Supplement To Corrosion Tests and Standards Application ASTM

Hibner | Hack | Scully
EDWARD L. HIBNER is a Metallurgical and Corrosion consultant. He was

most recently with Haynes International as a Senior Metallurgical Consultant
and prior to that a Code Manager at Special Metals Corporation, formerly
Inco Alloys International, in Huntington, West Virginia. He received his BS
in Chemistry from Marshall University and in Metallurgy from the University
of Cincinnati. He is the recipient of the ASTM Award of Merit, the ASTM
Committee G01 Francis L. LaQue Memorial Award, the ASTM Committee
G01 Certificate of Appreciation, and the NACE Fellow Award, and is currently
Vice-Chairman and the Editorial Review Chairman of ASTM Committee G01
on Corrosion of Metals. He has served as Chairman and as Trustee of the
West Virginia Section of NACE International and is currently serving on the
NACE MR0175/ ISO 15156 Maintenance Panel. He has extensive experience ASTM INTERNATIONAL
in alloy development for chemical process, flue gas desulfurization, marine, Helping our world work better
and oil field applications. He has written widely on materials applications and
corrosion topics in these fields and has four patents and 60 publications. In
Supplement to
Application and Interpretation: Second Edition

Supplement to Corrosion Tests and Standards:
addition to ASTM International, he is a member of the International Desalination
Association, the Society for Petroleum Engineers, ASME International, SAE
International, NACE International, and the Naval Submarine League.
Corrosion Tests and
HARVEY P. HACK Dr. Hack is a Northrop Grumman Fellow for Northrop
Grumman Corporation, where he does materials selection and corrosion Standards: Application
and Interpretation:
control for underwater vehicles and systems for the Department of Defense.
He received his B.S. and M.S. from Carnegie-Mellon University, and his Ph.D.
in Metallurgy from The Pennsylvania State University. He is the recipient of
Second Edition
the ASTM International Award of Merit and is past Chairman of the Board of
Directors of ASTM International. Dr. Hack has received the Distinguished
Service Award from NACE International (now AMPP), the Francis L. LaQue
Memorial Award from ASTM Committee G-1 on Corrosion of Metals, and the
Francis L. LaQue Award from the Sea Horse Institute. He is a Past President
of NACE International, a NACE Corrosion Specialist, Cathodic Protection
Specialist, and Coatings Inspector, a Fellow of NACE International, ASTM
International, the Washington Academy of Sciences, and the Institute of
Corrosion in the United Kingdom. Dr. Hack was the Associate Editor for the
Edward L. Hibner,
Materials Performance and Characterization section of the Journal of ASTM
International (JAI) and is a past President of the Council of Engineering and
Harvey P. Hack, and
Scientific Specialty Boards. Dr. Hack has approximately 100 publications and John R. Scully, Editors
is the author, editor, or major contributor to five books.
JOHN R. SCULLY received his B.S, M.S., and Ph.D. in Materials Science
and Engineering from Johns Hopkins University. While pursuing his Ph.D.,
he worked at David Taylor Naval Ship R&D Center in Annapolis, Maryland
in the Marine Corrosion Branch. He then joined Sandia National Laboratory
after a term as a Visiting Scientist at AT&T Bell Laboratories. In 1990, he
joined the faculty of the Department of Materials Science and Engineering
at the University of Virginia and is now the Charles Henderson Chaired
Professor of Materials Science and Engineering, Department Chair of MSE
and co-directs the Center for Electrochemical Science and Engineering.
He is the technical editor of CORROSION. Professor Scully has received
numerous awards for corrosion research and education of the next
generation of corrosion professionals. Professor Scully has published over
300 technical papers, given invited talks around the world, and edited
several books on corrosion.
www.astm.org
ISBN: 978-0-8031-7134-3
Stock #: MNL20-2ND-SUP
ISBN-EB: 978-0-8031-7135-0
Stock #: MNL20-2ND-SUP-EB
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Edward L. Hibner, Harvey P. Hack, and John R. Scully, Editors
Supplement to Corrosion Tests

