamels
C-620 Hydration Resistance of Pitch-Bearing Basic Refractory Brick
C-621 Static Test for Corrosion Resistance of Refractories to
Molten Glass
C-622 Simulated Service Test for Corrosion Resistance of Refrac-
tories to Molten Glass
C-650 Resistance of Ceramic Tile to Chemical Substances
C-675 Alkali Resistance of Ceramic Decorations on Returnable
Beverage Glass Containers
C-676 Detergent Resistance of Ceramic Decorations on Glass
Tableware
C-724 Acid Resistance of Ceramic Decorations on Architectural
Type Glass
C-735 Acid Resistance of Ceramic Decorations on Returnable Beer
and Beverage Glass Containers
C-738 Lead and Cadmium Extracted from Glazed Ceramic Surfaces
C-768 Drip Slag Testing Refractory Brick at High Temperature
C-777 Sulfide Resistance of Ceramic Decorations on Glass
C-863 Oxidation Resistance of Silicon Carbide Refractories at
Elevated Temperatures
C-872 Lead and Cadmium Release from Porcelain Enamel Surfaces
C-874 Rotary Slag Testing of Refractory Materials
C-895 Lead and Cadmium Extracted from Glazed Ceramic Tile
C-927 Lead and Cadmium Extracted from Lip and Rim Area of Glass
Tumblers Externally Decorated with Ceramic Glass Enamels
416 McCauley
MgO from the bulk material into the oxide surface layer. This sur-
face layer was composed of SiO2, MgSiO3, or glass phase, and
some unoxidized Si3 N4 and was porous because of released N 2 .
The oxidation of SiC has been described by Ervin [58] and is
similar to that of Si3Nlf. Silicon carbide and nitride are relatively
inert to most silicate liquids, as long as they do not contain signifi-
cant amounts of iron oxide. The reaction
SiC + 3FeO -> SiO2 + 3Fe + CO
can occur and becomes destructive at temperatures above about

1100°C [59]. McKee and Chatterji [60] described several different
modes of behavior of SiC in contact with gas-molten salt environ-
ments relating to the formation of various interfacial reaction layers.
An SiO2 protective layer will corrode in a basic salt solution but
not in an acid salt solution. With low oxygen pressures, active
corrosion takes place by formation of SiO.
The transition metal carbides and nitrides are chemically stable
at room temperature but exhibit some attack by concentrated acid
solutions. The one exception to this is VC, which slowly oxidizes
at room temperature.
Cemented carbide cutting tools are the major application for
these transition metal carbides, with WC, TiC, TaC, and NbC being
the most used. These cemented carbides are manufactured by press-
ing the carbide powder with a metal powder (such as Co) and then
sintering either in vacuum or hydrogen to temperatures as high
as 1600°C. This produces a very hard, pore-free compact.
Test Methods
Many test methods have been developed through ASTM to evaluate
the corrosion resistance of various ceramic materials. Rather than
discussing each method separately, they are listed in Table 2.
DEVELOPMENT AND APPLICATION OF CORROSION-

RESISTANT CERAMIC MATERIALS
Introduction
The most obvious method of providing better corrosion resistance
is to change materials; however, this can be done only to a certain
extent. There will ultimately be only one material that does the
job best. Once this material has been found, additional corrosion
resistance can be obtained only by property improvement or, occa-
sionally, by altering the environment.
Polycrystalline Ceramic Materials

Property Optimization
Because exposed surface area is a prime concern in corrosion, an
obvious property to improve is the porosity. Much work has been
done in finding ways to make polycrystalline materials less porous
or more dense. The most obvious is to fire the material during
manufacture to a higher temperature. Other methods of densification
have also been used. These involve various sintering or densification
aids: liquid-phase sintering, hot pressing, and others. If additives
are used to cause liquid-phase sintering, care must be exercised
that not too much secondary phase forms, which might lower corro-
sion resistance, even though porosity may be reduced.
Alterations in major component chemistry may aid in increasing
corrosion resistance, but this is actually a form of finding a new
or different material, especially if major changes are made.
The history of glass-contact refractories is a good example of
corrosion resistance improvement in a polycrystalline material. Porous
clay refractories were used originally. Changes in chemistry by
adding more alumina were made first to provide a material less
soluble in the glass. The first major improvement was the use of
fusion-cast aluminosilicate refractories. These provided a material
of essentially zero porosity. The next step was the incorporation
of zirconia into the chemistry. Zirconia is less soluble than alumina
or silica in most glasses. Because of the destructive polymorphic
transformation of zirconia, a glassy phase had to be incorporated
into these refractories. This glassy phase added a less corrosion-
resistant secondary phase to the refractory. Thus, the higher
resistance of the zirconia was somewhat compromised by the lower
resistance of the glassy phase. The final product, however, still
had a corrosion resistance greater than the old product without
any zirconia. Today several grades of ZrO2-Al2O3-SiO2 fusion-cast
refractories are available. Those with the highest amount of zireonia
and the lowest amount of glassy phase have the greatest corrosion
resistance.
The development of glass furnace regenerator refractories was
through the optimization of materials made of fireclay by using
higher-purity raw materials and then higher-firing temperatures.
Changes in chemistry were then made by switching from the fireclay
products to magnesia-based products. Again improvements were
made by using higher-purity raw materials and then higher-firing
temperatures. Minor changes in chemistry were also made during
the process of property improvement. The evolution of regenerator
refractories for the flat glass industry up to the mid-1970s has
been described by McCauley [61]. The latest development in
418 McCauley
regenerator refractories has been the use of fusion-cast alumina-

zirconia-silica cruciform products. These are in the shape of a
cross and are stacked in interlocking columns. This represents
not only a change in chemistry but also a change in the shape of
the product, both of which lead to better performance.
A part of the concept of improvement through chemistry changes
is that of improving resistance to corrosion of the bonding phases.
Bonding phases normally have a lower melting point and lower corro-
sion resistance than does the bulk of the material. The development
of high alumina refractories is a good example of improvement based
on the bonding phase. The best conventional high alumina refractories
are bonded by mullite or by alumina itself. To change this bond
to a more corrosion-resistant material compatible with alumina, knowl-
edge of phase equilibria played an important role. Alumina forms
a complete series of crystalline solutions with chromia, with the
intermediate compositions having melting points between the two
end members. Thus, a bonding phase formed by adding chromia
to alumina would be a solution of chromia in alumina with a higher-
melting point than the bulk alumina and thus a higher corrosion
resistance. In addition to the more resistant bonding phase, these
materials exhibit a much higher hot modulus of rupture (more than
twice mullite or alumina-bonded alumina). Nothing is ever gained,
however, without the expense of some other property. Here, the
crystalline-solution-bonded alumina has a slightly lower thermal
shock resistance than does the mullite-bonded alumina. Owing to
the excellent resistance of these materials to iron oxide and acid
slags, they have found applications in the steel industry.
The development of tar-bonded and tar-impregnated basic refrac-
tories to withstand the environment of the basic oxygen process
of making steel is yet another example of a way to improve the
corrosion resistance of a material. Tar-bonded products are manu-
factured by adding tar to the refractory grain before pressing
into shape. In this way each and every grain is coated with tar.
When the material is heated during service, the volatiles burn off,
leaving carbon behind to fill the pores. An impregnated product
is manufactured by impregnating a finished brick with hot tar.
This product, once in service, will similarly end up with carbon
in the pores. Impregnated products do not have as uniform a carbon
distribution, as do the bonded types. The carbon that remains
within the refractory increases the corrosion resistance to molten
iron and slags by physically filling the pores, by providing a non-
wetting surface, and by aiding in keeping iron in the reduced state,
which then does not react with the oxides of the refractory. A
thin layer on the hot face (1 to 2 mm) does lose its carbon to oxida-
tion, and various slag components penetrate and react within this
layer. This corrosion, however, is much slower than with a product

that contains no carbon.
The automotive industry, in their efforts to develop a gas turbine
engine, has conducted a considerable amount of research on the
low-expansion lithium alumino silicates (LAS) and magnesium alumino
silicates (MAS) for a rotary wheel heat exchanger. The LAS materials
are based upon solid solutions of the high-temperature polymorphs
of two different compounds—eucryptite (Li2O»Al2O3« SiO2) an< * s P°du-
mene (Li2O-Al2O3-4 SiO2). Both of these materials have an upper
use temperature of about 1200°C. Both have a very low thermal
expansion (B-eucryptite being slightly negative) that gives them
excellent thermal shock resistance. These materials, however, suffer
from corrosion problems when used in dirty environments. To over-
come these corrosion problems, an alumino silicate (AS) material
was developed by the acid leaching of lithium from LAS before
application. This material had acceptable thermal expansion, although
not as low as LAS, but it did not distort or crack as much.
The MAS materials are based on the solid solutions of the com-
pound cordierite (2MgO«2 A12O3«5 SiO2) with the $-quartz structure.
This material has a higher temperature capability and shows better
corrosion resistance than LAS and AS. Cordierite, however, does
exhibit rapid decreases in strength when thermally cycled owing
to the cracking of crystallites caused by anisotropy in axial expan-
sion, and it requires design adaptations to reduce thermal stresses.
It is currently used in the relatively low-temperature application
of automotive exhaust converter substrates and small compact finned
plate recuperators.
External Methods of Improvement
In the section on fundamentals, the importance of temperature was

stressed several times. Various techniques have been used to lower
the temperature of the interface or hot face of the material (lower
hot-face temperatures mean less corrosion). Many applications of
a ceramic material subject the material to a thermal gradient. By
altering the material or providing a means to increase the heat
flow through the material, the hot-face temperature can be lowered
significantly. One means of doing this is by forcibly cooling the
cold face. This provides faster heat removal and, thus, lowers
the hot-face temperature. Most industrial furnaces use some means
of forced cooling on the cold face by cooling-air systems or water-
cooled piping. If the thermal gradient through the material becomes
too steep, failure may occur (this depends on the thermal expansion
characteristics of the material).
Another method that has been used to lower the hot-face tempera-
ture is to place metal plates either within individual bricks or between
420 McCauley
them. A large portion of the heat is, thus, conducted through

the metal plate. A similar technique has been used by manufacturing
a product containing oriented graphite particles.
Another way to take advantage of increased cooling is to use
a thinner material in the beginning. This will automatically cause
a thinner reaction layer to form on the surface. In general, glass
furnace basin wall linings should not exceed 10 to 12 in. thickness.
Anything thicker than about 12 in. does not normally increase overall
life but adds an economic penalty in refractory cost per campaign.
In fact, most linings could probably be less than 10 in.; however,
the thermal environment will determine the ultimate thickness that
should be used.
If a refractory lining is insulated, a greater portion of the re-
fractory will be at a higher temperature and corrosion will proceed
at a faster rate. Here, a balance must be obtained between service
life and energy conservation. Because of the potential for increased
corrosion of insulated linings, the properties of the lining material
must be carefully evaluated before insulation is installed. Usually,
the engineer may want to upgrade the lining material if it is to
be insulated.
Glassy Materials
The development of more resistant glasses has been primarily through

optimization of compositions. In general, lowering the alkali content
increases the durability. This, however, has practical limits based
on melting temperatures, viscosities, softening points, and working
ranges. Borosilicate glasses are, in general, more resistant than
soda-lime silica glasses. In general, silicate glasses are less resistant
to alkali solutions than they are to acid solutions. Reference 22
lists the corrosion resistance of many glasses of varying compositions.
The development of coating technology has provided a means to

improve corrosion resistance, abrasion resistance, and strength.
Combinations of coatings applied while the glass is hot and after
it has cooled have been developed that form a permanent bond to
the glass. These coatings are not removed by cooking or washing.
The most commonly used metallic hot-end coatings are tin and
titanium. As the piece goes through the annealing lehr, the metal
oxidizes, forming a highly protective ceramic coating. Tin is easier
to work with because a thicker coating can be applied before prob-
lems of irridescence occur. These hot-end metallic coatings give the
glass a high glass-to-glass sliding friction and, thus, a cold-end

coating must be applied over these metallic coatings. The cold-end
coatings usually have a polyethylene or fatty acid base.
Another type of coating is one that reacts with the surface of
the glass to form a surface layer that is more corrosion-resistant
than the bulk composition. Chemically inert containers are needed
to contain various beverages and Pharmaceuticals. To provide in-
creased corrosion resistance, these containers are coated internally
to tie up the leachable components. Internal treatment with a fluoride
gas provides a new surface that is more corrosion-resistant than
the original and is more economical than the older sulfur treatment.
Carbon and Carbon- and Nitrogen-Containing

Ceramic Materials
Not much can be done with graphite to improve its high-temperature
properties, especially its resistance to oxidation.
Most of the items discussed earlier can also be applied to these
materials. The one property improvement that should be discussed
a little further is that of porosity. For example, SigN^ is predomi-
nantly covalent and does not densify on heating as do conventional
ionic ceramics. In applications, such as turbine blades, a theoretically
dense material is desired. Only through hot pressing with large
amounts (up to 10 wt%) of additives at very high temperatures
and pressures can theoretically dense Si3N4 material be obtained.
In contrast, SiC requires only a small percentage. The additives
in this process cause a small amount of liquid phase to form at
high temperatures and, therefore, densification can proceed through
liquid-phase sintering. The material that eventually crystallizes
from the liquid phase is of great importance, and much work has
been done investigating these phases.
Because of their lower exposed surface area, hot-pressed materials
are far more resistant to corrosion, including oxidation. However,
the high-temperature mechanical properties are limited by the grain
boundary phases. Hot pressing of an a-Si3Ni+ powder causes the
additives to react with the silica present and dissolve some a-Si3N1+.
The nitride precipitates from the liquid as elongated 3"Si3Nif. The
interlocking nature of these elongated crystals yields a product
of superior mechanical strength.
Reaction bonding of Si3N1+ (RBSN) is a process whereby silicon
metal is processed in situ by reaction with nitrogen gas. The Si3Ni+
crystallizes into the pores of the initial silicon metal compact and
results in substantial densification but negligible dimensional change
(< 1%). These materials inherently result in a product that is essen-
422 McCauley
tially a pure SigN^ with substantial porosity but quite small (mean
size ~0.2 ym). The microstructure of these materials is composed
of fine pores and elongated crystals. Their low mechanical strength
is governed by the number and size of the occasional large pore
(up to ~10 ym) that is always present.
Reaction-bonded SiC is produced by the reaction of either liquid
or gaseous silicon or SiO with carbon in a silicon carbide/carbon
compact. This results in a porous body with continuous silicon
carbide phase; however, these pores can be filled with nonreacted
Si (2 to 10%), yielding a dense product that results in excellent
mechanical properties. The excellent wetability between Si and SiC
allows this to be done for RBSiC but not for RBSN. This interpene-
trating grain boundary phase of silicon metal limits the high-
temperature mechanical properties to the melting point of Si (1410°C).
When exposed to aggressive environments the silicon may be attacked
relatively easily, leading to degradation of properties.
Chemical vapor deposition (CVD) is one of the most attractive
methods to produce high-purity, dense materials, because the sinter-
ing process is not required if a bulk material can be obtained directly
from the raw vapors or gases. Microstructures of CVD products
are strongly dependent upon the deposition temperature and total
gas pressure. Chemical vapor deposition can produce materials with
no grain boundary phases, but that are highly oriented. It is well
known that CVD materials contain residual internal stresses. At
present the effect of these stresses on high-temperature strength
and corrosion are not well known.
The development of 813^-based materials has now progressed
to the point of studying materials in SiaMÔcN^ systems, where M
has been confined mostly to trivalent cations. Most work has been
in systems where M = Al, Y, and/or Be. These materials form
secondary grain boundary phases that are highly oxidation resistant
and, thus, provide a better material than materials made from 813^
densified with MgO. Care must be taken so that grain boundary
phases that oxidize catastrophically (such as yttrium oxynitride)
do not form. Cemented carbide cutting tools made from WC wear
rapidly because of local welding of the tool to the steel piece being
cut. To overcome this welding, additions of TiC are made to the
WC to form a TiO surface layer that protects the tool from rapid
wear; WO3 also forms but it is volatile and produces no protective
layer. In addition, small amounts of TaC and NbC are added to
increase the overall oxidation resistance by increasing the melting
temperature of the carbide solution formed.
One approach to the oxidation problem of graphite has been the

development of protective coatings. If the coating is applied to the
outside surface only (as in vapor deposition), failure may result

because of coating failure from mechanical or chemical means. A
way to circumvent this problem is to provide an additive of refractory
metals to the graphite so that upon oxidation of the metal exposed
to the surface, a liquid will form and seal the graphite surface.
If the surface coating is destroyed by mechanical or chemical means,
a new surface can be regenerated in situ.
The first successful composition of this type contained B 2 O 3 ;
however, its service temperature was limited to 1400°C (2550°F).
Above this temperature B2O3 volatilizes and the viscosity of the
liquid is sufficiently low to allow drip from the surface, and above
1595°C (2900°F) the reaction pressure of B2O3 relative to graphite
is greater than 1 atm.
To improve this composition even further, addition of oxides
of zirconium, hafnium, and thorium have been very helpful in giving
oxidation protection to 1900°C (3450°F). These oxides, when heated
in contact with graphite, form highly refractory carbides; however,
CO and CO2 also form in the reaction. The evolution of CO and
CO2 may cause spalling of the coating if the reaction pressure ex-
ceeds ambient pressure.
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424 McCauley
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30. Das, C. R., and Douglas, R. W. (1967). Reaction between
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H. T. (1978). Mechanism of modifier release from lead-containing
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36. Boksay, Z., Bouquet, G., and Dobos, S. (1967). Diffusion
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140-144.
37. Doremus, R. H. (1975). Interdiffusion of hydrogen and alkali
ions in a glass surface, J. Non-Cryst. Solids 10:137-144.
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leached glass with water, J. Am. Ceram. Soc. 62:398-402.
39. Rana, M. A., and Douglas, R. W. (1961). Reaction between
glass and water: I, Phys. Chem. Glasses, 2:179-195.
40. Rana, M. A., and Douglas, R. W. (1961). Reaction between
glass and water: II, Phys. Chem. Glasses 2:196-205.
41. Das, C. R., and Douglas, R. W. (1967). Reaction between
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43. Wood, S., and Blachere, J. R. (1978). Corrosion of lead glasses
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45. Clark, A. E., Pantano, C. G., and Hench, L. L. (1976).
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426 McCauley
46. Katayama, J . , Fukuzuka, M., and Kawamoto, Y. (1978). Corro-

sion of heavy crown glass by organic acid solutions, Yogyo
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(1967). The chemical properties of heavy alkali metals inserted
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16
OF ELASTOMERS
INTRODUCTION
The term elastomer has come into use, particularly in scientific

and technical literature, as a name for both natural and synthetic
materials that are elastic or resilient and, in general, resemble
natural rubber in feeling and appearance. The American Society
for Testing and Materials (ASTM) definition of elastomer is "a poly-
meric material which at room temperature can be stretched to at
least twice its original length and upon immediate release of the
stress will return quickly to approximately its original length."
Compounding increases the utklity of rubber and synthetic elastomers.
In the raw state elastomers are soft and sticky when hot and hard
and brittle when cold. Vulcanization extends the temperature range
within which they are flexible and elastic. In addition to vulcanizing
agents, ingredients are added to make elastomers stronger, tougher,
and harder; to make them age better; to color them; and, in general,
to modify them to meet the needs of service conditions. Today, few
rubber products are made from rubber or elastomers alone.
SPECIFICATIONS
Specifications for rubber goods may cover the chemical, physical,

and mechanical properties such as elongation, tensile strength,
permanent set, and oven tests, minimum rubber content, exclusion
of reclaimed rubber, maximum free and combined sulfur contents,
429
430 Schweitzer
maximum acetone and chloroform extracts, ash content, and many

construction requirements.
It is preferable, however, to specify properties required, such
as resilience, hysteresis, static or dynamic shear and compression
modulus, flex fatigue and cracking, creep, electrical properties,
stiffening, heat generation, compression set, resistance to oils and
chemicals, permeability, and brittle point, in the temperature range
prevailing in service and to leave the selection of the elastomers
to a competent manufacturer.
NATURAL RUBBER
Natural rubber (NR) of the best quality is prepared by coagulating

the latex of the Hevea brasiliensis tree, cultivated primarily in the
Far East. Purified raw rubber becomes sticky in hot weather and
brittle in cold weather. Its valuable properties become apparent
after vulcanization.
Unloaded vulcanized rubber can be stretched to approximately
10 times its length, and at this point will bear a load of 10 tons/sq
in. It can be compressed to one-third of its thickness thousands
of times without injury. When most types of vulcanized rubber are
stretched, their resistance increases in greater proportion than
the extension. Even when stretched almost to the point of rupture,
they recover almost their original dimension on being released and
then gradually recover a part of the residual distortion.
Depending on the degree of curing, natural rubber is classified
as soft, semihard, or hard. Only soft rubber meets the ASTM
definition of an elastomer and, therefore, the information that follows
pertains only to soft rubber. The properties of semihard and hard
rubber are somewhat different, particularly in the area of chemical
resistance.
Dry heat up to 50°C (120°F) has little deteriorating effect; at
temperatures of 180 to 200°C (360 to 400°F) rubber begins to melt
and becomes sticky. At higher temperatures it becomes entirely
carbonized.
The electrical insulation properties of natural rubber are good,
but its flame resistance is poor.
Chemical Resistance
Mineral and vegetable oils, gasoline, benzene, toluene, and chlori-
nated hydrocarbons affect rubber. Strong oxidizing materials such
as nitric acid, concentrated sulfuric acid, permanganates, diehro-
mates, chlorine dioxide, and sodium hypochlorites severely attack
16. Development and Application of Elastomers 431
rubber, but rubber offers excellent resistance to most inorganic

salt solutions, alkalies, and nonoxidizing acids. Hydrochloric acid
reacts with soft rubber to form rubber hydrochloride and, therefore,
is not recommended.
Resistance to Sun, Weather, and Ozone

Cold water preserves rubber, but if exposed to the air, particularly
to the sun, rubber tends to become hard and brittle. In general,
it has poor weathering and aging properties. Its resistance to ozone
is only fair. Unlike the synthetic elastomers, natural rubber softens
and reverts with aging in sunlight or ozone.
Recovery from Deformation

Resilience is the primary superior property of natural rubber over
the synthetics. It has excellent rebound properties either hot or
cold.
Applications
The major uses for natural rubber are as pneumatic tires and tubes,
power transmission belts and conveyor belts, gaskets, mountings,
hose, chemical tank linings, printing press platens, sound or shock
absorption, and seals against air, moisture, sound, and dirt.
ISOPRENE
Natural rubber chemically is based on natural cis-polyisoprene.

Isoprene (IR) is synthetic cis-polyisoprene.
The properties of isoprene are similar with those of natural
rubber, with the advantage that it has no odor. This permits the
use of isoprene in certain food-handling applications.
BUTYL RUBBER
Butyl rubber (11R) is a general-purpose synthetic rubber whose

outstanding physical properties are low air permeability (approxi-
mately one-fifth that of natural rubber) and high energy-absorbing
qualities. The former property has resulted in butyl rubber replacing
natural rubber for inner tubes in tires. Its resistance to abrasion
and tear is about equal that of natural rubber.
Butyl rubber can be used to temperatures of 150°C (300°F) with-
out any effect. Its resistance to temperature and heat-aging is good.
432 Schweitzer
The electrical properties of butyl rubber are generally good

but not outstanding in any one area.
It has poor flame resistance.
Chemical Resistance
Butyl rubber exhibits excellent resistance to dilute mineral acids,
phosphate ester oils, acetone, ethylene, ethylene glycol, and water.
Unlike natural rubber, it is resistant to swelling by vegetable and
animal oils.
Its resistance to petroleum oils and gasoline is extremely poor.
Butyl rubber is also very nonpolar.

The resistance of butyl rubber to sun, weathering, and ozone is
excellent.

At room temperature, the resiliency of butyl rubber is low, but
it increases with increasing temperature.
STYRENE-BUTADIENE-STYRENE
Styrene-butadiene-styrene (SBS) is a pure or oil-modified block

copolymer rubber. It can be easily processed on standard thermo-
plastic processing equipment, and offers excellent impact resistance
and low-temperature flexibility.
Chemical Resistance
This polymer has excellent resistance to water, acids, and bases.
It will deteriorate with prolonged exposure to hydrocarbon solvents,
but short exposure can be tolerated.

In the stressed condition, SBS exhibits poor resistance to ozone,
sun, and weather. Resistance is only slightly improved in the un-
stressed condition.
STYRENE-ETHYLENE-BUTYLENE-STYRENE
Styrene-ethylene-butylene-styrene (SEBS) is a block copolymer,

capable of being processed on standard thermoplastic-processing
equipment and exhibiting excellent temperature flexibility and impact

resistance.
Chemical Resistance
This polymer has excellent resistance to water, acids, and bases.
Prolonged exposure to hydrocarbon solvents will deteriorate SEBS,
but short-term exposures can be tolerated.

The resistance of SEBS to sun, weather, and ozone is excellent.
Applications
Butyl rubber finds use as truck and automobile tire inner tubes,
curing bags for tire vulcanization and molding, steam hoses and
diaphragms, flexible electrical insulation, and shock and vibration
absorption.
SBR STYRENE
SBR styrene (Buna S) is a butadiene-styrene copolymer that is

manufactured by many companies. It was developed by the govern-
ment during World War II because of the natural rubber shortage
and became known as Government Rubber Styrene type (GR-S).
It is also known as Buna S.
Compared with natural rubber, it is lacking in tensile strength,
elongation, resilience, hot tear, and hysteresis, but these are offset
by its low cost, cleanliness, slightly better heat-aging, slightly
better wear than natural rubber for passenger tires, and availability
at a stable price.
SBR has relatively poor resistance to temperature, with a maximum
operating temperature of 80°C (180°F), which is somewhat lower
than that of natural rubber. At lower temperatures [-90°C (-120°F)]
SBR products are more flexible than those of natural rubber.
The electrical properties of SBR are generally good but not
outstanding in any one area.
SBR has poor flame resistance.
Chemical Resistance
In general, the chemical resistance of SBR is similar to that of
natural rubber, being unaffected by water, alcohol, dilute acids,
or alkalies, but it is attacked by oils and solvents.
434 Schweitzer

The resistance of SBR to sun, weather, and ozone is generally-
poor.

SBR is not as resilient as natural rubber.
Applications
SBR is used for the same applications as natural rubber.
NEOPRENE
Neoprene (CR) was actually the first commercial synthetic rubber,

and it is still the workhorse of industry because of its outstanding
properties.
It has excellent abrasion resistance, and it resists damage from
impact, flexing, and twisting. Because of its low heat buildup when
subjected to flexing, maximum fatigue from dynamic operations
results.
Neoprene has a practical high-temperature range of 80 to 90°C
(176 to 203°F) for continuous service. For intermittent use, products
made of neoprene can operate at a temperature of 120°C (248°F).
Heat exposure above these limits does not soften or melt neoprene;
rather, it causes a neoprene part to harden and lose resilience.
Neoprene products show little change in performance character-
istics down to -20 to -25°C (-4 to -13°F). Below that point, they
stiffen until their brittle temperature is reached at about -40°C
(-40°F). Specially formulated compositions, however, permit service
as low as -55°C (-67°F).
Neoprene can be compounded to satisfy a number of needs in
electrical applications. Its dielectric characteristics limit its use
as an insulator to low-voltage (600-V) and low-frequency (60-Hz)
applications. As a protective outer jacket for insulated cable, how-
ever, neoprene is used at all voltages. It is relatively unharmed
by corona attack.
In gum polymer form, neoprene, by virtue of its chlorine content,
is inherently more resistant to burning than are exclusively hydro-
carbon polymers.
In laboratory tests, normally compounded solid neoprene products
can be ignited by an open flame but will stop burning if the flame
is removed. Under the same conditions, natural rubber and many
other synthetic rubbers will continue to burn. However, despite
its superiority over these other materials in such laboratory tests,

neoprene will burn in an actual fire situation.
Chemical Resistance
Resistance to deterioration from waxes, fats, oils, greases, and
many other petroleum products is one of the best-known properties
of neoprene. Neoprene was originally developed as an oil-resistant
substitute for natural rubber, and it is still widely used for this
purpose. Its use is limited, however, to nonaromatic hydrocarbons,
and it will not withstand chlorinated solvents.
Neoprene is resistant to alkalies, dilute mineral acids, and in-
organic salt solutions. Acid and salt solutions of a highly oxidizing
nature will cause surface deterioration and loss of strength. Unlike
natural rubber and other general purpose elastomers, neoprene
gives excellent service in contact with aliphatic hydrocarbons, ali-
phatic hydroxy compounds, and most Freon refrigerants. In contact
with these fluids, neoprene displays minimum swelling, relatively
little loss of strength, and virtually complete recovery of initial
properties after removal of the liquid by drainage or evaporation.

The resistance of properly compounded neoprene to ozone, sun,
and weather accounts for its excellent aging characteristics.

Neoprene exhibits a relatively low degree of permanent deformation
from compression (compression set). Permanent deformation from
elongation (permanent set) will be approximately 5% for most neo-
prene products.
Applications
Products made from neoprene include wire and cable jackets; indus-
trial coated fabrics, gaskets, hose and belting; glazing and paving
seals; structural bearings; latex foam products; a wide variety
of adhesives and coatings; molded and extruded goods for industrial,
architectural, and automotive use; and a series of consumer products
in the shoe, paper, and tire fields.
Neoprene automotive parts have been in common use for over
40 years. Both engine and body components benefit from its heat,
oil, and weather resistance. Typical uses include hose, tubing,
sponge door and truck seals, dust boots, window channels, wire
436 Schweitzer
jacketing, adhesives, grommets, and seals. Neoprene-jacketed power

cable is used extensively in underground and underwater service.
NBR-NITRILE
NBR-nitrile (Buna N) is one of the four most widely used elastomers.

The big advantage of NBR is its improved resistance over neoprene
to oils, fuels, and solvents. Its physical properties closely match
those of SBR, except that it has much better heat resistance and,
considering cost (slightly above that of neoprene), it has the broad-
est resistance to chemicals, with a balance of properties, than any
other elastomer.
The heat resistance of NBR is high, with an operating range
of -15 to +150°C (-70 to +300°F).
The electrical properties of NBR are only fair and, consequently,
it does not find wide use in the electrical field, and its flame resist-
ance is poor.
Chemical Resistance
The nitrile rubbers show good resistance to alkalies, aqueous salt
solutions, oils, and solvents. A very slight swelling occurs in the
presence of aliphatic hydrocarbons, fatty acids, alcohols, and gly-
cols. The reduction of physical properties as a result of swelling
is small, which makes NBR suitable for gasoline- and oil-resistant
applications.
NBR is attacked by strong oxidizing agents, ketones, ether,
and esters, but it has excellent resistance to water.

NBR has poor resistance to sunlight, ozone, and weathering in
general.

The resiliency of NBR, either hot or cold, is good.
Applications
NBR finds use as carburetor diaphragms, aircraft hose, gaskets,
self-sealing fuel tanks, gasoline and oil hose, cables, printing rolls,
and machinery mountings.
CHLOROSULFONATED POLYETHYLENE (HYPALON)

Hypalon (CSM) is similar to neoprene, but it does possess some
added advantages in terms of extra properties. It has improved
heat and ozone resistance, improved electrical properties, improved
color stability, and improved chemical resistance.
Because of its chlorine content, hypalon is inherently more resist-
ant to burning than exclusively hydrocarbon polymers. It is classified
as self-extinguishing.
General purpose compounds can operate continuously at tempera-
tures of 120 to 135°C (248 to 275°F). Special compounds of CSM
can be used in intermittent service up to 150°C (302°F).
Conventional compounds are serviceable down to -18 to -23°C
(0 to -10°F). Special compounds retain their flexibility down to -40°C
(-40°F).
The electrical properties of CSM are good. It has proved to
be a valuable insulation, in service less than 600 V, for control
cable and secondary wire. For higher voltages, its use as a protec-
tive covering over other insulating materials has been successful
because of its outstanding resistance to weathering, ozone, and
corona.
Chemical Resistance
Compositions of CSM are very resistant to attack by oxidizing chemi-
cals, such as concentrated sulfuric acid and hypochlorite solutions;
properly compounded, it is especially useful in contact with oils
at elevated temperatures. It is also resistant to aqueous salt solutions,
alcohols, and weak and concentrated alkalies. It has poor resistance
to aliphatic, aromatic, and chlorinated hydrocarbons, as well as
aldehydes, ketones, and fuel oils.

Hypalon synthetic rubber can resist the long-term effects of weather-
ing.
It is so extraordinarily resistant to ozone that, although failures
can be induced with certain formulations in laboratory tests, no
known product failure owing to ozone attack has ever been reported.

Hypalon shows good resiliency.
438 Schweitzer
Applications
CSM is used as a jacketing and insulating material for wire and
cable; in fluid coating and laminated roofing systems; as sheeting
for pond, pit, and reservoir liners and covers; for industrial prod-
ucts such as hose, tarpaulins, equipment linings, gaskets, seals,
and diaphragms, maintenance coatings, and industrial rolls; and
for a variety of consumer items such as whitewall tires, waterproof
garments, appliance parts, coated fabrics, and shoe heels and soles.
POLYSULFIDE (THIOKOL ST)
The polysulfide elastomer is commonly known as Thiokol ST and

has the ASTM designation T. Compared with nitrile rubber it has
poor tensile strength, pungent odor, poor rebound, high creep
under strain, and poor abrasion resistance.
Polysulfides can be used in temperature range -15 to +120°C
(-60 to +250°F). They are also capable of short-term use at 150°C
(300°F) without any effect on its properties.
The electrical insulating properties of polysulfides are fair, but
they have poor flame resistance.
Chemical Resistance
Common alcohols, ketones, and esters used in paints, varnishes,
and inks have little effect on the polysulfides. Thiokol ST is espe-
cially resistant to aliphatic liquids, hydrocarbon solvents, or blends
of aliphatics and aromatics. Some chlorinated hydrocarbons can
be handled with little effect, but tests should be conducted before
using in this service.

The weathering properties and resistance to sun and ozone of the
polysulfides are excellent; consequently, Thiokol ST has wide appli-
cations for caulking purposes.

Polysulfide has good resiliency either hot or cold.
Applications
Caulking uses, seals, gaskets, diaphragms, valve seat disks, flexible
mountings, solvent-carrying hose, printers rolls, balloons, life
vests, and rafts.
POLYSULFIDE (THIOKOL FA)
Thiokol FA is comparable to Thiokol ST polysulfide, exhibiting the

same corrosion resistance, weathering properties, and resistance
to sun and ozone. The primary difference is in the operating tem-
perature range. This series of polysulfides have an operating
temperature range of -50°F (-45°C) to 250°F (121°C).
SILICONE RUBBERS
The silicone rubbers (FSI, PSI, VSI, PVSI, and SI) are a series
of compounds whose polymer structure consists of silicone and oxygen
atoms rather than the carbon structure of all other elastomers.
Silicon is in the same chemical group as carbon, but it is a more
stable element and, therefore, more stable compounds are produced.
The silicones are the most heat-resistant of the elastomers presently
available and the most flexible at low temperatures. The basic struc-
ture can be modified with such groups as vinyl or fluoride, which
improves such properties as tear resistance and oil resistance.
This results in a family of silicones that cover a wide range of
physical and environmental requirements.
Silicone rubbers have the best electrical properties of any of
the elastomers. The decomposition product of organic compounds
is conductive carbon black, which can sublime and, thus, leave
nothing for insulation, whereas the decomposition product of the
silicone rubbers is an insulating silicon dioxide. This property
is taken advantage of in the insulation of electric motors.
Silicone rubbers exhibit good flame resistance.
Chemical Resistance
Silicone rubbers can be used in contact with dilute acids and alkalies,
alcohols, animal and vegetable oils, and lubricating oils. Aromatic
solvents such as benzene, toluene, gasoline, and chlorinated solvents
will cause excessive swelling. These rubbers are not resistant to
steam at elevated temperatures.

The series of silicone rubbers exhibit excellent resistance to sun,
weathering, and ozone.

Silicone rubbers have good rebound properties.
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Applications
Because of their unique thermal stability properties and their insu-
lating values, the silicone rubbers are used primarily in electrical
applications such as appliances, heaters, furnaces, aerospace devices,
and automotive parts.
POLYBUTADIENE
Like isoprene, polybutadiene (BR) is a sterospecific controlled struc-

ture having outstanding properties of resilience and hysteresis,
almost equivalent to that of natural rubber. It is most similar to
SBR, and because it is so difficult to process, it finds wide use
as an admixture with SBR and other elastomers. It is rarely used
in a larger amount than 75% of the total polymer in a compound.
Its range of operating temperatures is only slightly better than
that of natural rubber, ranging from -65 to +90°C (-150° to +200°F).
Polybutadiene possesses good electrical insulating properties,
but its flame resistance is poor.
Chemical Resistance
The chemical resistance of polybutadiene is similar to that of natural
rubber. It shows poor resistance to aliphatic and aromatic hydro-
carbons and a fair resistance to animal and vegetable oils.

Polybutadiene has poor sunlight-aging characteristics, but it has
good oxidation resistance.

The resiliency of polybutadiene is excellent either hot or cold.
Applications
Polybutadiene is usually used as a blend with other elastomers to
impart better resiliency, abrasion resistance, and low-temperature
properties, particularly in the manufacture of automobile tire treads,
shoe heels and soles, gaskets, seals, and belting.
URETHANE RUBBERS
Very few materials offer the combination of hardness and resilience

possessed by urethane rubber (U). Compositions with a durometer
hardness of 95A (harder than a typewriter platen) are elastic enough

to withstand stretching to more than four times their normal lengths.
Standard compounds maintain their resilience with changing tem-
perature far better than most other rubbers through the range
10 to 100°C (50 to 212°F). This stability is valuable in certain shock-
mounting applications.
The load-bearing capacity of products made with urethane rubber
is far above that of conventional elastomers and only slightly below
that of structural plastics, yet the material possesses the resilience
of a true elastomer.
The outstanding abrasion resistance of urethane rubber has
led to many important applications for which severe wear is a prob-
lem.
Urethane rubber has a low unlubricated coefficient of friction
that decreases sharply as hardness increases. This characteristic,
coupled with its superior abrasion resistance and load-carrying
ability, are important reasons why urethane rubber is used in bear-
ings and bushings.
At room temperature, a number of the raw polyurethane polymers
are liquid, simplifying the production of many large and intricately
shaped molded products. When cured, these elastomeric parts are
hard enough to be machined on standard metalworking equipment.
Products of urethane rubber perform well at moderately elevated
temperatures; 85°C (185°F) is the usual temperature limit for con-
tinuous operation and 100°C (212°F) for intermittent exposure.
Urethane rubber remains flexible at very low temperatures and
possesses outstanding resistance to thermal shock. Standard compo-
sitions do not become brittle at temperatures below -62°C (-80°F),
although stiffening gradually increases as the temperature is reduced
below -18°C (0°F).
Urethane rubber has been used successfully at cryogenic tempera-
tures in handling nonoxidizing liquefied gases.
Urethane rubber has been used in potting and insulating compo-
sitions at frequencies up to 100 kHz and temperatures not exceeding
100°C (212°F). The basic polymer may be modified with epoxy resins
for improved electrical properties.
The urethane rubbers are classified as slow burning to self-
extinguishing, and they may be compounded with flame retardants
to produce nonburning products.
Chemical Resistance
The urethane rubbers are resistant to most mineral and vegetable
oils, greases and fuels, and aliphatic, aromatic, and chlorinated
hydrocarbons. Esters, ethers, and ketones attack urethane rubber;
alcohols soften and swell them.
442 Schweitzer
They have limited service in weak acid solutions, cannot be used

in concentrated acids, and are not resistant to steam or caustics.

Weather extremes do not impair the serviceability of urethane rubber
in outdoor applications. Prolonged exposure to ultraviolet light
will darken and somewhat reduce the physical properties of products
made of urethane rubber, but no significant surface deterioration
occurs. They can be protected against the effects of severe weather-
ing by pigmentation or by using ultraviolet screening agents.
Oxygen and ozone in atmospheric concentrations have no observa-
ble effect.

Products made from urethane rubber have good resistance to com-
pression set. This is shown by their successful use in die pads
for metal forming, where tens of thousands of indentations are
routine.
Applications
The versatility of urethane rubber has led to a wide variety of
applications. Typical products are industrial tires and rolls, mining
industry wear parts, sleeve bearings and bushings, die pads for
metal forming, equipment linings, transmission and conveyor belts,
marine products, a variety of sports and consumer items, coatings,
gaskets, seals, and shoe heels.
POLYESTER ELASTOMER
Polyester (PE) is a relatively new elastomer manufactured by Dupont

under the trade name Hytrel. It combines characteristics of thermo-
plastics and elastomers; and it is structurally strong, resilient,
and resistant to impact and flexural fatigue.
Polyester elastomers possess mechanical properties that make
them practical for a number of demanding applications. They combine
such useful features as excellent flex-fatigue resistance, high resist-
ance to deformation under moderate strain conditions, retention
of flexibility at low temperatures, and good abrasion resistance.
Resistance of PE to fatigue in cyclic load-bearing applications
is outstanding. This is particularly true in deformation in low-strain
ranges, where it may be considered to act like a perfect spring with
no, or very low, hysteresis. This means that a part made of PE,
engineered to operate in low-strain levels, can usually be expected

to exhibit complete recovery from deformation and to continue to
do so under repeated cycling for extremely long periods, without
heat buildup or distortion.
The polyester elastomers show high moduli in tension, compres-
sion, and flex. At comparable hardnesses, they are superior to
commercial polyurethane rubbers in load-bearing capacity. They
can be used in smaller, thinner sections to give equivalent perform-
ance.
These elastomers possess exceptional strength at elevated tempera-
tures, particularly the harder polymers. Above 120°C (248°F) their
tensile strengths far exceed those of other polymers.
All the polymers of PE have solenoid brittle points below -70°C
(-94°F). As would be expected, the softer members exhibit the
best low-temperature flexibility.
Chemical Resistance
In general, the fluid resistance of polyester elastomer increases
with increasing hardness of the polymer. Because they contain
no plasticizers, products of PE are not susceptible to solvent extrac-
tion or heat volatilization of such additives. Polyester elastomer
withstands a wide variety of oils, fuels, solvents, and chemicals,
but it is attacked by concentrated mineral acids and bases. It is
soluble in phenols, cresols, and certain chlorinated hydrocarbons.

For resistance to ultraviolet radiation, screening agents are required
with PE. Properly stabilized, these elastomers will provide satisfac-
tory service under extreme climatic conditions.
Applications
Today, products being made of PE include hydraulic hose, air and
heater hose, vacuum and industrial tubing, seals, gaskets, specialty
belting, noise-damping devices, low-pressure tires, industrial solid
tires, wire and cable jacketing, pump parts, electrical connectors,
flexible shafts, sports equipment, piping clamps and cushions,
gears, flexible couplings, and fasteners.
PERFLUOROELASTOMERS
Because the monomers used in the production of the base polymer

are expensive and the fabrication of finished parts of perfluoro-
444 Schweitzer
elastomer (FPM) requires difficult and complex techniques, these

rubber parts command very high prices. However, initial cost usually
is not a factor with FPM parts because they normally are specified
only when no other material can do the job or when overall cost-life
considerations are especially important.
The halogen groups present in these polymers provide stability.
The fluorinated rubbers are especially good for high-temperature
service, but they do not have as high an operating temperature
as the silicone rubbers. They may be used from -50 to +200°C (-90
to +400°F), have low permeability rates with air, and extremely
low water absorption. The latter property makes them highly desira-
ble for use in electrical and electronic equipment, which requires
excellent insulation.
Aging characteristics are excellent. Tensile strength and tear
resistance is good, but if these properties are important in the
application, fillers such as finely divided silica or carbon black
are used in the compounding.
Perfluoroelastomer has excellent resistance to flame, but it will
burn if involved in an actual fire situation.
Typical products in this category are Viton (Dupont), Kel-F
(3M), Fluorel (3M), and Kalrez (Dupont).
Chemical Resistance
A major advantage of FPM is that its nearly universal chemical
resistance makes it suitable for virtually all chemical process streams.
In general, FPM is suitable for service at temperatures 40 to
60°C (100 to 150°F), higher than any other commercial elastomer.
Given the retention of elastic properties, FPM perfluoroelastomer
parts can often be used continuously at temperatures up to 316°C
(600°F) in many fluid environments.
The fluoroelastomers are extremely resistant to aliphatic hydro-
carbons; chlorinated solvents; animal, mineral, and vegetable oils;
gasoline; jet fuels; dilute acids; alkaline media, and aqueous in-
organic salt solutions. In the presence of oxygenated solvents,
alcohols, aldehydes, ketones, esters, and ethers, their resistance
is fair to poor.
Resistant to Sun, Weather, and Ozone

Perfluoroelastomer is extremely resistant to the adverse effects
of the environment, including sunlight, ozone, weather, and moisture.
With a brittle point of -37°C (-35°F), it exhibits only moderately
useful low-temperature characteristics. Electrical properties are
not too different from those of other synthetic rubbers.

The resiliency of FPM depends on the particular elastomer and ranges
from poor to good.
Applications
Perfluoroelastomer parts are a practical solution wherever the sealing
performance of rubber is desirable but not feasible because of severe
chemical or thermal conditions. Alternatively, FPM is the O-ring
used for seals on equipment in the petrochemical industry. O-rings
of FPM are used in mechanical seals, pump housings, compressor
casings, valves, rotameters, and other instruments. Custom-molded
parts also are used as valve seats, packings, diaphragms, gaskets,
and miscellaneous sealing elements, including U-cups and V-rings.
Other industries where FPM contributes importantly are aerospace
(versus jet fuels, hydrazine, N2Ot+ and other oxidizers, Freon 21
fluorocarbon, etc.), nuclear power (versus radiation, high tempera-
tures), oil, gas, and geothermal drilling (versus sour gas, acidic
fluids, amine-containing hydraulic fluids, extreme temperatures
and pressures), and analytical and process instruments (versus
high vacuum, liquid and gas chromotography exposures, high-purity
reagents, high-temperature conditions).
Hose, belts, diaphragms, gaskets, and other industrial rubber
goods made of EPM rubber give excellent service with high-pressure
steam, hot water, and chemicals.
Good electrical and physical properties of EPM rubber suit it
for use in high-voltage accessories for cable and power equipment.
ETHYLENE-ACRYLIC ELASTOMER
Ethylene-acrylic (E-A) elastomer has good tear and tensile strengths

and high elongation at break, which is expected of a tough rubber.
In addition, exceptionally low-compression set values are an added
advantage, making the product suitable for many hose, sealing,
and cut gasket applications.
A unique feature is its practically constant damping characteristics
over broad ranges of temperature, frequency, and amplitude. Very
little change in damping value takes place between -20 and 160°C
(-4 and 320°F). This property, which shows up as a poor rebound
in resilience tests, is actually a design advantage. Combined with
E-Afs heat and chemical resistance, it allows the use of E-A in
vibration-damping applications.
This elastomer provides heat resistance surpassed by only the
more expensive specialty polymers, such as the fluorocarbon and
446 Schweitzer
fluorosilicone elastomers. Parts retain elasticity and remain functional

after continuous air-oven exposures from 18 months at 121°C (250°F)
to 7 days at 204°C (400°F).
Parts of E-A will perform at least as long as parts of Hypalon
or general purpose NBR but at exposure temperatures 10 to 40°C
(50 to 100°F) higher.
E-A is inherently superior to most other heat- and oil-resistant
polymers, including standard fluoroelastomers, chlorosulfonated
polyethylene, polyacrylates, and polyepichlorohydrin, in performance
at low temperatures. Typical unplasticized compounds are flexible
to -20°C (-4°F) and have brittle points as low as -60°C (-75°F).
Compounding E-A with ester plasticizers will extend its low-
temperature flexibility limits to -46°C (-50°F).
Chemical Resistance
Products of E-A have very good resistance to hot oils and hydrocarbon-
or glycol-based proprietary lubricants, transmission, and power-
steering fluids. The swelling characteristics of E-A permit it to
retain its original physical properties better than silicone after
oil immersion.
Ethylene-acrylic elastomer also has outstanding resistance to
hot water. It is not recommended for immersion in esters, ketones,
or highly aromatic fluids. Neither should it be used in applications
calling for long-term exposure to high-pressure steam.