and Standards: Application and
Interpretation: Second Edition
ASTM Stock Number: MNL20-2ND-SUP
ASTM International
100 Barr Harbor Drive
PO Box C700
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Printed in the U.S.A.
Library of Congress Cataloging-in-Publication Data
Names: Hibner, Edward L., editor. | Hack, Harvey P., editor. | Scully, John
R., 1958- editor.
Title: Supplement to corrosion tests and standards : application and
interpretation / Edward L. Hibner, Harvey P. Hack, John R. Scully,
editors.
Other titles: Corrosion tests and standards.
Description: Second edition. | West Conshohocken, PA : ASTM International,
2021. | “ASTM Stock Number: MNL 20-2ND-SUP.” | Summary: “There is a
variety of accelerated exposure tests that have been developed to aid
engineers in material selection for corrosion resistance. ASTM tests are
probably the most widely used tests for localized corrosion resistance.
Thus, an understanding of them can be of great importance in analyzing
the results of testing performed in other labs or by manufacturers”–
Provided by publisher.
Identifiers: LCCN 2021025326 (print) | LCCN 2021025327 (ebook) | ISBN
9780803171343 (paperback) | ISBN 9780803171350 (ebook)
Subjects: LCSH: Corrosion and anti-corrosives–Testing.
Classification: LCC TA462 .C666 2021 Suppl. (print) | LCC TA462 (ebook) |
DDC 620.1/1223–dc23
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ASTM Stock Number: MNL20-2ND-SUP

DOI: 10.1520/MNL20-2ND-SUP-EB
ASTM International is not responsible, as a body, for the statements and opinions advanced in the publication. ASTM International does not endorse any
products represented in this publication.
Printed in Hanover, PA
October, 2022
iii
Foreword
THIS PUBLICATION, Supplement to Corrosion Tests and Standards: Application and Interpreta-
tion: Second Edition, was sponsored by ASTM Committee G01 on Corrosion of Metals and edited
by Edward L. Hibner, Special Metals Corporation, Harvey P. Hack, Northrup Grumman Corporation,
and John R. Scully, University of Virginia. This publication is a supplement to MNL20-2ND of
ASTM’s manual series.
v
Contents
Preface vii
Types of Corrosion
1 Pitting 1
Robert G. Kelly, Ryan M. Katona, and Eric J. Schindelholz
2 Crevice Corrosion 15
Mariano Iannuzzi, Edgar Hornus, and Mobin Salasi
3 Galvanic 41
Harvey P. Hack, Carol Glover, and Jason Lee
4 Hydrogen Damage 59
Kevin Nibur and Brian Somerday
5 Microbiological Effects 73
Jason S. Lee and Brenda J. Little
6 Tribocorrosion 81
Jeremy L. Gilbert
Analysis, Testing, and Environments
7 Metallographic Analysis 93
William L. Mankins
8 Electrochemical Tests 109

John R. Scully, Carol F. Glover, and Raymond J. Santucci
9 Immersion Testing 141

Bradley D. Krantz
10 Atmospheric 153
Sheldon W. Dean, Jr.
11 Standards and Practices on Corrosion under Insulation 169

John P. Ludman and Bert J. Moniz
12 Freshwater 179
Walter T. Young
13 Seawater 187
David A. Shifler
vi Contents
14 Soils 217
Mike Horton, Lucien Veleva, and Edward Escalante
15 Petroleum Chemistry 241

K. Daniel Efird
16 Organic Liquids 251

C. Sean Brossia
Materials and Applications
17 Titanium 265
Ronald W. Schutz
18 Corrosion Testing of Nonmetallic Coatings 283

William L. Mankins
19 Metal-Matrix Composites 291

L. H. Hihara
20 Water Handling Systems 315

Walter Young
21 Pipeline 325
Abdelmounam M. El-Sherik
22 Highways, Tunnels, and Bridges 345

Stephen R. Sharp and Jason T. Provines
23 Automotive 359
Niamh Hosking
24 Commercial Aircraft 385

Edward L. Colvin
25 Military Aircraft and Associated Equipment 393

Diane Buhrmaster and Nicholas Wilson
26 Industrial Chemicals: Manufacture and Usage 399