Ethylene-acrylic elastomer provides excellent resistance to sun,
weathering, and ozone.
Applications
Ethylene-acrylic elastomer should be considered for any application
calling for a tough, set-resistant rubber with good low-temperature
properties and excellent resistance to the combined deteriorating
influences of heat, oil, and weather.
ETHYLENE-PROPYLENE RUBBER
Ethylene-propylene (EPM) rubbers have good tear resistance, even

at elevated temperatures, and are very durable when exposed to
abrasion and other forms of mechanical abuse. Their resilience is
between that of products made from SBR and those of natural rubber.
Ethylene-propylene rubber can be compounded in any color,

including white and delicate pastels. These colored products are
highly resistant to fading and discoloration when exposed out of
doors.
General purpose compounds of EPM hydrocarbon rubber are
serviceable at temperatures of 125 to 145°C (257 to 293°F). Special
compounds can be formulated for continuous use up to 155°C (311°F)
and in intermittent service up to 170°C (338°F).
Conventional compounds of EPM rubber are flexible and service-
able at temperatures as low as -50°C (-58°F). Special compounds
can function down to -68°C (-90°F).
This rubber has excellent electrical properties and is suitable
for high-voltage cable insulation. It also withstands heavy corona
discharge without sustaining damage; it is not flame resistant.
Chemical Resistance
Products made from EPM rubber resist attack by many acids and
alkalies, detergents, phosphate esters, ketones, alcohols, and gly-
cols. They give particularly outstanding service with hot water
and high-pressure steam. However, EPM rubber should not be used
in contact with hydrocarbon solvents and oils, chlorinated hydro-
carbons, or turpentine.
Resistance to Sun# Weather, and Ozone

The resistance of EPM rubbers to sun, weather, and ozone is excel-
lent.

After being held under compression for an extended period, EPM
rubber shows a low degree of permanent deformation.
Applications
Ethylene-propylene rubber is widely used in automotive and appliance
components; garden and industrial hose, belts, wire and cable insu-
lation; electrical accessories; bicycle tires; and a variety of other
molded and extruded parts for marine, agricultural, industrial,
and consumer applications, especially those requiring outstanding
ozone resistance.
448 Schweitzer
ACRYLATE-BUTADIENE
Acrylate-butadiene (ABR) and acrylic ester-acrylic halide (ACM)

have properties similar to the EA rubbers but with a somewhat
lower high-temperature rating. They exhibit good resilience and
tear resistance but poor impact resistance. Abrasion resistance
and compression set are good.
Chemical Resistance
The ABR and ACM rubbers have excellent resistance to aliphatic
hydrocarbons (gasoline, kerosene) and offer good resistance to
water, acids, synthetic lubricants, and silicate hydraulic fluids.
They are unsatisfactory for use in contact with alkali, aromatic
hydrocarbons (benzene, toluene), halogenated hydrocarbons, alcohol,
and phosphate hydraulic fluids.

The resistance of ABR and ACM rubbers to sun, weather, and
ozone is excellent.
Applications
These rubbers find applications where resistance to atmospheric
conditions and heat are required.
POL YAM IDES (NYLON)
The family of polyamides is the family of nylons, which consist

of four major types—nylon 6, nylon 6/6, nylon 11, and nylon 12.
Of these nylon 11 and nylon 12 find applications as elastomeric
materials.
Polyamide resins can withstand extremely high impact even at
extremely low temperatures. According to ASTM test D746, the
cold brittleness temperature is -94°F (-70°C).
The electrical insulating properties of nylons 11 and 12 are good
and offer excellent resistance to arc tracking.
Moisture has little effect on the mechanical properties, particularly
the modulus of elasticity.
Chemical Resistance
These resins exhibit excellent resistance to a broad range of chemi-
cals including oils, gasolines, hydraulic fluids, bases, saltwater and
spray, electrolytic corrosion, and harsh industrial environments.

Good resistance is exhibited to sun, weather, and ozone.

Nylon 11 and nylon 12 have an extremely high elastic memory, which
permits them to withstand repeated stretching and flexing over
long periods.
Applications
These polyamides find application as coiled air brake hose on trucks,
shoe soles, gaskets, diaphragms, seals, electrical insulation, high-
pressure hose and fuel lines, and as a low-friction, wear-resistant,
corrosion-resistant covering for aircraft control cables, automotive
cables, electrical wire, and other similar applications.
POLYETHERIMIDE (ULTEM)
Materials formed from polyetherimide resins provide high performance

with a unique balance of thermal, mechanical, and electrical proper-
ties. Ultem has a tensile strength of 15,200 psi at yield (unfilled)
and a modulus of elasticity in tension of 430,000 psi and 480,000
psi in flexure (unfilled).
Polyetherimide also has a high dielectric strength (620 V/mil
at 1/16") and a low dissipation factor with a low dielectric constant.
It also has inherent flame resistance.
Chemical Resistance
Ultem exhibits a broad range of chemical resistance to hydrocarbons
(gasoline and oils), alcohols, fully chlorinated and fluorinated hydro-
carbons, acids, and dilute bases.
POLYTETRAFLUOROETHYLENE
Polytetrafluoroethylene (PTFE) is the oldest and best known of

the fluoropolymers. Although not a true elastomeric material, it
does find some applications in the field of elastomers. It is manu-
factured under such trade names as Teflon (DuPont), Halon (Allied-
Signal), and Fluon (I.C.I.).
Of all the polymers, PTFE has the widest operating temperature
range—from cryogenic temperature to 500°F (260°C).
450 Schweitzer
Because it is the most expensive of the elastomeric materials,

its use is limited to those severe applications requiring the extremely
good corrosion resistance of PTFE.
Chemical Resistance
Polytetrafluoroethylene is virtually immune to chemical attack. Only
molten alkali metals, fluorides of chlorine or oxygen, and free
fluorine will attack it.

It is unaffected by sun, weather, or ozone contact.
FLUORINATED ETHYLENE PROPYLENE
Fluorinated ethylene propylene (FEP), a fully fluorinated thermo-

plastic, is similar in properties to PTFE, but it has a lower operating
temperature, 350°F (204°C). Its corrosion resistance, weathering
resistance, and resistance to sun and ozone is the same as that
of PTFE.
ECTFE (HALAR)
ECTFE is a copolymer of ethylene and chlorotrifluoroethylene and

has a maximum operating temperature of 320°F (150°C). It possesses
good electrical properties with excellent impact strength and has
the best abrasion resistance of any of the fluoropolymers.
Chemical Resistance
Because ECTFE is not completely fluorinated, there are sites along
the polymer chain where chemical attack can occur. Aliphatic and
aromatic amines, ethers, ketones, and chlorinated hydrocarbons
will attack ECTFE over 150°F (66°C); acetic acid over 200°F (93°C);
and aromatic solvents over 250°F (121°C). It is resistant to mineral
acids up to 250°F (121°C).

ECTFE is unaffected when exposed to sun, weather, or ozone.
Applications
Uses for this material are found in wire and cable insulations and
jacketing for all types of applications, seals, gaskets, tubing and
hose.
ETFE (TEFZEL)
This is a partially fluorinated copolymer of ethylene and tetrafluoro-

ethylene having a maximum service temperature of 300°F (149°C).
It also exhibits good electrical properties.
Chemical Resistance
ETFE has good resistance to strong mineral acids, inorganic bases,
metal salt solutions, and halogens. Testing should be performed
before using in contact with alcohols, ketones, esters, and chlori-
nated hydrocarbons, even though these classes of materials, in
general, have little effect on ETFE.
Strong oxidizers ( e . g . , nitric acid), organic bases (amines),
and sulfonic acid will attack ETFE.

Exposure to sun, weather, and ozone will not affect ETFE.
Applications
ETFE finds applications similar to those of ECTFE but with lower
maximum operating temperatures.
17
COATINGS
KENNETH B. TATOR KTA-Tator I n c . , Pittsburgh, Pennsylvania
INTRODUCTION
Paints (or coatings if used primarily for corrosion protection) are

something that we are all familiar with, to some degree. Virtually
everywhere one looks, paint can be seen: furniture, houses, auto-
mobiles, trucks, ships, airplanes, bridges, chemical plants, nuclear
power plants—literally everywhere. Additionally, paint is used for
a variety of purposes, for example in the house alone, paints can
be used to provide an aesthetically appealing interior and a protective
durable exterior, to provide mildew and add rot resistance to wood,
to seal masonry from water, and to seal the substrate and improve
sanitation and cleanup in such areas as the kitchen and bathroom.
The major advantage of paints and coatings, accounting for this
widespread use, is that they relatively inexpensively provide good
gloss, color, and decorative effects, while also protecting from
the effects of the environment. Most important, however, is that
paints are readily available and can be applied by a variety of
methods, ranging from simple brush and roller (commonly employed
by the do-it-yourself housepainter) to the rather sophisticated
automated finishing lines employing electrostatic spray, fluidized
bed (for powder coatings), coil coating and baking lines, and other
technically complex application methods. Accordingly, the ability
of a diverse variety of users to apply satisfactorily an almost end-
less variety of paint formulations, by a plethora of different means,
has led to the development of the painting industry (and allied
industries) as major factors in the economy. Of all methods of
453
454 Tator
corrosion prevention described in this book, painting and protection

by coatings is certainly the most widely used.
Coating for corrosion protection should be considered an engineer-
ing function, consisting of design considerations; selection of a
suitable coating system; surface preparation requirements; coating
application considerations, including control of ambient conditions
during application; certain special considerations (such as thickness,
variances for application condition, substrate condition, etc.); and,
finally, scheduled inspection and maintenance. Each of these subjects
is considered in order.
COATING SYSTEM SELECTION
Factors important in the selection of a coating system for corrosion

protection will be enumerated and discussed. The importance and,
therefore, weight of any single factor will vary from application
to application but, for most uses, the factors are listed in decreasing
order.
Service Environment
It is almost self-evident that different environments will require
different paints to protect from that environment. Not so evident
is that many environments are too severe for protection by any
kind of paint. As a general rule, corrosion rates exceeding 50
mil/yr (mpy) are too severe for protection by coatings: other
methods, such as lining, choice of a more resistant substrate,
other protection methods, or a combination of these in conjunction
with coatings should be used. As a general rule, the more severe
environments (chemical immersion, splash, or spillage, salt- and
freshwater immersion) require more durable coating systems, which
are specially pigmented, using synthetic resins as binders. Such
coatings often require more extensive surface preparation and more
exacting application, equipment, and techniques. In less severe
environments, appropriate compromises can be made in both the
coating type and the surface preparation and application require-
ments. Table 1 illustrates this principle.
Expected Longevity
The duration of corrosion protection afforded by the coating system
is of major importance. Most commonly, once a decision has been
made to coat, it is desirable to have the coating last as long as
reasonably possible. On the other hand, if protection longevity
17. Coatings 455
TABLE 1 Painting Systems for Environmental Zones
Painting system
Zone conditions suggestions
0 Dry interiors where structural steel is em- Leave unpainted

bedded in concrete, encased in masonry,
or protected by membrane or contact-type
firep roofing
1A Interior, normally dry (or temporary protec- Latex or one-
tion) ; very mild (oil-based paints now last coat
10 years or more)
IB Exteriors, normally dry (includes most areas Oil-based
where oil-based paints now last 6 years or
more)
2A Frequently wet by freshwater; involves con- Vinyl, coal tar
densation, splash, spray, or frequent epoxy, epoxy,
immersion (oil-based paints now last 5 years chlorinated
or less) rubber
2B Frequently wet by saltwater; involves con- Zinc-rich, vinyl
densation, splash, spray, or frequent coal tar epoxy,
immersion (oil-based paints now last 3 epoxy
years or less)
3A Chemical exposure, acidic (pH 5 or lower) Vinyl, polyester
3B Chemical exposure, neutral (pH 5 to 10) Zinc-rich
3D Chemical exposure, presence of mild Epoxy, urethane
solvents; intermittent contact with
aliphatic hydrocarbons (mineral spirits,
lower alcohols, glycols, etc.)
3E Chemical exposure, severe; includes oxi- Use specific
dizing chemicals, strong solvents, or com- exposure data
binations of these with high temperatures
is not of utmost concern (which happens more often than one might
think), less expensive systems may be chosen. The automotive
industry has long been accused of planned obsolescence—and auto
body rust-through and corrosion deterioration are said to be factors
in this. Some automobile manufacturers are now advertising their
use of more corrosion-resistant paints and materials but, for the
most part, automotive finishes do not last more than a few years.
456 Tator
Similarly, porch and lawn furniture and original equipment manufac-

tured (OEM) items, such as motor housing, pipe, conduit, and
electrical boxes, are painted to look good at the time of sale. How-
ever, if long-term corrosion protection is needed, a special painting
order must be placed far in advance, or additional painting for
protection must be done by the purchaser. Many industrial organi-
zations and nuclear power facilities purchase unpainted or OEM-
painted items and then routinely repaint with a more protective
coating system before placing the item in service.
Cost
Cost is an obvious, but often unplanned consideration. Most painting
operations can be best, and most economically, done in a fabricating
shop or commercial coating facility. Surface preparation can be
done by chemical cleaning in large vats or by mechanical blast clean-
ing in shop facilities. Both chemical and shop blast cleaning can
be done in controlled environments using automated facilities. Corre-
spondingly, the application of protective coating can also be done
under relatively controlled conditions during both application and
cure. The net effect to the consumer is a superior coating job at
a reduced cost. Too often, however, a specifier disregards, or
is not knowledgeable of, the appropriate coating economics, and
unnecessarily specifies surface preparation and coating in the field
at the time of, or after, erection or installation. In almost every
case, painting in a shop or commercial facility is less expensive
than painting at a job site. When painting structural steel, painting
on the ground is almost always cheaper than painting in the air.
In corrosion environments, surface preparation often, as a rule
of thumb, costs as much as 50% or more of the total painting cost.
Too often, specifiers are "penny wise and pound foolish" when
they specify a good commercial or near-white metal blast cleaning
followed by the application of an oil-based paint. Such paints oxidize
and age in the atmosphere and, by virtue of their oil, have good
wetting and penetrating properties (thus enabling their application
over poorly prepared surfaces). Perhaps a more suitable choice
over a thoroughly blast-cleaned surface would be the choice of
a synthetic resin coating, or zinc-rich primer, which can often
be applied at approximately the same cost but gives far superior
corrosion protection.
Table 2 illustrates a cost comparison using expensive and cheap
paint. The initial savings using the cheap paint usually cannot
be justified for corrosion protection. The cost of paint is only a
minor cost in the cost of a total coating job.
17. Coatings 457
TABLE 2 Cost of Painting: Cheap Versus Expensive Paint
Cheap Expensive
Prime
cost per gallon $10.50 $20.00
coverage per gallon 200 ft2 250 ft2
thickness per coat 1 mil 1 mil
Body
cost per gallon $10.50 $16.00
coverage per gallon 200 ft2 175 ft2
thickness per coat 1 mil 2 mil
Material cost/coat for prime — 5.6 cents
Material cost/coat for body 5.25 cents 9.0 cents
Number of coats for 5 mil 5 3
Paint thickness obtained 5 mil 5 mil
2
Cost/ft
material 26.25 cents 23.6 cents
surface preparation 40.0 cents 40.0 cents
application labor 35.5 cents 20.5 cents
scaffolding, misc. 6.0 cents 6.0 cents
Total direct applied cost 107.75 90.1
Suitability (or Availability) of Necessary Surface

Preparation and Application Means
In some environments, certain surface preparation and coating appli-
cation techniques are not permissible. For example, many companies
do not permit open blast cleaning where there is a prevalence of
electrical motors or hydraulic equipment. Refineries, as a general
rule, do not permit open blast cleaning, or for that matter, any
method of surface preparation that might result in the possibility
of a spark, static electricity buildup, or an explosion hazard. During
the course of construction or erection, many areas requiring protec-
tion are enclosed or covered, or so positioned that access is difficult
or impossible. Consideration must be given to painting such struc-
tures before installation.
By virtue of the equipment used, some methods of coating cannot
be done anywhere but at a specialized facility. Such facilities are
not readily transportable to field sites, and accordingly, these
458 Tator
methods are precluded from field use. Good examples might be most
chemical cleaning, including pickling and acid etching, automatic
rotary wheel blast cleaning, and automatic spraying, electrostatic,
or high-speed roller coating application.
ENVIRONMENTAL COMPLIANCE
Recently, there has been a considerable amount of enacted, or

proposed, legislation to limit the use of potentially harmful or toxic
coating materials, and to regulate surface preparation and coating
application techniques.
For example, although the use of lead in house paints has been
prohibited since 1973, lead-containing pigments (red lead, lead
chromate, lead suboxide) are still some of the best anticorrosive
pigments available. Consequently, these pigments have not been
regulated for nonhousehold uses. However, legislation pertaining
to worker and environmental protection is drastically curtailing
the use of lead pigments and other toxic pigments (such as chromates,
mercuries, and tin). Although such pigments can be legally used
in a paint, substantial costs for worker protection and environ-
mentally compliant containment and disposal are effectively precluding
the use of these pigments in most new coating formulations.
Similarly, restrictions on the volatile organic content (VOC)
of coatings has been legislated by many air pollution control districts
in California. It is felt that within a few years, such legislation
will be forthcoming throughout the United States. The California
VOC rule prohibits the manufacture, sale, or use of designated
industrial maintenance primers and topcoats if the VOC content
exceeds certain limits (commonly 420 g/L; 3.5 lb/gal) for most
paints. It has been determined that almost all volatilizing solvents
react under the influence of ultraviolet light and degrade to form
smog and to deplete the ozone layer. Because of the California
legislation and similar legislation in other states, many coating manu-
facturers are formulating water-based paints, or high-solids (low-
solvent) coating materials to comply with these environmental
concerns.
Of major concern are the many industrial facilities and highway
bridges that are coated with old, lead-containing paints. Environ-
mental Protection Agency (EPA) legislation requires the disposal
of removed paints (and spent abrasive) in hazardous waste disposal
sites if the leachate, after acid digestion (pH 5), contains more
than 5 ppm of lead or chromate, and 2 ppm of mercury. The costs
of such a disposal, not including collection costs, are estimated by
many painting contractors to be from 6 to 10 times as much as
17. Coatings 459
disposal costs in a normal sanitary landfill. The cost of containing

the spent abrasive and paint, as opposed to letting the spent abra-
sive fall to the ground during blast cleaning, may in itself double,
or triple, the cost of the paint job.
The recent expansion of the OSHA Hazardous Communication
Standard and the enactment of the Superfund Amendments and
Reauthorization Act of 1986 (SARA)—Title III Emergency Planning
and Community Right to Know Act of 1986 have focused attention
on both individuals' rights to knowledge about their exposure to
hazardous materials, and the potential for community exposure to
hazardous materials used in the workplace. The combination of in-
creasing awareness of, and regulatory restrictions for the use of
hazardous materials is, without doubt, changing the way coatings
are being formulated and applied in many areas of the country.
Accordingly, new VOC-compliant paints are being formulated
without use of lead, chromate, or other toxic pigments. Contingent
upon the laws (and enforcement) in various parts of the country,
perhaps a specifier may be able to choose from a limited number
of compliant coating materials. Similarly, when removing coatings
by blast cleaning, nonfree-silica-containing abrasives should be
used, and care must be taken to minimize worker exposure to in-
halation or ingestion of toxic pigments and to prevent environmental
contamination from the cleaning and paint operations. These con-
siderations will strongly influence a coating specifer in the choice
of a coating system and its prerequisite surface preparation and
application requirements.
Safety
Safety is, of course, an overriding concern in all aspects of com-
merce. Occasionally, however, besides the normal requirements
for ventilation, removal of solvents from a coating application area,
suitable and safe access to the work being painted, and so on,
other safety considerations must be anticipated. For example, most
steelworkers on high steel such as tall buildings or bridges dislike
walking on painted steel because of its slickness, and depending
on the paint color, the concealment of puddled water or surface
ice. Such a concern might eliminate most "barrierTT-type coatings
but would allow most zinc-rich coatings. Similarly, some coatings
(notably zinc-rich coatings) are formulated and applied as precon-
struction primers—to allow flame cutting without detrimental fumes
or weld quality deficiencies.
Local and federal jurisdictions have outlawed certain type of
paints (primarily those containing lead and asbestos) and are in
the process of restricting others with potentially harmful pigments
or other components.
460 Tator
Ease of Maintenance/Repair
Many coatings that offer good long-term protection after application
(particularly the thermosetting and zinc-rich coatings) are more
difficult to touch up or repair in the event of physical damage
or localized failure. Adhesion of a subsequently applied paint coat
to an older aged epoxy, urethane, or other catalyzed coating often
results in diminished adhesion, leading to peeling. Thermoplastic
coatings, as a rule, do not suffer this disadvantage because solvents
in the freshly applied coating soften and allow for intermolecular
mixing of the new and old coatings, with good intercoat adhesion
resulting. Heavily pigmented coatings (such as zinc-rich) require
agitated pots to keep the pigment in suspension during application.
Accordingly, touchup and repair of large areas, unless done by
spray using an agitated pot, is not recommended when using zinc-
rich coatings.
Generally, oil-based coatings (alkyds, epoxy esters, and modifi-
cations thereof) have a greater tolerance for poor surface preparation
and an ability to wet, penetrate, and adhere to poorly prepared
surfaces or old coatings. Often these coatings are specified for
these purposes, even though it is known that they offer less long-
term environmental protection.
Decoration /Aesthetics
Probably of least importance from a corrosion-protection viewpoint
are color, gloss, and overall appearance. However, corrosion protec-
tion coatings are available that not only offer good chemical and
environmental resistance but are aesthetically pleasing as well.
A good example of this is the aliphatic urethane, which at present
is quite expensive—but can often be justified solely on the basis
of superior appearance. The corrosion protection capability of such
coatings is not much different from some members of the epoxy
family of coatings, which are about half the cost. However, the
superior tinting ability, color, and gloss retention of the aliphatic
urethane has led to its widespread use on railroad cars, water and
fuel oil storage tanks close to public thoroughfares, aircraft, and
many structures for which public visibility is high and appearance
is important.
Certain other coatings can be modified with silicones, acrylics,
and other resins, at increased cost, to enhance their aesthetic appeal.
WHAT IS A PAINT/COATING?
A paint is generally thought of as a liquid coating applied to a sur-

face that dries or cures to form an aesthetically pleasing protective
17. Coatings 461
film. The film thickness may range from a few tenths of a mil to a
quarter of an inch or more, although thicknesses between 2 and
40 mil are by far the most common (1 mil = 1/1000 in. - 25.4 ym).
The "paint" really consists of various pigments, a resin system,
special additives of various types, and usually, water or a solvent
that evaporates shortly after application.
Resin Component
Commonly, paints are designated by their resin component (such
as vinyls, chlorinated rubbers, epoxies). The resin is the film-
forming agent of the paint, and generally the chemical and atmospheric
resistances of the paint are dependent on the specific properties
of the film former. Types of film formers and their characteristics
are presented in Table 3, and some of the most common are further
described later in the chapter.
Pigments
Pigments function to reinforce the film structurally and to provide
color and opacity as well as to serve special purposes for metal
protection.
Color or hiding pigments are selected to provide aesthetic value,
retention of gloss and color, as well as helping with film structure
and impermeability. Examples are iron oxides, titanium dioxide,
carbon or lampblack, and others.
Extenders lower the cost but are also beneficial in adding sag
resistance to the liquid paint so that edges remain covered. In
the dried paint, they reduce the permeability to water and oxygen
and provide reinforcing structure within the film. Two extenders
extensively used are talc and mica, the latter limited to about 10%
of the total pigment. Both, but mica in particular, reduce the
permeability through the film as platelike particles block permeation,
forcing water and oxygen to seek a longer path through the binder
around the particle.
Pigments must be compatible with the resin and also should be
somewhat resistant to the environment (e.g., calcium carbonate,
which is attacked by acid, should not be used in an acidic environ-
ment). Water-soluble salts are corrosion promoters, so that special
low-salt-containing pigments are used in primers for steel.
For special protective properties, primers contain one of three
kinds of pigments as follows:
1. Inert or chemically resistant These are for use in barrier coatings

in severe environments such as conditions below an acidity of pH
5 or above an alkalinity of pH 10; or as nonreactive extender
hiding or color pigments in neutral environments.
TABLE 3 Kinds of Industrial Paint and Their Characteristics
05
Coating type (SO
(formulation) Resistance Limitations Features—uses
Vinyls: polyvinyls Insoluble in oils, grease, Adhesion may be poor until Low toxicity, tasteless,
dissolved in aromatics, aliphatic hydrocarbons, all solvents have vaporized and odorless; used on
ketones, or esters and alcohols; resistant from coating; aromatics, surfaces exposed to
to water and aqueous ketones, and ester solvents potable water and on
salt solutions; not redissolve the coating; sanitary equipment;
attacked at room tem- thermoplastic; relatively widely used as industrial
perature by inorganic low thickness per coat; coatings
acids and alkalies; fire- temperature resistance:
resistant 180°F dry, 140°F wet
Chlorinated rubbers: Chemically resistant to Degraded by ultraviolet light; Excellent adherence to
resins dissolved in acids and alkalies; low hydrocarbon solvents attack metallic concrete and
hydrocarbon solvents permeability to water the coating; thermoplastic; masonry; nontoxic; used
vapor; abrasion- temperature resistance: on structures exposed to
resistant; fire-resistant 200°F dry, 120°F wet water and marine atmos-
pheres (i.e., swimming
pools)
Epoxies: polyamine Chemically resistant to Harder and less flexible than Greatest chemical and
plus epoxy resin acids, acid salts, other epoxies; less tolerant solvent resistance of
(polyamine epoxy) alkalies, and organic of moisture during applica- epoxies
solvents tion; temperature resistance:
225°F dry, 190°F wet
Poly amide plus epoxy Resistant to moisture; Chemical resistance is inferior Resistant to moisture:
resin (polyamide partially resistant to to that of the polyamine used on wet surfaces or
epoxy) acids, acid salts, alka- epoxies; temperature resist- underwater, as in tidal-
O
lies, and organic solvents ance: 225°F dry, 150°F wet zone areas of pilings,
oil rigs, etc.
Aliphatic polyamine Partially resistant to The adduct film has greater Flexible film; used on
plus partially pre- acids, acid salts, alkalies, permeability than the uni- surfaces requiring lati-
polymerized epoxy and organic solvents formly cross-linked film of tude of application o
o
(amine adduct epoxy) the amine epoxies; tempera-
ture resistance; 225°F dry,
150°F wet
Esters of epoxies and Resistant to weathering Resistance to chemicals and On surfaces requiring
fatty acids modified solvents is limited; attacked the properties of a
(epoxy ester) by alkalies; temperature high-quality oil-based
resistance: 225°F dry; appli- paint
cation time interval between
coats is critical
Coat tar plus epoxy Excellent resistance to Temperature resistance: Thick films to 10 mil
resin (amine or freshwater, saltwater, 225°F dry, 150°F wet per coat; used on clean
poly amide cured) inorganic acids, and blast-cleaned steel with-
various chemicals out a primer for immer-
sion or below-grade
service
Oil-based: coating Resistant to weather Chemical resistance is in- Lower cost than most
formulations with ferior to that of above coatings and the best
vehicles (alkyd, coatings; attacked by alka- penetrating power; used
epoxy, urethane) lies; temperature resistance: on exterior wood sur-
combined with dry- 225°F dry faces, for primers re-
ing oils quiring penetrability,
and in less severe
chemical environments
(continued)
Coating type
(formulation) Resistance Limitations Features—uses
Ur ethane
moisture cured Resistant to abrasion; Moisture-cured types require Ease of application, fast
isocyanate pre- resistant to chemicals and humidity during application; drying, toughness,
polymer reacts with solvents when cross- may yellow under ultraviolet clear or colorful formu-
atmospheric mois- linked light; temperature resistance: lations, high gloss, and
ture 250°F dry, 150°F wet ease of cleaning; used
on furniture and floors
catalyzed Very good chemical Not recommended for immer- Excellent gloss and color
aliphatic or aro- resistance (similar to sion or exposure to strong retention; used as a
matic isocyanate poly amide epoxy) acids / alkalies; temperature decorative coating of
reacted with poly- resistance: 225°F dry, tank cars and steel in
ester, epoxy, or 150°F wet; quite expensive highly corrosive en-
acrylic poly- vironments
hydroxyls
Silicones: two types Resistant (in aluminum High-temperature type re- Stable up to 1200°F;
with siloxane bond: formulation) up to quires baking for good cure; used on surfaces ex-
(1) high-temperature; 1200°F, and to weather- water repellant; water-solvent posed to high tempera-
(2) water-repellent ing at lower temperatures; formulations should be used ture as water-repellant;
in water or solvent resistant to water on limestone, cement, and ease of application, low
nonsilaceous materials; solvent cost, porosity (for
formulations on bricks and breathing), durability;
noncalcareous masonry used on masonry sur-
faces
2.
Water-based: aqueous Generally resistant to Limited penetrating power be- Ease of application, o
emulsions of poly vinyl weather cause of water surface ten- minimal odor, low cost,
acetate, acrylic, or sion; may flash-rust as a easy cleanup, compatible
styrene-butadiene latex primer over bare steel; not with other coatings;
suitable for immersion service used in general applica-
tions
o
o
Polyesters: organic Excellent resistance to Alkalies and most aromatic Inertness, tilelike
acids condensed with acids and aliphatic sol- solvents soften and swell appearance, good adhe- 5
polybasic alcohols; vents; good resistance these coatings; also, they sive and cohesive CO
styrene is a reactive to weathering have a short pot life and strength; used as lining
diluent must be applied with special materials for tanks and
equipment chemical process equip-
ment
Coal tar: distilled Excellent resistance to Exposure to ultraviolet light Used on submerged or
coking by-product in moisture; good resistance and weathering will degrade buried steel and con-
aromatic solvent to weak acids and alka- these coatings and tempera- crete
lies, petroleum oils, and tures of 100°F will soften
salts them
Asphalt: solids from Good moisture resistance; Heavy dark color hides Better weathering char-
crude oil refining in good resistance to weak corrosion under the coating; acteristics than coal
aliphatic solvents acids, alkalies, salts softens at 100°F tar; used in above-
ground weathering
environments and chemi-
cal fume atmospheres
Zinc-rich: metallic Best resistance to gal- Must have top coat in severe Organic type more toler^
zinc in an organic or vanic and pitting-type environments or when pH is ant of surface prepara-
inorganic vehicle corrosion below 6 or above 10.5; re- tion and topcoat; inor-
quires clean steel surfaces, ganic type more resist-
relatively difficult to apply ant to temperature (to
and topcoat 700°F) and abrasion;
best primer for severely
corrosive nonchemical
environments
TABLE 4 Characteristics of Pigments for Metal Protective Paints
Specific Special contribution to

Pigment gravity Color Opacity corrosion resistance
Active pigments
Red lead 8.8 Orange Fair Neutralizes film acids; insolubilizes
sulfates and chlorides; renders
water noncorrosive
Basic silicon lead chromate 3.9 Orange Poor Neutralizes film acids; insolubilizes
sulfates and chlorides; renders
water noncorrosive
Zinc yellow 3.3 Yellow Fair Neutralizes film acids; anodic
(chromate) passivator; renders water non-
corrosive
Zinc oxide 5.5 White Neutralizes film acids; renders
(French process) water noncorrosive
Zinc dust at low concentra- 7.1 Gray Good Neutralizes film acids
tion in coatings for steel
Galvanically protective pigments
Zinc dust sacrificial at 7.1 Gray Good Makes electrical contact; galvanic-
high concentration ally sacrificial
8
Barrier pigments
Quartz 2.6 Nil Translucent Inert; compatible with vinyl ester
Coat ing
additives
Extenders
CO
Mica 2.8 Nil Translucent Impermeability and inertness
Talc 2.8 Nil Translucent Impermeability and inertness
Asbestine 2.8 Nil Translucent Impermeability and inertness
Barytes 4.1 Nil Translucent Impermeability and inertness
Silica 2.3 Nil Translucent Impermeability and inertness
Colorants
Iron oxide 4.1 Red Impermeability and inertness
Iron oxide 4.1 Ochre Impermeability and inertness
Iron oxide 4.1 Black Impermeability and inertness
Titanium dioxide 4.1 White Excellent Impermeability and inertness
Carbon black 1.8 Black Good Imnermeabilitv and inertness
Note: Titanium dioxide has better "hiding" than any other pigment, by far.
468 Tator
2. Active Leads, chromates, or other inhibitive pigments are used

in linseed pil/alkyd primers.
3. Galvanically sacrificial Zinc is employed at high concentrations
to obtain electrical contact for galvanic protection in environments
between pH 5 and 10.
Types and characteristics of these pigments are presented in Table 4.
Solvents
Organic solvents (water is considered either as a solvent or an
emulsifier) usually are required only to apply the coating and,
after application, are designed to evaporate from the wet paint film.
The rate at which the solvents evaporate strongly influences the
application characteristics of the coating, and if the solvents are
partially retained and do not completely evaporate, quite often the
coating will fail prematurely by blistering or pinholing. As a general
rule, the synthetic resins (vinyls, chlorinated rubbers, epoxies,
etc.) are more polar and, therefore, are more readily dissolved
by polar solvents. However, polar solvents are most likely to be
retained by a polar resin system and, therefore, it is imperative
when using such resins, particularly in immersion service, to allow
sufficient time for the coating to cure or dry. Because such resins
are more dependent on solvents for penetration and flow, they
generally require a greater degree of surface preparation than
do oleoresinous or oil-modified coatings.
Most coatings are formulated to be most successfully applied
at ambient conditions of approximately 24°C (75°F) and 50% relative
humidity. At ambient conditions considerably higher or lower than
these optimum ranges, it is quite conceivable that the "solvent
balance" should be changed for better coating application and solvent
release. Generally, in colder weather, faster-evaporating solvents
should be used; conversely, in hot weather, slower solvents are
required. Classes and characteristics of some common solvents are
listed in Table 5.
Additives
Most additives are formulated into a paint in relatively minor, often
even trace amounts, to provide a specific function. For example,
cobalt and manganese naphthanates are used as dryers for alkyds
and other oil-based coatings to facilitate surface and thorough drying.
These drying additives are added to the paint in amounts usually
less than 0.1%.
TABLE 5 Characteristics of Solvent Classes
. Coating
Boiling Flash Evapora-
Specific range point tion
a
Class Solvent name Strength/ solvency Polarity gravity (°F) of TCC rate
CO
Aliphatic VM&P naphtha Low (32 KB) b Nonpolar 0.74 246-278 52 24.5
Mineral spirits Low (28 KB) Nonpolar 0.76 351-395 128 9.0
Aromatic Toluene High (105 KB)C Intermediate polarity 0.87 230-233 45 4.5
Xylene High (98 KB) Intermediate polarity 0.87 280-288 80 9.5
High solvency High (90 KB) Intermediate polarity 0.87 360-400 140 11.6
Ketone Methyl ethyl Strong High polarity 0.81 172-176 24 2.7
ketone (MEK)
Methyl isobutyl Strong High polarity 0.80 252-266 67 9.4
ketone (MIBK)
Cyclohexanone Strong High polarity 0.95 313-316 112 4.1
Ester Ethyl acetate Intermediate Intermediate polarity 0.90 168-172 26 2.7
Alcohol Ethanol Weak Intermediate polarity 0.79 167-178 50 6.8
Unsaturated Styrene Strong Intermediate polarity 0.90
aromatic
Glycol Cello solve Strong High polarity 0.93 273-277 110 0.3
ethers Butyl cellosolve Strong High polarity 0.90 336-343 137 0.06
a
Butyl acetate equals 1.
b
KB, Kauri-Butanol; a measure of solvent power of petroleum thinners (milliliters of thinner required to pro-
duce cloudiness when added to 20 g of a solution of karigum in butyl alcohol).
C
TCC-TAE closed cup.
470 Tator
Other additives are added for different purposes; for example,

zinc oxide can be added to retard deterioration of the resin by
heat and actinic rays of the sun. Mildew inhibitors (phenylmercury,
zinc, and cuprous compounds) are commonly added to oil-based
and latex paints. Latex paints (water emulsion) invariably have
a number of additives acting as surfactants, coalescing aids, emul-
sion stabilizers, freeze-thaw stabilizers, and so on. Vinyl paints
often have a 1% carboxylic acid (generally maleic acid) modification
to the vinyl resin to promote adhesion to metals. Conversely, a
hydroxyl modification (generally an alcohol) aids in adhesion of
vinyls to organic primers. The use of a particular additive may
be crucial to the performance of the paint, and because additives
are usually added in trace quantities, they may be most difficult
to detect upon analysis of the paint.
PAINT SYSTEMS
A paint system consists of the surface preparation, pretreatment,

if any, primer, and subsequent coats. In specifying a paint system,
TABLE 6 Typical Zone Defense System
Environment Recommendation
I. Dry interior: building interior Minimal hand or power tool

or outside exposure in an arid cleaning; painting for color,
climate, etc. aesthetics only
II. Normally dry but exposed to Hand or power tool cleaning;
weather: some bridges, tanks, alkyd- or oil-based coating
building steel, etc. system
III. Frequently wet or exposure Blast clean or pickle; alkyd
to high humidity: bridges, or oil-based with inhibitive
tanks, topside of ships, steel pigments, zinc dust, zinc
in paper mills, sewage treat- oxide paints
ment plants, etc.
IV. Continuously wet or immer- Blast clean: near-white or
sion: tank interiors, cold white metal; phenolic, epoxy,
steel, cooling towers, etc. urethane, vinyl, or zinc-rich
paint.
V. Special: exposure to specific Generally blast clean; specific
chemicals (acids, alkalies), coating for environment
heat, abrasion, etc.
17. Coatings 471
it is good practice to require a color difference for each successive

coat of paint, and to specify the thickness of each coat. In milder
environments (such as building interiors) a less thorough surface
preparation and less-resistant coating system may be specified com-
pared with the surface preparation and coating types required for
more severe environments. This philosophy is called the zone defense,
and a typical example is illustrated in Table 6.
SELECTION OF A SUITABLE COATING SYSTEM
Perhaps the first thing that should be done in the selection process
is to define the environment around the structure or item to be
protected. Is it predominantly wet (salt- or freshwater) or exposed
to a chemical contamination (acid or alkaline)? Is the atmosphere
or environment uniform over the entire structure? Is the environ-
ment predominantly a weathering environment subject to heat, cold,
daily or seasonal temperature changes, precipitation, wind (flexing),
exposure to sunlight, or detrimental solar rays? If an exterior
environment, are there nearby chemical plants, pulp and paper
mills, or heavy industries that might provide airborne pollutants?
Is color, gloss, and overall pleasing effect more important than
ultimate corrosion protection—or are the normal grays, whites, and
pastels of most corrosion-resistant coatings acceptable?
All of these questions do not have to be answered in explicit
detail, but the specifier should be generally aware of the environ-
ment in which the protective coating is expected to serve—even
before paints are chosen as the method of corrosion protection.
After the corrosive environment is categorized, a suitably resistant
coating can be selected. As mentioned previously, the resistance of
most coatings is determined by their organic components (resin or
binder). Characteristics of some of the more commonly used binders
are outlined in Table 3. This information, however, will not be
inclusive enough to select a coating system, and the reader will
require further information. Such information can be obtained readily
from a number of sources, notably books and technical papers.
Perhaps the best information source will be the local sales repre-
sentative of a paint manufacturing company specializing in corrosion
protective coatings.
Although Table 3 provides a summary of the resistances, limita-
tions, and uses of most of the more common industrial/maintenance
coating resins, the following is a somewhat more detailed discussion
of some of the more common generic types.
Thermoplastic Solvent-Deposited Resins

Protective coatings formulated from these resins do not undergo
any chemical change from the time of application until the attainment
472 Tator
of final properties as a dried protective film. Film formation is

achieved by solvent evaporation, concentrating the binder/pigment
solution and causing it ultimately to precipitate as a continuous
protective film over the surface to which it had been applied.
Shellacs and lacquers used in wood finishing fit this description,
together with other resin systems described below.
Vinyls
Vinyls are perhaps the best known and widely used resin for indus-
trial coatings in this class. Vinyl is a general term denoting any
compound containing the vinyl linkage (-CH = CH2 group). This
group, however, is contained by many compounds not commonly
thought of as vinyl coatings (such as styrene, diallylphthalate,
vinyl toluene, propylene, and many others in the ethylene family
of olefins).
For the most part, vinyl coatings are considered to be copolymers
of vinyl chloride and vinyl acetate copolymerized in approximately
86% vinyl chloride to 14% vinyl acetate. The chemical structure of
a vinyl chloride/vinyl acetate copolymer is as follows:
H H H H H. M H v / H
V / C
/ \ / \ /
c c c c
V
H-' CI Q/ S H H' NCI 0/ \
I 1
0=C - CH 3 0=C - CH 3
Often approximately 1% of the carboxylic acid or anhydride (usually

maleic acid or anhydride) is added to improve adhesion to metal
surfaces. To improve adhesion to other previously applied coatings,
1% of a hydroxyl modifier is often added, usually in the form of
an alcohol.
Because a relatively high amount of solvent (ketones and esters)
is required to dissolve a vinyl copolymer high in vinyl chloride
content, the volume of solids in solution is relatively low. As a
result, most vinyl coatings must be applied thinly (1 to 1.5 mil
per coat). Accordingly, a vinyl-coating system may require five
coats or more, and although protection generally is excellent in
the proper environment, the system is considered highly labor-
intensive. High-build vinyls have been formulated, allowing application
of the coating to 2 to 2.5 mil or more per coat. However, this ad-
vantage comes at the expense of lower performance, as the thixo-
tropes, fillers, and additives used to provide greater thickness
are also more susceptible to environmental and moisture permeation.
17. Coatings 473
Vinyls are widely specified in water immersion because of their

extreme toughness and impermeability. However, it is important
to ensure that essentially all solvents have evaporated before placing
a vinyl-coated object in immersion service. The high polarity of
the resin tends to retain the solvents used to dissolve the resin.
Solvent evaporation is retarded, with the resultant effect of solvent
voids within the vinyl coating, pinholes penetrating through a coat
or more than one coat, and blistering caused by volatilization of
retained solvents upon heating—or water-filled blisters because
of hydrogen-bonding attraction of water by the retained solvents
in the coating.
Chlorinated Rubber
Chlorinated rubber resins resulted originally from the chlorination

of natural rubber. Today, however, the term also includes the
chlorination of synthetic rubbers. The addition of chlorine to un-
saturated double bonds occurs until the final product contains
approximately 65% chlorine. The chemical structure of a segment
of the chlorinated rubber resin is as follows:
CHCI-CHCI CHCI-CHCI CHCI-CHCI

/ I / \ / • \
CHo-CCI CHOI CHo-CCI CHCI CHo-CCI CHCI
J 3 3
\ / \ / \ /
-CCI—C—CHCI-CHCI-CCI—C—CHCI-CHCI-CHCI-CCI-CHCI-CHCI-CCI—C—CHCI-CHCI-
I I I I
CH 3 CH 3 CH 3 CH 3
The result is a hard, brittle material with poor adhesion and elas-
ticity. For use in surface coatings, a plasticizer must be added.
Although a number of materials can be used as plasticizers for
chemical resistance, a nonsaponifiable plasticizer, usually of the
chlorinated paraffin or chlorinated diphenyl types, are used. The
type and amount of plasticizer in the chlorinated rubber play a
determining role in the final resistances and properties of the
chlorinated rubber paint. Chlorinated rubber resins are generally
soluble in most organic solvents—generally, all but aliphatic hydro-
carbons and alcohols. Chlorinated rubber resins have good compati-
bility with a variety of other resins, including alkyds, phenolics
(and medium to short oil resin modifications of each), acrylics,
melamine and urea formaldehyde resins, and many other natural
or synthetic resins. The addition of these materials may enhance
the ease of application but, occasionally, may diminish chemical
resistance. Unmodified chlorinated rubber resins are generally
formulated at a high molecular weight, and accordingly are somewhat
difficult to spray apply. "Cobwebbing" often occurs when spraying,
and brushing or roller application results in a noticeable "drag."
Volume solids of the coating is somewhat higher than a vinyl, and
474 Tator
a suitably protective chlorinated rubber system often consists of

only three coats.
Chlorinated rubber coatings are widely used on masonry surfaces
and as swimming pool paints. They, like vinyls, exhibit very good
adhesion after initial thorough-drying (usually 3 or 4 days to 2
weeks after application); and the same care must be taken for
solvent evaporation, as described previously for the vinyls. The
high chlorine content in the resin accounts for its inertness, its
good adhesion, and very importantly, its fire-retardant nature.
Acrylics
Acrylics can be formulated as thermoplastic resins, thermosetting
resins, and as a water emulsion latex. The resins are formed from
polymers of acrylate esters, predominantly polymethyl methacrylate
and polyethyl acrylate. The acrylate resins do not contain tertiary
hydrogens attached directly to the polymer backbone chain and,
as a result, are exceptionally stable to oxygen and ultraviolet light
deterioration. The repeating units of the acrylic backbone are joined
to make long polymer chains. The repeating units for the methacrylate
and the acrylate are as follows:
CHo
I
—CHo—C— — C H 9 — CH—
2 2
I I
0=C—OCH3 OssC—OCH2—CH3
Polymethylmethacrylate Polyethylacrylate
Acrylic resins, particularly the methacrylates, are somewhat
resistant to acids, bases, weak and moderately strong oxidizing
agents, and many corrosive industrial gases and fumes. This
resistance is mostly because the polymer backbone comprises only
carbon atoms. However, pendant side-chain ester groups although
quite resistant to hydrolysis, generally preclude the use of these
resins in immersion service or in strong chemical environments.
The resins are generally soluble in moderately hydrogen-bonded
solvents such as ketones, esters, aliphatic chlorinated hydrocarbons,
and aromatic hydrocarbons. Acrylic resins are generally quite com-
patible with most other resins (depending on the type of acrylic),
and the properties of many other resinous materials, such as alkyds,
chlorinated rubbers, epoxies, and amino resins are often "modified"
with an acrylic to improve application, lightfastness, gloss, or color
retention.
Thermosetting Resins
Thermosetting resins differ from thermoplastic resins in that a chemi-
cal change occurs after application and solvent evaporation. The
17. Coatings 475
coating is said to "cure" as the chemical reaction takes place. The

reaction can take place at room temperature, or in baked coatings,
at elevated temperatures. The reaction is irreversible and, unlike
a thermoplastic coating, high temperatures or exposure to solvents
does not cause the coating to soften or melt. Thermosetting resins
used as binders for industrial coatings have become increasingly
important for two primary reasons
1. They can be formulated and applied at low molecular weight

with the adherent advantage of low solvent demand, relatively
good penetration and wettability, and in-can stability and long
shelf life (all but moisture-curing thermosetting resins are pack-
aged as two or more components, and mixing of these components
is necessary before the chemical reaction can take place).
2. Once applied and allowed to cure, the resultant film is generally
a large macromolecule with a defined state of cross-linking density,
resulting in a flexibility and chemical resistance that can be
tailored for a given environment.
The more tightly cross-linked thermoset coatings, as a general

rule, are more chemical- and solvent-resistant, but they are also
less flexible, more brittle, and generally have poorer adhesion.
Care must be taken when topcoating an aged thermoset coating
because solvents in the freshly applied topcoat will not soften or
swell the aged undercoat, with the effect that poor intercoat adhesion
may result. Some of the more common thermoset resins will now be
described.
Epoxies
The epoxy resin itself is a common condensation product of epi-
chlorohydrin and bisphenyl acetone.
H H
H | I
C-C-C-C-CL
/ \ / I I
L H 0 H H
EPICHLORHYDRIN BISPHENOL ACETONE

H H Q
J
H H H
I 1 /=x I I II I
-0- 0 HCI
-o-c-c-c-
I I I
0 H H OHH
Epoxy resins themselves are not suitable for protective coatings

because when pigmented and applied, they dry to a hard, brittle
film with very poor chemical resistance. However, when suitably
476 Tator
copoly'merized with other resins (notably those of the amine or poly-

amide family) or esterified with fatty acids, epoxy resins will form
a durable protective coating. Epoxy resins copolymerized with amines
and polyamides are discussed in this section. Esterified epoxy resins
are discussed in the next section under autooxidative cross-linking
resins.
The epoxy resin can react through pendant hydroxyl groups
or the terminal oxirane ring. The characteristics of the final film
depend on the molecular weight of the epoxy resins used, the co-
reactirig resin, and modifiers such as phenolic resins or coal tars.
Amine resins, usually diethylene triamine or triethylene tetramine,
or similar aliphatic polyamines, react to give a relatively highly
cross-linked chemically resistant but hard-curing and relatively
inflexible film. The following structure is that of an epoxy cross-
linked with amine (e.g., diethylene triamine).
H ^ O
^ I I I I I •HO ~HO> ' ! ' '
N-C-C-N-C-C-N N-C-C-N-C-C-N
' ' ' ' ' \u u/ ' ' ' '
H H
CR
EPOXY ^ o °SSLINK > ~°H
— OH
H H
\ I I II / \ II II
N_C-C-N-C-C-N n w N-C-C-N-C-C-N OH
"A" ^°o v
o> '' ' '
EPOXY EPOXY
Active hydrogens from the amine nitrogen react to open epoxy rings
forming hydroxyl groups, thereby cross-linking the nitrogen atom
with the epoxy carbon. The hydroxyl groups may also open the
epoxy ring to further cross-link and eliminate H2O. Note that there
are no ester links. Increased flexibility with only a slight loss of
chemical resistance can be achieved by prereacting some of the
epoxy resin with an aliphatic polyamine during paint manufacture.
At the time of application, the prereacted resin is mixed with addi-
tional amine and applied. Paints formulated in this way are called
amine adducts.
Polyamide resins can also be reacted with e£>oxies to form durable
protective coatings. These resins are somewhat bulkier than the
amine by virtue of their fatty acid modification. Accordingly, they
impart more flexibility to the cross-linked resin. Polyamide-cured
epoxies are also more resistant to chalking, and are more receptive
to topcoating after extended intervals than are amine-cured epoxies.
Polyamide adducts can be made in a manner similar to that described
for amine adducts. Cross-linking takes place by opening the epoxy
17. Coatings 477
ring with active hydrogens from the polyamide nitrogen in the manner
illustrated for amine epoxies. A typical polyamide with epoxy resin
is as follows:
:o H:
: ii i :
: C 7 N :-CH 2 -CH 2 -N-R
AMINO LINKAGE-
H
/CH ^ :o
:„ H, I
C CH-(CH 2 ) 7 -:C-N - C H 2 - C H 2 - N - R '
c / CH-CH 2 -CH = CH ' (CH 2 ) 4 -CH 3

H
(CH2)5 TYPICAL POLYAMID RESIN MOLECULE
R AND R' ARE ALKYL OR ARYL GROUPS
CH 3
Ketimine-cured epoxies enable the application of a solventless

or 95 to 100% high-solids epoxy coating with standard spray applica-
tion equipment. A ketimine under dry conditions reacts very slowly
with epoxy resins, but in the presence of water or humidity, the
ketimine reacts to decompose into a polyamine and a ketone.
R, R, H H 0
1
\ / \ / II
C=N-R-N=C + 2H9O • N-R-N + 2R 1 -C-R O
1 2
/ \ / \
Ro ""o ^
KETIMINE + MOISTURE — • POLYAMINE + KETONE

R, R l , and R2 are Alkyl Groups
The ketone evaporates, and the polyamine then reacts with the
epoxy resin in a normal fashion. Ketimine-cured epoxies should
not be applied at thicknesses of more than 8 mil, or so, in one
coat to allow moisture access and complete curing.
Epoxy coatings, generally cross-linked with amines or polyamines,
are widely used as heavy-duty moisture- and chemical-resistant
coatings and linings in immersion and atmospheric fume environments.
Amine- and polyamide-cured epoxies, when combined with approxi-
mately 50% or so of refined coal tar, are one of the least water-
permeable coatings available. Coal tar epoxies, however, because
of the ultraviolet sensitivity of coal tar pitch, are normally not
used in atmospheric exposures. However, for below-grade protection
(e.g., buried pipelines) and in immersion service, they are con-
sidered excellent.
478 Tator
Other curing agents, such as imidazolines or any other resin

with an active hydrogen, can be used to cross-link an epoxy resin.
Such resins are of less commercial importance and will not be dis-
cussed.
Urethanes
Urethanes are reaction products of isocyanates with materials possess-
ing hydroxyl groups, and simply contain a substantial number of
urethane groups, regardless of what the rest of the molecule may
be.
1. With hydroxyl-bearing polyesters, polyethers, epoxies, and so on:

H 0
I II
R_N=C=O + R^-OH >R-N-C-O-R'
ISOCYANATE URETHANE
LINKAGE
2. With an amine:
H o H
I Hi
R-N=C=O + R'-NH2 > R-N-C-N-R'
A UREA
3. With an amide:
HO H0 0
I II I H I1
R-N=C=O + R'-N-C-R" > R-N-C-N-C-R"
R'
AN ACYLUREA
4. With moisture:
R-N=C=O + HOH > R-NH2 + CO2t
R-N=C=O > A UREA
SEE 2 ABOVE
The polyol side (hydroxyl-containing) may consist of a number

of materials, including water (moisture-cured urethanes), as well
as epoxies, polyesters, acrylics, and drying oils (discussed later
in this chapter). Epoxy and polyester polyols are more chemically
and moisture-resistant (and somewhat more expensive) than acrylic
polyols. The acrylic polyol, however, when suitably reacted to
form a urethane coating is entirely satisfactory for most weathering
17. Coatings 479
environments. The isocyanate can be either aliphatic or aromatic.

Up to the last 6 or 8 years, aromatic isocyanates (often toluene
diisocyanate and diphenylmethane diisocyanate) were most commonly
used for urethane coatings. Generalizing, however, the aromatic
urethanes have properties not significantly dissimilar from those
of the epoxy family of coatings. However, the cost for urethanes
is somewhat higher and, accordingly, widespread use of aromatic
urethanes has not occurred.
However, this is changing rapidly as a result of the increasing
availability of aliphatic isocyanates. While coatings formulated with
aliphatic isocyanates are extremely expensive (approximately twice
the cost of similarly formulated epoxy and aromatic urethanes), they
have superior color and gloss retention and resistance to deterioration
by sunlight. Whereas most other coatings will chalk or yellow some-
what upon prolonged exposure to sun, aliphatic urethanes continue
to maintain a glossy, "wet" look years after application. Furthermore,
they can be tinted readily, and a wide variety of deep and pastel
colors are available. Care should be taken to ensure that the pig-
ment used and the polyol-containing coreactant are light-stable
or, if not, used in small proportions. Aliphatic urethane protective
coatings, primarily because of the high initial molecular weight
of the aliphatic isocyanate, are generally formulated to be applied
at somewhat lesser thicknesses (1.5 to 2.0 mil per coat) than similar
aromatic urethane coatings.
Formulation of urethane coatings is important, as the isocyanate
component will, to some degree, always react with moisture in the
air. The reaction is accelerated by high humidities, and in the
presence of sunlight or heat, results in the liberation of carbon
dioxide gas. Poorly formulated coatings may foam, bubble, or gas,
and the dried film may have numerous voids or pinholes.
Urethane coatings are not suitable for immersion service or for
prolonged exposure to water or strong chemical environments.
Polyesters
The term polyester means many ester groups, and as such would
include alkyds, drying oils, and many ester-containing materials
O
ii
-C-O-). However, as used in the coatings industry, polyesters
are characterized by resins based on components that introduce
unsaturation (-C=C-) directly into the polymer backbone. The follow-
ing structure shows an isophthalic polyester resin:
0 0 HO 0 H H 0 O H H
I I
- O - Ci - O - Cii - / ~
/~- \\ - Cn- O - iC-C-O-C-C=C-C-»
II II I I II
OH-C-C=C-C- -O-C-C-OH
I I I I I I I
H H H H H H H
H H
n
n = 3 to 6
480 Tator
This unsaturation must be capable of direct addition copolymerization

with vinyl monomers (usually styrene). Most commonly, polyester
resins are polymerization products of maleic or isophthalic anhydride
or their acids. During paint manufacture, the polyester resin is
dissolved in the styrene monomer, together with pigment, and small
amounts of a reaction inhibitor. Additional styrene, and a free-radical
initiator, commonly a peroxide, are packaged in another container.
At the time of application, the containers are mixed or, because
of the fast initiating reaction (short pot life), mixed in an externally
mixing or dual-headed spray gun. After mixing (and application)
a relatively rapid reaction occurs, resulting in cross-linking and
polymerization of the monomeric styrene with the polyester resin.
The resultant coating is highly cross-linked, relatively brittle,
and resistant to most acids, mild alkalis, solvents, and so on.
Pigmentation of sprayed polyester coating is important because of
the high shrinkage of the resin system after application. Proper
pigmentation reinforces the coating and reduces the effect of the
shrinkage. With spray-applied polyester coatings, a small amount
of wax is often added to minimize surface evaporation of the volatile
styrene monomer. Such a wax, if used, together with a high degree
of cross-linking and solvent impermeability, may interfere with the
adhesion of subsequently applied coats.
Vinyl esters, a relatively new class of coatings said to have
higher temperature and greater acid resistance, are formulated
in a similar manner and have essentially the same application limita-
tions. Instead of using a polyester resin, the vinyl esters derive
from a resin based on a reactive end vinyl group which can open
and polymerize. The chemical structure of the vinyl ester is shown
below (contrast with an isophthalic polyester shown previously).
H H OH H-C-H H OH H 0 H
I I / v I / v I I I II /
c=c-c-o- .c-c-o-Q-c-Q-o-
-C-C-C-O-C-C=C
I I I I H
H H H-C-H H H H H
H n = 1 or 2
Note that there are fewer ester groups in the molecular structure
of a vinyl ester than in a polyester. Additionally, there is less
C=C unsaturation and a more symmetrical molecular structure, with
less polarity. Accordingly, the vinyl ester has better moisture and
chemical resistance and is more stable than the polyester.
When applying both polyesters and vinyl esters, care should
be taken to ensure that the surface is dry (particularly if applying
over concrete) because moisture may inhibit the curing reaction.
Additionally, excessive thicknesses should not be applied unless
special reinforcing (such as a fiberglass cloth) is introduced. Two
17. Coatings 481
or three thin coats is better than one thick coat, and the attainment
of a substantial surface roughness (a high anchor pattern of blast-
cleaned steel, or a broom-finished or otherwise roughened concrete
surface) will be necessary for proper adhesion.
Autooxidative Cross-Linking Coatings

Coatings of this type all rely on the reaction of a drying oil with
oxygen to introduce cross-linking within the resin and attainment
of final film properties. In every case, then, a drying oil is reacted
with a resin, which is then combined with pigments and solvents
to form the final coating. The formulated paint can be packaged
in a single can. After opening the can, mixing the paint, and apply-
ing it, the solvents evaporate and the coating becomes hard. How-
ever, the attainment of final film properties may occur weeks or
even months after application, as oxygen reacts with the coating,
introducing additional cross-linking.
For industrial maintenance paints, autooxidative cross-linking-type
coatings as a class are very commonly used. Alkyds, epoxy esters,
oil-modified urethanes, and so on, are frequently used in atmospheric
service. These resin-fortified "oil-based paints" are widely used
both in industry and around the house. By choice of an appropriate
resin, and the use of the proper amount of a given drying oil,
the properties of the coating can be varied considerably. The coat-
ings can be formulated as air-drying or baking types, and with
suitable pigments can be formulated to be resistant to a variety
of moisture and chemical fume environments; as well as for application
over wood, metal, and masonry substrates.
An example of an autooxidative coating is the epoxy ester, which
is made as follows:
0
\>
+ R C
-VC-V - ~OH •R-C-O-C + H20
OH \>
EPOXY RESIN FATTY ACID REACTION THRU HYDROXYL
0 O 0 0 0 O
6-U ] n _cQ• + H-LOH >R-£-O-[ ] n - ^ C + R-LOH-ÊTC.
REACTION THRU TERMINAL EPOXY
WHERE R IS A FATTY ACID SUCH AS LINOLENIC"

H H H H H H H H H H H 0
i i i i i i i i i ir i i H
H-C-C-C=C-C-C=C-C-C=C - C - C-OH
I I i i L i J7
7
H H H H H
OR A POLYBASIC ACID (MORE THAN ONE CARBOXYL GROUP).
482 Tator
The result is a large, bulky epoxy ester molecule with ester linkages
in both the backbone and pendant side chains.
The major advantage of these coatings is their ease of application,
their great versatility, excellent adhesion (wetting by virtue of
the oil modification), relatively good environmental resistance (in
all but immersion and high chemical fume environments), their wide-
spread availability, and tolerance for poorer surface preparation
than any of the coating systems based on synthetic resins (all de-
scribed previously). The major disadvantage is the lessened moisture
and chemical resistance compared with those coatings.
Water-Soluble Resins and Emulsion Coatings

Water-soluble resins, except for some baking formulations, have
not made inroads into the heavy-duty industrial or maintenance
coating market. However, because of increasing governmental legis-
lation restricting the amount of volatile organic solvents allowed
in the coating formulation, or to be emitted by a prospective user,
increasing attention will be given to these resins. Essentially, any
type of resin can be made water soluble. Sufficient carboxyl groups
are introduced into the polymer, giving it a high acid value. These
groups are then neutralized with a volatile base, such as ammonia
or an amine, rendering the resin a polymeric salt, soluble in water
or water/ether-alcohol mixtures. The major disadvantage to such
resins (and the reason they are not yet widely used) is that polymers
designed to be dissolved in water will remain permanently sensitive
to it. Because of water1 s abundance in nature, such sensitivity
is highly undesirable.
Water emulsion coatings, on the other hand, have gained wide
acceptance and are now by far the most popular paint sold to home-
owners and commercial painters.
Water-based latex emulsions consist of a high-molecular-weight
resin in the form of microscopically fine particles of high-molecular-
weight copolymers of poly vinyl chloride or poly vinyl acetate, acrylic
esters, styrene-butadiene, or other resins, combined with pigments,
plasticizers, UV stabilizers, and other ingredients. The water phase
carries a variety of thickeners, coalescing aids, and other additives.
Even a water-based epoxy has been manufactured, based on emulsion
principles, and is commercially available. The epoxy resin and a
polyamide copolymer are emulsified and packaged in separate con-
tainers. Upon mixing, coalescence, and ultimate drying, the polyamide
reacts with the epoxy to form the final film.
Emulsion coatings initially form a film by water evaporation.
As the water evaporates, the emulsified particles come closer and
closer together until they touch each other. The latex particles,
17. Coatings 483
with the aid of a coalescing agent (usually a slow-evaporating sol-

vent), ultimately merge to form a relatively continuous film. Because
of irregularities in the physical packing of the emulsion particles,
latex films are not noted for their impermeability. Also, initial
adhesion may be relatively poor as the water continues to evaporate,
and coalescing aids, solvents, and surfactants evaporate or are
leached from the "curing" film. Later, from as little as a few days
to as long as a few months after application, the latex coating
attains its final adhesion and environmentally resistant properties.
The major advantage of water emulsion coatings is their ease
of cleanup, their low atmospheric pollution (little or no solvent
evaporation), the high inherent durability of the organic emulsion
resins (because of their high molecular weight), and their wide
compatibility with virtually all other coatings (except bituminous
coatings—asphaltic and coal tar, which tend to bleed and discolor
most other coatings—and wax- or grease-based coating systems).
Disadvantages are the permanent water sensitivity of the coating
and, accordingly, their inability to be used in immersion or continu-
ally wet environments. Problems of initial adhesion exist, and water-
based coatings cannot be applied to blast-cleaned steel surfaces
with the same confidence as can solvent-based coatings.
Zinc-Rich Coatings
All the preceding coatings owe their final film properties, corrosion
protection, and environmental resistance in major part to the organic
composition of their constituent resin or binder. The pigment, al-
though playing an important role in the corrosion-inhibiting nature
of these coatings, is secondary to the resistance of the organic
binders.
On the other hand, the role of the pigment in a zinc-rich coating
predominates, and the high amount of zinc dust metal in the dried
film determines the coating's fundamental property: galvanic protec-
tion! Thus, although many of the binder systems described previously
(chlorinated rubber and epoxies in particular) are formulated as
zinc-rich coatings, the high pigment content dramatically changes
the characteristics of the formulated coating.
Recently, urethane zinc-rich coatings have been formulated. These
materials are easily applied compared with most other zinc-rich
coatings, but still provide galvanic protection typical of the zinc-
rich systems.
Zinc-rich coatings are commonly subcategorized as organic or
inorganic. The organic zinc-riches have organic binders, with poly-
amide epoxies and chlorinated rubber binders being the most common.
Additionally, high-molecular-weight polyhydroxyl ether epoxy (phenoxy
484 Tator
types) can also be used. Phenoxys are high-molecular-weight thermo-

plastic resins that do not have reactive terminal oxirane groups and
are, themselves, thermally stable with a long shelf life. Upon solvent
evaporation, the resin can be used by itself as a coating with no
chemical conversion, or it can be reacted with a coconstituent.
Organic zinc-rich coatings can also be formulated with other
binders, and formulations using alkyds and epoxy esters are widely
used in the automotive industry (but are not recommended as suitable
vehicles for field-applied, air-dried industrial or maintenance primers).
Vinyl and styrene-butadiene resins also have been used for zinc-rich
coatings; although some vinyl zinc-riches are still available, styrene-
butadiene is no longer used.
Inorganic zinc-rich binders are based on silicate solutions, which
after curing or drying, crystallize and form an inorganic matrix,
holding zinc dust particles together and to the steel substrate.
The ethyl silicate zinc-rich primer-curing reaction is
OR OR OR
i
2 RO-Si-OR + H 2 O - > R O - S i - O - S i - O R + 2ROH
L OR J OR OR Ethyl Alcohol
Tetra ethyl ortho silicate

(R=C 2 H 2 ) Partially Hydrolyzed Teos
I I I
-Si-O-Si-O-Si-
OR OR I I I
I I + n H2O 0 0 0 + n ROH
RO-Si-O-Si-OR I I I Ethyl Alcohol
I I Atmospheric -Si—0—Si—0—Si—
OR OR Moisture i I I
0 0 0
I I I
-Si—0—Si—0—Si—
I I I
Crosslinked Silicate Binder
The first zinc-rich coatings were postcured (by the application

of heat or acid) water-based sodium silicate solutions; and later
lithium, potassium, ammonium, and other alkali silicates were used.
It is still felt by many that the postcured inorganic zinc-rich silicates
provide the best binder and the longest protection of any zinc-rich
primer. However, they are rather difficult to apply and somewhat
labor-intensive because, after application, a curing solution must
be applied and—if topcoated—brushed off. Consequently, self-curing
inorganic silicates have been developed, based on some of these
same alkali silicates and, additionally, alkyl silicates (notably ethyl
silicate). These organic silicates, upon curing, react with atmospheric
17. Coatings 485
moisture to form alcohol, which volatilizes. The resulting film is

inorganic and essentially the same as that of the alkali silicate.
Single-package inorganic resins have recently appeared on the market.
Single-package materials are based on ethyl silicate or polyalcohol
silicate binders. For a coating to be considered zinc-rich, the common
rule of thumb is that there must be at least 75% by weight of zinc
dust in the dry film. Recently, however, this has been controversial,
as conductive extenders (notably di-iron phosphide) have been sold
to enhance weldability and burn-through, with supposedly equivalent
corrosion protection at lower zinc loadings. Resinous organic addi-
tives, such as vinyl butyrate, have been added to some inorganic
formulations to form a hybrid zinc-rich formulation that is between
the organic and inorganic. These, together with the addition of
conventional inhibitive pigments (such as the chromates, leads,
etc.), may result in equivalent performance (Particularly when
topcoated) at lower zinc-loading levels.
The major advantage of the use of zinc-rich coatings is that
they protect galvanically. The zinc pigment in the coating preferen-
tially sacrifices itself in the electrochemical corrosion reaction to
protect the underlying steel (which is cathodic to zinc in the electro-
motive series). This galvanic reaction, combined with the filling
and sealing effect of zinc reaction products (notably zinc carbonate,
zinc hydroxide, and complex zinc salts), provide more effective
corrosion protection to steel substrates than does any other type
of coating.
Zinc-rich coatings, by virtue of the amphoteric nature of the
zinc dust pigment, cannot be used in aggressive acid or alkaline
environments (pH outside the range 6 to 10.5). Furthermore, because
of their high pigment content, they are considered relatively porous,
and they are more difficult to topcoat (particularly the inorganics)
than are conventionally pigmented coatings. Because of the galvanic
protective nature, intimate contact with the underlying steel must
be attained, thus, resulting in the requirement for very thorough
blast cleaning or pickling before zinc-rich application. The high
pigment weight in the coating makes spray application more difficult
than most organic coatings and, additionally, increases the possibility
of "mudcracking" at excessive thicknesses. Generally, thicknesses
above 5 mil per coat are not recommended.
COATING APPLICATION, INSPECTION,

AND MAINTENANCE
Once the coating has been selected, it is imperative that it be applied

properly to attain its maximum corrosion protection benefits. This is
486 Tator
where the real work begins! The definition or determination of

the environment, and even the selection of the coating, can be
done, for the most part, in the safety and comfort of onefs office.
However, when it comes to coating application, the work must be
done at the fabricating shop, plant site, or piece of equipment,
tank interior, or whatever, that is to be coated. Here also, for
the most part, the comfort vanishes and the safety is diminished.
Surface preparation (often blast cleaning) and coating application
is dirty, dusty, demanding work, even when properly done. Proper
access, lighting, heating, and ventilation must be provided, and
workers must have safe work practices and equipment for the work
intended. Only when the proper equipment is on the job, and trained,
skilled workers are available with proper supervision to conduct
the actual coating work, should the coating application sequence
of operations begin.
Initially, a "pre-surf ace-preparation inspection" should be made.
This inspection is to determine if additional work needs to be done
by other crafts before the start of surface preparation for painting.
Such other work might include grinding and rounding of edges
and welds; removal of weld spatter, heavy deposits of oil, grease,
cement spatter, or other contaminants; moving equipment out of
the work area; masking or otherwise protecting equipment or items
not to be painted in the work area; and other such preliminary
activities. Only after this is done can the painters then begin to
work effectively.
Coating application, in the most basic terms, is the preparation
of the surface to receive paint and the application of the paint
in a proper manner to the specified thickness. The surface prepara-
tion specified is predicated by the coating system to be applied.
It is usually a good idea to specify a "standard" surface preparation
method. The most common standard methods are those defined by
the Steel Structures Painting Council.* Table 7 summarizes the
SSPC surface preparation methods. These standards, and others
prepared by the National Association of Corrosion Engineers, Society
of Naval Architects and Marine Engineers, various highway depart-
ments, and private corporations are almost always final appearance
standards. The standards give the desired end product but do
not describe in detail the means to achieve this end. It is important,
therefore, that the painter or person doing the surface preparation
be knowledgeable. It is important that the various pieces of equip-
ment be sized properly; that air and abrasives (if used) be cleaned,
graded, and free of moisture, oil, and other contaminants; and that
ambient conditions be controlled, or at least closely monitored.
* Steel Structures Painting Council, 4400 Fifth Avenue, Pittsburgh,

Pennsylvania 15213.
17. Coatings 487
TABLE 7 Summary of Surface Preparation Specifications
SSPC
specification Description
SP 1: Solvent Removal of oil, grease, dirt, soil, salts, and

cleaning contaminants by cleaning with solvent, vapor,
alkali, emulsion, or steam
SP 2: Hand- Removal of loose rust, mill scale, and paint
tool cleaning to degree specified by hand chipping, scraping,
sanding, and wire brushing
SP 3: Power- Removal of loose rust, mill scale, and paint
tool cleaning to degree specified, by power tool chipping,
descaling, sanding, wire brushing, and grind-
ing
SP 5: White- Removal of all visible rust, mill scale, paint,
metal blast and foreign matter by blast cleaning by wheel
cleaning or nozzle (dry or wet), using sand, grit, or
shot (for very corrosive atmospheres where
high cost of cleaning is warranted)
SP 6: Commer- Blast cleaning until at least two-thirds of the
cial blast surface area is free of all visible residues (for
cleaning rather severe conditions of exposure)
SP 7: Brush-off Blast cleaning of all except tightly adhering
blast cleaning residues of mill scale, rust, and coatings,
exposing numerous evenly distributed flecks
of underlying metal
SP 8: Pickling Complete removal of rust and mill scale by acid
pickling, duplex pickling, or electrolytic
pickling
SP 10: Near- Blast cleaning nearly to white-metal cleanliness,
white blast until at least 95% of the surface area is free
cleaning of all visible residues (for high-humidity,
chemical atmosphere, marine, or other corrosive
environments
The same is true for coating application. The coating thickness

should be achieved in one or more coats (usually three), and care
should be taken to assure that there is no contamination between
coats; that recoating is done within the proper time frame; and
488 Tator
that the coating materials are properly mixed in clean, well-functioning

equipment and are applied to controlled thicknesses. All reputable
coating contractors are well versed in this knowledge and have
the proper equipment and trained personnel available. Unfortunately,
it is the irresponsible, "fly-by-night" painting contractor that has
given many reputable contractors in the business a bad name. Often,
the relatively common practice of taking the low bid from painting
contractors has had very unfortunate ramifications. This is due
to the ease of entry into the business (often a contractor will rent
equipment and hire workers from a local hiring hall after being
awarded a lowest price contract). Additionally, without adequate
supervision or inspection, surface preparation can be skimped on,
paint coats omitted or applied at low thicknesses and, in general,
the work poorly done. The old adage "A painter covers his mistakes"
is often all too true, and paint jobs that are intended to last 10
to 15 years or more, with occasional touchup or repair, sometimes
fail within 2 to 3 years.
No matter what effort is put into defining the environment and
selecting the proper paint, the most important part of the job is
ensuring that the paint is applied properly. It is better to have
less effective paint applied properly than the best paint poorly
applied.
There are a wide variety of inspection instruments, aids, and
standards that can be used to assess the quality of the coating
system. These include devices for assessing the cleanliness of a
prepared surface; the depth of a blast-cleaning anchor pattern
or profile; and various magnetic, eddy current, and destructive
thickness gauges (capable of measuring the total paint thickness
or the thickness of each coat in a multicoat system). Additionally,
there are instruments and techniques available to monitor tempera-
ture, humidity, and dew point on a continual basis. After application,
adhesion tests and holiday tests (for pinholes and other discontinui-
ties) may also be specified.
Finally, it is important to realize that a paint job, even if properly
done, does not last forever. Within the first 6 months or year after
application, inadvertent misses, thin spots, or weak areas in the
coating system can often be observed by simple visual inspection.
Most reputable contractors will warrant work for a 1-year period,
and a thorough inspection and repair, if necessary, should be accom-
plished at the end of this time.
Later, as the coating breaks down and deteriorates because
of the effect of the environment, scheduled inspections are desirable
to assess the extent and rate of coating breakdown. Spot touchup
repair should be accomplished at localized areas of failure before
drastic deterioration of the entire coated surface has occurred.
17. Coatings 489
If the "planned maintenance approach" of periodic spot touchup,

followed occasionally by a full coat over the entire coated surface,
is done, the extensive costs of total surface preparation (such
as complete blast-cleaning removal of all old coating) can be avoided,
sometimes for periods approaching 30 years or more.
It is important that the entire coating sequential flow be main-
tained from beginning to end—definition of the environment, selection
of the proper coating system, proper surface preparation and appli-
cation, inspection, and periodic maintenance and repair. If all of
these operations are performed intelligently and competently, corro-
sion protection by coatings can be economically achieved for long
periods.
18
LIQUID-APPLIED LININGS
DEAN M. BERGER Berger Associates, I n c . , Leola, Pennsylvania
INTRODUCTION
Liquid-applied linings are coatings that may be spray applied or

troweled. They require the best surface preparation possible, Steel
Structures Painting Council (SSPC) SP5 white-metal blast cleaning
or National Association of Corrosion Engineers (NACE) 1. The coat-
ings should be applied under ideal conditions with full-inspection
procedures employed. These requirements are universal for any
tank-lining application, owing to the severity of constant immersion
(or partial immersion) that the tank lining must resist. All other
types of coating applications are less severe, because they will
alternate between corrosive contact and periods of little or no corro-
sive contact, thereby providing a recovery or cleaning period for
the coating surface. In a tank lining, there are usually four areas
of contact with the stored product that may lead to different types
of corrosion. These areas are the vapor phase (the area above
the liquid level), the interphase (the area where the vapor phase
meets the liquid phase), the liquid phase (the area always immersed),
and the bottom of the tank (where moisture and other contaminants
of greater density may settle). Each of these areas can, at one
time or another, be more severely attacked than the rest, depending
on the type of material contained, the impurities present, and the
amounts of oxygen and water present.
491
492 Berger
CRITERIA FOR TANK LININGS
All lining materials and tanks require intensive engineering, and

various criteria must be carefully established. These criteria are
listed in Table 1.
The coating of interior surfaces of steel or concrete tanks, pipe,
and equipment is most demanding for coating application expertise,
engineering design, and material performance. Most lining materials
are selected to prevent iron contamination of the product during
the processing operation. Strict application procedures must be
followed to provide maximum performance.
Lined tanks are used when chemicals are transported or stored.
Barges, hopper cars, tank cars, drums, bins, and storage tanks
may all have chemically resistant liquid-applied linings. But how
does the engineer select the proper lining for a given chemical?
Experience over many years has produced a considerable quantity
of data concerning the chemical resistance of liquid-applied lining
materials. However, unless the application is exactly similar to one
on which data are available, it is wise to test the proposed lining
before specifying it.
Proposed linings should be tested as prescribed in the National
Association of Corrosion Engineers procedure, NACE TM-01-74 [1].
Another NACE publication, NACE TPC 2, Coatings and Linings
for Immersion Service [2], should be used as a guide for material
selection and for inspection practices.
Two types of tests are described in NACE TM-01-74: one-side
testing and immersion testing. One-side testing consists of exposing
one side of a coated flat panel to the chemical solution, which is
contained in a special glass flask. The test coupons are bolted to
the glass flanged cylinder, using a double-flange ring. This test
cell is fitted with a heating mantle to control the temperature of
the solution.
TABLE 1 Criteria for Tank Linings
1. Design of the tank

2. Coating selection
3. Tank construction
4. Surface preparation
5. Coating application
6. Cure of the lining material
7. Inspection
8. Safety
9. Performance history and failure analysis
10. Operation instructions and temperature criteria
18. Liquid-Applied Linings 493
To provide product protection, the tank-lining coating must be

impervious to surface attack and must not react with any of the
materials to be contained in the tank. For food products, the lining
must not impart any taste, smell, or other harmful ingredient to
the contained product. For these special applications, it is absolutely
necessary that the surface coating in contact with the food product
be manufactured and tested in accordance with Food and Drug
Administration (FDA) Regulation 121.2514. To meet this requirement,
all components of the coating have to be selected from an FDA-
approved list of nontoxic coating ingredients. In addition to this,
the formulated coating must resist certain extraction tests as speci-
fied by FDA or the Environmental Protection Agency. The American
Water Works Association governs coatings for potable-water storage
tanks [3].
Tank Design
In designing a steel tank that is to receive a lining, always specify
welded construction. Riveted tanks will expand or contract and
damage the lining, causing leakage. Butt welds should be ground
smooth. If overlapping is used, specify a fillet weld and be sure
that all sharp edges are ground smooth. All weld splatter must
be removed before blast cleaning. A good way to judge a weld is
to run your finger over the surface. Sharp edges can be detected
easily.
All surfaces must be readily accessible for proper coating appli-
cation. When this is not possible, special caulking compounds may
be required. These should be applied before the initial lining appli-
cation .
Tanks larger than 25 ft in diameter may require three man ways
for working entrances. These are usually located two at the bottom
and one at the top. The minimum opening diameter should be 20
i n . , but 30-in. openings are preferred. The two bottom openings
should be side-mounted 180° apart. This will facilitate ease of venti-
lation.
Avoid the use of bolted joints. Butt welded joints are preferred.
Lap-welded joints should be properly filled. If bolted joints are
used, they should be made of corrosion-resistant materials and
sealed shut. The mating surface of steel surfaces should be gasketed.
The lining material should first be supplied.
Other appurtenances inside the tank must be located for accessi-
bility of coating application. Also make sure that the processing
liquor is not directed against the side of the tank but toward the
center.
Heating elements should be placed with a minimum clearance of
6 in. Baffles, agitator base plates, gauge devices, pipe, ladders,
Berger
and other devices can either be coated in place or detached and

coated before installation. The use of complex shapes such as angles,
channels, and I beams should be avoided. Sharp edges should be
ground smooth, and they should be fully welded. Structural rein-
forcement should be installed on tank exteriors.
Tanks that receive heat-cured linings should have bottoms perma-
nently insulated before erection.
Sharp edges and fillets must be ground smooth to a 1/8- or
1/4-in. radius. All welding should be of the continuous type. Spot
welding or intermittent welding should not be permitted. Gauges,
hackles, deep scratches, slivered steel, or other surface flaws
should be ground smooth.
Reinforcement pads, structural support members, and penetrations
should be mounted on the exterior surface whenever possible. All
protrusions should be ground smooth, and small apertures and pipe
should be previously lined. Instructions for designing steel tanks
are available from NACE [4].
Concrete tanks require special coating systems. Concrete tanks
should be located above the water table. In designing a concrete
tank, expansion joints should be avoided unless absolutely necessary.
Normally, small tanks do not require expansion joints. In larger
tanks, a chemical-resistant joint, such as PVC, has been used
successfully. The concrete-curing compound must be compatible
with the coating system or be removed before coating. Form joints
must be made as smooth as possible to provide a flat surface for
the coating. A strong, dense, concrete mix should be used, with
adequate steel reinforcement, to reduce movement and cracking
of the tanks. The coating manufacturer should be consulted for
special instructions. Concrete tanks generally are lined only by
a licensed applicator, and special surface preparation is required.
Coating Selection
When selecting the proper coating system, it is necessary to deter-
mine all the conditions to which the lining will be subjected. An
assessment of these conditions would involve consideration of per-
centages of all materials to be contained, operating temperature,
degree and type of abrasion, impact, thermal shock, and whether
or not the tank will be insulated for high-temperature service.
If a detail in any one of these areas is neglected, or considered
insignificant and not emphasized, an incorrect recommendation could
result. Examples of some of these variables are a fluctuation in
temperature or the presence of some minute, strong corrosive or
penetrant, such as free chlorine in chlorinated solvents.
Field performance, case histories, and ease of application are

important factors. Most corrosion engineers keep records of the
performance of coating systems they have used in a particular
service [1]. Such information is often available from the coating
manufacturer. Included in the case history should be the name
of the applicator who applied the coating, application conditions,
type of equipment used, degree of application difficulty, and other
special procedures required. A coating with outstanding chemical
resistance will fail rapidly if it cannot be properly applied, so it
is advantageous to gain from the experience of others.
When no previous history exists before use, tank-lining materials
should be tested in accordance with NACE Standard TM-01-74 [1].
This standard provides a procedure for immersion testing of the
total panel or one side of the panel. The glass atlas test cell may
contain any liquid, and partial immersion is also available. After
testing under these conditions, one may determine the type of lining
material suitable for the selected service.
Sometimes, case histories will be unavailable, or manufacturers
will be unable to make recommendations, as when the material to
be contained is of a proprietary nature or involves a solution that
contains unknown chemicals. When this occurs, tests should be
conducted by evaluating sample panels of several coating systems
for a minimum of 90 days. A 6-month test would be preferable;
however, because of normal time requirements, 90 days is a standard.
It is important to test at the maximum operating temperatures to
which the coating will be subjected. Such tests should simulate
actual operating conditions, including washing cycles, cold wall,
and effects of insulation.
Before applying a tank lining, a recommendation should be ob-
tained from the coating manufacturer, a technically capable lining
contractor, or from NACE literature for an identical problem. Table
2 shows various types of coatings available and their general area
of application.
Descriptions of the chemical compositions and application proper-
ties of some of the most popular coating materials can be found
in NACE TPC 2. This NACE publication also lists the chemical resist-
ance of some of these coatings. Recommendations are available for
specific chemical use.
Once the coating has been selected, the various manufacturers
should be consulted. Often recommendations are available about
the choice of coating applicator. A prejob conference should be
held between the owner, the engineer, the applicator, coating
supplier, and the job inspector. All lining work should receive
100% inspection.
496 Berger
TABLE 2 Polymeric Linings and Their Use
Type of coating Use
Inorganic zinc Jet fuel storage tanks, petroleum prod-

water-based postcure ucts
Inorganic zinc Jet fuel storage tanks, petroleum prod-
water-based self-cure ucts
Inorganic zinc coatings Excellent resistance to most organic
(solvent-based, self- solvents ( i . e . , aromatic, ketone, and
curing) hydrocarbons); excellent water resist-
ance; difficult to clean; often sensitive
to decomposition products of materials
stored in tanks
Graphite alkyl silicates Acid service
Acid-resistant cements Acid service: processing tanks, chemi-
cal treatment, and acid pickling tanks
Furan Mortar for acid brick: most acid-
resistant organic polymer; stack linings
and chemical treatment tanks
High-bake phenolic Most widely used lining material; excel-
lent resistance to acids, solvents, food
products, beverages, and water; poor
flexibility compared with other coatings
Modified air-dry May be formulated for excellent resist-
phenolics (catalyst ance to alkalies, solvents, freshwater,
required) saltwater, deionized water; mild-acid
resistance; nearly equivalent to high-
bake phenolics; excellent for dry
products
Epoxy (amine catalyst) Good alkali resistance; fair to good
resistance to mild acids, solvents, and
dry food products; widely used for
covered hopper-car linings and nuclear
containment facilities
Epoxy polyamide Poor acid resistance, fair alkali resist-
ance; good resistance to water and
brines; used in storage tanks and
nuclear containment facilities
Epoxy polyester Poor solvent resistance, good abrasion
resistance; used for covered hopper-
car linings
Type of coating Use
Epoxy coal tar Excellent resistance to saltwater,

freshwater, mild acids, and mild alka-
lies; solvent resistance is poor; used
for crude oil storage tanks, sewage
disposal plants, and water works
Coal tar Excellent water resistance; used for
water tanks
Asphalts Good water and acid resistance
Polyester unsaturated Excellent resistance to strong mineral
and organic acids and oxidizing
materials; very poor aromatic solvent
and alkali resistance
Vinyl ester Excellent resistance to strong acids
and better resistance to elevated
temperatures up to 350 to 400°F, de-
pending on thickness
Modified polyvinyl Excellent resistance to strong mineral
chloride (polyvinyl acids and water; poor solvent resist-
chloracetates), air- ance; used in water-immersion service,
cured potable and marine; most popular lining
for water storage tanks (beverage
processing)
Polyvinyl chloride (PVC) Popular acid-resistant lining; must be
plastisols heat-cured
Chlorinated rubber Excellent water resistance; poor solvent
resistance; used in marine applications
and for swimming pools
Chlorosulfonated poly- Chemical salts
ethylene (Hypalon)
Polyvinylidene chloride Excellent vapor barrier; good general
chemical resistance; used in food
packaging
Neoprene Good acid and flame resistance; chemi-
cal processing
Polysulfide (Thiokol) Good solvent resistance and water re-
sistance; used for caulking and lining
jet fuel tanks
(continued)
498 Berger
Type of coating Use
Butyl rubber Good water resistance; used for caulk-

ing
Fluoropolymers Lining for SO2 scrubber service; high
chemical resistance and fire resistance
Styrene-butadiene Food and beverage processing; con-
polymers crete tanks
Acrylic polymers Food and beverage processing
Urethanes Excellent resistance to strong mineral
acids and alkalies; fair solvent resist-
ance; superior abrasion resistance;
used to line dishwashers and washing
machines; used to modify asphalts
Vinyl urethanes Wood tanks, food processing, hopper
cars
Rubber latex Excellent alkali resistance; used to
line 50 and 73% caustic tanks 180° to
250°F
Vinylidene chloride latex Excellent fuel oil resistance; concrete
fuel tanks
Alkyds, epoxy esters, Water-immersion service; primers for
oleoresinous primers other top coats
Waxes and grease Coating systems for water storage
Tank Construction
In the design section, several features of construction were dis-
cussed. It is important that the coating applicator check out the
tank before painting. Such items as sharp edges and rough welds
could be overlooked. All of these should be ground smooth before
the applicator starts.
Sometimes certain parts of the tank, such as a bottom plate
for a center post, need to be dismantled and painted separately.
This particular section would then be reassembled after the tank
is blast cleaned and coated.
Penetrations are frequently coated before assembly, even though
welding may burn the lining.
For every steel tank-lining application, all seams and joints must
have continuous interior welds. All sharp edges and welds must
be ground smooth to a rounded contour, and all weld splatter
removed. It is not necessary that the welds be ground flush, as
long as they are smooth and continuous with a rounded contour.
Any sharp prominence may result in a spot where the film thickness
will be inadequate and noncontinuous and, thus, cause premature
failure.
Surface Preparation
The key to all coating application work is in obtaining maximum
adhesion of the lining material to the substrate. The basic require-
ment is to get the surface absolutely clean.
All steel surfaces to be coated must be abrasive-blasted to white
metal in accordance with SSPC Specification SP5-63 or NACE Specifi-
cation NACE 1. A white-metal blast is defined as removing all rust,
scale, paint, and so on, to a clean white metal, which has a uniform
gray-white appearance. No streaks or stains of rust or any other
contaminants are allowed. Frequently, a near-white, blast-cleaned
surface equal to SSPC SP-10 is used. This is satisfactory for most
lining materials and is more economical. Written surface preparation
standards are available from the SSPC [5].
A guide for the choice of abrasives is found in SSPC Volume I
[6] or NACE TPC 2.
After blasting, remove dust and spent abrasive from the surfaces
by brushing or vacuum cleaning. All workers and inspectors in
contact with the blasted surface should wear clean, protective gloves
and clothing to prevent contamination of the blasted surface. Any
contamination may cause premature failure by osmotic blistering or
adhesion loss. The first coat should be applied as soon as possible
after the blasting preparation is finished and always before the
surface starts to rust. If the blasted steel changes color, or rust
bloom begins to form, it will be necessary to reblast the surface.
Dehumidifiers and temperature controls are helpful.
Be certain that no moisture or oil passes through the compressor
and on to the blasted surface. Use a white rag to determine the
air quality. Also a black light may be used to identify oil contamina-
tion. Rotary screw, two-stage, lubrication-oil-free compressors
are available to provide 100% oil-free air.
To check visually the quality of the surface preparation, a num-
ber of standards are available for comparative purposes [7-11].
Concrete
Concrete surfaces must be clean, dry, and properly cured before
the coating application is performed. Remove all protrusions and
500 Berger
form joints. All surfaces must be roughened by blasting. The surface

preparation must remove all loose, weak, or powdery concrete to
open all voids and provide the necessary profile for mechanical
adhesion of the coating. Remove dust by brushing or vacuuming.
Special priming and caulking methods are often required for concrete
surfaces. Follow the coating manufacturers recommended procedures
for these.
Application
Coating application can be a problem, particularly when inexperienced
applicators are applying the coating. It is important that the appli-
cator be very familiar with the coating to be applied. Emphasis
should be given to choosing a professionally competent coatings
applicator.
Often, the lowest bidder is selected without adequately consider-
ing the quality of workmanship, with the net result of a tank-lining
failure. Because a tank lining requires a nearly perfect application,
a knowledgeable and conscientious applicator is needed. Evaluate
the applicator before awarding the coating contract, to assure that
the tank-lining contractor is experienced in applying the recommended
lining.
In reviewing the qualifications of an applicator, ask what jobs
he has done using the selected lining material and check out his
references. Ask what equipment he has available and, if possible,
visit his facilities and inspect his workmanship before placing him
on the applicators bid list. These precautions will be rewarded
in assuring total performance.
The primary concern is to deposit a void-free film of the proper
thickness on the surface. Any area that is considerably less than
the specified thickness may have a noncontinuous film. Also, pin-
holes in the coating may cause premature failure.
Films that exceed the maximum recommended film thickness may
entrap solvents, which can lead to improper cure, excessive brittle-
ness, bad adhesion, and subsequent poor performance. Avoid "dry
spraying" of the coating, because this causes it to be porous. Never
use thinners other than those recommended by the coating manufac-
turer; they, too, may cause poor film formation.
There are many types of equipment for determining the thickness
of the coating on steel. During the application, a Nordsen or El-
cometer wet-film thickness gauge should be used as a guide for
obtaining the desired dry-film thickness. If the wet-film thickness
meets the recommendations, this is a good indication that the dry-
film thickness will also meet the requirements.
To measure dry-film thicknesses, all gauges must be calibrated

before use by the manufacturers suggested technique. The samplings
should be numerous and at random, paying particular attention to
the hard-to-coat areas. Particularly useful instruments are the
Mikrotest and Elcometer. (Remember that the Elcometer has to be
prestandardized on the tank structure itself before obtaining measure-
ments.) Film thickness measurements should be taken in accordance
with SSPC PA2-73T [12].
The best method for calculating film thickness on concrete tanks
(also useful on steel tanks) is to measure the area covered and
the material consumed to see that the proper coverage as shown
by the manufacturer is met. (You must take into consideration the
material losses during application and mixing.) Although destructive,
a Tooke gauge will determine the approximate dry-film-coating thick-
ness on concrete.
Safety Precautions During Application