Sheldon W. Dean, Jr.
27 Flue Gas Desulfurization 409

James R. Crum and Ralph W. Ross
28 Nuclear Power 419

Barry M. Gordon and George J. Licina
29 Food and Beverage 429

Dipak Negandhi
Index 435
vii
Preface
Corrosion continues to be a problem of worldwide importance, the revisions. In other cases, new authors have been chosen, or
costing roughly 3% of the gross domestic product of any coun- the editors performed that task. In still other cases, the technol-
try for which data is available. This supplement has been pre- ogy described in the chapters has not changed sufficiently
pared to address updates to the technology that addresses since the last edition for those chapters to need updating, in
this form of degradation. Corrosion is often neglected but it which cases those chapters have not been included in this sup-
not only seriously impacts our economy, but also jeopardizes plement. Users of the manual will find that chapters in this
human health and safety, wastes valuable resources, and supplement plus those not revised from the previous edition
impedes technological progress. The most important factors in are an invaluable and instructive tool, as well as a sourcebook
addressing corrosion and its control are: (1) recognizing and on how to conduct corrosion tests, interpret results, and use
understanding the mechanisms, (2) developing solutions to standards.
the problems, and (3) implementing those solutions. Corrosion The supplement to the manual is the result of a massive
tests and standards are very significant in addressing each of effort of planning, writing, reviewing, editing, production, and
these factors. Therefore, this manual includes guidelines for marketing. It would not have been possible without the out-
recognizing types of corrosion as well as fundamentals of test- standing efforts of the ASTM staff and the valuable and compe-
ing and provides the tools required for making calculations, tent work of the editors and more than four hundred experts in
interpretations, and correlations. It serves as a sourcebook of the field that donated their time as authors and reviewers. They
procedures, equipment, and standards used in testing. represent industrial, educational, industrial, and government
The editor and section editors have coordinated this update organizations, and their contributions are greatly appreciated.
so that the most recent technologies are included in each sec-
tion. In some cases, the original authors of chapters have made Edward L. Hibner
Types of Corrosion
1
Chapter 1 | Pitting
Robert G. Kelly,1 Ryan M. Katona,1,2 and Eric J. Schindelholz3
Introduction limitations. The first section describes coupon exposure testing, and
the second section describes electrochemical testing.
Pitting corrosion occurs when discrete areas of a material undergo
rapid attack, although the vast majority of the surface remains vir-
tually unaffected. This morphology is in sharp contrast to uniform
Coupon Testing
corrosion in which all parts of the exposed surface recede at The exposure of test coupons to corrosive solutions to evaluate
approximately the same rate. Essentially, all metals and alloys localized corrosion resistance has a long and successful history.
undergo pitting corrosion under some set of experimental condi- The materials of interest are typically machined into coupon
tions, although the relative susceptibility varies widely. The basic form before being measured, cleaned, weighed, and exposed to
requirement for pitting is the existence of a passive state for the the corrosive medium. After a set period of time, the coupons
material in the environment of interest. Pitting occurs when por- are removed; the surfaces are carefully cleaned and evaluated for
tions of the metal surface lose their passivity and dissolve rapidly. attack. General requirements and information on coupon testing
This loss of passivity often occurs at heterogeneities in the surface can be found elsewhere in this manual as well as in other sour-
(either physical or chemical). Pitting of a given material depends ces.5,6 ASTM G1, Standard Practice for Preparing, Cleaning, and
strongly on the presence of an aggressive species in the environ- Evaluating Corrosion Test Specimens, describes the details of the
ment and a sufficiently oxidizing potential (e.g., Cl- ion in neutral, preparation of test coupons. ASTM G4, Standard Guide for Con-
aerated aqueous solution for Type 304 stainless steel). Many ducting Corrosion Tests in Field Applications, details related
metal–environment combinations can lead to pitting, as exten- information on the performance of such tests in plant equipment
sively reviewed by Szlarska-Smialowska,1 Frankel,2 and more under operating conditions. The advantages of properly con-