All applicators are aware of the hazards within their own working
environment. Tank-lining work involves more specific requirements
and the use of specialized rigging and equipment. The Occupational
Safety and Health Act of 1970 provides many requirements. These
are found in the Federal Register 39(122), June 24, 1974. An analy-
sis of these data and a recent review of the pertinent information
is readily available from the Painting and Decorating Contractors
of America (PDCA) [13].
Safety is of prime importance in any type of job, particularly
where protective coatings containing solvents are being used.
Obviously, all coatings and thinners must be kept away from any
source of an open flame. This means that "no smoking" must be
the rule during coating application. Welding in areas adjacent to
that of coating application must be discontinued.
Vapor concentration inside tanks should be checked regularly
to make sure that the maximum allowable vapor concentration is
not reached. This lack of air observation caused five deaths in
the United States in 1975. An explosion from solvent vapors will
occur only within a small range of concentration—for most solvent
vapors, there must be between 2 and 12% vapors in the air for
an explosion to happen. As long as the vapor is kept below the
lower level, there will be no explosion. All electrical equipment
must be grounded and the sandblasting unit equipped with a dead-
man control. Precautions must also be taken on the exterior of
the tank, because the flammable solvents are being exhausted and
will travel a considerable distance at ground level. No flames,
sparks, or ungrounded equipment can be nearby.
502 Berger
The Occupational Safety and Health Administration (OSHA) issues

a form called the Material Safety Data Sheet. The information con-
tained on this form is supplied by coating manufacturers. They
are required to list all toxicants or hazardous materials and provide
a list of the solvents used. Included also would be the threshold
limit value (TLV) for each substance. The TLVs are published
annually for all chemicals [14]. Explosive hazards, flash points,
and temperature limits will be established for safe application of
each lining material.
Basically, all tank-lining work requires a proper air supply
and ventilation. Never take chances or t r y to skimp on the required
equipment. Never allow one worker in a tank alone. Use safety
belts and all the necessary rigging for maintaining safe working
conditions. Recommended ventilation for various size tanks has
been discussed by Weaver [15] and Munger [16]. All the require-
ments of safety are listed and discussed in NACE TPC 2 [2] as
well as in SSPC Volume I [ 6 ] .
Scaffolding and ladders must be carefully checked to ensure
that they are sturdy and sound. Blasters must wear protective
clothing, and sprayers should wear fresh airline respirators in
confined areas such as tank interiors. Some coatings contain ingredi-
ents that may be irritating to some people (particularly the strongly
alkaline amine-type catalysts used in epoxies).
Free toluene diisocyanate (TDI) or isocyanate monomer will also
cause severe skin irritation. All workers spraying these materials
should wear protective creams on exposed parts of the body, such
as face and hands, or complete protective clothing. Water must
always be readily available for flushing accidental spills of such
materials from the skin. Safety rules of the plant where materials
are being applied must be known and observed. OSHA Material
Safety Data Sheets should be on file at the first-aid station and
in the job superintendents office.
Estimating
Before application, the coating applicator must estimate the cost.
Usually, this can be done rapidly by experienced people. In addition
to information available from SSPC and NACE, an estimating guide
is published annually by the PDCA [17]. Estimates are always rela-
tive and based on the total surface area to be coated and the com-
plexity of the tank. Safety, surface preparation, material, and
application costs are basic requirements. Location of the job, rigging,
and logistics must be considered. Beware of low bidders. Make sure
of the final contract and try to obtain a performance guarantee.
Guidelines for Proposal-Contract-Specification Forms are available
from the Georgia Municipal Association [18].
Curing the Applied Coating

During and after application, thorough air circulation must be pro-
vided until the coating is cured. To obtain proper air circulation,
no tank should be lined unless it has at least two openings. The
air circulation should be accomplished by a fresh-air intake [tempera-
ture over 10°C (50°F) and relative humidity less than 89%] at the
top of the tank, and an exhaust at the bottom, fed by forced-air
fans whenever possible. This requirement is necessary because
the solvents used in coatings are almost always heavier than air;
therefore, proper exhausting can only be obtained downward.
The curing time and temperature of the substrate must be in
accordance with the manufacturers application instructions for each
individual product, to prevent solvent entrapment between coats
and to ensure a proper final cure. Do not allow application to take
place at temperatures below those recommended by the manufacturer.
For a faster and more positive cure of all linings, a warm, forced-air
cure should be used between coats and as a final cure before placing
the lining into service. This added heat provides a dense film and
tighter cross-linking, which yields superior resistance to solvents
and moisture permeability. Before placing the tanks in service,
most linings should be thoroughly washed down with water to remove
any loose overspray. For linings in contact with food products, a
final warm, forced-air cure and water wash is essential.
It is important that linings be allowed to attain a full cure before
use. This frequently requires 3 to 7 days for room-temperature-cured
coatings.
Inspection of the Lining

It is necessary in many instances to check for porosities. The first
visual inspection is mandatory to detect pinholing and provide recoat
instructions. After repairs of visible defects, inspection may be done
by using low-voltage (75 V or less) Holiday detectors that ring, buzz,
or light up to show electrical contact through a porosity within the
coating to the metal or concrete surfaces. It is preferable to check
the lining in this manner after the primer or second coat, so that such
areas may be touched up and be free of porosities before the final top
coat [1]. If a wet-sponge detector is used, any surface contamination
must be removed before application of a topcoat.
The inspector should participate in the following functions: (1)
prior work conference, (2) prejob inspection, (3) surface preparation
inspection, (4) coating application inspection, (5) daily inspection
reports, and (6) final acceptance report.
Visual inspections are performed with either the unaided eye
or by the use of a magnifying glass. Sometimes, visual inspections
504 Berger
require the use of telescopic observation or the use of low-power

magnification. A Pike magnifier is one of several types available
for this use.
By employing the standard visual techniques, the inspector identi-
fies areas that have been missed, damaged areas, or thin areas.
White primers have been used to spot areas of low film thickness
or inadequate coverage of the substrate. The use of instruments
provides an inspector with an accurate appraisal of what dimensional
requirements have been met by the applicator.
The inspector should examine coatings during and after coating
application and report on the items indicated in Table 3, when
applicable. Pictorial standards are available from the American Society
for Testing and Materials (ASTM) [19] and the Federation of Societies
for Coatings Technology (FSCT) [20] that can aid an inspector in
reporting the degree of failure in terms readily interpreted.
Before the application of a paint or coating, the surface must
be properly prepared to receive the material. This can be accom-
plished in a number of ways. The most common way is through
the employment of abrasive blast cleaning. Prior to blast cleaning,
the inspector should look for the removal of all visible oil and grease.
This is done by solvent cleaning with an approved solvent or by
some other approved means. Only slight oil traces will be removed
by blast cleaning, especially when the abrasive is not recycled.
The inspector should take a clean white rag and rub the surface
to be coated. If the surface is clean, the rag should remain clean.
Welds must be ground smooth, although not necessarily flush.
Sharp protrusions should be rounded, and weld crevices should
be manually opened enough so that the coating can penetrate. If
this procedure is not done, the projections should be removed by
grinding. Sharp edges should also be ground smooth. A good way
to establish a smooth weld criteria is to rub your finger rapidly
over the surface. If you can do this without cutting your finger,
the weld is smooth enough. Naturally, the inspector will slowly
check the smoothness of the weld.
Back-to-back angles, tape or stitch welding, and so on, cannot
be properly cleaned and coated. Thus, they should be sealed with
caulking to prevent crevice corrosion. Also, electric welding flux
should be neutralized or removed before painting.
The inspector is expected to work quickly so that the application
of the coating to the surface is not delayed. But there is usually
no harm in allowing the steel to stand unprotected for a few hours
before beginning application of the coating.
In most work environments, fallout is ever present. Make sure
that the surface is clean and free of dust before the coating is
applied. Brush off, blow off, or vacuum the dust collecting on
the surface to be coated.
TABLE 3 Inspection Report Items for Applied Coatings
g
Inorganic Organic Organic
Tank Concrete Concrete zinc primer top coats
Item Item linings surfacer top coats primer steel steel
1 Pinholes X X X X
2 Blisters X X X X §'
3 Color and gloss uniformity X X 5'
4 Bubbling X X X X X
5 Fish eyes X X X X X
6 Orange peel X X X X X
7 Mud cracking X X X
8 Curing properties X X X X X X
9 Runs and sags X X X X X X
10 Film thickness, dry X X X X
11 Film thickness, wet X X
12 Holidays, missed areas X X X X X X
13 Dry spray X X X X X X
14 Foreign containments X X X X X X
15 Mechanical damage X X X X X X
16 Uniformity X X X X X X
17 Adhesion X X X X X X
o
506 Berger
Surface Profile
Without an adequate "key" provided by abrasive blasting or mechani-
cal grinding, many coating systems will not provide adequate long-
term performance. Too little anchor pattern will result in too smooth
a surface and, thus, poor adhesion. A deep profile will require
additional paint. A good rule to go by would be to keep the profile
depth about 25% of the total paint thickness. Therefore, if 6 mil
is specified, the proper profile would be 1.5 mil.
Profile varies, of course, with the type of abrasive employed.
There are many ways to determine surface profile in the field.
The Keane-Tator Surface Profile Comparator contains a metal
disk with nominal surface profiles of 0.5, 1, 2, 3, and 4 mil. This
flashlight magnifier is used as a handy pocket-type comparator
to check on sandblast-cleaned surfaces. Also available is a metal
disk for comparison of anchor patterns prepared with shot or grit
blast.
Clemtex offers a series of four steel coupons with profile gauges
ranging from 1 to 4 mil.
A Testex tape has been developed that is pressed into the profile.
The tape is removed and the profile that remains in the tape is
measured with a micrometer, subtracting the thickness of the tape.
COATING APPLICATION
Good painters who have a "handle on spray application of coatings"

keep their guns parallel to the surface of the work at all times.
They will release the gun trigger at the end of each pass to avoid
heavy deposits of paint. They will frequently use the crosshatched
method of laying up high-solid materials to prevent them from sagging.
When a painter applies paint or coatings far too heavily for the
temperature of the substrate and for the viscosity of the material
being applied, runs, sags, drips, and curtains will develop. These
inconsistencies are the result of poor technique. When you see
these problems, the work should be stopped and the runs, sags,
and so on, should be brushed out before they are allowed to cure.
Careful adjustment of the gun and a better application technique
should help reduce these problems.
An inspector should witness the performance of the painters
on the job. Remember that heavily applied paint may never cure
because of solvent entrapment, or if it does cure, the film buildup
can cohesively weaken the entire paint film.
If large areas exist where the coating system does not have
the specified dry-film thickness, tell the painters that you want
them to follow the minimums specified. Review the manufacturers
18, Liquid-Applied Linings 507
literature with the painters to determine what, if anything, must

be done to prepare the painted surface for the additional coat that
will be needed to meet the thickness prescribed by the specifications.
Special considerations are required for a wide range of materials.
Check with the coating manufacturer before allowing the work to
continue.
An inorganic zinc primer may mud-crack if applied too heavily.
Follow the manufacturers instructions for the best results.
Overspray problems occur whenever winds, temperature, or
humidity are rapidly changing. A partially dried coating material
that does not wet and flow into the previously applied coat will
appear on the surface.
Inorganic zinc primers are susceptible to overspray. They should
never be topcoated unless the overspray is removed by abrading
with a wire screen.
It should be rather obvious that paints and coatings must be
suitably mixed before their application to a given substrate. Proper
mixing redisperses the heavier pigments to ensure that the coating
material is completely homogenized before painting. Follow the coat-
ings manufacturers mixing instructions.
One-Component Coatings
These materials are packaged to be mixed in their original containers.
A paddle, mechanical agitator, or power mixer is employed to do
the job. Thinners, if required, are added slowly after initial mixing
of the material. The painter should be mixing the paint long enough
so that no portion of the coating appears as "swill" on the surface.
After mechanical mixing, a skilled journeyman will "box" the paint
by pouring it from one clean can to another and back again. This
will not be necessary where power agitation equipment is used.
Two-Component Coatings
Catalyzed coatings are normally packaged in separate containers
or, occasionally, in separate portions of a larger container. Be
sure that the base is thoroughly mixed before the addition of the
catalyst. See that the catalyst is added slowly and that the combined
portions are thoroughly mixed. Some catalyzed epoxies must be
allowed to stand for approximately 30 min before painting begins.
This 30-min induction period will ensure a more unified curing of
the applied film. Make sure that the temperature limitations corre-
spond to the manufacturers instructions. Induction periods are
not required for polyester materials or amine adduct epoxies.
508 Berger
Cure
Many factors affect the cure of a coating or lining. Surface tempera-
ture and room temperature should be a minimum of 18°C (60°F)
for best results. The thickness of the coating, the type of solvent
used, and the paint vehicle characteristics will influence the cure.
Solvent Rub
After an epoxy paint or an inorganic coating cures, use a color-
contrasting cloth dipped in a strong solvent [methyl ethyl ketone
(MEK) or methyl isobutyl ketone (MIBK)J to rub the surface of
the coating. If the material was improperly mixed or cured, the
material will redissolve and the color can be seen on the cloth.
Sandpaper Test
A number of paints and protective coatings will remain slightly
tacky when they have not cured properly. When you abrade them
with fine sandpaper, no coating material should be seen on the
face of the sandpaper. It should be removed as a fine, powdery
residue.
Hardness Test
By using your fingernail, you should soon be able to employ your
judgment rather effectively. Other techniques, such as the Barcol
impressor or the pencil-hardness test, are also used to check on
the hardness of a film. For inorganic zincs, a coin scratched against
the surface should not remove the film.
Adhesion
The best method to determine adhesion is to use the pocket knife.
Cut a "V" in the film and pick off the coating at the vertex. Good
adhesion is expected. The coating should be very difficult to remove.
Dollies may be cemented onto the coated surface. An Elcometer
adhesion test may be run. Epoxies usually far exceed 200 psi and
frequently attain 800 psi adhesion. For nuclear-grade coatings,
200 psi is the lowest acceptable adhesion.
Crosshatch adhesion has also been used for thin-film coatings.
Film Thickness
Nondestructive test instruments for determining dry-coating thickness
on steel substrates fall into two main categories: magnetic and eddy
current. The most popular and commonly used instruments employ

the magnetic principle. The magnetic gauge in its simplest form
measures magnetic attraction, which is inversely proportional to
coating thickness. There are several pulloff gauges available that
employ this simple magnetic principle, for example, the BSA-Tinsley
thickness gauge manufactured by Evershed & Vignoles, London,
England, and the Elcometer 157 pulloff gauge manufactured by
Elcometer Instruments Ltd., Manchester, England.
The pulloff gauge is intended for use in the field as a rough
guide to determine if the protective coating is within the thickness
specification. The manufacturers stated accuracy is ±15%, provided
that the gauge is used within a true vertical plane. If the gauge
is used in a horizontal or overhead position, more error will result.
If the gauge must be used in positions other than the true vertical,
it is recommended to plot a correction curve for each different
position for best results.
Care should be exercised to inspect visually the hemispherically
tipped magnet for dirt, small steel particles, tacky paint film, and
tip wear before use. Wear on the hemispherically tipped magnet
will alter the calibration of the gauge. Never expose any magnetic
gauge to strong AC or DC fields because the magnet will change,
affecting the tracking and calibration of the gauge.
Besides accuracy limitations, the pulloff gauge has other disad-
vantages: (1) the eye must record the coating thickness as the
magnet breaks away from the coating, and (2) erroneous readings
will result if the magnet is allowed to slide over the coating before
break away or lift-off.
The Type 7000 Tinsley gauge, however, contains a dial-like
scale with a balanced pointer that is not affected by angular positions.
It offers a direct readout from a lock-in zero reset which provides
an accuracy of 10%.
A more sophisticated version of the magnetic pulloff principle
is incorporated into the "banana-type" thickness gauge. This particu-
lar type of gauge has been termed a "banana" gauge because of
the shape of the case. A permanent magnet is mounted at one end
of a balanced, pivoted arm assembly, and a coil spring is attached
to the pivot and to a calibrated, rotatable dial. The operator moves
the rotatable dial forward until the magnet sticks to the coating.
Variations in film thickness above the steel substrate will alter
the attractive force of the magnet. This unknown force is determined
by turning the rotatable dial backward, applying tension to the
spring. When the spring tension exceeds the unknown magnetic
attractive force, the magnet breaks contact with the coated surface.
At this point, an audible click will be heard and the coating thick-
ness will be shown on the graduated, rotatable dial.
510 Berger
There are several gauges available using the guided or controlled

magnetic pulloff principle: Mikrotest thickness gauge, Model 102/FIM,
and Mikrotest II FM manufactured by Elektro Physik, Cologne,
West Germany, and Inspector thickness gauge, Model III /IE, manu-
factured by Elcometer Instruments Ltd.
This type of gauge will measure coating thickness in any position
without recalibrating, because the pivot arm is balanced. The In-
spector gauge has an external calibration adjustment (screwdriver
slot) located under the nameplate.
Another version of the magnetic principle applies to the Elcometer
thickness gauge, which utilizes a magnetic reluctance technique.
One could define reluctance as the characteristic of a material that
resists the creation of a magnetic flux in that material (e.g., iron
has less reluctance than air).
The Elcometer gauge contains a permanent magnet that is located
between two soft-iron poles resembling a horseshoe magnet. (The
magnet is adjustable to produce an air gap.) A meter-pointer assem-
bly with a soft-iron vane is placed in the center of this horseshoe
configuration, making a magnetic circuit with an indicating device
that requires no power supply or battery.
When the Elcometer gauge is placed onto a dry coating applied
to steel, the magnetic flux will change in strength across the air
gap in the magnetic circuit, thus moving the meter pointer across
a calibrated scale, indicating the coating thickness in either mils
or micrometers.
Care should be exercised when using the Elcometer always to
hold the gauge at a right angle to the surface to be measured be-
cause tilting it will give erroneous measurements. Always recalibrate
the gauge when changing from vertical to horizontal or, perhaps,
to the overhead position [12].
External calibration is provided with a zero-knob located on
the side of the instrument. A small button must be depressed to
take readings. Basically, the gauge is very sensitive to surface
roughness, residual magnetism in the substrate, edge effect, and
tilt of head. Blind-hole measurements cannot be made with this
gauge.
In making film-thickness measurements of any kind, avoid measure-
ments close to the edge of a steel surface. The magnetic properties
of the steel influence the reading, causing distorted results. This
is also true of corners, angles, crevices, welds, and joints. A
recommended practice is to keep at least 1 in. away from the edge.
Always measure a clean surface, never an oily or dirty one.
There are electronic gauges that possess greater accuracy than
the mechanical ones mentioned previously. The General Electric
(Schnectady, New York) Model B thickness gauge uses the magnetic
induction principle. A coating between the coil probe and steel
substrate represents an air gap that is measured and displayed

on the front panel meter. The General Electric gauge requires a
115-V AC source and is not portable for field use.
The Model 158 Minitector thickness gauge and Model 102/F100
Minitest thickness gauge are in some respects similar to the GE
gauge, in that a probe senses and a meter displays coating thickness.
The Minitector uses a permanent magnet in the probe for a flux
source, thus making a magnetic circuit that measures coating reluc-
tance. The thicker the coating, the higher the reluctance; also,
the thinner the coating, the lower the reluctance. When the Minitector
probe is placed onto a dry coating over steel, the magnetic flux
adjusts to the particular thickness of coating. The change in flux
is then measured and displayed on the meter scale in either mils
or micrometers of coating thickness. This gauge is portable and
uses standard transistor radio batteries that are readily available;
it is manufactured by Elcometer Instruments Ltd. [22].
The Model 102/F100 Minitest thickness gauge utilizes the eddy
current principle. A coil of wire in the probe tip is energized with
a high-frequency, alternating current, creating a magnetic field.
When the probe tip is brought into close proximity to a metallic
object, as when the probe is placed onto a dry coating applied
to steel, eddy currents are induced into the steel substrate, altering
the electrical characteristics of the probe coil. This electrical charac-
teristic change in the probe coil is then measured and displayed
on the meter scale in mils of coating thickness. The Minitest is
battery operated and comes equipped with an automatic battery
power-off switch to extend battery life; it is manufactured by Elektro
Physik.
Thickness standards are recommended as a ready reference to
check the accuracy and calibration of gauges. A range of thickness
standards is commercially available from various sources. Chrome-
plated steel panels are available from the National Bureau of Stand-
ards. Four plated thickness standards mounted in a plastic case
are offered by Elektro Physik (102/TSFIM). A range of plastic,
color-coded precision shims and color-coded glass on steel panels
(101/7) is offered by Elcometer Instruments Ltd. Digital gauges
are also available from Zurmaco Electronics. The Positector is a
decimal gauge available from DeFeesco.
PERFORMANCE HISTORY AND FAILURE ANALYSIS
After the tank lining has been placed into service, a thorough
inspection should be made at regular intervals for any visual defects,
such as blistering, rusting, softening, or cracking. In addition,
soon after the tank has been placed into service (depending on
512 Berger
the corrosive nature of the contents), an inspection and touch-up

is recommended to repair any defects resulting from application
(such as holidays). Minor touch-up at this time could prevent
catastrophic failure later. Inspection records should be kept to
describe precisely the condition of the lining versus time. These
records can be used to support failure recommendations based on
actual field performance. If repairs are recommended, do them
immediately. Do not wait for the condition to get worse.
Operating instructions should include the maximum temperature
and service level expected. The outside of the tank should be labeled
DO NOT EXCEED X°C (X°F). THIS TANK HAS BEEN LINED WITH
. IT IS TO BE USED ONLY FOR
SERVICE.
A tank-lining failure should be prudently analyzed by the engineer

to determine the cause. A tank lining may fail for numerous reasons.
The tank lining must not impart any impurities to the material
contained. If the product is contaminated by color, taste, smell,
or by any other means, even though the tank lining is intact, the
application is a failure. This contamination can be caused by the
extraction of impurities from the coating leading to blistering between
coats or to metal. If the lining is unsuited for the service, complete
failure may occur by softening, dissolution, and finally complete
disintegration of the coating. This type of problem is prevalent
between the interphase and the bottom of the tank. At the bottom
of the tank and throughout the liquid phase, penetration is of great
concern. Contrary to what one would think, failure of penetration
is more prevalent with materials of mild corrosive qualities than
it is with concentrated acids and alkalies. Water, for example, is
very penetrating, especially when heated or deionized. The vapor
phase of a tank is subject to corrosion from concentrated vapors
mixed with the oxygen present and can cause extreme corrosion.
It is often very difficult to determine on any given application which
area of a tank will be subject to the greatest corrosion attack.
The most common types of failure are due to misuse of the tank
lining, which may cause blistering, cracking, hardening or soften-
ing, peeling, staining, burning, and undercutting; overheating
during operation is a frequent cause of failure. Never change chemi-
cals for tank use without consultation with the lining-materials engi-
neer. Cracking usually occurs when a very heavily pigmented surface
or thick film begins to shrink, forming stresses on the surface.
The cracks do not always expose the steel and may not penetrate.
The best practice is to remove these areas and recoat according
to standard repair procedures before use. Do not take a chance.
18, Liquid-Applied Linings 513
An automatically controlled cathodic protection system of water-

storage tanks will greatly prolong a tank lining. A surveillance
system for monitoring tank-to-water potentials can be easily installed
and operated to provide practical information to field activities on
the protection of tank interiors. Silver/silver chloride reference
half-cells are used for such a purpose.
Hardening or softening is the result either of aging or poor
resistance to the corrosive. As the coating ages (more characteristic
of epoxy and phenolic amines), it becomes brittle and may chip from
the surface. Peeling can result from a number of causes, such as
poor surface preparation, a wet or dirty surface, or improperly
cured undercoats. Staining can result from a reaction of the corro-
sive on the surface of the coating, or slight staining from impurities
in the corrosive. It is necessary to determine the true cause by
scraping or detergent-washing the film. If the stain is removed
and softening of the film is not apparent, failure has not occurred.
Undercutting can result from any of the defects noted previously.
After the corrosive penetrates to the substrate, corrosion will pro-
ceed to extend under the film areas that have not been penetrated
or failed. Some coatings are more resistant to undercutting or under-
film corrosion than others. Generally, if the coating displays good
adhesive properties, and if the prime coat is chemically resistant
to the corrosive environment, underfilm corrosion will be greatly
retarded.
SUMMARY
A tank-lining application is probably the most critical of all coating

applications. The coating itself must be resistant to the corrosive,
and there must be no pinholes through which the corrosive can
penetrate to reach the substrate. Thin-film linings should be used
mainly when the corrosion rate of the steel is 25 mpy or less for
the chemical used. Care and observation may be required.
The severe attack that many corrosives have on the tank itself
emphasizes the importance of using the correct procedure in lining
a tank to obtain a perfect lining. First select a coating that resists
the corrosive media and an applicator who has clearly demonstrated
the ability to apply that particular type of lining properly. Consider
the tank design and construction. If it is a new tank, be sure it
is built with the coating application in mind; if it is an old tank,
be sure adjustments are made to compensate for its design. Inspec-
tion should be made during application, after curing when the tank
is ready for service, shortly after the tank has been put into service,
and at scheduled intervals thereafter. Records should be kept and
514 Berger
the coating supplier informed of the performance of the lining—both

good and bad performance. Safety is an important part of a quality
application.
ACKNOWLEDGMENTS
The author is grateful to Wallace Cathcart Tank Lining Corp., Oak-

dale, Pennsylvania, for his contributions. Much of the information
contained herein is a result of over 25 years of NACE T6A Coating
and Lining Materials for Immersion Service committee and subcommittee
activities.
APPENDIX
Shown here in a series of 11 figures are the essentials for the

design and preparation of steel tanks for lining.
Full seam weld
Round corners
2 channels
back to back
DO DON'T
FIGURE 1 All construction involving pockets or crevices that will
not drain or that cannot be properly sandblasted and lined must
be avoided. [From Kiewit, J. (1976). The Paint Manual, USDA Bureau
of Reclamation, Denver.]
Pinhole Rough
^-Undercut
i J
Grind smooth
DO DON'T
FIGURE 2 All joints must be continuous solid welded. All welds must
be smooth with no porosity, holes, high spots, lumps, or pockets.
Peening is required to eliminate porosity, and grinding to remove
sharp edges. [From Kiewit, J. (1976). The Paint Manual, USDA
Bureau of Reclamation, Denver.]
Weld
-Clean "spatter
Grind smooth -Weld flux
DO DON'T
FIGURE 3 All weld spatter must be removed. [From Kiewit, J. (1976).

The Paint Manual, USDA Bureau of Reclamation, Denver.]
Weld
Sharp_
corner
1/8 radius
D 0 DON'T
FIGURE 4 All sharp edges must be ground to a minimum of 1/8-in.
radius. [From Kiewit, J. (1976). The Paint Manual, USDA Bureau
of Reclamation, Denver.]
516 Berger
FLANGED OUTLET
-Round corners 1 1
^-Weld
Min. -Weld
INSIDE OF VESSEL
_Shorp
Weld corners
-Threads
PAD TYPE
Round these
corners
Sharp,
corner
DO DON1!
FIGURE 5 Outlets must be flanged or pad type rather than threaded.
Within pressure limitations slip-on flanges are preferred as the inside
diameter (ID) of the attaching weld is readily available for radiusing
and grinding. If pressure dictates the use of weld neck flanges the
ID of the attaching weld is in the throat of the nozzle. It is, there-
fore, more difficult to repair surface irregularities such as weld
undercutting by grinding.
-Weld
J
-Grind smooth Gap-
^-Inside of vessel
-Round corners
Interior -Continuous fillet weld
r\
\\
Gap-
DO DON'T
FIGURE 6 Butt welding should be used, rather than lap welding
or riveted construction.
Skip weld
Inside of
vessel
Inside of
vessel
Angle stiffener
DO DON' T
FIGURE 7 Stiffening members should be on the outside of the vessel
or tank.
-Cone or dome head

Very bad, inaccessible void
-Shell
FIGURE 8 Standard field storage tank head. [From Kiewit, J.

(1976). The Paint Manual, USDA, Bureau of Reclamation, Denver.]
518 Berger
Protective coating
Alloy (cathode)
FIGURE 9 Dissimilar metal (galvanic) corrosion will occur where

an alloy is used to replace the steel bottom of a tank. If a lining
is then applied to the steel and for several inches (usually 6 to
14 in.) onto the alloy, any discontinuity in the coating will become
anodic. Once corrosion starts it progresses rapidly because of the
bare exposed alloy cathodic area. Without the coating, galvanic
corrosion would cause the steel to corrode at the weld area, but
at a much slower rate. The recommended practice is to line the
alloy completely as well as the steel, thereby eliminating the possible
occurrence of a large cathode-to-small anode area.
Tank
shell
Screwed nipple and Internal head

plug for venting
space during
fabrication and
heat curing lining
1-1/2 curved (prefferred)
or flat plate
Lower compartment
Note: It is impossible
to apply a lining
in this blind
inaccessible area
FIGURE 10 Technique (detail of fabrication) to allow for good con-

tinuity of lining application to inaccessible areas in multicompartment
tanks.
Threaded Nipple
2 x I reducing flange
Slip-on flange
1
—Line completely to bolt circle
Inside of
vessel -Full fillet weld. Grind and radius
FIGURE 11 Nozzle l i n i n g detail.
REFERENCES
1. Laboratory Methods for Evaluation of Protective Coatings Used

as Lining Materials in Immersion Service Materials Performance
(1974). National Association of Corrosion Engineers, Houston,
NACE TM-01-74, January.
2. Coatings and Linings for Immersion Service (1972). NACE TPC 2,
National Association of Corrosion Engineers, Houston.
3. Painting Steel Water Storage Tanks (1978). AWWA-D102-78,
American Water Works Association, Denver.
4. Recommended Practice, Design, Fabrication, and Surface Finish
of Metal Tanks and Vessels to Be Lined for Chemical Immersion
Service Materials Performance (1978). NACE RP-01-78, National
Association of Corrosion Engineers, Houston, January.
5. Volume II, Systems and Specifications (1982). Steel Structures
Painting Council, Pittsburgh.
6. Volume I, Good Painting Practice (1982). Steel Structures Paint-
ing Council, Pittsburgh.
7. Visual Standards for Surface of New Steel Airblast Cleaned
with Sand Abrasive (1970). NACE Standard TM-01-70, National
Association of Corrosion Engineers, Houston.
8. Pictorial Surface Preparation Standards for Painting Steel Surfaces
(1988). SSPC Vis. I-88T, Steel Structures Painting Council.
Pittsburgh.
520 Berger
9. Pictorial Surface Preparation Standards for Painting Steel Surfaces

(1967). ASTM D-2200-78, American Society for Testing and
Materials, Philadelphia.
10. Near White (1974). Maryland Pictorial Standard Ser. No. 001-A,
and Commercial, Ser. No. 001B, Maryland State Highway Adminis-
tration, Baltimore.
11. Abrasive Blasting Guide for Aged or Coated Steel Surfaces
(1969). SNAME Technical and Research Bulletin No. 4-9, Society
of Naval Architects and Marine Engineers, New York.
12. Measurement of Dry Paint Thickness with Magnetic Gages (1982).
SSPC PA2, Steel Structures Painting Council, Pittsburgh.
13. OSHA Reference Manual (1976). Painting and Decorating Con-
tractors of American, Falls Church, Va., August.
14. TLVfs Threshold Limit Values for Chemical Substances and Physi-
cal Agents in the Workroom Environment with Intented Changes
for 1988, American Conference of Governmental Industrial
Hygenists, Cincinnati.
15. Weaver, P. E. (1973). Industrial Maintenance Painting, National
Association of Corrosion Engineers, Houston.
16. Munger, C. G. (1965). Corros. Control Rep. 16(4), Ameron
Corp.
17. Estimating Guide, 21st ed. (1988). Painting and Decorating
Contractors of America, Falls Church, Va.
18. Water Tank Maintenance and Repair practices for Georgia Munici-
palities (1973). Georgia Municipal Association, Atlanta.
19. Evaluating Degree of Rusting on Painted Steel Surfaces (1979).
ASTM Method D-610 (also SSPC Vis. 2-87), and Evaluating
Degree Blistering of Paints, ASTM Method D-714, American
Society for Testing and Materials, Philadelphia.
20. Exposure Standards Manual (1979). Federation of Societies for
Coating Technology, Philadelphia.
21. Proposed Manual of Coating Work for Light Water Nuclear Power
Plant Primary Containment and Other Safety Related Facilities
(1979). American Society for Testing and Materials, Philadelphia.
22. Berger, D. M., and Mroz, S. E. (1976). Instruments for inspec-
tion of coatings, J. Test. Eval. 4:29-39, January.
23. Mixer, R. A., and Oechsle, S. J . , J r . (1956). Materials of
construction part I—protective lining systems, Chem. Eng.
181-182, November.
19
CEMENTS AND MORTARS
GEORGE W. READ, JR., CURTIS E. ZIMMER, and GARY R. HALL

Sauereisen Cements Company, Pittsburgh, Pennsylvania
INTRODUCTION
Corrosion-resistant cements are available for use as mortars with

acid-proof brick and as monolithic linings to be poured, cast, gunned,
or troweled into place. Typical installations are for lining acid tanks,
waste treatment tanks, process vessels, sumps, pits, foundations,
trenches, sewers, chimneys, stacks, ducts, and floors.
Several factors will influence the selection of the proper systems
for a specific installation.
1. The corrosive chemicals involved, their concentrations, and the

pH range.
2. The operating temperature and thermal shock conditions.
3. Mechanical abuse, abrasion, and traffic conditions.
4. Type of substrate to be protected, and its condition.
5. Nature of cleaning or washdown. There is no point in installing
a lining designed to withstand acid and then using a strong
caustic such as sodium hydroxide to clean it if the lining is
not resistant to alkalies. In such a case, the cleaning operation
would do more damage to the lining than the actual service it
would receive.
6. Whether the installation will be outdoors or indoors.
It is difficult to make a direct cost comparison between a brick

and mortar lining and a monolithic lining because of the number
of variables involved. Factors, such as special brick shapes or
521
522 Read, Zimmer, and Hall
extensive cutting, that may be necessary when using brick will

increase costs tremendously. Brick must be handled individually
and the corrosion-resistant cement applied with a trowel, so con-
struction is slow and the time before the installation is ready for
service is extended.
The installed or in-place cost per square foot of a monolithic
lining will vary with the type used and the method of installation,
just as the cost of brick linings will vary with the size and quality
of the brick and type of corrosion-resistant cement used. Generally,
a gunned monolithic lining will cost approximately half as much
as a comparable brick and mortar installation, whereas a trowel-
applied monolithic may be one-third the cost of a brick lining. Of
course, the cost per year of service life should also be considered
when choosing a protective lining system. Often, the brick or tile
floors will be more economical on this basis because of their extended
life expectancy and lower maintenance costs per year.
CORROSION-RESISTANT MASONRY
Corrosion-resistant masonry provides maximum protection from highly

corrosive chemicals, abrasion, and thermal shock. It adds years
to equipment life, reduces maintenance expense, and eliminates
costly shutdowns.
Brick and mortar linings provide some thermal insulation, but
do transmit a great deal of heat through them to the substrate.
Because the coefficient of thermal expansion of the brick and mortar
lining will generally not match that of the substrate, provisions
must be made to ensure that tensile stresses are not generated
in the masonry by the substrate expanding more rapidly and at
a greater rate than the masonry.
High tensile stresses should be avoided in brick and mortar
linings, and they should be designed so that the brickwork is placed
in slight compression. Cylindrical vessels and tanks employing arched
or domed tops are best. Bowed and battered walls serve to place
long walls in compression.
Corrosion-resistant masonry is not a liquid-tight barrier in itself
and should not be designed to serve as such. For liquid-tight
installations it is necessary to provide a backup impervious membrane
and the masonry will protect it from mechanical shock, abrasion,
and temperature. It is sometimes necessary to incorporate a mono-
lithic corrosion-resistant refractory between the brickwork and
the impervious membrane.
19. Cements and Mortars 523
Impervious Membranes
Impervious membranes are classified as either true membranes or
semimembranes. Examples of true membranes are
1. Rubber and related synthetic elastomers

2. Poly vinyl chloride (PVC)
3. Lead
4. Various synthetic resin formulations with glass cloth reinforcing
5. Rigid or semirigid plastic sheets
6. Baked-on coatings, including resins and glass
7. Urethanes or other spray-applied elastomers
Semimembranes
1. Asphalts or bituminous mastics

2. Unimpregnated asbestos or ceramic fiber felt applied with a sili-
cate solution
Chemical-Resistant Brick
ASTM C-279 lists the two types of chemical-resistant brick used
for these installations as
Type H: brick intended for use where thermal shock is a service

factor and minimum absorption is not required
Type L: brick intended for use where minimum absorption is required
and thermal shock is not a factor
These brick differ from ordinary face brick in that they are
manufactured of raw materials of extremely low flux content and
their low porosity and nonabsorbent qualities are imparted by the
method of manufacture and the high temperature at which they
are fired. Both types are available as red shale or fireclay, with
the latter being higher in cost and of better size tolerances. The
red shale type generally contains some readily available iron that
may be leached out in acid service; therefore, when halogen acids
are involved, the best choice would be the fireclay equivalent for
that type of brick.
Carbon brick are recommended for use in hydrofluoric acid,
acid fluorides, and strong caustic solutions, and for severe thermal
shock conditions. They have higher absorption than either the red
shale or fireclay types, but are more shock resistant and have
lower coefficients of thermal expansion and higher thermal conductivi-
ties.
CHEMICAL-RESISTANT MORTARS
One of the most important steps in corrosion-proof construction

is the selection of the proper mortar for bonding the brick. Because
there is no "all-purpose" mortar, there are several different types
with individual characteristics designed to meet specific service
requirements.
Silicate Mortars: Air-Drying Types

Mortars that are based on soluble silicate comprise some of the
original corrosion-resistant cements used. The first silicate mortars
were simply mixtures of fillers such as silica, quartz, clay, or
barytes, and a sodium silicate solution. Mortars of this type harden
by loss of water and require exposure to air or heat to set. Con-
struction with such mortars is extremely slow. Although thin joints
are used, the fluid mixture squeezes out if more than three or
four courses of brick are laid at one time. Usually, brickwork
heights of not more than 6 ft could be laid at one time. Very care-
ful drying was also necessary, and a 30-day period was usually
recommended before putting the structure into service. Because
of these drawbacks and the development of improved mortars, air-
drying mortars are no longer used for brick linings.
Sodium Silicate Mortars: Chemical-Setting Types

Chemical-setting sodium silicate mortars came into use early in the
1930s. These utilize a setting agent that reacts with the soluble
sodium silicate to cause the mixture to harden. The setting agent
may be either an acid or a compound that will decompose and liberate
acid to accelerate the cure. Typical setting agents used are ethyl,
acetate, zinc oxide, sodium fluorosilicate, glyceryl diacetate, form-
amide, and other amides and amines.
These mortars are supplied as either two-component systems,
which consist of the liquid sodium silicate solution and the filler
powder containing setting agents and selected aggregates; or they
may be one-part systems in powder form to be mixed with water
when used. Chemical-setting mortars take initial sets in 15 to 45
min and final sets in 24 to 96 hr or longer, depending on the tem-
perature and the formulation. Continuous bricklaying is possible
because the mortars harden quickly as a result of the chemical
reaction and do not require exposure to air or heat to achieve a set.
Large quantities of chemical-setting sodium silicate mortars have
been used in industry for the past 45 years, and mortars of this
type are still employed in some types of acid service.
Potassium Silicate Mortars: Chemical-Setting Types

When potassium silicates became commercially available early in the
1960s, new chemical-setting mortars were developed in which potassium
silicates were substituted for the sodium silicates previously used.
Several fundamental properties of potassium silicates combine to
make them preferable to sodium silicates.
Potassium silicates have better workability because of their smooth-
ness and lack of tackiness. They do not stick to the trowel and do
not run or flow from the joints of the brickwork. They possess
greater resistance to strong acid solutions as well as to sulfation.
Still another special value of potassium silicate mortars is that they
do not effloresce or bloom and they have less tendency to form
hydrated crystals in the hardened mortar.
Chemical-setting potassium silicate mortars are supplied as two-
component systems that comprise the silicate solution and the filler
powder and setting agent. Mortars are available that use inorganic
setting agents, organic setting agents, or a combination of the two.
The properties of the mortar are determined to a great extent by
the setting agent and the alkali-silica ratio of the silicate used.
Such properties as absorption, porosity, strength, and water resist-
ance are affected by the choice of setting agent. For example,
organic setting agents will burn out at low temperatures, thereby
increasing porosity and absorption. Organic setting agents are
water-soluble and can be leached out if the mortar is exposed to
steam or moisture. Mortars made with organic setting agents generally
take a longer time to gain any substantial strength because they
remain in the plastic state for 96 hr or more at normal temperatures.
In addition, they remain water-soluble for up to 14 days.
Mortars that use inorganic setting agents are water- and moisture-
resistant immediately upon final set, normally within 24 hr at 21°C
(70°F). They permit rapid, continuous construction without danger
of the brickwork slipping or sliding out of line.
Silica Mortars
Silica mortars contain over 95% silica in the cured state. The binder
is colloidal silica instead of the potassium or sodium silicates used
in other mortars. These mortars are two-component systems that
comprise a powder composed of high quality crushed quartz and
a hardening agent, which are mixed with the colloidal silica solution
to form the mortar. These mortars are particularly recommended
for use in hot concentrated sulfuric acid, especially when iron or
aluminum salts are present. They are also used for weak acid condi-
tions up to a pH 7.0. Typical applications are in brick linings for
acid concentrators, absorbers, stacks, process vessels, and storage
tanks.
Sulfur Mortars
Sulfur mortars are available in powder, flake, and ingot forms.
They are hot-melt compounds and must be heated to a temperature
of approximately 120°C (250°F) and poured into the joints while
hot. These mortars consist of sulfur, inert silica, carbon fillers,
and plasticizers. The plasticizers reduce brittleness, improve the
mechanical properties, and prevent the conversion of the sulfur
to an inappropriate crystalline form. Sulfur mortars are particularly
useful for protection against oxidizing acids. When they are carbon
filled they are suitable for protection against combinations of oxidizing
acids and hydrofluoric acid. The heat resistance of sulfur mortars
is relatively low and, therefore, their use is limited to installations
with operating temperatures below 88°C (190°F). Chemical resistance
to strong alkaline solutions and certain organic solvents is poor.
The recommended pH range for use is 1.0 to 14.0. The shelf-life
is indefinite.
Phenolic Resin Mortars

The phenolic resin mortars have phenol-formaldehyde resin binders
with inert powder fillers containing an acid catalyst. Fillers may
be silica, carbon, coke flour, or barytes. They have good resistance
to most mineral acids and solutions of inorganic salts and to mildly
oxidizing solutions, but they are rapidly attacked by strong oxidizing
agents such as nitric, chromic, and concentrated sulfuric acids.
They are satisfactory in mild alkaline solutions and in many solvents,
but they have poor resistance to strong alkalies. The temperature
limit is 175°C (350°F), and they are effective from a pH of 0.7
to 9.0. These mortars have poor storage life and must be kept
under refrigeration until used.
Furan Resin Mortars

Furan resin mortars have been used with chemical-resistant brick
and tile floors and vessel linings for over 40 years. They are
supplied as two-component systems consisting of a liquid furan
resin and a powder filler containing an acid catalyst. The filler
is usually carbon, barytes, coke flour, or silica. Furan mortars
have a wide range of chemical resistance and are suitable for use
in nonoxidizing acids, alkalies, many solvents, salts, gases, oils,
greases, detergents, and at temperatures up to 175°C (350°F).
They have an effective pH range of 1.0 to 13.0. Heat accelerates
the cure or hardening, and cold slows it. These furan mortars
have long been the standard in many demanding industries such
as food, beverage, pharmaceutical, and steel.
Polyester and Vinylester Mortars

Polyester and vinylester resin mortars may be supplied as either
two- or three-component systems. The filler powder is generally
silica, but carbon can also be used. These mortars are excellent
in most acids and are recommended for use in bleach vessels and
for mild oxidizing agents. They lack resistance to strong caustics
and some solvents. Their temperature limit is 120°C (250°F), and
they have an effective pH range of 0.9 to 14.0. These mortars
are relatively inexpensive and provide excellent chemical resistance
and mechanical properties. They are used extensively for laying
brick, tile, and steel plate floors.
Epoxy Resin Mortars

Epoxy resin mortars are usually two- and three-component systems
consisting of the resin solution, a setting agent, and inert fillers
and formula modifiers. They have excellent physical and mechanical
properties and adhere strongly to many surfaces. Resistance to
nonoxidizing acids and alkalies is excellent and they have good
resistance to some organic solvents. They are attacked by oxidizing
acids and bleaches. Their temperature resistance will range from
95 to 120°C (200 to 250°F); the effective pH range is 2.0 to 14.0.
Epoxies are among the strongest materials available with tensile
strengths sometimes exceeding 10,000 psi. They are, therefore,
especially well suited for service where severe physical abuse is
expected.
Application of Mortars
Many times, combinations of mortars offer not only the least expen-
sive but the ideal construction as well. A combination of a sulfur
cement and a furan resin cement is often used in lining acid pickling
tanks in steel mills. In this two-course construction, the inner
course of brick, which will be in contact with the acid, is bonded
with the furan resin mortar; then the sulfur cement is poured in
to fill the back course joints. The furan resin mortar acts as a
seal to prevent leakage of the molten sulfur mortar, and the hot
sulfur mortar speeds up the cure or set of the furan resin mortar.
Sulfur mortar joints must be 1/4 in. or more in thickness to
allow the molten compound to flow in around the brick and completely
fill the joints. With either silicate or resin mortars, the joints should
be kept as thin as possible to minimize shrinkage and provide the
most economical and the strongest possible joint. These mortars
are considerably higher in cost per unit volume than brick, so
joints should be kept as thin as possible—preferably not more than
1/8-in. thick.
It is also highly recommended that mortar be applied to five

sides of the brick in floor construction by using a bed joint as
well as buttering the sides of the brick. This will assure a level
base on which the brick can be placed because neither the subfloor
nor the brick are ever perfectly level and, without a bed joint,
the brick could move or wobble and eventually crack.
The same practice should be followed in wall or lining construction
using two or more courses of brick. All circumferential or back verti-
cal joints in the lining should be completely filled with mortar for
maximum impermeability and strength.
MONOLITHIC LININGS
Monolithic corrosion-resistant linings have been used successfully

for more than 25 years for both new and existing installations.
These linings may be cast poured or applied by pneumatic gunning.
They have the following advantages:
1. Curved or irregular surfaces can be covered uniformly.

2. Monolithic linings bond to steel, brick, and concrete.
3. Monolithic linings can be gunited horizontally, vertically, or
overhead, without complex forms, supports, or scaffolds.
Monolithic linings are composed of a single, generally massive

element, with or without expansion joints, and are applied in thick-
nesses from 1/2 in. up to several inches, depending on the service.
Linings must be anchored with wire mesh, studs, or anchors, with
a minimum of 1-in. cover over the highest point. The anchoring
system is necessary to retain the lining in intimate contact with
the shell during application and curing of the lining.
Castable monolithics are mixed and cast in a manner similar to
procedures used in handling concrete. They are poured or cast
into forms to harden. Trowel applications are generally thin coatings
of less than 3/4 in., and they are troweled in place, with or without
reinforcement. The largest tonnage of monolithic linings for corrosion-
resistant service is applied by pneumatic gunning.
Monolithic linings have limitations that must be considered. For
example, like all cementitious materials, they are inflexible and
tend toward brittleness. The modulus of elasticity will range from
105 to 106 psi and flexural strength will range from 500 to 2000 psi.
Tensile strengths will vary from 150 to 400 psi, and compressive
strengths will range from 1800 to 5000 psi. They also have porosity
ranging from 5 to 35%.
The thermal properties of monolithics vary considerably. In

general, the coefficient of thermal expansion of the monolithic should
be matched as closely as possible to that of the substrate over
which it will be applied. If it cannot be matched, a bond-breaker
or membrane should be considered. The thermal conductivity of
monolithic linings is lower than either steel or concrete. This is
usually advantageous, because the lower temperature on the substrate
reduces corrosion rates exponentially and also reduces thermal move-
ment and stresses in the substrate.
Care must be exercised in placing monolithic linings over sub-
strates that are still experiencing curing shrinkage in excess of 1%.
They can be expected to develop shrinkage cracks if placed directly
on such substrates. Here, it is necessary to provide expansion
joints and to place the monolithic over a bond-breaker such as
an impervious membrane.
As a rule, inorganic monolithic materials must be placed over a
suitable membrane material because of the previously described
tendency toward porosity and cracking. This is especially true
in those applications in which the exposure is to liquid media or
to halogens, and where these corrodents can condense from a hot-
gas stream.
Sodium Silicate-Based Monolithics

The original acid-resistant monolithic was an inorganic silicate base
which consists of two components, a powder and a liquid. The
powder is basically quartzite of selected gradation and a setting
agent. The liquid is a special sodium silicate solution. When the
monolithic is used, the two components are mixed together and
hardening occurs by a chemical reaction.
This monolithic may be cast or poured into construction forms,
or it may be applied by guniting. It has excellent acid resistance
and is suitable for use over a pH range of 0.0 to 7.0. These mate-
rials are prone to the sulfation-hydration-expansion phenomena
described previously for the sodium silicate mortars.
Potassium Silicate-Based Monolithics

The original potassium silicate monolithic cements first appeared
in 1981. These materials offer the same degree of chemical resistance
as described earlier for the potassium silicate mortars. They are
not as prone to sulfation-induced swelling and spailing as the sodium
silicate materials. Because of their superior performance in sulfur-
based acids, which are the most common acids encountered in
industrialized countries, the potassium silicate monolithics are p r e -

ferred over the sodium silicate materials.
Some manufacturers of both sodium and potassium silicate mono-
lithic materials and mortars have published claims that their materials
will withstand alkaline and caustic environments up to a pH of 12
or greater, regardless of the source of the alkalinity. Extensive
testing done by several independent laboratories has shown the
claims to be greatly exaggerated. Although it is true that certain
amines and ammonium-based alkalies will not be especially harmful
to the silicate materials, generally speaking, silica-containing mate-
rials are best restricted to acidic conditions.
Calcium Aluminate-Based Monolithics

Monolithics of this type consist of a calcium aluminate-based cement
and various inert aggregates and are supplied in powder form to
be mixed with water when used. They may be cast, poured, or
applied by guniting. Calcium aluminate-based monolithics are hy-
draulic and consume water in their reaction mechanism to form
hydrated phases. In this respect they are similar to portland cement
compositions; however, their rates of hardening are very rapid
and essentially full strength is attained within 24 hr at 23°C (73°F).
They have better mild-acid resistance than portland cement, but
they are not useful in acids below pH 4.5 to 5.0. They are not
recommended for halogen service, nor are they recommended for
alkali service above a pH of 12.0.
ADDENDUM
The American Society for Testing and Materials has a number of

published standards that have been developed for chemically resistant
materials, in the Index of the 1987 Annual Book of Standards.
ASTM C-279 Chemical-Resistant Masonry Units

ASTM C-287 Chemical-Resistant Sulfur Mortars
ASTM C-395 Chemical-Resistant Resin Mortars
ASTM C-466 Chemically Setting Silicate and Silica Chemical-Resistant
Mortars
There are also Methods of Tests available for the following:
ASTM C-267 Chemical Resistance of Mortars

ASTM C-307 Tensile Strength of Chemical-Resistant Resin Mortars
ASTM C-308 Working and Setting Times of Chemical-Resistant
Resin Mortars
ASTM C-321 Bond Strength of Chemical-Resistant Mortars

ASTM C-413 Absorption of Chemical-Resistant, Nonmetallie Mortars,
Grouts, and Monolithic Surfacings
ASTM C-414 Working and Setting Times of Chemical-Resistant
Silicate and Silica Mortars
ASTM C-531 Shrinkage and Coefficient of Thermal Expansion of
Chemical-Resistant Mortars, Grouts, and Monolithic Surfacings
ASTM C-579 Compressive Strength of Chemical-Resistant Mortars,
Grouts, and Monolithic Surfacings
ASTM C-580 Flexural Strength and Modulus of Elasticity of
Chemical-Resistant Mortars, Grouts, and Monolithic Surfacings
There are Recommended Practices for the Use of
ASTM C-386 Chemical-Resistant Sulfur Mortars

ASTM C-397 Chemically Setting Chemical-Resistant Silicate and
Silica Mortars
ASTM C-398 Hydraulic Cement Mortars in Chemical-Resistant
Masonry
ASTM C-399 Chemical-Resistant Resin Mortars
20
SHEET LININGS
GENERAL CONSIDERATIONS
Tanks and other processing vessels have for many years been
successfully lined with various rubber formulations. Many of these
vessels have given over 20 years of service. These linings were
usually applied over steel substrates.
With the development of newer synthetic elastomeric and plastic
materials, the variety of lining materials available has been greatly
increased. In addition, the substrate has also undergone changes.
More frequently, fiber-reinforced plastic (FRP) is being used as
the structural substrate.
As with coatings or liquid-applied linings, the corrosion resist-
ance, allowable operating values, and cost varies with each material.
Care must be taken when selecting the lining material that operating
conditions will not exceed the allowable limits of the material and
that it is compatible with the corrodants to be handled.
Permeation and absorption are two factors that must be taken
into account when specifying a lining material. All materials are
somewhat permeable to chemical molecules, but plastic materials
tend to be an order of magnitude greater in their permeability rates
than metals. This permeation has also been a factor in rubber-lined
steel vessels where corrodants have permeated the rubber and formed
bubbles between the rubber lining and the steel substrate. Permea-
tion can result in
1. Bond failure and blistering. This results from an accumulation

of fluids at the bond when the substrate is less permeable than
533
534 Schweitzer
the lining or from corrosion /reaction products if the substrate

is attacked by the corrodant.
2. Failure of the substrate from corrosive attack.
3. Loss of contents through lining and substrate as a result of
eventual failure of the substrate.
The thickness of a lining is a factor affecting permeation. For

general corrosion resistance, thicknesses of 0.010 to 0.020 in. are
usually satisfactory. However, when mechanical factors, such as
thinning caused by cold flows, mechanical abuse, and permeation
are considered, thicker coatings are required.
An increase in thickness will normally decrease permeation by
the square of the thickness. Although this would appear to be
the approach to follow to solve the problem, there are disadvantages.
First, as the lining thickness is increased, thermal stresses on the
bond are increased, resulting in bond failure. Temperature changes
and large differences in coefficients of thermal expansion are the
most common causes of bond failure. For example, an 8-ft (2.4-m)
length of polyvinylidene fluoride polymer (PVDF) will expand 0.5
in. (13 mm) more than steel for each 100°F (56°C) rise in tempera-
ture. As can be seen, high stresses will result if these two materials
are bonded together. The thickness and modulus of elasticity of
the lining material are two of the factors that influence these stresses.
Second, as the thickness of the sheet of lining material increases,
it becomes much more difficult to form, and heat may have to be
supplied. In addition, the thicker sheets are also much more difficult
to weld. Third is cost. As the thickness increases so does the
cost of the material. Labor costs are also increased because of the
greater difficulty of working with the material. If materials such
as fluorinated ethylene propylene (FEP), tetrafluoroethylene (TFE),
or PVDF are being used the cost may become prohibitive.
The rate of permeation is also affected by temperature and tem-
perature gradient in the lining. Lowering of these will reduce the
rate of permeation. Lined vessels working under ambient conditions,
such as in storage tanks, provide the best service.
Absorption of corrodant by the lining material can result in
swelling, cracking, and penetration to the substrate. Swelling can
cause softening of the lining material, introduce high stresses and
failure of the bond. If an organic lining has a high absorption,
permeation will probably result. Some materials such as tetrafluoro-
ethylene polymer (PTFE) permeate easily but have very little absorp-
tion.
An approximation of the expected permeation or absorption through
a lining material may be made based on the absorption of water.
This data is generally available.
20. Sheet Linings 535
The shell into which the lining is placed is usually fabricated

from carbon steel, although recently FRP shells are being used
more frequently. Either material is relatively inexpensive. The use
of FRP as the structural substrate has several advantages:
1. The outer shell itself provides protection from atmospheric corro-

sion.
2. Bonding of the lining material is made easier and, sometimes,
permits a bonding of materials that cannot be accomplished with
a carbon steel shell.
3. The FRP is lighter in weight than the comparable carbon steel
shell.
SHELL PREPARATION
The first step in the satisfactory installation of a sheet lining in

a vessel is the preparation of the vessel shell before lining. Although
details of the shell preparation may vary somewhat between manufac-
turers and types of linings, certain basic principles are equally
applicable in the design of vessel shell and are as follows:
1. Vessel must be of butt-welded construction

2. All internal welds must be ground flush.
3. All weld spatter must be removed.
4. All sharp corners must be ground to a minimum of 1/8-in. radius.
5. All outlets to be of flanged or pad type. Certain lining materials
require that nozzles be not less than 2 in. (50 mm) in diameter.
Check with lining contractor.
6. No protrusions are permitted inside of vessel.
Surface Preparation
Surface preparation is an extremely critical step. Unless the surface
is properly prepared, proper bonding of the lining to the shell
will not be achieved. The basic requirement is that the surface
be absolutely clean. To achieve proper bonding, all surfaces to
be lined should be abrasive blasted to white metal in accordance
with 55PC specification Tp-5-63 or NACE specification NACE-1.
A white-metal surface condition is defined as being one from which
all rust, scale, paint, and the like, have been removed and the
surface has a uniform gray-white appearance. Streaks or stains
of rust or other contaminants are not allowed. On occasion, a near-
white blast-cleaned finish equal to SSPC SP-10 is allowed, which
is a more economical finish. It is essential that the finish that the
536 Schweitzer
lining contractor specifies be provided. Some lining contractors

will also undertake the fabrication and surface preparation of the
vessel as well as installing the lining. Placing the total responsibility
on the lining contractor can simplify the problem of coordination
and will usually result in a better-quality product.
A word of caution. Do not perform external welding on the vessel
after the lining has been installed.
TESTING OF LINING
The normal procedure for testing the integrity of lining welds is

the use of a high-voltage spark tester. Voltages usually range
from 10,00-0 to 30,000 VAC. The actual voltage to be used is depend-
ent upon the lining material and lining thickness. These tests should
only be conducted by someone experienced in such work.
Lined metal vessels can be tested very readily because the entire
outer shell is a conductor. Shells of FRP require that a conductive
"target" be installed behind lining weld areas and any other areas
where spark testing is desired. The most common target material
is a mixture of at least 33% carbon black and the resin used in
the FRP vessel. Metal strips installed behind the welds as targets
can become the source of delamination and, therefore, are not
popular.
A recent development has been the use of a carbon fiber paper
covering the entire inner surface of the FRP vessel. This permits
spark testing at any location.
ELASTOMERIC LININGS
Elastomer linings have given many years of service in providing

protection to steel vessels. Both natural and synthetic materials
are used. These materials are sometimes referred to as "rubbers."
In addition to being used as lining many of these materials also
find application as gaskets, O-rings, and seals of various types.
Each of the materials can be formulated to improve certain of
its properties. A complete specification for a lining using these
elastomers should include the specific properties required for the
application, such as resilience, hysteresis, static or dynamic sheer
and compression modulus, flex fatigue and cracking, creep resistance
to oils and chemicals, permeability, and brittle point, all in the
temperature range to be encountered in service. This will permit
a competent manufacturer to propose the proper lining material
for the application.
Elastomeric linings are sheet-applied and bonded to the steel

surface. The bonding material to be used is dependent on the
specific elastomer to be installed. Repair of these linings is relatively
simple. Many older vessels with numerous repair patches are still
operating satisfactorily.
Elastomeric membranes are used in acid-brick-lined vessels to
protect the steel or concrete shell from acid attack. The acid brick
is designed to protect the membrane from abrasion and excessive
temperature.
Natural Rubber
The degree of curing to which natural rubber is subjected will
determine whether it is classified as soft, semihard, or hard. Soft
rubber is the preponderant form used as a lining material, although
some hard rubber linings are also produced.
Excellent resistance is offered to most inorganic salt solutions,
alkalies, and nonoxidizing acids. Hydrochloric acid reacts with soft
rubber to form rubber hydrochloride and, therefore, is not recom-
mended. Most organic materials and strong oxidizing agents will
attack natural rubber causing it to soften, dissolve, and debond.
Isoprene
Natural rubber is chemically a natural cis-polyisoprene, whereas
isoprene (IR) is a synthetic cis-polyisoprene, consequently its corro-
sion resistance is the same as that of natural rubber. However,
isoprene has no odor and, therefore, can be used for certain food-
handling applications.
Butyl Rubber
Butyl rubber (IIR) is a general-purpose synthetic rubber having
excellent resistance to dilute mineral acids, acetone, phosphate
esters, oils, ethylene, ethylene glycol, and water. It will be attacked
by petroleum oils and gasoline, but it is resistant to swelling by
vegetable oils and animal oils which attack natural rubber.
Neoprene
Neoprene (CR) is resistant to alkalies, dilute mineral acids, inorganic
salt solutions, aliphatic hydrocarbons, aliphatic hydroxy compounds,
and most Freon refrigerants. Aromatic hydrocarbons, highly oxidizing
acid, and salt solutions, and chlorinated solvents will attack neo-
prene.
538 Schweitzer
Chlorosulfonated Polyethylene (Hypalon)

This rubber is resistant to attack by strong oxidizing agents such
as concentrated sulfuric acid and hypochlorite solutions, as well
as aqueous salt solutions, alcohols, weak and concentrated alkalies.
It will be attacked by aliphatic, aromatic, and chlorinated hydro-
carbons, aldehydes, ketones, and fuel oils.
Perfluoroelastomers
Perfluoroelastomers (FPM) materials are relatively expensive and
are used only in severe chemical service. They offer almost universal
chemical resistance, being extremely resistant to aliphatic hydro-
carbons, chlorinated solvents, animal, mineral, and vegetable oils,
gasoline, jet fuels, dilute acids, alkaline media, and aqueous salt
solutions. Only a fair to poor resistance is exhibited in the presence
of oxygenated solvents, alcohols, aldehydes, ketones, esters, and
ethers.
Included in this group are Viton (duPont), Kel-F (3M), Fluorel
(3M), and Kalrez (duPont).
THERMOPLASTIC LININGS
Thermoplastic linings are used more extensively than any other

type of linings. Several of the most common are
Poly vinyl chloride (PVC)

Chlorinated polyvinyl chloride (CPVC)
Polyvinylidene fluoride (Kynar) (PVDF)
Polypropylene
Polyethylene
Tetrafluoroethylene (PTFE)
Fluorinated ethylene propylene (FEP)
Halar ECTFE
ETFE
The materials listed provide a wide range of corrosion resistance

and operating conditions. Table 1 lists the general area of corrosion
resistance for each material and Table 2 shows the physical proper-
ties. As can be seen a wide choice is available based on the applica-
tion. The resistance of the lining material to a specific corrodent
should always be checked, Table 1 is only a general guide.
These materials are used not only as linings for vessels, but
also as liners for pipe and fittings [1]. Most of the lined pipe have
loose-fitting liners (the lining material is not bonded to the inside
TABLE 1 General Corrosion Resistance of Thermoplastic Lining

Materials
Esters
Strong Strong Chlorinated and Strong
Material acids bases solvents ketones oxidants
PVC (type 1) F F P P P
CPVC F F F P P
PVDF E P E P E
Polypropylene G E P F P
Polyethylene F G P P E
PTFE E E E E E
FEP E E E E E
ECTFE E E E E E
E, excellent; G, good; F, fair; P, poor.
of the pipe). Although the lining provides the advantage of corrosion

resistance to the material being conveyed, there are some disadvan-
tages to these piping systems.
1. Although the inside of the pipe is protected, the external portion
is subject to corrosion. It may be necessary in certain atmospheres
to apply a protective coating to the exterior of the carbon steel
pipe.
2. Flanged joints are the common method of joining pipe sections,
although some of the lining materials can be utilized with threaded
joints. With the use of flanged joints, odd lengths must be fabri-
cated by using special field fabricating techniques or be ordered
from the factory.
When vessels are lined, the linings, with the exception of plasti-
cized poly vinyl chloride (PVC), are fabricated from sheet stock
that must be cut, shaped, and joined. Joining is usually accomplished
by hot-gas welding. Several problems are present in the installation
of a bonded thermoplastic lining to a metal shell, primarily the
large differences in the coefficient of thermal expansion and the
difficulty of adhesion. If the vessel is to be used under ambient
conditions (such as a storage vessel) the problem of thermal expan-
sion differences is eliminated. However, the problem of adhesion
is still present. Hence, many of the linings are installed as loose
linings in the vessel.
To overcome the problem of adhesion, techniques have been
developed that use an intermediate mechanical bond. One approach
TABLE 2 Physical Properties of Thermoplastic Lining Materials
Coeff. of
Max. use thermal Modulus of elasticity
temp. Tensile strength expansion (tensile) at 73°F
Material °F °C psi kPa x 10-6/(in.- OF) psi x io 6 kPa x io 6
PVC (type 1) 140 60 7000 48230 30 0.3-0.6 2.07-4.13
CPVC 200 93 7500 51675 38 0.3-0.5 2.07-3.45
PVDF 275 135 5000 34450 50-70 0.05 0.34
Polypropylene 180 82 5000 34450 38-50 0.2 1.38
Polyethylene 120 49 1400-4000 9646-27560 100 0.2-0.04 0.14-0.28
PTFE 500 260 3300 22737 90 0.05 0.34
FEP 375 190 3000 20670 50 0.06 0.41
ECTFE 340 170 7000 48230 100 0.24 1.65
00
o
is to heat the thermoplastic sheet, then impress into one surface

a fiber cloth or nonwoven web. This provides half the bond. Bond-
ing to the metal surface is accomplished by the use of an epoxy
adhesive that will bond to both the fiber and the metal.
Welding techniques for joining the thermoplastic sheets are very
critical. Each weld must be continuous, leak tight, and mechanically
strong. It is important that only qualified welders be used for this
operation. Poor welding is a common cause of lining failure.
Polyvinyl Chloride
Polyvinyl chloride (PVC) linings can be applied as sheet linings,
by dipping, or by spray coating. Plasticized PVC plastisols can
be directly bonded to a metal substrate. Unplasticized PVC cannot
be bonded directly, but it may be bonded to the plasticized material
forming a dual laminate that can then be bonded to the metal sub-
strate. Sheet linings are of plasticized (type 1) PVC and a plastisol,
because the plastisol can be bonded directly to the metal substrate.
Plastisols do not have the overall range of corrosion resistance
as plasticized PVC. Because plasticized PVC is compounded of a
polyvinyl chloride dispersion of high-molecular-weight vinyl chloride
polymers in a suitable liquid plasticizer, formulations can be made
for specific applications. By selective compounding, both physical
and corrosion-resistant properties can be modified. For certain
applications this feature can be most advantageous.
Sheet linings with either material, must have their joints joined
by hot-gas welding. The plastisol material is flexible enough to
withstand thermal stresses and can be stretched to cover minor
irregularities on the vessel surface.
These linings have found many applications in marine environments
as well as for the handling of highly corrosive and abrasive materials.
Chlorinated Polyvinyl Chloride

Chlorinated polyvinyl chloride (CPVC) is very similar in properties
to PVC, except that it has a higher allowable operating temperature
and a somewhat better resistance to chlorinated solvents. It can
be installed as a sheet lining and the joints hot-gas welded. How-
ever, CPVC is extremely difficult to weld. This factor should be
considered when consideration is given to using this material.
Polyvinylidene Fluoride (Kynar)

Linings of polyvinylidene fluoride (PVDF) are sheet applied. This
polymer is one of the most popular lining materials because of its
542 Schweitzer
range of corrosion resistance and high allowable operating tempera-

ture. Because of this factor it is much more difficult to weld the
PVDF than lower-melting materials such as PVC. Kynar linings,
unless a dual laminate is employed, will be loose. The PVDF can
be extruded and is available as solid pipe or as a loose liner inside
of steel pipe.
Polypropylene
Polypropylene is also available in an extruded form used to line
steel pipe. Sheet material is used to line vessels. To be bonded
to the substrate, a backing sheet is necessary, otherwise the lining
will be loose.
Polyethylene
Polyethylene is the least expensive of all the plastic materials. Large
quantities are used as thin, sheet or film liners in drums and other
packages. It can be readily joined by heat sealing and fusion weld-
ing, when sheet linings are installed in vessels.
Polyethylene is also available as a pressure-sensitive tape that
is being used to wrap electrical conduit and pipe as a means of
supplying corrosion protection.
If the material is to be exposed to weathering, then a carbon-
filled grade should be used, because the unfilled grades have poor
weathering resistance.
Tetrafluorethylene (PTFE)
Extruded tubing is used to line pipe and sheet material to line
vessels. This is one of the most expensive lining materials, but
also the one having the greatest range of corrosion resistance.
Usually, the linings are loose because the PTFE cannot be bonded
directly. It can be bonded by using a laminated fiberglass sheet as
backing.
Lining thicknesses vary from 60 to 120 mil. The material tends
to creep under stress or at elevated temperatures. When the vessel
is designed, this should be taken into account and provisions made
to contain the material. Tetrafluoroethylene is also a relatively weak
material.
Perfluoralkoxy (PFA) is often used in conjunction with PTFE
lining. Because this material is readily fabricated, it is often used
for the production of the more difficult portions of the lining.
Perfluoralkoxy is a copolymer of tetrafluoroethylene and perfluoro-
vinyl ether and is fully fluorinated, making it chemically inert. It
has a maximum service temperature of 232°C (450°F) which is some-

what lower than that of PTFE. However, its tensile properties at
elevated temperatures are slightly better than those of PTFE and
its permeability to most chemicals is somewhat lower.
Fluorinated Ethylene Propylene

Fluorinated ethylene propylene (FEP) has essentially the same
corrosion-resistant properties of PTFE and PFA but is less expensive
and considerably easier to fabricate. The allowable operating tempera-
ture of FEP is somewhat lower than that of PTFE (refer to Table 2).
In general the applications for FEP are the same as for PTFE.
Ethylene-Chlorotrifluoroethylene (Halar)
Ethylene-chlorotrifluoroethylene (ECTFE) is a copolymer of ethylene
and chlorotrifluoroethylene. Because this fluorinated thermoplastic
is not completely fluorinated there are sites along the polymer chain
that are subject to chemical attack. It is resistant to mineral acids
up to a temperature of 121°C (250°F). This polymer will be attacked
by acetic acid at temperatures over 93°C (200°F); by aliphatic and
aromatic amines at over 66°C (150°F); by chlorinated hydrocarbons,
functional aromatics, ethers, and ketones at over 66°C (150°F);
and by aromatic solvents at over 121°C (250°F).
The maximum service temperature of ECTFE is 170°C (340°F).
It is suitable for vessel linings and can be installed in the same
manner as PTFE.
Ethylene-Tetrafluoroethylene
Ethylene-tetrafluoroethylene (ETFE), a partially fluorinated copolymer
of ethylene and tetrafluoroethylene, has a maximum service tempera-
ture of 149°C (300°F). It is fairly inert to strong mineral acids,
halogens, inorganic bases, and metal salt solutions. Under most
conditions ETFE is resistant to alcohols, ketones, ethers, and chlori-
nated hydrocarbons. However, before use of these materials, a test
program should be conducted. Strong oxidizers ( e . g . , nitric acid),
organic bases ( e . g . , amines), and sulfonic acids will attack ETFE.
This material is suitable for use in applications as vessel linings.
CAUSES OF LINING FAILURE
Linings, when properly selected, installed, and maintained, will

provide long years of satisfactory service. Despite this there are
544 Schweitzer
occasionally reports of lining failures that can be traced to one

or more of the following causes.
Liner Selection
The first step is to select the proper lining material—one that has
the required chemical resistance and the necessary physical and
mechanical properties to meet the application. If necessary corrosion-
resistance testing should be done to guarantee the resistance of
the liner material.
Inadequate Surface Preparation

As indicated previously, the surface preparation is critical. If not
done properly poor bonding can result or mechanical damage to
the liner is possible. It is important to see that the specifications
for surface preparations are followed.
Thermal Stresses
Stresses produced by thermal cycling can eventually result in bond
failure. Proper design can control this problem.
Permeation
Permeation through the lining to the steel substrate can cause de-
bonding when corrosion products or fluids accumulate at the inter-
face. In addition, deterioration of the substrate can also result.
Proper selection of the lining material can help to control this prob-
lem.
Absorption
As with permeation, absorption of the corrodant by the liner material,
can result in swelling of the liner, cracking, and eventual penetra-
tion to the substrate. This can lead to high stresses and debonding.
Welding Flaws
A welding flaw is a common cause of failure. Therefore, it is essen-
tial that only qualified personnel perform the welding and only
qualified experienced contractors be used to install linings.
Debonding
In addition to debonding occurring as a result of one of the preced-
ing causes, it can also occur as a result of the use of the wrong
bonding agent. Care should be taken that the proper bonding agent
be employed for the specific lining being used.
Operation
It is important that those personnel operating lined equipment be
thoroughly familiar with the allowable operating characteristics of
the liner. Most failures from this cause usually result while vessels
are being cleaned or repaired. Temperatures may be exceeded if
live steam is used, or chemical attack may occur if the vessel is
solvent cleaned.
REFERENCE
1. Schweitzer, P. (1985). Handbook of Corrosion Resistant Piping,

2nd e d . , Robert E. Krieger Publishing.
21
CORROSION MONITORING
GENE FREDERICK RAK Exxon Company, USA, Baton Rouge,

Louisiana
INTRODUCTION
To monitor the condition of process equipment both onstream and

off stream, the engineer must rely on nondestructive testing. Non-
destructive testing may be defined as testing to detect internal,
external, and concealed flaws in materials by use of techniques
that do not damage or destroy the items being tested. Nondestructive
tests are an essential component of production processes. They can
be applied, if necessary, to all critical components and assemblies.
In many applications, these indirect tests have greater sensitivity,
accuracy, and reliability than do widely accepted and more costly
direct tests. Nondestructive testing can be utilized as an early-
warning device to indicate when process equipment is approaching
its retirement limit or when process conditions are such that increased
corrosion rates are occurring. It is important that the engineer
understand the operation methods and limitations of nondestructive-
testing equipment so that the data extracted from inspection reports
can be analyzed properly to give meaningful results.
Often, corrosion-monitoring equipment can be used to optimize
process conditions to achieve the maximum capabilities throughout,
without sacrificing the integrity of the equipment. Process changes,
such as increases or decreases in temperature, pressure, velocity,
and concentration, can accelerate corrosion rates. When these process
changes occur, it is imperative that the engineer monitor the effect
on corrosion rates to prevent failure of equipment caused by corro-
sion and, thus, avoid unscheduled shutdowns of process units.
547
548 Rak and Schweitzer
Occasionally, engineers are limited in the amount of onstream

testing they can perform and, therefore, must rely on offstream
testing methods. Onstream inspection tools and techniques are limited
because of the inaccessibility of equipment, extreme temperatures,
extreme pressures, physical shapes and configurations, and so on.
This chapter addresses several tools and techniques available to
the engineer to monitor equipment both onstream and off stream.
ONSTREAM MONITORING EQUIPMENT

Electrical Resistance Principle
The Rohrback Corrosometer probe (Fig. 1) operates on the electrical
resistance principle. The measuring element, consisting of a wire,
tube, or strip section, is exposed to the gas or liquid stream.
As the measuring element corrodes, the cross-sectional area reduces
and the electrical resistance increases. The thickness of the measur-
ing element is directly proportional to a corrosion dial reading.
A Corrosometer, Model CK-3, instrument (Fig. 2) is used to monitor
the progress of corrosion in the measuring element. The difference
in dial readings is plotted against time as shown in Figure 3. Slope
A corresponds to a moderate corrosion rate, slope B corresponds
to a slight corrosion rate, and slope C corresponds to a high corro-
sion rate. The actual corrosion rate, described in mils per year
(mpy) can be determined as follows:
A dial reading _ ___ , ... ..

mpy = ——: : — . ° * 0.365 * probe multiplier
*J A time, in days ^ *
Example 1: Corrosion rate of slope A
mpy = 1 ?S "" 1° x 0.365 x 10

la - o
= 10.4 mpy
Example 2: Corrosion rate of slope C
mpy = 1 §f-r-ff >< 0-365 x 10

= 43.8 mpy
Corrosometer readings should be recorded daily until a pattern is

established. At that time, reading intervals may be increased or
decreased to obtain an accurate corrosion rate. The engineer should
21. Corrosion Monitoring 549
Vessel or Pipe
Packing Gland Body
^rig^^^^l
Corrosometer Probe
Packing Gland Nut
Access Valve
FIGURE 1 Rohrback Corrosometer probe assembly. (Courtesy of

Rohrback Corporation, Santa Fe Springs, Calif.)
avoid determining a corrosion rate based on only two successive

readings, because small deviations may distort the actual corrosion
rate. Readings can be obtained using either a portable manual instru-
ment or an automatic recorder system.
While the process unit is shut down, a 1-1/2-in. nipple and
valve is usually installed in the area in which the maximum corrosion
is expected. The Rohrback Corrosometer retractable probe (Fig. 4)
can be inserted during a process run. Occasionally, connections
are not available in areas of interest and onstream connections can
FIGURE 2 Rohrback Corrosometer, Model CK-3 instrument. (Courtesy

of Rohrback Corporation, Santa Fe Springs, Calif.)
200
CO
o 180
I—I
CO
cy
160
I—I
140
I—I
Q 120 > /
R /
-7
100
| 1
m mmmmm
Q
80 -R-
O 60 ^**
| 1
•• CORROSION RATE (MPY) =
CO A DIAL READING PROBE
o 40 X 3 X
cr A TIME (DAYS )
M ULTIPLIER
20 ..,„.
o
CJ
10 15 20 25 30 35 40
TIME DMYS TO
FIGURE 3 Plot of data from corrosion probe. (Courtesy of Rohrback Corporation, Santa Fe
Springs, Calif.)
FIGURE 4 Rohrback retractable probe. (Courtesy of Rohrback

Corporation, Santa Fe Springs, Calif.)
be added using hot-tapping equipment. Hot tapping is a procedure

for making a pipe connection into a line or vessel without removing
it from service. Adequate wall thickness must be established before
hot tapping the equipment.
The retractable probe is connected to the 1-1/2-in valve as shown
in Figure 1, and the packing gland is then tightened to prevent
leakage. The valve is opened slowly. When the valve is fully opened
the packing is loosened, and the probe is inserted through the
valve and into the process stream. The packing is then tightened
and should be checked frequently to ensure that leakage does not
occur through the packing gland. Safety clamps are available to
ensure that the corrosometer probe does not retreat beyond the
packing gland. Although the safety clamp was designed for high-
pressure systems, it should be included in all installations.
Figure 5 shows a typical installation of a retractable process
probe. The measuring element should be located as close as possible
to the metal surface being monitored. Also, the probe should be
installed in a manner to avoid impingement of high-velocity streams
or abrasive particles. Electrical connections can be dropped to
ground level to minimize climbing on equipment when gathering daily
readings.
The corrosometer probe can be used in most process equipment
and is available in a variety of alloys. The probe can be either
fixed or the retractable type. The fixed probe is designed to be
inserted in equipment when there is no pressure or flow in the
system. As expected, the process equipment must be isolated and
depressurized before the removal of a fixed probe. The retractable
FIGURE 5 Installation of a retractable probe. (Courtesy of Rohrback

probe can be operated at a maximum pressure of 1000 psig and

a maximum temperature of 1000°F. The fixed probe can operate
at a maximum pressure of 3000 psig and a maximum temperature
of 1000°F. Both the fixed and the retractable probes can be modified
by using a Grant Oil Tool Cosasco high-pressure access fitting to
allow their use at a maximum pressure of 6000 psig. Selection of
a seal material to isolate the measuring element from the probe body
is based on process conditions. The manufacturer of the probe
should be consulted in the selection of a proper seal material.
The main disadvantage of the resistance probe is that, normally,
it requires several days or weeks to determine a corrosion rate.
If process conditions are such as to cause a wide swing in dial
readings, it becomes necessary to gather a significant amount of
data to establish corrosion rates. Because the resistance wire element
is available only in 40- and 80 mil diameters, the measuring element
life is fairly short in highly corrosive environments.
Linear Polarization Principle

The Petrolite Pair probe operates on the linear polarization principle.
Figure 6 shows the Petrolite M-510 standard industrial probe, and
Figure 7 illustrates the circuitry. The corrosion rate is determined

by measuring electrical current flow between the test and auxiliary
electrodes. That current either cathodically protects or anodically
accelerates the corrosion rate of the test electrode, depending on
the flow. The current is measured on a microammeter that has been
converted to read the corrosion rate directly (in mils per year) of
the test electrode. The Petrolite Portable Industrial Meter, Series
M-212 instrument (Fig. 8) is designed for manual, nonrecording
use in the field. The Petrolite M-510 probe is built on a 2-in. pipe
plug base and is designed to be operated at a maximum pressure
of 3000 psig and a maximum temperature of 400°F. The probe can
be supplied in either mild steel or 304 stainless steel.
With the addition of a Petrolite In-8101 E/R corrosion-monitoring
transmitter, signals from these probes can be relayed to a Petrolite
FIGURE 6 Petrolite M-510 standard industrial probe. (Courtesy

of Petrolite Corporation, Stafford, Tex.)
Current
Adjustable Source
Zero
Position
FIGURE 7 Principle of three-electrode probe. (Courtesy of Petrolite

Corporation, Stafford, Tex.)
IN-8102 E/R receiver, which is an auxiliary readout device. Data

are shown on an LED display in either loop current in milliamperes,
probe life units, or total metal loss in mils.
If extremely close monitoring is required or a large number of
probes are located within a small geographic area Petrolite's IN-8200
monitoring system is available. The IN-8200 monitor is complete
with the ability to handle 16 channels, with the capability of expan-
sion to 48 channels.
The Rohrback Corrater operates similarly to the Petrolite Pair
Probe. Figure 9 shows several types of Corrater probes. The two
(or three) elements are immersed in the corrosive stream and a
small millivolt potential is then supplied across the two electrodes.
The effect of this potential is to increase slightly the anodic activity
that is occurring on the surface of one of the electrodes and the
cathodic activity on the other. A small current flows through the
electrolyte and is measured by the Rohrback 1120 Portable Corrater
Meter (Fig. 10).
The main advantage of the linear polarization method is that
instantaneous corrosion rates can be determined. This is extremely
helpful in determining the effect of process changes. Any changes
in temperature, pressure, velocity, concentration, or pH will cause
increases or decreases in corrosion rates, and a decision can be
made instantaneously about the effect on the integrity of the equip-
ment. The probes are not operable in nonconductive gas or hydro-

carbon process service.
The Petrolite Flush-Mounted probe (Fig. 11), operates on the
same principle as the three-electrode instantaneous polarization
method. The small ring is the test electrode and the probe body
is an auxiliary electrode. The planar probe surface has the reference
electrode in the center. The advantage of this probe is that the
monitoring device is flush with the surface in question and accurately
simulates the corrosion rate occurring on the wall of piping or equip-
ment. The Petrolite Flush-Mounted probes are pressure rated to
3600 psig at 21°C (70°F), with insertion pressure ratings dependent
FIGURE 8 Petrolite M-212 portable industrial meter. (Courtesy

of Petrolite Corporation, Stafford, Tex.)
FIGURE 9 Rohrback Corrater probes. (Courtesy of Rohrback

on the access system rating. The process equipment must be isolated

and depressurized before the probe is removed.
Hydrogen Test Probe

The Cosasco hydrogen test probe (Fig. 12) operates on the principle
that hydrogen will diffuse through the thin wall and set up a pres-
sure within the tube. The rate at which the pressure increases
is measured by a pressure gauge. The rate at which hydrogen
is penetrating per unit area can then be determined, using the
exposed surface area and internal volume of the probe. If hydrogen
diffusion rates exceed 0.25 cm 3 /(cm 2 -day), severe hydrogen damage
can be anticipated. The advantage of this instrument is that it
alerts the engineer that hydrogen levels could lead to hydrogen
blistering, hydrogen embrittlement, or hydrogen stress-corrosion
cracking. A disadvantage of the hydrogen probe is that because
its measurement of corrosion is relative, it cannot be directly
correlated with other monitoring techniques.
FIGURE 10 Rohrback 1120 portable corrater. (Courtesy of Rohrback

FIGURE 11 Petrolite flush-mounted probe. (Courtesy of Petrolite

The Petrolite Hydrogen Patch probe is shown in Figure 13. A

thin piece of palladium foil (0.010 in.) is placed against the pipe
wall. An electrochemical patch is mechanically strapped onto the
palladium foil using a thin Viton gasket and a thick Teflon gasket
which has been shaped to fit the contour of the pipewall. The cell
itself contains a Hastelloy B reference electrode. The palladium
foil is the working electrode. The cell is filled with 20 to 30 ml
of 90% sulfuric acid. The instrument polarizes the palladium to a
potential at which hydrogen is oxidized quantitatively. Therefore,
after an initial pump-down period of several hours, the current
being read on the recording instrument is equivalent to the hydrogen
penetration occurring at the time.
Because the hydrogen being measured by the Petrolite Hydrogen

Patch Probe is being produced as a part of the corrosion reaction,
the hydrogen penetration rate (which is being measured directly)
is related to the internal corrosion rate. It must be noted that
hydrogen measurement is only an indirect measure of corrosion
rate because the amount of atomic hydrogen that dissolves in the
steel, relative to that produced in the corrosion reaction, is a com-
plex function of several variables such as stream composition, surface
condition, temperature, and corrosion rate.
Ultrasonic Testing
Ultrasonic testing is a nondestructive method of determining wall
thickness or the location of flaws within any material capable of
conducting sound. In normal ultrasonic testing, a beam of high-
frequency (megahertz) vibrations is passed into the material under
Assembly
Needle Valve Probe
Detail Of Probe
Weld
: Valve
Drill and Tap to

Suit Pressure
Gauge
FIGURE 12 Cosasco hydrogen test probe. (Courtesy of Grant Tool

Company, Cosasco Division.)
STEEL PIPE WALL
ELECTROLYTE SOLUTION
IMATELY 40 CC
SULFURIC ACID
POLYPROPYLENE
CELL BODY
TEST ELECTRODE
AUXILIARY
PALLADIUM
ELECTRODE
FOIL
(Approx. 2 x 2 x .010 }
FIGURE 13 Petrolite Hydrogen Patch probe. (Courtesy of Petrolite

test. Reflections are obtained from the surfaces of the material

and from various physical discontinuities within it. These vibrations,
by means of a transducer, are converted into electrical signals
that are amplified and fed to a cathode ray tube for interpretation.
In general, ultrasonic testing is a method of transforming electrical
pulses into mechanical vibrations and transforming the mechanical
vibrations back into electrical pulses. Figure 14 illustrates the princi-
ple of straight-beam ultrasonic nondestructive testing. Figure 14
(top) represents the propagation of sound within a test specimen
that does not contain any flaws. A typical cathode ray tube (CRT)
screen presentation is illustrated to show the initial pulse, time
base line, and back reflection. Figure 14 (bottom) represents the
propagation of sound within a test specimen containing a known
flaw. Note the flaw indication as shown on the CRT screen display.
BACK REFLECTION
INITIAL PULSE
TRANSDUCER
SOUND -
BEAM
i il
IIMI
TEST SPECIMEN (NO FLAWS) CRT SCREEN
BACK REFLECTION
INITIAL PULSE
TRANSDUCER
SOUND -
BEAM
TEST SPECIMEN (WITH FLAW) CRT SCREEN
FIGURE 14 Principle of straight-beam ultrasonics. (Courtesy of

Krautkramer-Branson, Inc., Stratford, Conn.)
-INITIAL PULSE
TRANSDUCER
-WEDGE
SOUND BEAM
WELD
TEST SPECIMEN (NO FLAWS) CRT SCREEN
INITIAL PULSE
FLAW 1ST NODE (A)

(A) (B)
TRANSDUCER POSITION TRANSDUCER POSITION
1ST NODE 2ND NODE FLAW 2ND NODE (B)
•FLAW
II
TEST SPECIMEN (WITH FLAW) CRT SCREEN
FIGURE 15 Principle of angle-beam or shear-wave ultrasonics.

(Courtesy of Krautkramer-Branson, Inc., Stratford, Conn.)
Angle-beam or shear-wave ultrasonic testing can be defined as

testing in which the sound beam is sent into the test piece at an
angle by using a type of ultrasonic sound wave known as a shear
wave. Angle-beam testing is used to locate flaws or cracks that
are not oriented properly in the test piece to be located by means
of straight-beam tests. This method of testing is most favorable
for weld inspection. Figure 15 represents ultrasonic evaluation of
welded test specimens using the angle-beam (or shear-wave) method

of sound propagation. Note the angular position of the transducer
within the wedge. The CRT screen presentation illustrates the initial
pulse of sound produced by the transducer in a welded test specimen
that does not contain any flaws. The absence of the back reflection,
which indicates material thickness and is usually visible in straight-
beam tests, is attributed to the angle of the sound beam. A welded
test specimen containing a known flaw is also illustrated. Note the
transducer position and the distance between the transducer and
the weld area. The flaw indication as illustrated on the CRT screen
display is also shown. Figure 16 illustrates one of the Krautkramer-
Branson portable ultrasonic instruments that can be utilized for
both straight- and angle-beam flaw detection and wall thickness
measurements.
By using an ultrasonic flaw detector such as that shown in
Figure 16, an operator can also measure wall thickness on pipes
and pressure vessels as well as inspect for cracks and other material
flaws. The left-to-right position of the back reflection that appears
on the CRT screen during straight-beam testing indicates the thick-
ness of the material being tested. The thinner the material, the
farther to the left this signal appears; the thicker the material,
the farther to the right it moves. Thus, the operator can measure
wall thickness by monitoring the position of this back reflection
signal on the CRT.
There is, of course, a limit to how accurately an operator can
visually judge the position of the back reflection and this, in turn,
limits the accuracy of the wall thickness measurement. Flaw detectors
are now available that give digital thickness and flaw location read-
outs in addition to the CRT screen presentation, and these readouts
are generally more accurate than simple visual monitoring of the
screen. However, even the accuracy of visual screen monitoring
can be improved by use of what is known as the "multiple reflection
method."
In the multiple reflection method, the flaw detector1 s screen
is usually adjusted to show five times the wall thickness (Fig. 17).
Each multiple of the thickness is indicated by an additional back
reflection known as a "multiple back reflection." The fifth back
reflection will move five times more screen distance than the first
reflection will move for a given change in wall thickness. Therefore,
the operator can read wall thickness with five times greater accuracy
by monitoring movement of the fifth rather than the first back
reflection.
Ultrasonic wall thickness measurement can also be accomplished-
much more easily, in fact—by the use of digital readout ultrasonic
thickness gauges. These lightweight, portable, battery-powered
FIGURE 16 Krautkramer-Branson 303 ultrasonic flow detector/thickness

tester. (Courtesy of Krautkramer-Branson, Inc., Stratford, Conn.)
ultrasonic thickness gauges are widely accepted and highly reliable.

Figure 18 illustrates a typical application of the Krautkramer-Branson
direct-reading (D meter) digital thickness gauge.
Onstream metal thickness measurements can be obtained at tem-
peratures above 900°F by use of cooling mediums with the transducer.
The higher the surface temperature, the greater the potential for
error because of material expansion and a lower acoustic velocity.
The engineer must take this into account and adjust the readings
downward to indicate actual wall thickness. Ultrasonic testing can
be used to determine wall thinning, pitting, erosion, and flaws
in metals, plastics, and rubbers. Several disadvantages include
numerous readings are required to describe general condition of
material; pitting corrosion is not easily located; readings must be
taken over a period to determine the corrosion rate; and high tem-
perature measurements may have to be adjusted.
Engineers must have a good understanding of where to expect
corrosion in equipment, such as towers, drums, heat exchangers,
and piping, if they are to take maximum advantage of ultrasonic
methods to monitor corrosion. In towers, areas of concern include
behind downcomers, liquid-vapor interfaces, and across from gas
or liquid inlets. For drums and heat exchangers, areas of concern
include liquid-vapor interfaces, stagnant areas, and across from
gas or liquid inlets. In piping systems areas of concern include
elbows, tees, downstream of valves and pumps, and small connections.
\
Figures 19-22 illustrate typical locations where corrosion would be
\
TRANSDUCERS^ B
C
D
\
i
E
1 SOUND
'"Ijljll
»-/11
F
1 [_
J BEAM III 1 . i <L \ \
<CL // 1 111
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1
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TEST SPECIMEN
A. INITIAL PULSE
B. FIRST REFLECTION FROM BACK SURFACE
C-F. MULTIPLE BACK REFLECTIONS
FIGURE 17 Typical CRT display of the multiple-reflection method.

(Courtesy of Krautkramer-Branson, Inc., Stratford, Conn.)
FIGURE 18 Use of the Krautkramer-Branson D meter for wall thick-

ness measurement. (Courtesy of Krautkramer-Branson, Inc., Strat-
ford, Conn.)
MONITORING ZONE
FIGURE 19 Typical corrosion monitoring of a reducer.

MONITORING ZONE
FIGURE 20 Typical corrosion monitoring of a tee.
MONITORING ZONE
FIGURE 21 Typical corrosion monitoring of an elbow.

MONITORING ZONE
FIGURE 22 Typical corrosion monitoring of a pipe.
most likely to occur in a piping system. The number of measurements

or the locations depends on the corrosive environment and configura-
tion and, therefore, vary among piping systems. Where there are
small connections or branch connections, size or configuration may
not be feasible for ultrasonic measurements. In these instances,
radiography should be considered for determining wall thickness.
Radiography
Radiography is one of the most important, and most versatile, of
all the nondestructive test methods used by industry. Employing
highly penetrating x-rays, gamma rays, and other forms of radiation,
radiography provides a permanent visible film record of internal
conditions, containing the basic information by which soundness
can be determined. X-ray equipment is portable but bulky, and
requires electrical connections to operate. X-ray equipment is nor-
mally used for the inspection of thin material, 0.125- to 0.750-in.
steel.
The most widely used gamma radiographic sources are iridium-
192 ( 192 Ir) and cobalt-60 ( 60 Co). Iridium-192 is used for material
thickness of 0.250- to 3.500-in. steel, and cobalt 60 for 2.500- to
8.000-in. steel. Gamma radiographic sources do not require electrical
connections and are totally portable. Therefore, they are more widely
used. The use of radiography for onstream corrosion monitoring
is often overlooked. Radiography is particularly useful in detecting
corrosion or corrosion erosion in elbows, welds, heat-affected zones,
return bends on furnace tubes, small connections, and thermowells.
Radiography can also be employed to indicate wall thickness, erosion,
and weld integrity. Some disadvantages are the physical limitations
of the area where it can be applied; difficulty in detecting cracks
lying in the plane perpendicular to the rays; and the safety pre-
cautions involved in radioactive material handling.
There are two main types of radiography employed: sealed-source
techniques that are used for onstream testing and are external to
the process; and unsealed-source or tracer techniques that are
also used for onstream testing. The latter technique, however,
involves the injection of small amounts of radioactivity into the
system.
Sealed-source techniques can be used to verify the mechanical
condition of a distillation column as well as to locate and identify
operational problems. By lowering a small radioactive source down
one side of a column while simultaneously lowering a detector down
the opposite side, the gamma rays being emitted through the column
can be measured and recorded. The average density of the material
between the source and the detector will determine the quantity
of gamma rays measured. Aerated liquid on trays will absorb a
larger quantity of the gamma rays than the vapor spaces between
the trays. Mechanical damage, such as a collapsed bed of packing
or a missing tray, will appear as a deviation from the standard
pattern developed for the rest of the column. Therefore it is possible
by this technique to determine the
Condition of packed beds

Presence or absence of trays
Soundness of demister pads
Location of tray flooding
Location of foaming areas
Location and extent of entrainment
Regardless of how simple this technique appears, a great deal of

knowledge and experience is required to correctly interpret the
results. Experienced technicians should be employed for this purpose.
Gamma-ray scanning can also be used to detect blockages in
pipe lines, liquid levels, and interface levels.
Unsealed-source, or tracer, techniques are employed mainly
to detect leakage sources or to solve processing problems.
pH Instrument
The pH instrument can be a useful tool for determining whether
process conditions are such that increased corrosion can occur.
The engineer must have a good understanding of the construction
materials and their limitations during pH swings. The main advantage
of the pH instrument is that it will show immediate changes in process
conditions. Disadvantages are that the extent of corrosion occurring
in the process equipment cannot be determined by the instrument,
and pH instrumentation requires a high level of maintenance.
Infrared Thermography
The infrared thermographic camera is used to identify hot spots
on the process equipment. The camera works on the theory that
the hotter the object, the higher the frequency of radiation. The
infrared (IR) detector in the camera detects the IR rays emitted
by the object and converts them to an electronic video signal. The
signal is then sent to a display unit showing the thermal image
and temperature range. The temperature range of the equipment
is -30 to +1000°C (-20° to +1830°F). The camera can be used to
determine hot spots on reactors, furnaces and furnace tubes, stacks,
structural members, and rotating equipment.
Corrosion Coupons
Corrosion coupons are the most widely used tools to monitor corrosion
in process equipment. Figures 23 and 24 show several typical methods
of mounting corrosion coupons. Coupons can be made in any size
or shape, such that they are retrievable from process equipment
without shutting the process unit down. This method of monitoring
corrosion has the advantage that the corrosion observed has actually
occurred on the sample and allows for a visual examination, physical
measurements, and the chemical analysis of corrosion products.
Corrosion coupons can be mounted in different configurations to
study different types of corrosion mechanisms, such as crevice
corrosion, galvanic attack, and stress corrosion.
Normally, the corrosion coupons are carefully weighed and
measured before assembly on the corrosion test rack. Once the
coupons are assembled, they should be stored in a desiccator until
installation. During assembly the coupons are arranged such that
they are electrically insulated from the corrosion rack, to avoid
galvanic attack. Upon completion of the test, the corrosion rack
is disassembled and the corrosion coupons are cleaned, weighed,
and measured. The formula for calculating the uniform corrosion
rate is
534W
where
W = weight l o s s , mg
D = d e n s i t y of specimen, g/cm 3
A = a r e a of specimen, i n . 2
T = e x p o s u r e time, h r
The main a d v a n t a g e s for corrosion coupons are low c o s t , t h e ability

to t e s t s e v e r a l different materials at o n c e , and closer resemblance
FIGURE 23 Corrosion t e s t r a c k .
Corrosion Coy poo
Insyfator
Pipe Plug
FIGURE 24 Corrosion coupons mounted on a pipe plug.
to actual conditions of equipment. The main disadvantages include

the test location of coupons is limited and the time involved in pre-
paring and evaluating coupons to determine corrosion rates after
a sufficient exposure time. In addition, this method of monitoring
does not allow the engineer to evaluate the effects of varying process
operating conditions.
Acoustic Emission Testing

Acoustic emission testing (AET) is used most often to requalify
pressure vessels and tanks during a hydrostatic test. Acoustic
emission is defined as the pressure of stress waves generated in
metals by the energy released as the metal deforms or fractures.
The AET sensors are placed at various locations on the surface
of the equipment being tested to pick up signals emitted from flaws
and discontinuities. These signals are then amplified and through
use of computerized equipment are analyzed to determine the severity
of the defects and their locations. This method provides a means
of detecting certain types of defects that cannot be detected by

other means such as deficiencies in FRP equipment, early-stage
stress-corrosion cracking, and contamination of titanium and zirconium
welds by nitrogen and oxygen. During recent years a considerable
amount of research has been devoted to developing AET techniques.
As a result, it has been shown that specific defects have unique
acoustic emission characteristics, which can be used to define the
presence and type of structural defect.
Initially AET could not be used for onstream testing. However,
continued development of this technique has resulted in the ability
to use AET for onstream testing. It is capable of detecting such
in-service problems as corrosion, stress-corrosion cracking, mechani-
cal damage and thinning, as well as the severity of the damage.
By testing periodically, a comparison of results of the latest test
with those of previous tests can be made and an evaluation of the
rate of attack or the extent of the new damage obtained.
Acoustic emission testing is widely used for the testing and
monitoring of FRP vessels, piping, and equipment. There is no
other satisfactory test for evaluating the integrity of FRP equipment.
Hydrostatic tests are not recommended because such tests can result
in permanent damage to the equipment, leading to a reduced service
life.
The main advantages of AET are that flaws can be detected
early, and, therefore, catastrophic failures can be prevented, and
AET has a potential use for onstream monitoring, particularly in
heavy vessel sections as the equipment is heated or cooled. The
main disadvantages are the high cost and the highly skilled test
personnel who are required to interpret the findings.
OFFSTREAM MONITORING EQUIPMENT

Eddy Current Inspection
Eddy current inspection is based on the principle of electromagnetic
induction and is used to identify or differentiate between a wide
variety of physical, structural, and metallurgical conditions in con-
ductive ferromagnetic and nonferromagnetic metal components. Eddy
current inspection can be used to detect cracks, voids, and inclu-
sions; to sort dissimilar metals; to detect differences in their chemical
composition; and to measure the depth of nonconductive coatings
on conductive metals. Some disadvantages of eddy current inspection
are lift-off factor, fill factor, edge and skin effects, and permeability
variations in magnetic materials.
The Krautkramer-Branson Model 700 Probolog (Fig. 25) is a
portable instrument for the nondestructive inspection of nonferrous
FIGURE 25 Krautkramer-Branson Model 700 Probolog. (Courtesy of

Krautkramer-Branson, Inc., Stratford, Conn.)
exchanger tubes. The instrument operates on the principle of eddy

current. The magnetic field generated by a coil to which an alternat-
ing current is applied will cause eddy currents to flow in metal
objects near the coil. The eddy current density will be greatest
at the surface of the metal adjacent to the coil and will decrease
rapidly in the metal as the thickness increases. Any discontinuity
in the tube wall (such as a hole, pit, or crack) will interrupt or
distort the normal eddy current flow pattern. As the probe is pulled
through a tube, results can be monitored on a storage oscilloscope
and a strip-chart records the tube condition. Figure 26 illustrates
a sample strip-chart recording corresponding to tube wall discontinui-
ties. The Probolog can be used in the field to determine the condition
of a heat exchanger tube bundle. The disadvantages are the tubes
must be clean; it is a slow process because only one tube can be
O
o
CO
16 BWG CALIBRATION SAMPLE 5'
o
3.
.050 30% WALL 20% WALL 10% WALL .030

HOLE REDUCTION _ REDUCTION REDUCTION . HOLE
1
f
\
\1 /
I
|\ 1 /
- 0
1
II
\ i
I
VwJ
r -10
-20
IIll i vw
-30
-40
f
FIGURE 26 Calibration sample versus strip-chart. (Courtesy of Krautkramer-Branson,
Inc., Stratford, Conn.)
examined at a time (2 to 3 min per tube); and only nonferrous

tubes can be evaluated.
The Eddy Current ID tube-testing system (Fig. 27), manufactured
by the Magnaflux Corporation, is used for testing ferrous and non-
ferrous materials. The instrument operates on a principle similar
to the Probolog. For testing ferromagnetic tubing, the permeability
must be minimized. A constant magnetic field within the tube wall
must be induced.
The Magnaflux eddy current system (see Fig. 27) consists of
six essential parts. The ED-800 eddy current instrument, part A,
supplies the electrical energy to the ID probe, part B. An air gun,
part C, is used to move the probe to the end of the tube. The
probe puller, part D, is used to pull the probe back through the
tubes at a uniform rate. As the probe is uniformly pulled through
the tube, it monitors changes in the electrical field. Any change
is amplified by the instrument and simultaneously displayed on the
ED-800 cathode ray tube and the dual-channel strip-chart recorder,
part E. A separate power supply, part F, energizes an electromagnet
in the probe when inspecting ferromagnetic tubing. Figure 28 shows
the probe being inserted into a tube opening at the tube sheet.
The advantage of using eddy current instruments for evaluating
tube condition is that many times the corrosion is localized in a
FIGURE 27 Magnaflux eddy current ID tube testing system.

(Courtesy of Magnaflux Corporation, Chicago.)
FIGURE 28 Typical application of Magnaflux eddy current test

equipment. (Courtesy of Magnaflux Corporation, Chicago.)
tube bundle. Using this type of instrument allows the engineer to

determine the extent of damage and to consider whether plugging,
partial retubing, or complete retubing is necessary. When the strip-
chart recorder is used, a permanent record is available; the rate
of corrosion can be monitored; and it becomes feasible to predict
when failures will occur. This advance warning makes it possible
for tubes to be purchased and on hand before failure, thus avoiding
or reducing the downtime for repairs/ replacement.
Magnetic Particle Inspection

Magnetic particle inspection is a nondestructive means for detecting
surface and slightly subsurface discontinuities in ferromagnetic
materials. This method of nondestructive testing consists of four
basic operations: (1) establishing a suitable magnetic field in the
test object, (2) applying magnetic particles to the surface of the
test object, (3) examining the test object surface for accumulations
of the particles (indications), and (4) evaluating the serviceability
of the test object. Magnetic particle inspection depends upon the
magnetic properties of the test objects and is suitable only for
metallic materials that can be intensely magnetized. Nonferromagnetic
materials that cannot be strongly magnetized cannot be inspected
by this method. Inspection surface areas must be clean and free
of random dirt, rust, and scale. Any part made of ferromagnetic
material can be inspected by the magnetic particle method; there
are no restrictions on the shape and size of the part. Magnetic
particle inspection can be accomplished using either the wet or
dry method. The wet method of magnetic particle inspection is used
with stationary equipment and is best suited for the detection of
fine surface discontinuities such as fatigue cracks. The dry method
of dry particle inspection is most sensitive for use on very rough
surfaces and for detecting defects beneath the surface. The dry
method is normally used with portable equipment.
Liquid Penetrant Inspection

Liquid penetrant inspection is basically a simple process. First
a liquid penetrant is applied to the surface of the part. It is per-
mitted to remain on the surface for a specified time, during which
it penetrates into any defects open at the surface. The excess
penetrant that remains on the surface is removed. Then an absorbent,
light-colored, powdered material, called a developer, is applied to
the surface. The developer acts as a blotter and draws out a portion
of the penetrant that had previously seeped into the surface open-
ings. As the penetrant is drawn out, it diffuses into the coating
of the developer, forming indications that are much wider than
the surface openings with which they are associated. The inspector
then views the part and looks for these colored indications, noting
the surface condition, against the background of the developing
powder. The penetrant method is a quick and low-cost method of
nondestructive testing to determine surface defects. The most common
type of penetrant inspection is accomplished using a colored visible
dye. Fluorescent penetrants have been developed for use with a
black light and provide greater sensitivity. The main disadvantages
of penetrant inspection are that it can only be used to identify

surface defects and the surface must be clean and fairly smooth.
Boroscopes (Visual Inspection)
Although many techniques and methods have been developed for

nondestructive testing, visual inspection is still a very important
means of determining the condition of equipment and components.
When the area of equipment or component is readily accessible,
visual inspection can be accomplished easily, quickly, and econom-
ically. Frequently, the area to be inspected is inaccessible for direct
visual inspection. Under these conditions the use of a boroscope
becomes necessary. These instruments provide a means of visual
inspection that also can be accomplished quickly and economically.
The boroscope is a sophisticated optical device that is available
in many styles for specific types of applications. Rigid boroscopes
are similar to telescopes; they are long, tubular instruments with
optical lenses. They differ from telescopes in that they spread
your field of view for close-up work, whereas telescopes narrow
your field of vision for observation at a distance. Boroscopes have
relay lenses along their length to preserve precise resolution while
providing a magnification of 3X to 4X.
Flexible boroscopes are useful in applications for which there
is no straight passageway to the area to be inspected. These operate
entirely with fiber optics. Each flexible boroscope holds two optical
bundles: one to transmit light to the inspection area and one to
carry the image back to the eyepiece. The optical bundles are pro-
tected by a flexible metal housing that allows the boroscope to bend
around corners or sharp elbows.
Boroscopes are also available with the capability of measurement.
They can be used to measure grooves, rings, slots, holes, pits,
and other internal surface features.
When selecting a boroscope there are several factors that must
be taken into consideration.
Illumination
When using the boroscope to inspect plastic or rubber surfaces,

the heat generated by the lamp should be considered, as well as
when the boroscope is used around certain gases. Explosion-proof
light sources are available if required.
Reflectivity
The reflectivity of the area to be inspected must be taken into

account. High- and low-contrast backgrounds will determine the
types of illumination and lenses best suited for your application.
Power
Although boroscopes are normally supplied with 110 V wiring, they
are available in other voltages or for battery operation. The latter
option provides a boroscope with maximum portability.
Black Light
Certain applications require black light illumination, which is avail-
able. Units can also be supplied with both black and visible light.
Camera Fittings
In many instances, records will be desired. Boroscopes are available
for use with still, motion, or TV cameras.
Environment
Conventional boroscopes are designed to operate at 150°F (66°C)
maximum, but can be designed to operate from -30 to 3500°F (-34
to 1927°C). They can also be designed to operate in fluids, pres-
sures above atmospheric, and in the presence of radiation. When
any of these conditions exist, make sure the supplier is aware of
the condition.
Flexible or Rigid
Unless it is absolutely necessary to use a flexible boroscope, a
rigid unit should be employed. A rigid scope with a quartz lamp,
a movable mirror, and variable magnification (zoom) will usually
provide the quickest and most economical approach. Consult with
your supplier.
Although the boroscope appears to be a very simple instrument,
the technology of its operation and application tends to be complex.
To assure that your selection will be the best suited for your needs,
it is advisable to consult with your supplier. Provide your supplier
with all of your requirements and what results you expect to achieve
by use of the boroscope, and then between you the final selection
will be one that will fill your needs.
Miscellaneous Equipment
Table 1 lists several other tools that are commercially available
to aid in monitoring offstream corrosion.
Monitoring of Polymer-Coated Metals

Numerous electical methods have been developed to determine the
protective properties of coatings. Among these are measurements
o
o
3
03
TABLE 1 Offstream Monitoring Equipment
Type Application Advantages Limitations O

3.
Chemical spot testing Identify alloy constituents Economical, quick Not precisely
of unknown materials quantitative
TV camera Visual aid to inspect tubes, Actual view of equipment Access to equip-
pipes, vessels, etc. condition ment
Halography Three-dimensional imaging No physical contact with Type of flaw not
equipment easily defined
Texas Nuclear Analyzer Positive material identifi- Accuracy and reliability Size and shape
cation of findings of test specimen,
accessibility,
temperature
oo
of coating conductivity; of equivalent AC resistance at constant

frequency; of impedance as a function of frequency; and of the
ratio of capacitive/resistive components at constant frequency. By
using measured values of the DC resistance and the membrane poten-
tial of the film, the rate of diffusion of sodium chloride through
the coating can be determined. The amount of water absorbed by
a coating can be determined by the AC properties of the coating.
Although these methods are effective, radiotracer measurements
are preferred. All of these methods provide data that is useful
in predicting the life of a coating.
The quality control of coating components can be monitored by
dielectric techniques. This method is also useful in determining
the glass transition temperature of the coatings and the effects
of coating composition and structure [19].
Evaluations of the properties of organic coatings by impedance
procedures are becoming more readily accepted [19]. Straight lines
are obtained when impedance/log frequency plots are drawn if the
coating permits no significant ionic transport through, which indi-
cates that it is acting as a pure capacitor. Using the same plot
at low-frequency values will provide the coating resistance. If
measurements are made at a single frequency, data can be obtained
about the water uptake and DC conductivity [20]. Leidheiser [21]
has made the empirical observation that corrosion under the coating
becomes appreciable when the equivalent DC resistance of the coating
is less than 10 ohm/cm2 of measured area. An equivalent DC resist-
ance of 10 9 -10 n ohms/cm2 of measured area is indicative of a highly
protective coating.
Wolstenholme [22] has summarized the applicability of corrosion
potential measurements to coated metals. In general it can be con-
cluded that movement of the corrosion potential in the noble direction
indicates that the cathodic/anodic surface area is increasing and
that oxygen and water are penetrating the coating and reaching
the coating/metal interface. Movement of the coating potential in
the active direction indicates that the anodic/cathodic surface area
is increasing and that the overall corrosion rate is becoming signifi-
cant. The increase of positive potentials with time indicates that
alkaline conditions caused by the oxygen reduction reaction are
taking place locally at the coating/metal interface and if allowed
to continue could result in delamination. The increase of active
potentials with time indicates corrosion (rusting in the case of steel)
under the coating and is a warning that the remaining coating life
is limited.
SUMMARY
This chapter has only scratched the surface of the many nondestruc-
tive tools available to the engineer. These instruments play an important
role in monitoring onstream and offstream corrosion. Corrosion costs

the chemical and refining industries billions of dollars annually.
The challenge to the engineer is to use the tools and techniques
available to control and monitor corrosion to avoid unscheduled
shutdowns and to educate others about the true value of corrosion
controls. The days of bringing equipment down only for inspection
are rapidly coming to an end; much greater emphasis is now placed
on keeping units running. The engineer must understand the proc-
esses and rely on corrosion monitoring to ensure safe and continual
operation of process equipment.
ACKNOWLEDGMENTS
The author acknowledges the Rohrback Corporation, Petrolite Cor-

poration, Magnaflux Corporation, and Krautkramer-Branson for
supplying photographs and literature on the nondestructive testing
equipment described in this chapter.
An expression of sincere appreciation is due to A. J. Pron and
B. H. Elliott for their able assistance in preparing illustrations
and comments regarding the text.
GLOSSARY
Angle testing An ultrasonic testing method in which the angle

of incidence is greater than zero.
Angle transducer A transducer used in angled testing in which
the sound beam is set to some predetermined angle to achieve
a special effect (e.g., setting up shear or surface waves in
the tested piece).
Back reflection The ultrasonic echo from the back surface of the
part.
Beam A directed flow of energy into space or matter.
Black Light Light energy just below the visible range of violet
light, often predominantly of about 3650 A. This wave length
reacts strongly on certain dyes to make them fluoresce in a
range visible to the eye.
Cobalt-60 A radioisotope of the element cobalt.
Color-contrast dye A dye that can be used in a penetrant to impart
sufficient color intensity to give good color contrast in flaw
indications against the background of the surface being tested,
when viewed under white light.
Color-contrast penetrant A penetrant incorporating a dye-usually
nonfluorescent—sufficiently intense to give good visibility to
flaw indications under white light.
Conductivity This is the inverse of resistance and refers to the
ability of a conductor to carry current.
Contact testing Testing with transducer assembly in direct contact

with material through a thin layer of couplant.
Corrosion The deterioration of a metal by chemical or electrochemical
reaction with its environment.
Couplant A substance used between the search unit and a surface
to permit transmission of ultrasonic energy.
Defect A discontinuity, the size, shape, orientation, or location
of which makes it detrimental to the useful service of the part
in which it occurs.
Developer (penetrant) A finely divided material applied over the
surface of a part to help bring out penetrant indications.
Discontinuity Any interruption in the normal physical structure
or configuration of a part, such as cracks, laps, seams, inclu-
sions, or porosity. A discontinuity may or may not affect the
usefulness of a part.
Echo See Reflection.
Electrochemical corrosion Corrosion that occurs when current flows
between cathodic and anodic area on metallic surfaces.
Electromagnet When ferromagnetic material is surrounded by a
coil carrying current, it becomes magnetized and is called an
electromagnet.
Embrittlement Reduction in the normal ductility of a metal because
of physical or chemical change.
Erosion Destruction of metals or other materials by the abrasive
action of moving fluids, usually accelerated by the presence
of solid particles or matter in suspension. When corrosion occurs
simultaneously, the term erosion corrosion is often used.
Ferromagnetic materials The materials that are most strongly affected
by magnetism are called ferromagnetic materials because iron
and steel exhibit the strongest magnetic characteristics of all
substances.
Flaw An imperfection in an item or material which may or may
not be harmful.
Fluorescent dye A dye that becomes fluorescent, giving off light,
when it is exposed to short-wavelength radiation such as ultra-
violet or near-ultraviolet light.
Fluorescent penetrant A penetrant incorporating a fluorescent
dye to improve the visibility of indications at the flaw.
Gamma rays High-energy, short-wavelength electromagnetic radiation
emitted by a nucleus. Energies of gamma rays are usually between
0.010 and 10 MeV. X-rays also occur in this energy range but
are of nonnuclear origin. Gamma radiation usually accompanies
alpha- and beta-emissions and always accompanies fission. Gamma
rays are very penetrating and are best attenuated by dense
materials such as lead and depleted uranium.
Hydrogen embrittlement A condition of low ductility in metals result-

ing from the absorption of hydrogen.
Indication In nondestructive inspection, a response, or evidence
of a response, that requires interpretation to determine its
significance.
Interface A common boundary between two surfaces.
Iridium-192 A radioactive isotope of the element iridium that has
a half-life of 75 days. It is used extensively as a source of
gamma radiation.
Node A point in a standing wave where some characteristic of
the wave field has essentially zero amplitude.
Nondestructive testing (NDT) Testing to detect internal and con-
cealed defects in materials using techniques that do not damage
or destroy the items being tested.
Particle motion Movement of particles in an article brought about
by the action of a transducer.
Penetrant This is the fluid—usually a liquid, but it can be a g a s -
that is caused to enter the discontinuity to produce an indication
at the flaw.
Permeability (magnetic) The ease with which a magnetic field or
flux can be set up in a magnetic circuit. It is not a constant
value for a given material: it is a ratio. At any given value
of magnetizing force, permeability is B/H, the ratio of flux
density B to magnetizing force H.
Reflection The indication of reflected energy.
Sensitivity The smallest quantitative increment detectable in using
a measuring instrument.
Shear wave A wave in which the particles of the medium vibrate
in a direction perpendicular to the direction of propagation.
Source The origin of radiation; an x-ray tube or a radioisotope.
Source material In atomic energy law, any material, except special
nuclear material, that contains 0.05% or more of uranium, thorium,
or any combination of the two.
Transducer Any device that is capable of converting energy from
one form to another.
Ultrasonic testing A nondestructive method of testing materials
by transmitting high-frequency sound waves through them.
X-ray Penetrating electromagnetic radiation emitted when the inner
orbital electrons of an atom are excited and release energy.
Thus, the radiation is nonnuclear and is generated by bombarding
a metallic target with high-speed electrons.
REFERENCES
1. Hutton, P. H. (1967). "Acoustic Emission in Metals as a NDT

Tool," 27th Nat. Conf. Soc. Nondestructive Test., Cleveland,
Ohio. October 18.
2. Callow, L. M., Richardson, J. A., and Dawson, J. L. (1976).

Corrosion monitoring using polarization resistance measurements,
Br. Corros. J. JJ:OOO.
3. Burda, P. A. (1975). Linear polarization method for corrosion
rate measurements in limestone slurry scrubber, Matr. Perform.
June.
4. Holloway, L. W., and Foreman, D. M. (1972). "Eddy Current
Inspection of Tubular Equipment Containing Nonferrous Material."
Baton Rouge Sect. NACE, Baton Rouge, La., November 27.
5. Fincher, D. R., and Nestle, A. C. (1973). "New Developments
in Monitoring Corrosion Control," NACE Int. Corros. Forum,
Anaheim, Calif., March 19-23.
6. Lanaman, J. H., and Azar, L. (1973). "A New Instrument for
Measurement of Corrosion by Electrical Resistance Techniques,"
NACE Int. Corros. Forum, Anaheim, Calif., March 19-23.
7. Miller, K. J . , J r . (1973). "Infrared scanning for Nondestructive
Testing," NACE Int. Corros. Forum, Anaheim, Calif., March 19-
23.
8. Bovankovich, J. C. (1973). "On-Line Corrosion Monitoring,"
NACE Int. Corros. Forum, Anaheim, Calif., March 19-23.
9. Petrolite Instruments General Catalog (1977). Stafford, Tex.
10. Corrosion Measurement and Control Systems (1975). Rohrback
Corporation, Santa Fe Springs, Calif.
11. McMaster, R. C. (ed.) (1959). Nondestructive Testing Handbook,
Ronald Press, New York.
12. Elonka, S. (1958). Nondestructive testing, Power, March.
13. Harrell, J. B. (1978). Corrosion monitoring in the CPI, Chem.
Eng. Prog. March.
14. Instrument Catalog (1976). Krautkramer-Branson, I n c . , Strat-
ford , Conn.
15. French, E. C. (1975). Flush-mounted probe measures pipe
corrosion, Oil Gas J. , November.
16. Johnson, G., and McFarland, T. W. (1978). Better data with
eddy current, Hydrocarbon Proc. , January.
17. McFarland, T. W. (1976). "Nondestructive Testing of Ferro-
magnetic and Nonferromagnetic Heat Exchanger Tubing from
the ID for Wall Thinning and Cracks," Joint Pet. Mech. Eng.
Press. Vessels Piping Conf., Mexico City, September.
18. Fowler, T. J. (1987). Acoustic emission testing of vessels and
piping, Chem. Eng. Prog. May.
19. Mansfield, F . , Kendig, M. W., and Tsai, S. (1982). Corrosion
38:478.
20. Touhsaent, R. E., and Leidheiser, H., J r . (1972). Corrosion
28:435.
21. Leidheiser, H., J r . (1979). Prog. Org. Coatings 7:79.
22. Wolstenholme, J. (1973). Corrosion Sci. 13:521.
22
CORROSION-TESTING TECHNIQUES
CHARLES G. ARNOLD Dow Chemical Company, Texas Division,

Freeport, Texas
INTRODUCTION
The most reliable corrosion-testing technique is that of exposing

actual parts in their intended service environment and then evaluating
the corrosion that took place. Usually, this technique is not used
because it is too expensive and time-consuming, and the results
of the evaluation are often subjective which makes it difficult to
compare metals. Reliable corrosion data can be obtained with a
number of techniques, if the corrosion tests are designed and con-
ducted properly. The simplest techniques involve the determination
of a change in dimension or weight and observation of the corroded
surface. More complex techniques involve measurement of hydrogen
diffusion or electrical resistance or determining electrochemical char-
acteristics. The use of these techniques, together with their advan-
tages, are discussed in the remainder of this chapter.
DIMENSION CHANGE
Ultrasonic Thickness Measurement
One of the most straightforward corrosion-testing techniques is
ultrasonic thickness measurement of parts, either under service
conditions or after they have been removed from service. The thick-
ness of the part is measured at the start of the test period and
after regular service intervals. From a practical standpoint, the
accuracy of ultrasonic thickness measurement that could involve
587
585 Arnold and Schweitzer
50
40
30
20
10
1 2 3 4 5 6
T i m e , Years
FIGURE 1 Change in thickness versus time. (A) plant startup-

corrosion rate equals 15 mpy; (B) continuous operation—corrosion
rate in the second year equals 5 mpy, overall corrosion rate equals
10 mpy; (C) process changed—corrosion rate in the third year
equals 2 mpy, overall corrosion rate equals 7 mpy; (D) plant shut-
down; (E) vessel put in pilot plant—corrosion rate in the fourth
year equals 18 mpy, overall corrosion rate equals 8 mpy; (F) con-
tinued pilot plant service—corrosion rate equals 6 mpy. If the vessel
had an initial corrosion allowance of 0.125 in., it now has 0.080 in.
remaining, or an expected life of 13 years given the overall corrosion
rate or 16 years which is based on the last yearfs corrosion rate.
different instruments and technicians is ±0.010 in. (more accurate

measurements can be made using a single instrument and a highly
qualified technician). The difference between thickness measurements
can be divided by the time interval to obtain the corrosion rate.
The change in thickness should be plotted against time as shown
in Figure 1 so that changes in corrosion rate can be more easily
traced to changes in the environment. This technique is not accurate
enough for most laboratory testing, but it is the most accurate
technique available that can be used to measure the thickness of
a part while it is in service. It is extremely useful when one wants
to determine the corrosion rate of a pressure vessel or pipeline
that is being used and to determine the real effects of process
changes or inhibitor additions. An instrument with a cathode-ray
tube should be used if there is a possibility of nonuniform corrosion,
because digital instruments can give misleading readings [1].
22. Corrosion Testing Techniques 589
Eddy Current
The amount of corrosion that has taken place in a nonferromagnetic
tube can be measured nondestructively using an eddy current
instrument and a probe that fits inside the tube. This procedure
makes it possible to measure the corrosion that has taken place
in tubes while they are still in a heat exchanger so that their remain-
ing life can be predicted. These instruments must be calibrated on
a tube of known thickness of the same metal as the tube to be tested.
After calibration, changes in thickness can be measured with an
accuracy of ±2%. Nonuniform corrosion can be detected very easily.
Microscopic Examination
It is often necessary to examine a polished cross section to determine
how much unaffected metal is left when testing for either dealloying
or high-temperature corrosion. In both of these types of corrosion,
considerable damage can take place either because of the removal
of some of the elements from the solid alloy or because of inward
diffusion of a corrodant such as oxygen or sulfur. The amount
of damage that has taken place will not be proportional to either
a change in external dimensions or in weight. It is necessary to
prepare a cross section of corroded metal for metallographic examina-
tion and determine microscopically how much metal is left, as shown
in Figure 2. The determination of a penetration rate is simplified
if the test specimen is either round or has flat sides, but complex
geometries such as airfoils can be used.
Original sample size
Final sample size
Remaining good metal
FIGURE 2 Microscopic corrosion measurement is often used in de-

alloying and high-temperature corrosion testing to determine how
much good metal is left.
WEIGHT CHANGE
Weight-loss corrosion testing is used more than any other technique.

When results of other techniques are in question, they are usually
verified with weight-loss testing. More materials or changes in con-
ditions can be evaluated for a given amount of money with weight-
loss testing than with any other technique. In addition, weight-loss
testing can be used in the laboratory or in the field. In weight-loss
corrosion testing, a prepared specimen is exposed to the test environ-
ment for a period and then removed to determine how much metal
has been lost. The exposure time, weight loss, surface area exposed,
and the density of the metal are used to calculate the corrosion
rate of the metal. Over the years, a number of expressions have
been developed to express corrosion rate, and these are well covered
by Fontana and Greene [2], Penetration rate, expressed in either
mils per year (mpy) or millimeters per year (mm/y), is one of the
best methods of expressing corrosion rate because it can be used
by designers to determine the corrosion allowance of a part.
Calculations
Corrosion rates may be calculated using the equation
WL x 22,273
( 1 ))
D x A xT
where
WL = weight loss, g
D = density, g/cm 3
A = area, in. 2
T = time, days
The weight loss should be measured to the nearest milligram
(0.0001 g ) . Densities for most alloys can be found in either the
Metals Handbook [3] o r Properties of Some Metals and Alloys [4].
Dimensions should be measured accurately enough so that the area
can be calculated to ±1%. The area of all exposed surfaces, including
thin edges, should be included in the A term. Specimen area that
is masked by gaskets or holders should be omitted from the A term.
Time should be measured to an accuracy of ±1% of the total exposure
time.
Specimen Preparation
Most authors recommend that one of the final steps in specimen
preparation be abrasion with 120-grit abrasive paper or cloth. This
step helps the investigator obtain reproducible results, and it should

be used when effects of changing the environment (inhibitor concen-
tration, amount of oxidizer, etc.) are being studied on a metal or
group of metals. If grinding is used, new abrasive paper should
be used for different types of alloys, and wet grinding should
be used for alloys that work harden easily (austenitic stainless
steels, nickel-based alloys, titanium, etc.). It is necessary to grind
or machine all edges that have been cut or sheared because preferen-
tial attack can start at the rough surfaces, which contain numerous
fissures.
When corrosion testing is being conducted to determine which
metals are most suitable for a given service, it is best to test them
with a surface condition that is representative of how they will be
used in practice. For this, "as-rolled" surfaces with sheared edges
should be used on the corrosion coupons. When materials are suscep-
tible to stress-corrosion cracking, cold-worked or stressed specimens
should be considered. Welded coupons should be used whenever
there is a possibility that the weld could be anodic to the base
metal (dissimilar weld metals) or when there is a possibility of heat-
affected zone corrosion (stainless steels and nickel-based alloys
with a carbon content exceeding 0.03%).
Specimen Holders
The test specimens should be physically separated from each other
and supported on inert racks. Glass racks are often used in labora-
tory tests. Metal racks are usually used in the field and are some-
times used in the laboratory. The test specimens must be insulated
from a metal rack as shown in Figure 3. Some examples of how
coupon racks can be installed in the field are welded in place in
a pipeline, nozzle, or vessel as shown in Figure 4; connected to
Test Coupon
Metal Washer-
Double Nut
Insulating Washer
Insulating Sleeve
hreaded Rod
FIGURE 3 Corrosion coupons insulated from each other and the

coupon rack.
-Wall
Weld
Spacer
^-Coupons
FIGURE 4 Specimen rack welded to the wall.
a pancake and held in place with a blind flange (Fig. 5); and in-
stalled through a valve using a packing gland (Fig. 6). This latter
method eliminates the need to shut the system down to remove and
evaluate the test coupons. Figure 7 shows a unit that would be
installed on a threaded valve. This style is used for low pressures
and up to approximately 7500 psi. For higher-operating pressures
the flanged style shown in Figure 8 would be used. Procedures
for operating these holders are as follows (refer to Fig. 9):
Installing coupons
Attach the corrosion coupon (13) to the insulator (12). Pull

the insertion rod (3) and coupon as far into the housing cavity
(11) as possible.
Tighten the locking screw (5). This prevents movement of the
insertion rod when the entry valve is opened.
Install the holder on the entry valve. Check bleeder valve (10)
to make certain that is is closed.
Screw the standard retractor tool onto the threads on top of
the body.
Turn the handle (1) clockwise until the standard tool-retrieving
rod (15) is butted against the insertion rod bushing.
Loosen the locking screw (5). If using flat coupons proper align-
ment can be assured with an aligning pin (not shown).
Turn the handle (1) clockwise until coupon is placed at the
desired depth.
Tighten the locking screw (5) securely with a wrench.
Remove the retractor tool and screw vented safety cap (16)
with warning indicator in place.
Removing coupons
Check to see that the locking screw (5) is tight.

After checking the locking screw for tightness remove the vented
safety cap.
Blind Flange
Pancake
-Nozzle
• Coupons
FIGURE 5 Coupons installed in a nozzle using a blind flange as

a backup.
Blowout Preventer
Packing Gland
-Bleeddown Valve
Nozzle
Vessel or Pipe Wai 1
• Coupons
FIGURE 6 Coupons installed through a valve. A bleed-down valve

is often used with high temperatures, high pressures, and so on,
to ensure that the primary valve is closed and tight before removing
the packing gland. A blowout preventor is used when the internal
pressure is high.
FIGURE 7 Coupon holder for installation on a threaded valve.

(Courtesy of Accurate Corrosion Monitoring Co., Longview, Texas.)
FIGURE 8 Coupon holder for installation on a flanged valve.

(Courtesy of Accurate Corrosion Monitoring Co., Longview, Texas.)
FIGURE 9 Coupon holder parts list. (Courtesy of Accurate Corrosion

Monitoring Co., Longview, Texas.)
3. Screw the retractor tool in place.

4. Turn handle clockwise until the retrieving rod (15) is butted
against the insertion rod and bushing.
5. Loosen the locking screw.
6. Turn handle counterclockwise allowing the insertion rod to rise
into the tool housing (14) until it is fully withdrawn from the
system.
7. Close entry valve.
8. Open the bleeder valve (10) to vent trapped pressure and to
ensure that the entry valve is not leaking.
9. Remove the retractor tool. Then unscrew the housing from the
entry valve.
10. Push the insertion rod in to expose the corrosion coupon. It
can now be visually inspected or removed for analysis.
The insulators should be stable in the test environment, and Teflon

is used quite often at low to moderate temperatures and ceramics
at high temperatures.
Specimen holders for atmospheric corrosion testing are often
made using ceramic electrical insulators as shown in Figure 10.
Atmospheric corrosion coupons are usually mounted either at an
angle of 20 to 30° from horizontal (Fig. 11) or vertically.
Test Conditions
Corrosion testing to determine which metal is best for a given process
should be conducted under actual field conditions whenever possible.
Coupons should be exposed under all of the conditions for which
a metal is needed. Examples of where coupons should be located
in a tower of a chemical plant or refinery are the feedstream, tower
overhead, tower bottoms, and reboiler outlet line. When it is not
1 I
1 1
I I Coupon
1 1
t 1
Ceramic I n s u l a t o r 1 - 1 1 / 2 in. high
FIGURE 10 Atmospheric corrosion coupons held with ceramic elec-

trical insulators.
Coupons
Insulators
South
FIGURE 11 Atmospheric corrosion test rack.
possible to test the metal in all locations, the areas of highest ex-
pected corrosion (highest velocity, highest temperature, etc.) should
be chosen as exposure sites.
When field testing is not possible, laboratory testing is sometimes
helpful in screening metals. When laboratory testing is required,
it should be remembered that very small changes in the environment
can produce large changes in the corrosion rates of some metals,
especially those that can be either active or passive, and laboratory
test results may not represent field conditions. Field conditions
should be duplicated as nearly as possible in the laboratory and
the corrodant volume/exposed metal area ratio should be as high
as practical. In addition, when trace amounts of materials that may
act as corrodants, oxidizers, inhibitors, or chelating agents are
present, it may be necessary to change the corrodant sample fre-
quently. Condensate is often more corrosive than the bulk of the
sample, so it becomes necessary to fabricate test devices similar
to that shown in Figure 12 for corrosion testing. Materials that
are being evaluated for use as a heat-transfer surface are often
tested using appartus like that shown in Figure 13. When using
a heat-transfer corrosion test appartus, the temperature of the
heater should be kept constant so that the test conditions can be
duplicated. This is usually accomplished by running a blank to
determine the heater voltage necessary to maintain either the correct
metal or liquid temperature. Laboratory tests to determine the mate-
rials of construction for a batch process are often misleading because
the products that are present and, thus, the corrosivity of the
mixture changes as the batch process reactions take place. Figure
14 is a corrosion rate-versus-time plot that is typical of a batch
process.
New metals, inhibitors, and treatment chemicals are usually
screened with carefully controlled laboratory tests so that the test
results can be compared with the results of other tests. A large
amount of corrosion data is available from manufacturers of new
products or metals, but it is still usually necessary for users to
Condensors
Condensate Level
Stopcock
Liquid Level
Heating Mantle
FIGURE 12 Apparatus for measuring corrosion rates in a liquid,

its hot vapor, and condensate.
conduct their own laboratory screening tests to determine if field

tests should be conducted. New metals should be evaluated for
their resistance to pitting, crevice corrosion, inter granular corrosion,
and stress-corrosion cracking before extensive field testing is started.
Inhibitors and other treatment chemicals should be tested at several
concentrations under different conditions of pH, temperature, and
aeration in the laboratory to blanket the conditions under which
they can either decrease of increase the corrosion of metals.
Temperature Measurement
Stirrer
Liquid Level
Coupons
Heat Transfer Coupon

Heat Sink with Thermocouple
Heater
FIGURE 13 Simple heat-transfer test apparatus.

200
150
100
50
20 40 60 80 100 120
Time, Minutes
FIGURE 14 Corrosion rate versus time. The average corrosion

rate during a 2-hr batch reaction was in excess of 100 mpy. A
2-week exposure test gave a corrosion rate of less than 10 mpy.
This shows that long-term weight loss data can be misleading.
The duration of the tests is determined by the type and purpose

of the test. When the test specimens are welded or bolted into a
process vessel or piping, the test time is the time between two
or more shutdowns of the equipment. When the coupons are inserted
through a valve by using a packing gland in field tests or when
laboratory tests are conducted, the time of the test can and should
be controlled. The following equation [5] is often used to determine
the duration of a test:
200
Duration of test (hr) = (2)
corrosion rate (mpy)
A moderate corrosion rate of 10 mpy would require an exposure

time of 200 hr, or a little over 8 days. A low corrosion rate of
2 mpy would require an exposure of over 41 days. Commonly used
laboratory test times are 2, 7, and 14 days. Field tests are usually
14, 30, or 90 days and sometimes last over 1 or more years. Atmos-
pheric corrosion tests usually last at least 1 year and very often
extend to 3 to 5 years.
Specimen Cleaning
The specimens should be examined thoroughly before they are
cleaned. A binocular microscope should be used when possible.
The location and type of deposits and localized corrosion should
be recorded and photographs should be taken when they would

be of value. Samples of deposits and corrosion products should
be removed for chemical analysis when necessary.
The corrosion products should be removed completely from the
coupons using an appropriate cleaning solution [ 6 ] , and they should
be weighed to determine the weight loss. The corrosion rate is
calculated using Eq. (1).
Evaluation of Results
The cleaned and weighed coupon should be examined thoroughly
and a binocular microscope should be used if any localized corrosion
is either visible or possible. Edges should be examined for end
grain attack, gasket areas for crevice corrosion, and the identifying
stamping for stress-corrosion cracking. The size and depth of pits
and crevice corrosion should be recorded.
A cross section of dealloyed specimens should be examined
microscopically to determine the depth of the attack.
Data Recording
The type and amount of data that are recorded for a corrosion
test will depend on the purpose of the test. The checklist below
is included as a guideline for what data should be recorded.
1. Corrosive media: overall concentration and variation in concen-

tration during the test.
2. Volume of test solution: laboratory tests.
3. Temperature: average, variation, and was it a heat-transfer
test?
4. Aeration: technique or conditions for laboratory tests—process
exposed to the atmosphere in field testing
5. Agitation: technique for laboratory tests and velocity for field
tests
6. Apparatus and type of test rack
7. Test time
8. Test metals: chemical composition, trade name, product type
(plate, sheet, rod, casting, etc.), metallurgical condition (cold
rolled, hot rolled, quenched and tempered, solution heat treated,
stabilized, etc.), and the size and shape of the coupons
9. Exposure location
10. Cleaning technique
11. Weight loss
12. Type and nature of localized corrosion: stress-corrosion cracking,
intergranular corrosion, pitting (maximum and average depth),
crevice corrosion, and so on
13. Corrosion rate: may be misleading if localized corrosion is

present.
Specialized Tests
Most industrial groups have developed specialized corrosion tests
to fit their needs. Most of these test methods are listed in the
Manual of Industrial Corrosion Standards and Control [ 7 ] .
A number of stress-corrosion cracking tests have been developed
[8-10] and these are detailed in the literature. The U-bend is the
most widely used stress-corrosion cracking test and a typical sample
is shown in Figure 15. Stress-corrosion cracking specimens are
usually acid cleaned, degreased, and weighed before exposure,
but the base and weld metal surfaces are usually not ground because
the object is to test the metal in a condition very near to how it
would be put into service. Sheared edges and punched holes are
usually used. After exposure, the samples are examined carefully,
cleaned, weighed, and examined again. The sheared and stamped
edges and the ends of welds should be examined very carefully
OO o
I'l'j'iVitint'utifiU'Wt^'et'l1 -Weld
Cold Worked Cold Worked

and Stressed
FIGURE 15 Stress-corrosion cracking specimen. The hole that is
not used in this figure is for mounting the specimen on a coupon
rack.
FIGURE 16 Slotted washer for crevice corrosion. The grooves are

0.020 to 0.030 in. deep and 0.040 to 0.050 in. wide. The groove
size is not critical. The area of crevices should be one-tenth or
less of the total coupon area.
for cracks. The specimens are then flattened and the bend is
examined again to determine if any additional cracks were opened
up. Dye penetrant inspection is frequently used to help locate
small cracks. Weight-loss corrosion rate is sometimes reported,
but it can be misleading on welded specimens because the weld
has a different composition than the base metal, and galvanic corro-
sion occurs.
The area under washers, insulators, and gaskets should be
examined to determine if crevice corrosion is a problem. A more
-Variable-Speed Motor
• Bearings
-Shaft
•Vortex Breaker
.Coupon
FIGURE 17 Rotating disk corrosion test apparatus.

604 Arnold arid Schweitzer
Coupons
FIGURE 18 Paddle wheel test.
rigorous method of measuring crevice corrosion is to use a slotted

washer or nut [11] as shown in Figure 16, which allows the results
to be analyzed statistically.
Galvanic corrosion tests may be conducted by bolting, wiring,
or welding specimens together. If the specimens are bolted or wired
together, it is possible to measure a weight-loss corrosion rate,
but the coupons should be examined carefully to ensure that crevice
corrosion is not clouding the results. The test results will be sub-
jective when welded specimens are used.
The effects of velocity on corrosion can be studied in a number
of ways. The simplest is by rotating a metal disk in the test liquid
as shown in Figure 17. The next step up is a paddle wheel test,
in which a number of coupons are bolted to a disk (Figure 18)
which is rotated. Other techniques involve putting coupons in
nozzles or Venturis or vibrating them [12].
HYDROGEN DIFFUSION
The atomic hydrogen that is produced at the cathode of some corro-

sion reactions can diffuse through steel and most other metals if
it does not combine to form hydrogen molecules. When sulfides are
present, as in sour service and some refinery streams, the atomic
hydrogen produced by the corrosion reaction readily diffuses through
steel. If hydrogen diffusion is detected, corrosion is taking place.
Hydrogen diffusion can be measured using either a hydrogen probe
(pressure measurement) or a hydrogen-monitoring system (electro-
chemical) .
Pressure Measurement
The cross section of a hydrogen probe is shown in Figure 19. The
body of the probe is made from pipe that has a section machined
down to a very thin wall thickness. A rod is inserted into the pipe
so that the free volume is very small. The hydrogen diffuses into
the free volume, and the increase in pressure is easily detected
using either a pressure gauge or a transducer. This type of probe
has been used for some time in refineries to help in process modifi-
cation and inhibitor addition to prevent hydrogen blistering and
embrittlement.
Electrochemical Detection
The hydrogen that diffuses through a pipe wall can be detected
electrochemically using a "patch probe," shown in Figure 20. Palla-
dium foil is used as the working electrode because hydrogen diffuses
through it very rapidly and it has very good corrosion resistance
in the sulfuric acid electrolyte. A potentiostat is used to maintain
the palladium foil at a potential at which the hydrogen atoms are
oxidized, and the amount of current necessary to oxidize the hydro-
gen is a measure of the amount of hydrogen that diffuses into the
• Pressure Gage or Transducer
Tee or Plug with very small holes

Bleed Valve with very small internal
volume
-0.025 - 0.030 i n . wall thickness
0.0002 - 0.0003 i n . clearance per side
. Rod welded to outer wall at both ends
r
FIGURE 19 Hydrogen probe.
- Vessel or Pipe Wall
Vent
Auxiliary Electrode
Reference Electrode
Housing
•Electrolyte
Gaskets
Palladium Foil Working Electrode
Transfer Medium
FIGURE 20 Electrochemical hydrogen probe.
cell. These systems have proved reliable at temperatures up to

105°C (220°F). The amount of hydrogen that diffuses through the
wall will be proprotional to the corrosion rate in a given system
[13], but identical diffusion rates may result from different corrosion
rates if the system changes. Temperature will increase the rate of
hydrogen diffusion and wall thickness will decrease it.
ELECTRICAL RESISTANCE
The electrical resistance technique of corrosion measurement was

developed [14] as a method of measuring low corrosion rates without
removing the products of corrosion. Very small changes in resistance
occur when corrosion takes place, and changes in temperature can
result in larger changes in resistance that will give erroneous corro-
sion readings. To overcome the problems encountered from changes
in temperature, a noncorroding reference section of the test element
was included in the probe, as shown in Figure 21. This reference
element is able to handle small or gradual changes in temperature,
but because it is encased in the tip of the probe, its temperature
would still fall behind that of the test element. Numerous modifica-
tions have been made to probes over the years, but it is still not
Measuring Element
Seal
Housing
• Reference
Wires to Instrument
FIGURE 21 Electrical resistance corrosion probe.
possible to measure very small changes in corrosion rate with a

single reading unless you are absolutely sure that no changes in
temperature have occurred.
Probes (Fig. 22) are available, with test elements made from
all of the common alloys used for the fabrication of process equip-
ment [15], that can operate at temperatures up to 400°C (750°F)
Probe Insert with Wire

Test Element
Probe Housing
FIGURE 22 Electrical resistance corrosion probe.

at a pressure of up to 4000 psi. Probes are also available that can

be inserted into a process stream through a 0.75- or 1-in. full
port valve.
In measuring corrosion using an electrical resistance probe,
a reading is first taken on the test and check element. The probe
is then inserted into the test environment and allowed to come to
the test temperature (usually 30 to 60 min). Another reading is
taken on the test and check element and corrosion is allowed to
take place for a few hours. Another new set of readings is taken,
and if they have changed, the corrosion rate is calculated using
the following equation:
-, . , . change
a in reading S2 x probe multiplier * 365
Corrosion rate (mpy) = ~:—f: «AAn
" c h a n g e i n time x 1000
(3)
"Change in reading" is the current reading minus the initial reading

in the test environment or the previous reading. If the change
in reading is negative, the results are not corrosion. They are
either temperature of a conductive film or the test element.
"Change in time" is in days.
"Probe multiplier" is a number marked on each probe that reflects
the life of the probe. Higher numbers mean that the probe will
last longer and be less sensitive.
"1000" is the maximum instrument reading.
"365" is the number of days per year.
It is useful to calculate both the overall corrosion rate (or corrosion

rate over the total exposure time) and the corrosion rate between
readings to determine if the corrosion rate is changing with time.
Sometimes it is useful to plot the instrument readings versus time
to follow changes as they are occurring, as shown in Figure 23.
Manual and automatic instruments are available to measure the
change in electrical resistance of the probe, and two instruments
are available that will calculate the corrosion rate of the test element.
When automatic instruments are used, the lead wires from the probe
to the instrument are part of the circuit and their change in tempera-
ture can affect the resistance readings [16] and, thus, the calculated
corrosion rates. This can trip the alarm on an automatic instrument
and cause it to display incorrect corrosion rates.
When the limitations of the system are taken into account, the
electrical resistance technique can be used to measure very small
corrosion rates while they are occurring. It is also useful in detect-
ing changes in corrosion rate and spotting upsets in process plants.
1000
900
800
700
600
500
400
300
200
1Q0
10 20 30 40 50 60 70
Time, Days
FIGURE 23 Electrical resistance corrosion probe readings.
ELECTROCHEMICAL TECHNIQUES
Electrochemical techniques are particularly useful in determining

what is actually hapening to a metal at any given time. The three
techniques most often used involve polarization curves, linear polar-
ization curves, and zero-resistance ampmeters.
Polarization Curves
Polarization curves may be determined galvanostatically, potentio-
statieally, or potentiodynamieally. During a galvanostatic measure-
ment, a predetermined amount of current is passed from an auxiliary
or counterelectrode to a working or test electrode, and the resulting
shift in potential of the test electrode away from a reference elec-
trode is measured using a high-input impedance voltmeter, as shown
in Figure 24. Potentiostatic measurements are made using a bipolar
operational power supply (potentiostat) to supply the current neces-
sary, in either direction, to move the test electrode away from
its open circuit or rest potential, as shown in Figure 25. Adding
a sweep unit or wave generator to the potentiostatic allows the
test electrode to sweep through a range of potentials.
When active corrosion is taking place and the log of the applied
current density is plotted versus the potential difference of the
test electrode away from a reference electrode, the corrosion current
of a metal may be estimated, as shown in Figure 26. The corrosion
High-Input Current
Impedance Source
Voltmeter and Meter
Reference Test Auxiliary

Electrode Electrode Electrode
FIGURE 24 Galvanostatic polarization circuit. The input impedance

of the voltmeter should be 100 Mft or greater. The current meter
should have ranges from 10 yA to 1A and should have an accuracy
of at least 0.5%. The current source can be batteries or a power
supply with less than 100 yV ripple.
Potentiostat
High-Input
Impedance Current
Voltmeter Meter
Reference Test Auxiliary

Electrode Electrode Electrode
FIGURE 25 Potentiostatic polarization circuit. The potentiostat

should be able to maintain the test electrode within 1 mV of its
set value over a ±1-V range and have an output current of at least
1A.
Anodic Polarization Curve
Corrosion Potential (Ecor)
-400 r
Cathodic Polarization Curve
1 10 102 103 105
Log of Current Density, /cm2
FIGURE 26 Anodic and cathodic polarization curves for a metal

that is corroding actively. The Tafel slopes on 3a and 3c are the
slopes of the anodic cathodic polarization curves.
or exchange current can be used to calculate the corrosion rate

using FaradayTs law. Figure 27 shows the shape of the anodic
polarization curve of an active-passive metal measured with a poten-
tiostat. The dashed lines in Figure 27 show what would be measured
using a galvanostat. If the cathodic polarization curve intersects
the anodic curve only in the passive region, the corrosion rate
of the test metal will be very low (Fig. 28). Deep pitting can occur
when corrosion occurs in the transpassive zone. Crevice corrosion
(often mistaken for shallow pitting) occurs when the metal is corroding
both passively and actively at different locations at the same time.
In the laboratory, good reference electrodes can be used, and
it is almost always possible to measure the polarization curves accu-
rately. High temperatures or pressures sometimes make it impossible
to place a reference electrode near the test electrode under field
conditions. When this occurs, either a corroding or remote electrode
may be used. When a corroding electrode is used, it is not possible
to determine the potential of the test electrode, but it is possible
to determine if the corrosion is active, passive, and if small changes
in the process could change the type of corrosion that is taking
place. A remote reference electrode can be used by placing a corrod-
ing reference electrode near the test electrode and connecting it
to the potentiostat by using a large electrolytic capacitor. The remote
600
Transpassive
400
200
Passive
'Z -200
CD
4->
O
Active
1 10 102 TO3 TO4 TO5

Log o f C u r r e n t D e n s i t y , MA /cm2
FIGURE 27 Anodic polarization curve for an active-passive metal.

The solid lines are for potentiostatic polarization. Galvanostatic
polarization will follow the dashed line and the passive area will
not be seen.
600
400
Measured Curve
200
0
Real Curve
-200
1 10 10 2 103 105
FIGURE 28 Anodic and cathodic polarization curves for an active-

passive metal that is corroding passively.
Auxiliary
Electrode
iostat
Test
c Electrode
i
Pot
Electrolytic Corroding
Capacitor Reference
Electrode
Remote Reference Salt Bridge

Electrode or
Porous .Wood
Electrolyte
FIGURE 29 Remote reference electrode.
reference electrode is then connected directly to the potentiostat,

as shown in Figure 29. In almost all cases, the tafel slopes can
be measured for use with the linear polarization technique, as
described in the next section.
Linear Polarization
The linear polarization technique makes it possible to measure the
corrosion rate of a metal at any instant. This technique will only
work when electrodes are exposed to an electrolyte that has a con-
tinuous path between them. The technique is based on the Stern
and Geary [17] equation:
AI 3a3c
Icor = (4)
AE 2.3(3a + 3c)
where
Icor, 3a, and 3c are as shown in Figure 26

AI • = applied current
AE = change in potential from the freely corroding potential
(because this is the change potential, a corroding reference
can be used).
Equation (4) holds only when there is a linear relationship between

AI and AE and usually only over a range of ±10 to 50 mV for AE.
When 3a and 3c are known and AE is preset, it becomes possible
to manufacture a meter that will read out directly in corrosion rate
because Icor is directly related to the amount of metal loss through
Faraday1 s law. Equation (4) can be reduced to
C.R. = AI K (5)
where
C.R. = corrosion rate, mpy

K = meter constant
Both manual and automatic linear polarization instruments are avail-

able that can be used under laboratory and field conditions. An
automatic instrument installed in a cooling-water system will usually
pay for itself in 6 to 12 months by reducing the treatment chemical
usage [18]. The corrosion rate of any metal can be measured. As
with the electrical resistance technique, probes are available for
laboratory and field use. Linear polarization probes normally use
a corroding reference electrode. Standard reference electrodes and
platinum counterelectrodes are often used in laboratory tests.
Most of the instruments that are available go through the follow-
ing steps during their operation:
1. Measure potential from reference to test.

2. Add or subtract AE from the potential measured in step 1.
3. Change the potential of the test electrode to the potential deter-
mined in step 2 by applying current between the test and auxil-
iary electrodes.
4. Hold the test electrode at the potential determined in step 2
for a predetermined time.
5. Display the corrosion rate. Some instruments have an alarm circuit
that can be activated during this step.
6. Go to the next probe and repeat steps 1 through 5. Instruments
are available that will handle up to 10 probes and can polarize
them all in one direction and, then, all in the opposite direction.
This sequence of events is shown in Figure 30 for an instrument

with two active probes and a meter proven on a third channel.
When the polarization curves are recorded on a strip-chart recorder,
it is possible to detect when nonuniform (pitting, crevice, etc.)
corrosion is taking place, as shown in Figure 31. The corrosion
rate measured in the cathodic direction will be slightly higher than
Repeat all channels on cathodic

linear polarization
1 Repeat all steps below on a "dummy

load"
Repeat all steps below on a probe on
another channel
-Display and alarm
-Anodic linear polarization reading
^Measure potential from reference
to test electrodes
Cathodic Anodic
FIGURE 30 Linear polarization readings on two-probes and a meter

prover or dummy load. The probes are on stations 1 and 2, and
the meter prover is on station 3.
Active corrosion
Active corrosion plus shallow pits
Passive corrosion
Passive corrosion plus deep pits
Meter prover
FIGURE 31 Linear polarization nonuniform corrosion detection.

Log Current Density Log Current Density

Passive Corrosion Diffusion Limited
FIGURE 32 Linear polarization measurements in the passive (anodic <
cathodie rate) and cathodic (anodic > cathodic rate) regions.
that measured in the anodic direction when passive corrosion is

taking place and the opposite will be true if diffusion is limiting
the rate of reaction, as shown in Figure 32.
Instrument manufacturers size their electrodes for a "known"
valence change (usually +2 for iron) and Ba$c/(Ba + £c) can be
measured at the end of a test and the readings of corrosion rate
can be factored or new electrodes can be made using an area that
will make the instrument direct reading.
Zero-Resistance Ammeter
A zero-resistance ammeter is a potentiostat that has been programmed
for zero potential difference between the reference and test electrode,
and in addition, the current lead to the counterelectrode is connected
to the reference electrode. This makes it possible to measure the
amount and direction of the current that flows between two electrodes
that are electrically short-circuited. When galvanic corrosion measure-
ments are being made on two materials of similar chemical composition,
the test should be allowed to run for several days because the
direction of current flow often reverses [19]. The galvanic current
cannot be used to calculate directly the corrosion rate of the anode
because it is only a measure of how much faster the anode is corrod-
ing than the cathode.
REFERENCES
1. Minton, W. C. (1970). "Wall Thickness Measurements—Quick

and Easy," NACE Corrosion/70, Paper No. 76, March, Philadel-
phia.
2. Fontana, M. G., and Green, N. D. (1967). Corrosion Engineer-

ing, McGraw-Hill, New York, Chap, 2.
3. Metals Handbook, Vol. 1, 8th ed. (1961). American Society
for Metals, Metals Park, Ohio.
4. Properties of Some Metals and Alloys. (1968). International
Nickel Company, New York.
5. Wachter, A., and Treseder, R. S. (1947). Corrosion testing
evaluation of metals for process equipment, Chem. Eng. Prog.
43:315-326.
6. Laboratory Corrosion Testing of Metals for the Process Industry.
(1969). NACE Standard TM-01-69, National Association of Corro-
sion Engineers, Houston.
7. Cocks, F. H. (1973). Manual of Industrial Corrosion Standards
and Control, STP 534, American Society for Testing and Materials,
Philadelphia.
8. Ugiansky, G. M., and Payer, J, H. (1979). Stress Corrosion
Cracking—The Slow Strain-Rate Technique, STP 665, American
Society for Testing and Materials, Philadelphia.
9. Craig, H. L., J r . (1972). Stress Corrosion Cracking of Metals—
A State of the Art, STP 518, American Society for Testing
and Materials, Philadelphia.
10. Stress Corrosion Testing. (1967). STP 425, American Society
for Testing and Materials, Philadelphia.
11. Anderson, D. B. (1976). Statistical Aspects of Crevice Corrosion
in Seawater, Galvanic and Pitting Corrosion—Field and Laboratory
Studies, STP 576, American Society for Testing and Materials,
Philadelphia, p p . 231-242.
12. Compton, K. G. (1971). Seawater corrosion tests, Handbook
on Corrosion Testing and Evaluation, Wiley and Sons, New
York, p p . 507-529.
13. Martin, R. L., and French, E. C. (1978). Corrosion monitoring
in sour systems using electrochemical hydrogen patch probes,
J. Pet. Technol. 1566-1570, November.
14. Dravnieks, A., and Cataldi, H. A. (1954). Industrial applications
of a method for measuring small amounts of corrosion without
removal of corrosion products, Corrosion 10:224.
15. Corrosometer Fixed Probe Selection Guide, Rohrback Instruments,
Santa Fe Springs, Calif.
16. Scholten, D. L. (1976). "Process Plant Uses of Corrosion Rate
Measurements," Paper No. 40, NACE Corrosion/76, March,
Houston, Texas.
17. Stern, M., and Geary, A. L. Electrochemical polarization:
I. A theoretical analysis of the shape of polarization curves,
J. Electrochem. Soc. 104:56, 1957.
18. Arnold, C. G. (1975). "Instrumentation in Cooling Water Sys-

tems," Cooling Tower Inst. Annu. Meet., February 11, Houston.
19. Arnold, C. G. (1980). "Corrosion Measurement of Weldments."
Paper No. 71, NACE Corrosion/80, Chicago, March 3-7.
23
SELECTING MATERIALS OF CONSTRUCTION
LEWIS W. GLEEKMAN+ Materials and Chemical Engineering Services,

Southfield, Michigan
PRINCIPLES
In engineering practice the selection of materials of construction

depends on the item being designed and the service requirements
imposed on the item. Simple as this statement is, there are many
complications involved in the choice of the preferred material of
construction for a particular item. It almost goes without saying
that one would not use aluminum foil as a structural roof deck on
a building. Conversely, one would not use poured concrete as the
load-carrying member on a jet aircraft. These two extremes point
to the fact that in selecting materials one has to balance many
requirements; these requirements, somewhat in order of decreasing
importance, include the following:
Cost
Availability
Ability to be fabricated
Ability to be joined
Mechanical properties as a function of temperature
Strength/weight ratio
Physical properties (including thermal and sound properties) as
a function of temperature
Electrical properties as a function of temperature
Corrosion properties as a function of environment
tDeceased.
619
620 Gleekman and Schweitzer
Currently, the most common starting material is steel. This is

because steel is relatively inexpensive; it is readily available; it
is fabricated by a wide variety of techniques, including casting
and wrought methods; it is easily joined by a wide variety of inex-
pensive techniques to itself and to other materials; and its mechanical
properties are well established and can be changed as a function
of composition and temperature. Indeed, by alloying, steel can
meet the extremes of relatively high, as well as relatively low,
temperatures. Under most circumstances its thermal and electrical
properties are well known, and its ability to carry sound is quanti-
tatively recorded. Although the strength/weight ratio of steel is
not as favorable as those of certain aluminum alloys and titanium
alloys, when combined with cost, steel often is quite favorable.
Finally, the corrosion properties of steel in most environments have
been determined, and techniques of protecting steel against corrosion
in these environments are also widely developed.
However, this has not always been true. It must be recognized
that steel has been widely used as an item of commerce since about
only the middle of the nineteenth century. Before that, before
the development of the Bessemer process and modern high-speed
rolling mills, cast iron was the common material of construction.
It was well known that cast iron had poor tensile strength, but
the engineers of the pre-1850s were able to design around the poor
properties of cast iron in tension (but great in compression) and,
thus, cast iron was widely used in certain aspects of the chemical
process industry for which, indeed, it was used right up to the
1970s. Even before cast iron, wood was a common material of con-
struction, and in modified form, it is still widely used for certain
items in industry. Consider, for example, the construction of an
atmospheric storage tank handling a product that is corrosive only
under aerated conditions; for example, a sodium chloride brine
solution. The number of materials that can be used for such a storage
tank to handle this product is mind-boggling when it is considered
that virtually every material (with one or more modifications) could
be used for this purpose. Wood-staved brine storage tanks (particu-
larly cypress and redwood) can give long service provided that
the vertical staves of the wood storage tank are reinforced with
steel hoops. It is the steel hoops that are usually the weak link
in the construction of wood-staved tanks because part of the hoop
(where the hoop rests against the wood) is subject to crevice corro-
sion as brine exudes through the wood and wets the hoops. Rubber,
particularly in its reinforced form, has been used for brine storage
tanks either in the form of pond liners or in the form of pillow
storage tanks with all-welded seams. Rubber has also been used
as a lining for steel tanks.
23. Selecting Materials of Construction 621
Steel itself has been used for brine storage tanks; where, the
only problem is that of corrosion at the liquid level. Some companies
in the past made a practice of letting the steel corrode in an initial
high level of brine in the tank and then dropping the level an
inch or two each year to get around corrosion in the higher portions
of the tank. Ultimately, when the corrosion has proceeded down
the tank with lowering liquid levels to the point at which the capacity
of the tank was insufficient, new steel plates would be installed to
replace the corroded plates. This is not as unusual a practice as
it may seem; one of the major chemical companies was doing this
as recently as the 1960s. Now, the more common approach, because
of economic considerations such as loss of production and the rela-
tively high cost of maintenance labor, is to put a lining on the
interior of the tank that will offer protection to the steel substrate.
This lining, usually, can be a nominal 5-mil vinyl coat, or in certain
instances, can be a relatively heavy coal tar epoxy or sprayed
glass flakes dispersed in polyester resin.
In fact, with the advances in the fiberglass industry, it is now
quite common to find brine storage tanks or other such tanks made
from fiber-reinforced plastic (FRP); this material not only resists
the corrosive effects of brine on the interior but also protects the
exterior against corrosion from atmospheric contaminants or overflow-
ing conditions of the tank. The fiberglass industry has advanced
to the point where vessels can be field fabricated to provide large-
diameter, large-volume vessels, somewhat analogous to the field
erection of steel storage tanks. If temperature and trace element
considerations demanded, the tank can be constructed of titanium,
either as a discrete metal or as a lining on steel (loose lined, ex-
plosive clad, or metallurgically roll-bonded)*
One could go down the list of present materials of construction
item by item and point out that in one form or other, and for one
or more specific conditions, these materials could be used for brine
storage tanks. This could include glass, concrete, acid brick and
resin mortar, and even paper with resin impregnants; proper con-
struction for the known strength considerations allow such materials
to be used for this service.
With such a variety of materials of construction available, there
is obviously a need to differentiate among the materials to arrive
at the one that is most economical both in terms of first cost and
in terms of annual cost (including maintenance cost) over a given
period.
Experience has taught that many materials have widely used
or unique properties that extensively govern their utilization for
particular facets of design; thus, the design engineer needs not
reinvent the wheel for each particular problem, but frequently needs
only to check handbooks or textbooks or, at worse, do a compre-

hensive literature search in the technical journals in the appropriate
fields. Whatever is forthcoming from the recorded experiences of
others needs to be tempered with developments that may have taken
place based on recent experiences. As simple a thing as fluctuations
in the precious metals market can establish whether titanium-0.2%
palladium alloy, with its great resistance to crevice corrosion in
the presence of hot brine solutions, is a feasible material of con-
struction or whether one should use instead titanium-nickel (1%
nickel) alloy, for which the price of the material would not be influ-
enced by the demand for noble metals such as gold, platinum, or
palladium.
Another example would be that certain cast alloys with great
corrosion resistance in particular environments have been modified
to produce an equivalent wrought alloy with the same corrosion
resistance but with somewhat different metallurgy; this points out
that designers need not restrict themselves to relatively heavy
cast metal sections but, instead, can think of fabrications involving
somewhat thinner wrought sections.
This whole matter of cast versus wrought construction is an
ever-fluctuating one and often depends on the number of items
being produced in a given shape. For one-of-a-kind units, cast
construction is often expensive. On the other hand, 50 or more
similar items can often be economically justified as sand casting,
and 500 or more of a given item can be economically justified as
permanent mold castings. In the manufacture of a new valve, the
prototype valve could well be made from bar stock of a given material
with whatever machining was necessary to accomplish the configura-
tion and desired shape. After the prototype valve had proved itself,
it would be feasible to consider fabricating one or more of the com-
ponents as castings to minimize machining time and scrap from the
machining operation. This decision would also require determining
that the cast alloy had equivalent corrosion resistance for the antici-
pated environments in which the wrought alloy had originally been
tested.
Historically, one can point to the use of titanium pump impellers
in chlorohydrin-HCl solutions in the manufacture of either ethylene
or propylene oxide. Here, problems had been encountered with
the use of a nickel-chrome-molybdenum cast alloy (Hastelloy C)
because of sensitization that occurred during the welding operation.
The first titanium impeller was made by hot working wrought stock
into blades and welding the blades to a previously machined back
plate, which itself had been made from wrought stock. After several
years of successful operation in the hot corrosive environment it
was decided that three other pumps should be equipped with titanium
impellers. At that time, one of the titanium companies then proposed

to die cast the titanium in steel molds, even though only four im-
pellers were going to be ordered. The economics of this means
of manufacture was chosen because of future anticipated business.
STRENGTH/WEIGHT RATIO
Strength/weight ratio had been of historical significance to designers

of lighter-than-air vehicles such as blimps and zeppelins, for which
the lifting capacity of the vehicle depended on the buoyancy imparted
by helium (or occasionally, hydrogen). Therefore, the weight of
the structural members giving rigidity to the vehicle became of
critical consideration relative to the live load-carrying capacity
of the vehicle. Duraluminum was originally a German development,
based on magnesium, that found wide use in the construction of
zeppelins. As the switch took place from the lighter-than-air vehicle
to powered aircraft, weight was also a consideration in the air frame,
and the strength/weight ratio factor was important in the early
stages of aircraft design. Strength/weight ratio became even more
important when considerations of live load of passengers, freight,
or in military aircraft, bomb loads, again came into play. Aluminum
alloys were developed that had higher strength than the conventional
alloys and yet had the relatively low density of aluminum itself.
Great improvements came about through the use of titanium alloys
in which, in spite of an approximate doubling of the weight of
aluminum, the strength advantage became more than fourfold greater
than that of the aluminum alloys, thereby reducing the strength /weight
ratio of a given part when using titanium alloy.
Yet further advances have come into being in recent years, as
carbon fibers impregnated with epoxy resin have given a structure
that can be readily formed and has extremely high strength for
its relatively low weight. Even certain synthetic fibers of the aramid
type (Kevlar), when used as a reinforcement with either epoxy or
polyester resins, result in a material with an extremely high strength/
weight ratio. Such materials are not limited to aircraft, but their
use is now being directed toward the entire transportation field,
in view of the present consideration toward reducing the weight
of automobiles and other vehicles in order to achieve a conservation
of fuel. The construction of the Corvette body out of molded fiber-
glass has not only reduced the weight of the vehicle but has achieved
a step toward a noncorroding material of construction relative to
the corrosive effects of salt, moisture, and other contaminants in
the atmosphere.
CORROSION CONSIDERATIONS
Because this is a handbook directed toward corrosion control and

prevention, it would not be appropriate to emphasize the other
considerations involved in selection of materials, such as the mechani-
cal, physical, and electrical properties. Instead, it should be pointed
out there are three relatively simple actions that can be taken to
stop corrosion: (1) change material, (2) change environment, and
(3) protect material. Although these may oversimplify the process
of corrosion control, they do indicate to the practicing engineer
steps to be used in stopping corrosion.
Relative to changing materials to minimize or stop corrosion is
the practice of using a more corrosion-resistant material, usually
achieved by alloying, or occasionally achieved by upgrading the
material to a more resistant material, after considering reported
experiments and experience. In addition to changing by alloying,
one can also change to nonmetallic materials such as plastics (with
and without reinforcement), elastomers, ceramics, stoneware, glass,
carbon, graphite, and woods, among others. The matter of changing
materials is not merely a function of selecting material that has
approved corrosion resistance; other factors, such as thermal and
electrical properties, ease of fabrication, and all the other aspects
previously indicated, must be considered.
It should be recognized that every material has at least one
Achilles' heel, if not two or more. These weaknesses in a material
must always be considered in their selection for a given part. In
fact, the design engineer would do well when considering any mate-
rial to think immediately of the drawbacks associated with that
material and assure that these factors are not applicable to the
given situation. Listed in Table 1 are some of the more common
weaknesses of a variety of engineering materials.
When one speaks of changing the environment to reduce corrosion,
the easiest and most obvious method is to lower the temperature.
Because corrosion processes are chemical reactions, every 10°C
(18°F) decrease in temperature reduces the reaction rate by half.
Thus, if one lowers the temperature, the rate of corrosivity will
be retarded. In addition, the atmosphere can be changed by the
presence of certain gases; some metals are corroded in the absence
of air and others in the presence of air. Other environmental changes
involve agitation, aeration, and velocity, all of which have a decided
influence on many materials. Also, a change that is fairly easily
brought about in some processes is adjustment of the pH, which
is a measure of the acidity or basicity of the solution. For most
materials, increasing the pH to the alkaline side reduces the corro-
sivity. The presence of trace additives is a change in environments
TABLE 1 Engineering Materials and Weaknesses
Material Weakness
Mild steel Caustic embrittlement of stressed areas

High-temperature oxidation
Alternate wetting and drying—"rusting"
Austenitic stainlesses Chloride-containing solutions, especially
in crevices and on welds or stressed areas
Pitting
High-temperature fusion from certain
sodium and vanadium compounds
Nickel and Monel Contact of heated surfaces with sulfur
and its compounds; ammonia, mercury
Copper Essentially the same as nickel
Aluminum Galvanic effects with iron, copper, and
other nobler metals; mercury
Titanium (C.P.) Crevice corrosion in hot brine solutions;
nonoxidizing environments; dry chlorine
Hastelloy C Reducing high-temperature environments
Hastelloy B Oxidizing high-temperature environments
Thermoplastics Temperatures above 120°C (250°F) (excep-
tions being most fluorinated polymers);
some organic solvents
Thermosetting Oxidizing effects (including concentrated
polymers H2SO{+) on epoxies; strong hot alkalies
on many polyesters; certain solvents;
loss of properties on long-term tempera-
ture exposure
Rubber Temperature; solvents; certain oxidizing
chemicals depending on specific elastomers
Wood Temperature; strong acids and alkalies
and oxidizing chemicals; certain impregnat-
ing resins can be used to overcome these
effects
Glass Fragility unless protected by "armor"
cladding of FRP; strong hot caustic and
HF (HC1 under certain conditions)
that can be either good or bad for certain metal systems. It is

necessary to know the behavior of the metal toward various additives
to establish whether a positive or a negative effect will be brought
about. For example, the presence of copper ions improves the corro-
sion resistance of stainless steels in certain environments, whereas
the presence of copper irons will cause localized pitting and attack
of aluminum alloys in other solutions. There is yet the wider option
of adding inhibitors to a solution that suppress the corrosivity
of the main species in the solution.
Protecting a material to reduce corrosion often means isolating
the metallic surface from the corrosive environment. This can be
done with either organic or metallic coatings on the surface. Organic
coatings can be thick or thin and can be paint film, solid lining,
or plastics, in the form of tape, sheet, or powder, fused to the
surface. Metallic coatings are often applied as an electroplated mate-
rial, although some metals can be deposited by chemical means in
an electrodeless deposition similar to silvering glass to make a mirror.
A metal may be coated by diffusion at moderate temperatures, such
as the application of zinc in galvanizing or aluminum in aluminizing,
or metalizing the surface by spray application of partially melted
materials. Selection of any one of these protective methods depends
on such considerations as service factors, environmental conditions,
economics, ease of application of material, and complexity of parts.
In addition, one can protect the metal surface by applying an elec-
trical potential under conditions that make the surface cathodic
or anodic depending on the environment and the metal being pro-
tected. The more widely used of these two methods is that of
cathodic protection, often applied to underground pipelines, tank
bottoms, or water boxes on exchangers. The application of cathodic
protection is sometimes done with a sacrificial anode of magnesium,
zinc, or aluminum, or by the application of applied potential from
a rectifier or battery, for which one uses a more permanent anode
of graphite, Duriron, or platinized titanium.
Determining Corrosion-Resistant Properties

In many instances the choice of suitable materials of construction
to resist the corrosive properties of the environment will be known—
either from past experience or from published data. When this is
so, it becomes a relatively simple matter to match the requirements
of the system with the properties of the various materials. However,
it is essential that all of the characteristics of the medium and the
operating conditions are known including
Complete analysis of the medium

Maximum and minimum operating temperatures
Maximum operating pressures

pH of system
Maximum and minimum concentrations of all materials in the system
Possibility of trace contaminants
All of the preceding must be considered when making a selection

of potentially suitable materials for construction.
On occasion, a suitable construction material may not be selected
from experience or published data because neither experience in
handling the corrodants nor published data is available. Under
these conditions it is necessary to undertake a test program to
determine the corrosion resistance of various materials in a specific
application. Before undertaking such a program, some thought should
be given to the other factors of material selection such as
Cost
Availability
Ability to be fabricated
Ability to be joined
Mechanical properties as a function of temperature
Strength/weight ratio
Physical properties as a function of temperature
Electrical properties as a function of temperature
There have been instances when a testing program was completed

and a material of construction selected only to find that the material
was unavailable in the form required, or that it was not possible
to fabricate it as required.
Today1 s marketplace is filled with a myriad of materials to choose
from. Such a wide assortment tends to create a dilemma when a
selection must be made. Cost invariably plays an important part
in the final choice. But the cost should be the overall final cost
based on the desired service life of the unit and the maintenance
costs during its life. Many times the lowest first cost does not
prove to be the true overall least cost.
Because the most economical material to use may not be the one
having the lowest initial cost, it becomes prudent to include as
many materials as practical in the test program for corrosion resist-
ance so that a final decision can be made based on reliable data.
It may be that a material having inferior corrosion resistance, in
comparison with other materials, may be selected because it is the
least expensive and will provide a satisfactory service life. Con-
versely, a more expensive material of construction may be selected
on the basis of an overall lower cost that results from the ability
to use a thinner section and still have a suitable service life because
of improved corrosion resistance and reduced maintenance costs.
A range of materials should be tested for yet another reason.

All equipment and accessories are not available in all materials of
construction. For example, although it would be possible to fabricate
a vessel from Inconel 600 metal, it may not be possible to secure
piping materials or other accessory items in this same material.
In addition, price becomes a factor. It may be possible to utilize
a piping system of either thermoset or thermoplastic materials, even
though the processing vessels cannot be fabricated from these mate-
rials. If data on a variety of materials are collected during the
test program, options of this sort can be taken advantage of.
The use of coatings and of linings is another one that should
be considered and investigated. Applying a protective coating or
a lining to a less-expensive material of construction may be the
most economical course to follow.
In the final selection procedure, consideration should also be
given to external corrosion resulting from the environment. There
is a tendency to concentrate on the need to resist the corrosive
effects of the materials being handled and, sometimes, overlook
the problem of atmospheric corrosion that is also present. There
have been occasions when tetrafluoroethylene (TFE)-lined steel
pipe was installed to convey a corrosive medium, The lining did
a fine job of resisting internal corrosion, but the outer shell of
steel pipe corroded away as a result of atmospheric attack. The
problem was corrected by applying a protective coating to the steel
pipe.
Other items that may be considered in the final selection are
the use of inhibitors and cathodic protection.
The data collected should be complete enough so that the design
engineer will be in a position to make a complete and comprehensive
analysis, thereby resulting in the selection of the most overall eco-
nomical and satisfactory material of construction for each step of
the process and providing a satisfactory service life.
Types of Corrosion
Although the various types of corrosion are discussed in detail
elsewhere in this handbook, they bear repetition here because it
is only as one recognizes the type of corrosion and the materials
that are susceptible to specific corrosion attack (under the specific
environmental conditions or construction and operating conditions)
that one can avoid costly errors in materials selection.
Macroscopic types
Uniform
Galvanic
Crevice
Pitting
Erosion (velocity)
Microscopic types
Selective leaching (parting or "dezincification")
Intergranular
Stress-corrosion cracking
NONMETALL1C MATERIALS
Metallic contamination of products has become a very important

consideration and, in some instances, is responsible for limiting
the use of metals for process equipment. The use of nonmetallic
material, in particular plastics and elastomers, has been very
successful in avoiding metallic contamination. For most aqueous
environments, nonmetallic materials will often provide greater chemi-
cal resistance than metallic construction, at lower cost.
Plastics
Traditionally, the use of plastics has been limited to relatively low-
temperature services and to low-pressure applications, except where
they were used as a lining bonded to or otherwise supported by
a strong substrate. This is true of the nonreinforced plastics cate-
gorized as thermoplastic materials, specifically those materials that
are softened by heat. However, the development of reinforcing
materials, combined with the class of plastics known as thermoset
materials (materials that are not softened by heat), and the further
development of many thermoplastic materials that have relatively
high thermal-distortion temperatures, has meant that present-day
technology uses plastics for moderately high temperatures and for
high-pressure applications.
Notable among the thermoplastic materials are polyethylene, poly-
propylene, polyvinyl chloride, the styrene-synthetic rubber blends,
the acrylics, and the fluorocarbons. Notable among the thermosetting
reinforced materials are the polyesters, epoxy, and the furane resins
as custom-made reinforced materials, and the phenolic and epoxy
resins as molded, filament wound, or extruded with reinforcement.
All these materials are available as piping, sheet stock, and mis-
cellaneous molded and fabricated items. These materials, particularly
polyvinyl chloride, polypropylene, and reinforced polyesters, are
now being used extensively for ventilating ductwork in handling
corrosive fumes: In many instances they have proved to be econom-
ically superior to metals such as stainless steel, lead, and galvanized
steel. Not only are these materials used for the ductwork but they
can be used to fabricate the scrubbers, pumps, blowers, fan wheels,
and virtually all the components of a system. They are generally
not subject to pitting, stress-corrosion cracking, and other forms
of corrosion common to metal. However, there are design limitations
and they usually cannot be substituted for metals part for part.
A point that should not be overlooked is that nonmetallics do not
require painting for protection against external corrosion. Plastic
materials are replacing metals in many applications because of their
better resistance to chemical exposures and improved service life
and economy.
The most chemically resistant plastic commercially available today
is tetrafluoroethylene (Teflon or Halon). This is a thermoplastic
material that is practically unaffected by all acids, alkalies, and
organics at temperatures up to about 260°C (500°F). It has proved
to be an outstanding material for gaskets, packing diaphragms,
O-rings, seals, and other relatively small molded items. Its chemical
inertness makes normal bonding and cementing operations difficult
and impractical. It can be cemented to metal and other materials
by using special sheets that have rough backing surfaces that pro-
vide mechanical adherence through any one of a number of resin
cements. Techniques have also been worked out that make it possible
to heat-seal sheets of material together. Loose linings, including
nozzle linings, may now be installed in tanks, ductwork, and other
straight-sided and nonintricate equipment.
Kynar, a chlorofluoroethylene, also possesses excellent chemical
resistance to almost all acids and alkalies at temperatures up to
about 180°C (350°F). It, too, is difficult to bond to itself and other
materials, but the use of tape-bonded laminated construction has
widened the use of the material. It can be extruded readily and
thus, is available in the form of solid pipe and also as a lining
material for steel pipe.
Polyethylene is the lowest-cost plastic that has excellent resistance
to a wide variety of chemicals. Its greatest use has been as piping
and tubing in corrosive services, but large quantities are also used
as thin sheet or film liners in drums or other packages. Polyethylene
tape with pressure-sensitive adhesives on one side is receiving
increasing attention and is used as a wrapping material to protect
conduit and pipe from corrosion. Unfortunately, its mechanical
properties are relatively poor, particularly at temperatures above
50°C (120°F), and it must, therefore, be supported for most appli-
cations. It can be readily joined to itself by heat-sealing and fusing,
and a wide variety of equipment has been satisfactorily made using
heat-sealing techniques. Weathering resistance of the unfilled grades
is poor, but the carbon-filled grades have good resistance to sun-
light and are satisfactory for outside use.
The unplasticized polyvinyl chloride materials have excellent

resistance to oxidizing acids, other than nitric and sulfuric, and
to nonoxidizing acids in all concentrations and are satisfactory for
use at temperatures up to about 65°C (150°F). They are also resist-
ant to both weak and strong alkaline materials and to solutions of
most chemical salts. The resistance to aromatic and aliphatic hydro-
carbons is generally good, but resistance to chlorinated hydrocarbons
is poor. They are not satisfactory for use with ketone or ester
solvents. They are self-extinguishing relative to flame resistance
and have been known to give off large volumes of smoke when
involved in a fire. They are resistant to sunlight and outdoor
weathering. Two general types are available, regular and high
impact. The latter has appreciably better impact resistance but
somewhat lower strength and lower overall chemical resistance.
Both are readily fabricated and can be joined by fusion and solvent-
welding techniques.
The styrene-synthetic rubber blend materials, which are a mixture
of styrene-acrylonitrile polymer and butadiene-acrylonitrile have
good resistance in nonoxidizing weak acids but are not satisfactory
for handling oxidizing acids. As with most common thermoplastic
materials, the upper useful temperature limit is about 65°C (150°F).
Resistance to strong alkaline solutions is fair, and to weak alkaline
chemical-salt solutions it is generally good. They are not satisfactory
for use with aromatic or chlorinated hydrocarbons, and they possess
only fair resistance to aliphatic hydrocarbons. They are not satisfac-
tory for use with ketone and ester solvents. These materials normally
will burn, but fire-retardant grades are commercially available.
Resistance to outdoor weathering is generally good. They can be
readily fabricated and can be joined with solvent-welding techniques.
The use of resin systems that are applied as liquids, reinforced,
and then converted to solids by catalytic action has increased tre-
mendously in the last 20 years. These include polyester resins
with the peroxide catalysts, epoxy resins with the basic amine
catalysts, and furane resins with acid catalysts. The nature of
furane resins is such that they are available only as a black material,
which sometimes limits their application. Polyester and epoxy materials
are available as translucent materials that can be pigmented to any
desired color. Epoxy resins have excellent resistance to nonoxidizing
and weak acids and to alkaline materials but poor resistance to
strong oxidizing acids. The upper temperature limit is generally
about 90°C (200°F). The epoxy resins also have resistance to aro-
matic and aliphatic hydrocarbons but have only fair resistance to
chlorinated hydrocarbons, ketones, and ester solvents. Polyester
resins have good resistance to nonoxidizing and oxidizing acids,
both weak and concentrated, with moderate resistance to many
alkaline solutions and excellent resistance to chemical salt solutions.
The upper temperature limit is again 90°C (200°F), although there

is a loss of physical properties at this high a temperature. Polyester
resins have good resistance to aromatic and aliphatic hydrocarbons
but only fair resistance to the strong solvents. The material will
burn, but fire-retardant grades, based on the addition of antimony
trioxide and the use of halogenated compounds in the manufacture
of the polyester resins, have been developed. Resistance to sunlight
and outdoor weathering is good. Overall resistance of the resin is
often improved for severe chemical services by the use of a chemi-
cally resistant synthetic-fiber cloth such as Orion acrylic fiber
or Dacron polyester fiber. The glass-fiber laminates are not satis-
factory for use in hydrofluoric acid, and it has been found that
they are subject to attack and penetration in other acids and alkalies,
including hydrochloric acid under certain conditions. Furane resins
have broad chemical resistance to acids and alkalies as well as to
many solvents. Otherwise, the material is similar to the epoxy and
polyester laminates.
Urethane resins, based on the isocyanate molecule, are finding
increasing use in maintenance engineering work, primarily as an
insulation material in the form of a foam and as an abrasion-resistant
material in the form of a compounded elastomer. Although urethane
foams have been made to meet certain requirements of the various
regulatory agencies (for flame retardance, extreme caution is recom-
mended in the use of these materials when the application require-
ments differ from the flammability characteristics. The insulation
properties are outstanding, as is the ease of fabrication, because
urethane foam can be applied as a mixture of two solutions, each
sprayed simultaneously onto a substrate. Other resins systems,
including the epoxy, can also be spray-applied to form a foam,
although their properties are somewhat different from those of the
urethane foam. Top coating of the urethane foam with a flame-
retardant coating is virtually requisite, along with the additional
protection given to the foam from ultraviolet degradation.
Rubber and Elastomers

Natural rubber has been used for many years as a material for
molded and lined equipment for chemical service. It can be com-
pounded for maximum resistance for a number of service conditions
and has proved to be a very useful material for many conditions
that are highly corrosive to metals. Natural rubber compounds will
resist a wide variety of chemical solutions, including all concentra-
tions of hydrochloric acid, phosphoric acid, sulfuric acid, up to
about 50% concentration; saturated salt solutions such as ferric
chloride, brine, bleaching solutions; and most plating solutions.
They are readily attacked by strong oxidizing acids, such as nitric

and chromic, and by aliphatic, aromatic, and chlorinated solvents.
The maximum temperature at which rubber compounds can be used
varies with the chemical and the strength of solutions. The tempera-
ture limitation for continuous exposure for most soft rubber com-
pounds is about 60°C (140°F) and that for hard rubber is about
80°C (180°F). However, heat-resisting compounds are available
that may be used at somewhat higher temperatures. Soft rubber,
especially compounded for maximum temperature resistance, may
be used for continuous exposures under some chemical conditions
up to 90°C (200°F), and hard rubber may be compounded for service
temperatures as high as 110°C (230°F).
A number of synthetic rubbers and elastomeric materials have
been developed with special characteristics that extend the overall
usefulness of the elastomers for corrosion-resistant equipment.
Notable among these are Buna S(GR-S), Buna N(GR-A), butyl
(GR-1), neoprene (GR-M), Hypalon (chlorosulfonated polyethylene),
and Thiokol compounds. In addition, polymers of ethylene and
propylene have been developed with elastomeric properties. Like
natural rubber, each of these may be compounded in several ways
to maximize resistance to specific chemical exposures. Natural rubber
and other elastomers are frequently used in combination with brick
linings for temperature conditions that are above that allowed for
elastomeric material alone; they have proved to be excellent membrane
linings for such construction.
Brick Linings
Brick-lining protection can be used for many conditions that are
severely corrosive even to high-alloy materials. It should be con-
sidered for tanks, vats, stacks, vessels, and similar equipment
items. Brick shapes commonly used for such construction are made
of carbon, red shale, or acid-proof refractory materials. Carbon
bricks are useful for handling alkaline conditions as well as acid,
whereas the shale and the acid-proof refractory materials are used
primarily for acid solutions. Carbon can also be used where sudden
temperature changes are involved that would cause spalling of the
other two materials. Red shale brick generally are not used at tem-
peratures above 150°C (300°F) because of poor spalling resistance.
Acid-proof refractories are sometimes used at temperatures up to
870°C (1600°F).
There are a number of cement materials that are regularly used
for brick-lined construction. The most commonly used are sulfur,
silicate-based, and resin-based. The resin cements include the
phenolic epoxy- and furane-resin-based materials, which are used
at temperatures up to 180°C (350°F). The carbon-filled phenolic

resin cements have excellent resistance to all nonoxidizing acids,
salts, and most other solvents. The carbon-filled furane resins
have excellent resistance to all nonoxidizing acids and alkalies,
salts, and organic solvents. The silica-filled resin compositions
are available in all types of resins and are almost equally resistant,
except to hydrofluoric acid and alkalies. Sulfur-based cements are
limited to a maximum temperature of about 90°C (200°F). In general,
they have excellent chemical resistance to nonoxidizing acids and
salts but are not suitable for use in the presence of alkalies or
organic solvents. The sodium silicate-based cements have good resist-
ance to all inorganic acids, except hydrofluoric, at temperatures
up to about 400°C (750°F). The potassium silicate-based cements
are useful at somewhat higher temperatures, the upper limit depend-
ing on specific conditions and requirements.
Concrete
Concrete is a construction material not usually used under severe
corrosive conditions other than as a substrate. For example, there
are tanks, vessels, and so on, whose shape and size make concrete
an economical material of construction, provided that there is a
barrier that separates the corrosive environment from the concrete.
Such a barrier sometimes is an elastomer or plastic sheet cemented
in place, and often it is a protective coating applied by spray or
trowel. For weathering atmospheres, concrete is protected against
abnormal deterioration by the use of either a clear penetrating
coating or a protective pigmented coating. The most common of
the clear penetrating coatings are the silicone resins, whereby
the water repellency of the silicone and the penetrating characteris-
tics of the vehicle prolong the life of the concrete. Because concrete
is inherently alkaline (until it has weathered and reacted with the
natural acids of the environment such as carbonic acid), it is neces-
sary to use an alkaline-resistant protective coating on new concrete.
Such materials include vinyls, chlorinated rubber, and epoxies.
Particularly not to be used on fresh concrete (unless acid-etched)
are the oil-based paints; the presence of free alkali in the concrete
will cause the oil base to saponify and possibly be removed by
rain or other weathering factors. The two major reasons for protect-
ing concrete are (1) appearance and (2) improved longevity based
on the fact that most concrete structures are reinforced, usually
with steel in one form or another. If the concrete is not dense or
is not protected, there is the possibility that moisture or other
chemicals will penetrate the surface; under conditions of severe
freezing and thawing the concrete will then spall, ultimately either
exposing the reinforcing steel or allowing the moisture and its con-
taminants to attack the reinforcing material. When steel is attacked

in a crevice condition, such as exists when reinforcing rod or mesh
is embedded in concrete, rust is formed, which results in an expan-
sion of force, further lifting the concrete and further exposing
the reinforcing material.
In building construction of reinforced concrete, it is necessary
to know whether the moisture has a driving force causing it to
go from outside the building into the inside or whether the conditions
inside the building are such in terms of moisture transmission and
moisture-vapor driving force, together with the temperature driving
force, to cause the moisture to go from the inside of the building
outward. In the latter, it is particularly requisite to have a breath-
ing coating such as a silicone, on the outside of the building because
nonbreathing mastic coating or other pigmented protective coating
will be lifted as the moisture vapor from the inside attempts to
reach the lower moisture potential on the outside.
The use of low-alloy, high-strength steel on certain highway
construction has caused some minor concern among engineers and
architects with regard to the reinforced concrete used as the piers
upon which the steel beams rest. The staining, aging, and weather-
ing of the steel have, in the absence of protective coating (which
is no longer required because of the good weathering corrosion
resistance of the steel), caused staining of the concrete piers.
One either makes the concrete less absorptive or uses a "pigmented"
concrete that blends with the rust from the steel.
Protective Coatings
Protective coatings are probably the most widely used and, at the
same time, the most controversial material employed for minimizing
corrosion of steel and certain other materials. Because of its impor-
tance, the subject of protective coating and painting is discussed
in a separate chapter (Chap. 17). It is important here to emphasize
that it is unwise, and generally uneconomical, to try to use steel
equipment with a chemically resistant coating for containing chemicals
that are quite corrosive to the steel. This results because it is
almost impossible to avoid some pinholes or holidays in the coating.
Rapid attack of the steel will occur at such points, and continued
maintenance attention will be required. This is the reason for the
more stringent requirements on coatings for continuous-immersion
service such as tank linings. Such requirements include thickness
(sometimes minimum and sometimes maximum), number of coats,
freedom from pinholes, and degree of cure.
The chemically resistant coatings, such as the baked phenolics,
baked epoxies, and the air-dried epoxy, vinyl, and neoprene coat-
ings, are ideal for minimizing contamination of chemicals handled
in steel equipment. They should not be used where 100% protection

from corrosion is required. An excellent material for immersion
service has been developed that consists of flakes of glass dispersed
in a polyester resin. This is applied by spray to a properly prepared
surface and the wet coating is rolled with a paint roller to orient
the glass flakes in a plane parallel to the substrate and to provide
maximum resistance to chemical attack.
Glass Linings
Glass-lined equipment is available from a chemically resistant stand-
point for handling all acids except hydrofluoric and concentrated
phosphoric acid (at ambient and elevated temperatures) and for
many alkaline conditions at ambient and slightly higher temperatures.
The glass lining is resistant to all concentrations of hydrochloric
acid at temperatures up to 150°C (300°F), to dilute concentrations
of sulfuric acid at their boiling points, to concentrated solutions
of B^SO^ up to about 230°C (450°F), and to all concentrations of
nitric acid up to their boiling point. An acid-resistant glass with
improved alkali resistance is commercially available for use under
alkaline conditions up to pH 12 at temperatures of 90°C (200°F).
Equipment items such as tanks, pressure vessels, and reactors,
pipelines, valves, and accessory equipment are available. Improved
resistance to impact has been developed for the glass linings.
Methods of field repair of glass linings have been developed that
include the use of cover plates and plugs of tantalum in combination
with resin cements and Teflon.
Wood
All woods are affected adversely by acids, particularly the strong

oxidizing acids, but they are regularly used in dilute hydrochloric
acid solutions at ambient temperature. Improved corrosion resistance
can be imparted to wood by impregnating the wood under pressure
conditions with certain resin solutions that include asphalt, phenolic,
and furane. This greatly extends the area of application of woods
in corrosion services. Strong alkaline solutions, particularly caustic,
generally cause disintegration and cannot be used with impregnated
wood. Weak solutions can be used with wood equipment with reason-
ably good service life.
Inhibitors
The corrosion of iron and other metals in aqueous solutions can fre-
quently be minimized or inhibited by the addition of soluble chromates,
phosphates, molybdates, silicates, and amines or other chemicals,

singly or in combination. Such materials are called inhibitors and
are generally attractive for use in recirculating systems or closed
systems. They are also used in neutral or very slightly acid solu-
tions. Sodium silicate has also been effectively used as a inhibitor
for aluminum in alkaline solutions. The concentration of an inhibitor
for maximum control depends on the solution, composition, tempera-
ture, velocity, metal system, and the presence of dissimilar metals
in contact in the solution. Care should be taken in the selection
and application of inhibitors because, in some instances, they can
cause increased localized attack.
Although chromate treatment is widely used, it does require
attention to keep concentration at the required minimum for specific
environmental conditions. In addition, there is the always danger
of pollution from loss of chromate to the surrounding environment.
One of the most common uses of inhibitors is in brine systems.
When calcium or sodium chloride brine is used in steel equipment,
it is generally recommended that sodium dichromate be used. When
chromates cannot be used, disodium phosphate is recommended for
sodium chloride brines. When aluminum equipment is used in service,
it is recommended that 1% as much sodium dichromate be used as
there is chloride present.
For recirculating-water systems made of steel, it has been found
that 0.2 ml of sodium silicate (40° Baume) per liter is effective in
inhibiting corrosion. Sodium dichromate at 0.01% concentration is
also effective and can be used where toxicity effects are not impor-
tant.
For preventing corrosion of steel in ferrous-based materials,
particularly in protecting machine parts and storage equipment,
the use of volatile (VL1) or vapor-phase (VPI) corrosion inhibitors
has been found to be effective. These materials are amine nitrite
salts. They can also be used to protect steel process equipment
when idle or in standby condition. These materials are also available
as crystals or as impregnated paper. The inhibitors are slightly
volatile at atmospheric temperature; the protection obtained results
from the diffusion and condensation of the vapors on the surface
of the items being protected.
Cathodic Protection
Fundamentally, cathodic protection is the use of an impressed current
to prevent or minimize the corrosion of metal by making the metal
a cathode in the system. The current is provided either by the
use of rectifiers or by sacrificial galvanic anodes. Graphite, titanium,
and high silicon iron are used as anodes in conjunction with recti-
fiers. The most commonly used sacrificial materials are magnesium,

zinc, and aluminum. Cathodic protection is recognized as a proved
method of control of corrosion of steel and other metals under many
environmental conditions. It has been used successfully for minimizing
corrosion of equipment such as buried pipeline, water storage tanks,
condensers, heat exchangers, and dock piling.
24
DESIGNING TO PREVENT CORROSION
INTRODUCTION
It is impossible to completely eliminate corrosion—but it is possible

to control the corrosion rate and, thereby, keep it within tolerable
limits. Many principles have already been discussed in the preceding
sections of this handbook, primarily dealing with material selection,
design considerations, and items relating specifically to each material
of construction. This chapter will deal with other aspects of the
prevention and the control of corrosion.
There are nine basic forms of corrosion that can take place,
which frequently can be prevented if the proper material selection
is made, or if appropriate design practices and specific in-plant
procedures are followed.
Uniform Corrosion
Uniform corrosion takes place uniformly over the surface of the
metal by means of a chemical/electrochemical reaction. Prevention
of this form of corrosion can be achieved by the use of the proper
construction material, by applying cathodic protection, by use of
inhibitors, or by the application of a suitable protective coating,
or combinations of these measures.
Intergranular Corrosion
Intergranular corrosion is a localized attack taking place at and
adjacent to grain boundaries. The grains themselves suffer relatively
639
640 Schweitzer
little corrosion. Carbide precipitation during welding operation per-

mits this attack to occur. Prevention can be accomplished if the
carbide precipitation is prevented. This is accomplished by use
of alloys with an extra-low carbon content, by use of stabilized
grades of alloys, or by specifying solution heat treatment followed
by a rapid quench, which will keep the carbides in solution.
Pitting
Perforations or holes develop on the metal surface as the result
of extremely severe localized or selective attack. The first step
to prevention lies in the proper material selection, followed by a
design that will prevent stagnation of material and alternate wetting
and drying of the surface. An increase in the stream velocity will
also help.
Crevice Corrosion
Shielded areas or crevices on metal surfaces are subject to attack
when exposed to corrodants. Prevention is accomplished by proper
design and operating procedures. Designs should be avoided that
contain tight crevices, sharp corners, or stagnant areas. Riveted
or bolted joints should be discarded in favor of fully penetrated,
butt-welded joints. Equipment should be drained and all deposits
thoroughly removed on a regular basis. Nonabsorbent gasketting
material should be used, and all wet packing material should be
removed during shutdown periods.
Galvanic Corrosion
When two dissimilar metals or alloys are immersed in a corrosive
or conductive solution, corrosion occurs as a result of the difference
in potential existing between the materials. Because the further
apart two metals are from each other in the galvanic series, the
greater is the rate of corrosion, it is wise when it is necessary
to use two dissimilar metals to select two that are relatively close
to each other in the galvanic series. Also, avoid having a small
anode area and large cathode area. This condition will accelerate
corrosion completely, also, insulate dissimilar metals from each other.
The use of inhibitors and coatings can also help, but be cautious
when using coatings because pinholes in the coating can lead to
unfavorable area effects (anode vs. cathode).
Erosion Corrosion
Erosion corrosion is the result of the relative movement between
a corrodant and the metal surface. Prevention can be accomplished
24. Designing to Prevent Corrosion 641
by selection of the proper materials of construction and by the

proper design, shape, and geometry of the equipment. The use
of coatings and cathodic protection can also help. Some relief can
be achieved as well by reducing stream velocities, filtering out
solids, changing temperatures, and aerating process streams.
Corrodant-Sensitive Cracking
There are two forms of this failure: stress-corrosion cracking and
hydrogen embrittlement.
Stress-corrosion cracking occurs at points of stress. Usually
the metal or alloy is virtually free of corrosion over most of its
surface, yet fine cracks penetrate through the surface at the points
of stress. Certain metals or alloys are subject to this type of attack
more than others in certain mediums; therefore, the proper selection
of materials of construction is essential. Installation techniques
should not induce any stresses into the material. Any stresses
induced during fabrication should be removed by an appropriate
stress-relieving operation. Avoid stagnant areas in the design and
use lower operating temperatures if possible. The use of inhibitors
and cathodic protection will also help.
Hydrogen embrittlement is the result of the penetration of hydro-
gen into the metal, causing a loss of ductility and tensile strength.
The proper material selection will help, as will the reduction of
hydrogen evolution by reducing the corrosion rate. Any procedure
that will reduce the amount of hydrogen present will prove beneficial.
Dezincifi cation
When one element in a solid alloy is removed by corrosion the process
is known as dezincification. The most common example is the removal
of zinc in brass alloys. Selection of the proper material of construc-
tion, reduction of the amount of oxygen present, and the use of
cathodic protection all are steps that can be taken.
Biological Corrosion
Corrosive conditions can be developed by living organisms as a
result of their influence on anodic and cathodic reactions. Because
this form of corrosion gives the appearance of pitting it is necessary
to first diagnose the presence of bacteria. Once established, preven-
tion can be achieved by selecting more resistant materials of construc-
tion or by the use of biocides. For some species of bacteria, a
change in pH will provide control.
642 Schweitzer
CORROSION UNDER INSULATION
Insulation is applied to vessels and piping as a means of conserving

heat or of providing personnel protection from hot surfaces. As
a result, the selection of a particular insulating material is normally
based on installed cost versus energy saved. However, there are
other costs associated with insulation that are generally overlooked—
namely, the cost of corrosion and maintenance.
Corrosion that takes place under the insulation can be caused
by the insulation itself or by improper application. If, after a period,
it is necessary to remove sections of insulation to make repairs on
the equipment, these costs and the cost of repairing the insulation
should be considered during the selection process.
Types of Corrosion Under Insulation

There are three types of corrosion that can take place under insula-
tion.
1. Alkaline or acidic corrosion

2. Chloride corrosion
3. Galvanic corrosion
Alkaline or acidic corrosion takes place as the result of either

acid or alkali being present in contact with moisture in the insulating
material. When these materials are applied to hot surfaces at tem-
peratures above 121°C (250°F), the water is driven off, but it
may condense at the edge of the insulation, dissolving any alkaline
or acidic materials present. This results in corrosion of aluminum
with certain alkaline waters.
Some insulating cements, before drying, contain alkaline chemicals
and water. During the drying operation these alkaline chemicals
will attack such metals as stainless steel, copper, brass, or alumi-
num. If the vessel being insulated is constructed of one of these
metals, it may be subject to corrosion. Under normal circumstances
steel would not be affected during the time required for the cement
to dry.
Foam insulations containing fire-retardant chemicals, such as
brominated or chlorinated compounds, can produce acidic solutions.
This has been found to be true with polyurethane and phenolic
foams.
Steps can be taken to prevent this type of corrosion. When
external corrosion of the jacket is a problem, a good all-weather
plastic jacket should be considered. If a metal jacket is to be used,
a moisture barrier should be installed on the inside of the insulation.
It goes without saying that all joints must be tightly sealed to pre-
vent external water from entering the insulation.
Care should be taken in selection of the insulating material.
Insulating cements are best mixed with clean potable water. The
use of distilled water will increase the aggressiveness of the attack.
Chloride corrosion results when the insulating material contains
leachable chlorides, temperatures are above 60°C (140°F), and the
substrate surface is a 300-series austenitic stainless steel. The
attack will usually be a typical stress-corrosion cracking. Corrosion
is propagated when water enters the insulation and diffuses inward
toward the hot surface, eventually finding a "dry" spot. Adjacent
to this dry spot will be found an area in which the pores of the
insulation are filled with a saturated salt solution—in which chlorides
may be present. As the vessel wall cools down, this saturated area
"moves" in to the metal wall. When the wall is reheated, it will
be temporarily in contact with the saturated salt solution and any
chlorides present. This will initiate stress-corrosion cracking.
The most efficient means of preventing chloride corrosion under
insulation is to use the proper insulating materials. Insulation that
meets ASTM C-795 or MIL-I-24244 specifications can safely be used
over 300-series stainless steels. Care must be taken, however,
to prevent chlorides in the atmosphere from impregnating the insula-
tion.
As with acidic or alkali corrosion, care must be taken when
installing the outer insulation jacket and barrier, making sure that
all joints are properly sealed.
Galvanic corrosion under insulation occurs when wet insulation,
that has an electrolyte salt present, allows a current to flow between
dissimilar metals—such as the insulated metal surface and outer
metal jacket or other metallic accessories. This can result in the
corroding of the metal jacket, or of the vessel, depending upon
which is the less-noble metal.
Galvanic corrosion can be prevented by using a cellular insulation
and applying a synthetic rubber or plastic jacket over the insulation.
Hypalon performs well in this application.
Summary
Corrosion under insulation can be prevented by taking into account
Insulation selection
Equipment design
Weather barriers
The type of insulation to be used will be dependent upon the appli-

cation, keeping in mind the types of corrosion that can occur.
644 Schweitzer
Equipment design also enters into the picture. Adequate insulation

supports should be provided and additional protection should be
considered where leakage or mechanical damage is possible. Additional
flashing should also be installed where spills or hosing down are
prevalent.
Weather barriers are a must because all corrosion under insulation
requires moisture of some kind. Therefore, it becomes a necessity
to make sure that all joints are properly sealed and that an adequate
weather barrier is installed.
STRUCTURES
Under the heading of structures are included many ancillary items

found in chemical-processing plants, waste-treatment facilities,
water-control plants, utilities, fertilizer plants, food-manufacturing
and processing plants, power plants, smelting and refining plants,
pharmaceutical plants, textile plants, and other miscellaneous facili-
ties. Included are such items as ladders, gratings, guard rails,
and support structures.
The general practice has been to use steel, galvanized iron,
or aluminum for these applications. Corrosion of these elements
has always been a problem that has resulted in high maintenance
and replacement costs.
Over the years much time and effort has been spent to provide
materials that will reduce or eliminate the problems of corrosion
for these applications. A result of these efforts has been the develop-
ment of glass-reinforced polyester and vinyl ester materials. There
are now available over 100 standard structural shapes from which
structures, platforms, supports, and decking can be fabricated.
It is also possible to have the finished product fabricated by the
manufacturers of the materials.
The advantage of these materials follow.
Three basic resins are used: isophthalic polyester, which is the
least expensive and is used in most general applications for which
it is not necessary for the material to have fire-retardant properties;
isophthalic polyester resin with a fire-retardant additive that has
the same general properties and area of application as the basic
isophthalic resin; and vinyl ester resin, which is the most expensive
but has the greatest corrosion resistance, superior strength, and
physical properties, and is also fire-retardant. Table 1 shows the
typical mechanical properties of the standard shapes using these
TABLE 1 Typical Mechanical Properties of Fiberglass-Reinforced Standard Shapes
Resin system
Mechanical Polyester Vinyl ester
5
Longitudinal direction <
ultimate tensile strength, psi 35,000 37,500 o
ultimate compressive strength, psi 40,000 45,000 13
ultimate flexural strength, psi 37,500 37,500
tensile modulus, psi x 106 3.0 3.0
compressive modulus, psi x 106 3.0 3.0
flexural modulus, psi x 106 2.0 2.0 O
ultimate shear strength, psi 6,000 7,000 o
ultimate bearing stress, psi 35,000 37,000 2
izod impact strength, (ASTM D-256) ft-lb/in. of notch CO
(sample thickness 1/8 in. except 1/4 in. for rod) 30 30 5

Traverse direction
ultimate tensile strength, psi 8,000 10,000
ultimate compressive strength, psi 17,500 20,000
ultimate flexural strength, psi 11,000 14,000
tensile modulus, psi x 106 1.0 1.0
compressive modulus, psi x 106 1.2 1.2
flexural modulus, psi x 106 1.0 1.0
ultimate sheer strength, psi 5,500 5,500
ultimate bearing stress, psi 30,000 30,000
izod impact strength, (ASTM D256) ft-lb/in. of notch 5 5
Bar col hardness 50 50
(continued)
Resin system
Mechanical Polyester Vinyl ester
Full section in bending

modulus of elasticity, psi x io 6 2.8 2.8
tensile strength, psi 25,000 25,000
compressive strength, psi 25,000 25,000
Electrical
electric strength, short-term in oil, 1/8 in (ASTM D-149) Vpm 200 225
electric strength, short-term in oil, kV/in.k 50 50
dielectric constant, 60 Hz (ASTM D-150)a 5.2 5.2
dissipation factor 60 Hz, (ASTM D-150)a 0.03 0.03
arc resistance (ASTM D-495), sec c 120 120
CO
Thermal o
thermal coefficient of expansion (ASTM D-696), in./(in.*°F) c 5 x 10~6 5 x 10"6
thermal conductivity, BTU/(ft2 h r ^ F - i n . " 1 ) 4 4
specific heat, BTU/db^F-in." 1 ) 0.28 0.28 CO
Other
24. Desigr\ing to Prevent Corrosion

density (ASTM D-792) lb/in c
solid shapes 0.065(S-525) 0.065(S-525)
hollow shapes 0.066(S-525) 0.066(S-525)
specific gravity (ASTM D-792)
solid shapes 1.80(S-525) 1.80(S-525)
hollow shapes 1.83(S-525) 1.83(S-525)
water absorption (24-hr immersion) (ASTM D-570)
max. % by wt 0.50 0.50
Flame-retardant properties (isophthalic polyester with flame-
retardant chemical additive)
flame resistance (FTMS 406-2023) ign/burn, sec 75/75 75/75
intermittent flame test (HLT-15) rating 100 100
flammability test (ASTM D-635)
average time of burning, sec; <5 <5
average extent of burning, mm 15 15
surface burning characteristics (ASTM E-84), max. 25 25
UL approved (yellow component card)
UL 94 flammability classification V-O V-O
temperature index, °C 130 130
a
Specimen tested perpendicular to laminate face.
^ l - i n . long specimen tested parallel to laminate face using 2-in. diameter electrodes.
c
Reported value measured in longitudinal direction.
648 Schweitzer
resins. Complete corrosion-resistant properties can be found in

Corrosion Resistance Tables, Second Edition published by Marcel-
Dekker, but in general these materials are resistant to most corrod-
ants found in the atmosphere and to a wide range of material that
may spill on the surfaces.
Nonconductive Materials
Nonconductive materials are excellent insulators and are neither
thermally nor electrically conductive. As a result, they are ideally
suited to be used for cable-trays, utility truck booms, ladders,
support structures for electrical devices and systems, and power
junction boxes.
High Strength Materials

On a pound-for-pound basis these fiber-reinforced plastic (FRP)
materials are stronger than steel. Shapes have been used to form
the superstructures of multistoried buildings and floating bridges.
Jointing is accomplished using fiberglass studs and nuts. The
threads are standardized to be compatible with metal studs. Table 2
shows typical mechanical properties of FRP studs.
Lightweight Materials
FRP structural shapes are easily transported, handled, and set
into place as a result of their light weight. They weigh 80% less
than a corresponding steel shape and 30% less than a corresponding
aluminum shape.
Dimensional Stability
Proper design does not permit these materials to sag or creep under
prolonged deformation or fatigue loading. Its coefficient of thermal
expansion is slightly less than that of steel but considerably less
than that of aluminum or wood.
Given the foregoing properties, use should be made of these
materials for structural supports and decking wherever atmospheric
or plant conditions promote corrosion.
Maintenance of these materials is greatly reduced over that of
their metallic counterparts. These shapes, handrails, deckings,
and such, are available in color, with the color completely penetrating
the material. This eliminates the need of periodic painting for pro-
tection or esthetic reasons.
TABLE 2 Typical Mechanical Properties of Fiberglass Studs
Size
Property 1/8-16 UNC 1/2-13 UNC 5/8-11 UNC 3/4-10 UNC 1-8 UNC
Thread shear strength using

fiberglass nut in tension, lb 1250 2200 3100 4500 6500
Traverse shear on double-
threaded rod—double shear i
TO
ASTM-B-565, load/lb 3000 5000 7500 12,000 22,000
Traverse shear on threaded o
rod-single shear, load/lb 1600 2600 3800 6200 15,000 o
CO
Compressive strength-
longitudinal ASTM D-695, psi 54,000 54,000 54,000 54,000 65,000
Flexural strength—
ASTM D-790, psi 55,000 55,000 55,000 55,000 60,000
Flexural modulus—
ASTM D-790, psi x 106 2.0 2.0 2.0 2.5 2.75
Torque strength using fiber-
glass nut lubricated with SAE
10w30 motor oil, ft/lb 8 18 35 50 110
Dielectric strength-
ASTM D-149, kV/in 35 35 35 35 35
(continued)
Size
Property 1/8-16 UNC 1/2-13 UNC 5/8-11 UNC 3/4-10 UNC 1-8 UNC
Water absorption, 24-hr

immersion-threaded—ASTM
D-570 - (90) 1 1 1 1 1
Coefficient of thermal
expansion—longitudinal,
in./(in.-°F) 5 x 1O~6 5 x 10"6 5 x 10"6 5 x 10~6 5 x 10"6
Max. recommended operating
temperature based on 50%
retention of ultimate thread
shear strength, °F/°C all 212/100
Stud weight, lb/ft 0.07 0.12 0.18 0.28 0.50
Notes:
Test results are for bolts with single nuts only.
Properties do not apply when fiberglass stud is used with metal nut.
o
CO
CO
Many applications can be found for these fiberglass-reinforced

resin systems. Typical uses to which they have been put include
Ladders
Support structures
Operating platforms
Pipe supports
Cable trays
Enclosures
Handrails
Walkways
Roof supports and decking
Stairs
Initial purchase cost may be slightly higher than that for steel,
but the final installed cost, including maintenance costs, makes
the total installation highly competitive with less expensive materials.
INSTRUMENT ROOMS
Within the areas of chemical-processing plants, papermills, steel

mills, oil refineries, power plants, sewage-treatment facilities, and
other similar installations, various corrosive fumes are generated.
Most of the newer plants maintain control rooms, electric motor
control centers, and computer centers under a slight positive pres-
sure with makeup air being introduced from the outside. In many
instances, it is possible for this air to be contaminated with corrosive
gases such as mercaptans, sulfur oxides, chlorine, hydrogen sulfide,
chlorine, chlorine dioxide, hydrogen chloride, and others. These
gases can cause serious damage to sensitive circuitry found in com-
puters, microprocessors, microswitches, and other delicate electronic
equipment. If corrosive gases are removed from these make-up
streams, costly maintenance and downtime can be prevented.
The removal of these gases and particulate materials from the
makeup air stream is, therefore, strongly advised. It can be accom-
plished by treating incoming air streams in the following manner:
1. Install a filter, with a rating of approximately 25-35% ASHRAE,

on the fan inlet.
2. On the discharge side of the fan, pass the air through an acti-
vated carbon bed, making sure that the carbon bed is designed
to remove the particular gases or vapors that are present.
3. After the carbon bed, pass the treated air through a final filter
to remove micron size particulates.
652 Schweitzer
Many older control rooms and electric motor control centers cannot
be maintained under a positive pressure because of air leakage and
the inability to limit access. Under these conditions an installation,
similar to the aforementioned, can be incorporated on a recirculating
and makeup air system.
When these systems are designed, care must be taken in selection
of the construction materials for the various components and to
make sure that they are compatible with the corrodants to be en-
countered. Installations of this type will greatly reduce maintenance
costs and down time on control equipment and electrical components.
ELECTRICAL COMPONENTS
The common practice in most industrial plants is to use galvanized

iron or aluminum conduit and enclosures for the electrical distribution
systems. These materials are often subject to corrosive attack from
materials present in the local atmosphere.
To overcome this attack, the selection of alternative materials
can be considered. Included under this category are such items as
PVC-coated conduit and enclosures

FRP enclosures
Stainless steel enclosures
Hazardous operating areas require the use of seals at appropriate

points in the installation. These seals prevent hazardous fumes
from entering the enclosure (motor starter, disconnect switch, motor,
etc.). In nonhazardous areas, the use of these seals will prevent
corrosive fumes or vapors from entering the enclosures and, thus,
reduce corrosion of the working parts.
Enclosures and conduits should also be located such that free
drainage can occur and that places in which water and dirt can
accumulate are eliminated, thus helping to prevent corrosion. In
general, the recommended design practices found in Chapter 2,
Atmospheric Corrosion, should be followed for the electrical installa-
tion.
Index
Acoustic emission testing, [Aluminum alloys, compatibility

572-573 with]
Acrylate-butadiene rubber, 448 food, 180-181
Adsorption layers, 25 waters, 179-180
Alclad products, 170 Aluminum bronze, 136-149
Aluminum, 32 Aluminum coatings, 68
chemical nature of, 160-161 Aramid fibers, 355
Aluminum alloys, 153-186 Atmospheric corrodants, 28-29
corrosion, electrochemical Atmospheric corrosion, 23-32,
aspects, 162-165 58-59
corrosion, exfoliation, 175-176 Atmospheric types, 24
corrosion, other types, 176- Austenitic stainless steels,
177 69-76
corrosion resistance, general, chemical composition, 71-72
154-160 corrosion resistance, 76
galvanic relations, 165-168 mechanical properties, 70-75
reduction of ions of other physical properties, 73-74
metals, 167-168
stress corrosion cracking,
170-173 Barrier coatings, 14
and tempers, 173-175 Blistering, 16-17
tensile properties, 156-157 Bonded titanium, 210-211
weathering, 178-179 Boroscopes, 579-580
Aluminum alloys, compatability Brasses, 132-133
with Brick, chemical-resistant,
chemicals, 181-183 523, 633-634
653
654 Index
Bronzes, 133-149 Cements, 521-531

Butyl rubber, 431-432 Ceramic materials, 395-427
carbides, 414-415
carbon materials, 413-414,
C-glass, 351 421-423
Cadmium coating, 66 fundamentals of corrosion,
Carbon fiber, 354 395-398
Carbon steel, 29-30, 53-68 glassy materials, 408-413,
atmospheric corrosion, 58-59 420-421
general resistance, 59-60 nitrides, 414-415
Case hardening, 58 polycrystalline materials,
Cast alloys, 283-322 398-408, 417-420
aluminum, 311 Chlorides, 29
carbon and low alloy steels, Chlorosulfonated polyethylene
285-287 rubber, 437-438
copper-based, 307-311 Chrominizing, 68
iron-carbon alloys, 285 Clad steels, 60-63
magnesium, 316 Coatings, 453-489
nickel-based, 303-307 acrylics, 474
stainless steels, 292-303 chlorinated rubber, 473-474
titanium, 311-313 epoxies, 475-477
zirconium, 313-315 polyesters, 479-481
Cast aluminum, 311 system selection, 471-483
Cast copper-based alloys, 307- urethanes, 477-479
311 vinyls, 472-473
Cast irons, 287-292 water-soluble, 482-483
Cast magnesium alloys, 316 zinc-rich, 483-485
Cast nickel-based alloys, 303- Coating application, 485-489
307 Composite laminates, 359-360
Cast stainless steels, 292-303 Concentration cells, 10
Cast titanium, 311-313 Concrete, 634-635
Cast zirconium, 313-315 Copper, 32, 125-152
Casting design, 316-318 alloys, high-copper, 131-132
Casting quality, 318-320 chemical composition, 129
Cathodic protection, 14-15, 33- corrosion resistance, 126-
45, 637-638 127
anode materials and backfill, Copper alloys, 132-151
42 copper-aluminum, 136-149
anode requirements, 37-40 copper-nickel, 149-151
current requirements, 41 copper-tin, 134-136
method of application, 36-41 copper-zinc, 132-133
sacrificial anodes, 37 Corrosion coupons, 590-604,
testing for completeness of 570-572
protection, 42-44 data recording, 601
theory, 34-36 evaluation of results, 601
use with coatings, 40-41 specialized tests, 602-604
Index 655
[Corrosion coupons] [Duplex stainless steels]

specimen cleaning, 600-601 mechanical properties, 82-84
specimen holders, 591-597 physical properties, 83
specimen preparation, 590-591 Dust, 27
test conditions, 597-600 Dynel, 355
Corrosion inhibitors, 47-51
inhibitor evaluation, 50
organic inhibitors, 49-50 E-glass, 351
passivation inhibitors, 48-49 ECTFE, 450-451
precipitation inhibitors, 50 Eddy current inspection, 573-
Corrosion monitoring, 547-586 577, 589
glossary, 583-585 Effect of alloying elements on
off-stream monitoring equip- the properties of steel,
ment, 573-581 56-58
on-stream monitoring equip- Elastomeric linings, 536-538
ment, 548-573 butyl rubber, 537
polymer-coated metals, 580- chlorosulfonated polyethylene,
582 538
Corrosion testing techniques, hypalon, 538
587-618 isoprene, 537
dimension change, 587-589 natural rubber, 537
electrical resistance, 606-609 neoprene, 537
hydrogen diffusion, 604-606 perfluoroelastomers, 538
polarization curves, 609-616 Elastomers, 429-452; 632-633
weight change, 590-604 acrylate-butadiene, 448
Corrosion, types of, 2, 628, butyl rubber, 431-432
639-641 chlorosulfonated polyethylene,
Corrosion under insulation, 437-438
642-644 ECTFE, 450-451
ETFE, 451
ethylene-acrylic elastomer,
Designing to prevent corrosion, 445-446
639-652 ethylene-propylene rubber,
corrosion under insulation, 446-447
642-644 FEP, 450
electrical components, 652 Halar, 450-451
FRP structures, 644-651 hypalon, 437-438
instrument rooms, 651-652 isoprene, 431
types of corrosion, 639-641 natural rubber, 430-431
Dew, 26 NBR nitrile, 436
Dissimilar metal corrosion, 5-9 neoprene, 434-436
Drawing, 56 nylon, 448-449
Duplex stainless steels, 82-85 perfluoroelastomers, 443-445
chemical composition, 83 polybutadiene rubber, 440
corrosion resistance, 84-85 polyester elastomer, 442-443
656 Index
[Elastomers] Galvanic corrosion, 5-9

polyetherimide, 449 Galvanic series, 7-8
polysulfide, 438-439 Galvanizing, 66
PTFE, 449-450 General rusting, 18-19
SBR styrene, 433-434 Glass fibers, 412
SBS, 432 Glass lining, 636
SEBS, 432-433 Glass materials, 408-413, 420-
silicone rubbers, 439-440 421
styrene-butadiene-styrene, Grounding plastic systems,
432 368-373
styrene-ethylene-butylene-
styrene, 432-433
Tefzel, 450 Halar, 450-451
urethane rubbers, 440-442 Hardening, 55
Electrical resistance principle Hastelloy alloy:
(corrosion monitoring), B-2, 98-103
548-552, 606-609 C-4, 115-116
Electrochemical corrosion, 3-5 C-22, 116-117
Electrolyte, 5 C-276, 113-115
Engineering materials and weak- G, 107-109
nesses, 625 G-3, 109
Epoxies, 335-336 G-30, 110-111
ETFE, 451 H-9M, 111-112
Ethylene-acrylic elastomer, 445- S, 117-119
446 X, 109-110
Ethylene-propylene rubber, Haynes alloy 214, 122
446-447 Haynes alloy 230, 122-123
Exfoliation corrosion, 175-176 Haynes alloy 556, 119-120
Explosion cladding, 63, 210 Heat-treating operations, 55-
56
Hydrogen diffusion, 556-559,
Factors affecting atmospheric 604-605
corrosion, 25-28 Hydrogen sulfide, 29
FEP, 450 Hydrogen test probe, 556-559,
Ferritic stainless steels, 79-81 604-605
chemical composition, 80 Hypalon, 437-438
corrosion resistance, 81
mechanical properties, 81
physical properties, 80 Incoloy alloy 800, 104-105
Fluor el, 444 Incoloy alloy 825, 105-106
Fluoroplastics, 333 Inconel alloy 600, 103-104
Fog, 27 Inconel alloy 625, 112-113
FRP structures, 644-651 Inconel alloy 690, 106
Furans, 336-337 Industrial paints, 462-467
Index 657
Infrared thermography, 570 Mechanism of corrosion, 2-3

Inhibitors, corrosion, 47-51; Membranes, 523
636-637 Metallic corrosion, 1-22
Insulation, corrosion under, Metallic protective coatings,
642-644 63-68
Isoprene, 431 Mortars, 521-531
application, 527-528
epoxy resin, 527
Kalrez, 444 furan resin, 526
Kel-F, 444 phenolic resin, 526
polyester, 527
potassium silicate, 525
Laminate surfacing systems, 352 silica, 525
Lead coatings, 65 silicate, air-drying, 524
Linear polarization principle sodium silicate, chemical-
(corrosion monitoring), setting, 524
552-556, 606-619 sulfur, 526
Linings, liquid-applied, 491- vinyl ester, 527
520
Linings, monolithic, 528-530
Linings, plastic, 378-380 Natural rubber, 430-431, 632
Linings, sheet, 533-545 NBR nitrile, 436
causes of failure, 543-545 Neoprene, 434-436
elastomeric linings, 536-538 Nickel, 95
shell preparation, 535 Nickel and high-nickel alloys,
surface preparation, 535 89-125
testing, 536 chemical composition, 91-92
thermoplastic linings, 538-543 mechanical properties, 94
Liquid penetrant inspection, physical properties, 93
578 Nickel-chromium-iron, 103-106
Loose lining, 61 Nickel-chromium-iron-
Low-alloy steel, 53-68 molybdenum, 106-112
Nickel-chromium-molybdenu,
112-119
Magnetic particle inspection, Nickel coatings, 64-65
578 Nickel-copper alloys, 96-98
Martensitic stainless steels, Nickel-molybdenum alloys,
76-79 98-103
chemical composition, 77 NOX, 28-29
corrosion resistance, 79 Nonfibrous enhancers for
mechanical properties, 76-79 plastics, 355-359
physical properties, 78 Normalizing, 55
Masonry, corrosion resistant, Nylon, 448-449
522
658 Index
Off-stream corrosion monitoring Patenting, 56

equipment, 573-581 Patina, 126
horoscopes, 579-580 Perfluoroelastomers, 443-445
eddy current inspection, 573- pH instrument, 570
577 Phase layers, 26
liquid penetrant inspection, Phenolics, 337-338
578 Phosphating, 60
magnetic particle inspection, Pitting, 9-11, 19-20, 164-165
578 Plastic families, 328-347, 629-
miscellaneous equipment, 581 632
On-stream corrosion monitoring thermoplasts, 328-334
equipment, 548-573 thermosets, 330-347
acoustic emission testing, Plastic materials, 323-393
572-573 causes of failure, 360-368
corrosion coupons, 570-572 grounding (electrical), 368-
electrical resistance principle, 373
548-552 nondestructive testing, 380-
hydrogen test probe, 556-559 383
infrared thermography, 570 sandwich construction, 383-
linear polarization principle, 384
552-556 service and use, 347-350
pH instrument, 570 Plastic piping systems, design
radiography, 568-570 checkpoints, 375-376
ultrasonic testing, 559-568 Plastics, chemical attack, 360-
Oxygen, 29 365
Plastic tanks, design check-
points, 376-378
Paint application, 485-489 Polarization curves, 609-616
Paint components, 461-470 Polybutadiene rubber, 440
additives, 468-470 Polycarbonate, 332
pigment, 461 Polycrystalline ceramic mate-
resin, 461, 468 rials, 398-408, 417-420
solvents, 468 Polyester elastomers, 442-443
solvent classes, 469 Polyester resins, 338-390
Painting cost, 457 bisphenol, 343-344
Painting systems, 455 brominated, 344-345
Paints, 453-489 chlorinated, 344-345
acrylics, 474 general-purpose, 338-340
chlorinated rubber, 473-474 high-performance, 339-342
epoxies, 475-477 isophthalic 338-339
polyester, 479-481 Polyethylene, 328
system selection, 477-479 Polymeric tank linings, 496-
vinyls, 472-473 498
water-soluble emulsions, 482- Polyphenylene, 331
483 Polypropylene, 330-331
zinc-rich, 483-485 Polysulfide rubbers, 438-439
Index 659
Polytetrafluoroethylene, 449-450 Spherodizing, 36

Polyurethane, 347 Spot rusting, 16-17
Polyvinyl polymers, 331-332 Stages of corrosion, 16-22
Preventing corrosion, 11-13 Stainless steels, 69-88
Process annealing, 55 austenitic, 69-76
Protective coatings, 16, 635-636 clean-up procedures, 87-88
ferritic, 79-81
iron contamination, 85-86
Quenching, 55 martensitic, 76
organic contamination, 86
preparation for service,
Radiography, 568-570 85-88
Rain, 26 welding contamination, 86-87
Reinforcement (plastics), 351- Structure of steel, 53-55
355 Styrene-butadiene-styrene
Resistance cladding, 61-62 rubber, 432
Roll cladding, 62-63, 210-211 Styrene-ethylene-butylene-
Rubber, 430-431, 632 styrene rubber, 432-433
S-glass, 353 Tank linings (liquid-applied),

Sacrificial anodes, 37 491-520
Sacrificial coatings, 13-14 application, 500-502, 506-511
SBR styrene, 433-434 coating selection, 494-495,
SBS, 432 499
SEBS, 432-433 criteria, 492-493
Selecting Materials of construc- inspection, 503-506, 508-511
tion, 619-638 polymeric linings, 496-498
brick linings, 633-634 service preparations, 499-
cathodic protection, 627-628 500
concrete, 634-635 tank design, 493-494, 514-
corrosion consideration, 624- 519
626 Tantalum, 213-229
determining corrosion resistant alloys, 215
properties, 626-628 corrosion resistance, 220-225
elastomers, 632-633 deep-drawing, 224
glass lining, 636 fabrication, 225-227
inhibitors, 636-637 forming, 228
plastics, 629-632 machining, 227-228
principles, 619-623 manufacture, 214-215
rubber, 632 mechanical properties, 216-
strength/weight ratio, 623 219
wood, 636 physical properties, 219
Silicone rubbers, 439-440 quality descriptions, 215
SO X , 28 spinning, 228
660 Index
Tefzel, 451 [Titanium]

Temperature, 27 types of corrosion, 2, 639-
Tempering, 56 641
Terne plate, 66-68
Thermal spraying, 62
Thermoplastic alloys, 333 Ultrasonic testing, 559-568,
Thermoplastic fibers, 333-334 587-588
Thermoplastic linings, 538-543 Urethane rubbers, 440-442
chlorinated poly vinyl chloride,
541
CPVC, 541 Vinyl ester resins, 345-347
ECTFE, 543 Viton, 444
ETFE, 543
FEP, 543
Halar, 543 Weathering, aluminum, 178-179
Kynar, 541-542 Weathering, steels, 30-31
polyethylene, 542 Weld bonding, 211
polypropylene, 542 Weld overlayment, 62
polyvinyl chloride (PVC), 541 Wood, 636
polyvinylidene fluoride
(PVDF), 541-542
tetrafluoroethylene (PTFE), Zinc, 31-32
542 Zinc coatings, 66
Thiokol ST, 438 Zirconium, 231-281
Tin coatings, 66-68 corrosion protection, 263-267
Tinplate, 66-68 corrosion resistance, 240-260
Titanium, 187-212 crevice corrosion, 263
alloys, 187-189 fabrication practices, 270-
bonded titanium, 210-211 275
corrosion resistance, 194-207 fretting, 261
corrosion resistance, effect galvanic corrosion, 262
of inhibitors, 206 physical and mechanical
hydrogen embrittlement, 208- properties, 232-240
209 pitting, 260
mechanical properties, 189-190 stress corrosion cracking,
physical properties, 190-194 261
stress corrosion cracking, typical applications, 267-270
208 Zirconium products, 275-277

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Corrosion and

1. Corrosion Protection Handbook, Second Edition, Revised and Expanded,

Additional Volumes in Preparation

Philip A. Schweitzer, PE.

MARCEL DEKKER, INC. N E W YORK • BASEL

Copyright © 1989 by MARCEL DEKKER, INC. All Rights Reserved

Neither this book nor any part may be reproduced or transmitted in

MARCEL DEKKER, INC.

Current printing (last digit):

As in the first edition, theory is only touched on to provide a

Philip A. Schweitzer, P.E.

1. Solve existing corrosion problems

Based on the areas covered and the practical approach established,

Philip A. Schweitzer, P.E.

Preface to the Second Edition iii

1. FUNDAMENTALS AND PREVENTION OF

Philip A. Schweitzer, P.E.

General Factors Affecting Atmospheric Corrosion 25

5. CARBON STEEL AND LOW-ALLOY STEEL 53

General Corrosion Resistance 59

7. NICKEL AND HIGH NICKEL ALLOYS 89

8. COPPER AND COPPER ALLOYS 125

High Copper Alloys 132

9. ALUMINUM ALLOYS 153

10. TITANIUM 187

11. TANTALUM 213

12. ZIRCONIUM 231

13. CAST ALLOYS 283

Stainless Steels 292

14. DEVELOPMENT AND APPLICATION OF

Introduction and History 323

15. DEVELOPMENT AND APPLICATION OF

Fundamentals of Corrosion 395

16. DEVELOPMENT AND APPLICATION OF ELASTOMERS 429

17. COATINGS 453

18. LIQUID-APPLIED LININGS 491

19. CEMENTS AND MORTARS 521

20. SHEET LININGS 533

Philip A. Schweitzer, P.E.

General Considerations 533

Shell Preparation 535

21. CORROSION MONITORING 547

22. CORROSION-TESTING TECHNIQUES 587

23. SELECTING MATERIALS OF CONSTRUCTION 619

24. DESIGNING TO PREVENT CORROSION 639

Charles G. Arnold Dow Chemical Company, Texas Division, Free-

Ronald A. McCauley Department of Ceramic Engineering, Rutgers,

DEAN M. BERGER Berger Associates, Inc., Leola, Pennsylvania

Corrosion is defined as a gradual wearing away or alteration by a

they are expected to survive for long periods without protection.

Corrosion in metals, whether in the atmosphere, underwater, or

Uniform Corrosion fatigue

Water readily dissolves a small amount of oxygen from the atmos-

In addition, oxygen will usually be present as a depolarizing

Anode (metal 1) Cathode (metal 2 )

Reduction reaction occurs

Current flow through

FIGURE 1 Simple cell showing components necessary for corrosion.

If the metallic conductor were replaced with a voltmeter, a difference

presence of contaminants such as sulfur compounds and salt particles.

Technical Definition of an Electrolyte

1. 4Fe -> 4Fe2+ + 8e

According to a number of investigations, the most stable form

The Galvanic Series of Metals guide provides details of how the