recently by Soltis.3 Additionally, a new framework has been pro- ducted coupon testing include the fact that actual process
posed by Frankel, Li, and Scully.4 In many situations, pitting can streams can be used, a large number of coupons can be exposed
severely limit the performance of the material. simultaneously, and various forms of corrosion can be detected.
Testing for localized corrosion resistance usually aims at meet- Disadvantages include the inability to monitor the time depen-
ing one (or more) of four general goals: (1) alloy ranking for selec- dence of the corrosion process and the long exposure times usu-
tion or development; (2) failure analysis; (3) determination of the ally required to characterize both the initiation period and the
effects of changes in process parameters; and (4) prediction of pene- propagation rate.
tration rates. Of the four, the last is by far the most difficult to
accomplish, but it is also the most important in many cases. This
COUPON PREPARATION AND ANALYSES
chapter discusses the different types of tests that have been devel-
Because detailed information on coupon testing is available else-
oped for pitting corrosion. The physical and chemical basis for each
where, this section focuses on the aspects of such testing that are
test is described, as are some of the practical applications and
specific to the evaluation of pitting corrosion. When performing
1
coupon exposures, it is important to include alloys whose corro-
Dept. of Materials Science and Engineering, University of Virginia, P.O. Box
sion behavior in the environment of interest is well characterized
400745, 295 McCormick Rd., Charlottesville, VA 22904, USA R. G. K. http://
orcid.org/0000-0002-7354-0978, R. M. K. http://orcid.org/0000-0001-9158- and reproducible to serve as an internal standard. This protocol
4651 is of particular importance when localized corrosion is studied.
2
Sandia National Laboratories, 1515 Eubank Blvd. SE, Albuquerque, NM 87123, USA Because pitting has a stochastic nature, the use of these
http://orcid.org/0000-0002-8809-9230 “controls” increases the confidence with which final material
3
Dept. of Materials Science and Engineering, The Ohio State University, Columbus,
selection choices are made. If the control materials behave as
Ohio 43210, USA
The authors acknowledge the previous author of this chapter, Robert G. Kelly, expected, it is probable that the results for the other materials
University of Virginia, Charlottesville, VA. will reflect typical behavior for the environment of interest.
DOI: 10.1520/MNL202NDSUP20190041
Copyright VC 2022 by ASTM International, 100 Barr Harbor Dr., PO Box C700, West Conshohocken, PA 19428-2959
ASTM International is not responsible, as a body, for the statements and opinions expressed in this chapter. ASTM International does not endorse any products represented in this chapter.
2 Supplement to Corrosion Tests and Standards, 2nd Edition
Although mass loss characterizes the rate of uniform corro- experimenter should not feel bound by the structures of the
sion well, such measurements can be extremely misleading for ASTM standards if the experimenter can justify that by changing
pitting corrosion. Badly pitted specimens can exhibit negligible the procedure, more relevant information can be gained. Note,
weight loss if the attack is extremely localized. In fact, the more a however, that these ASTM tests are probably the most widely
given amount of attack is localized, the more severe the pitting used tests for localized corrosion resistance. Thus, an under-
problem. ASTM G46, Standard Guide for the Examination and standing of them can be of great importance in analyzing the
Evaluation of Pitting Corrosion, describes different methodolo- results of testing performed in other labs or by manufacturers.
gies used to evaluate pitting corrosion attack. Visual attack of
both cross sections and plane views of pitted specimens can be
ASTM G48, Standard Test Methods for Pitting and Crevice
ranked as shown in the standard. Pit density (number/cm2) is
Corrosion Resistance of Stainless Steels and Related Alloys by
important, but pit depth measurement is often the most directly
the Use of Ferric Chloride Solution
applicable measurement.7 Values for both average pit size and
This test involves exposure of the material to a highly oxidizing,
for the deepest pit observed are useful. To quantitatively evaluate
highly acidic, concentrated metal chloride solution. In essence, it
the depth of attack, a variety of measurement methods can be
is an attempt to simulate very roughly the composition of the
used, including depth gages, metallographic examination of cross
environment within a localized corrosion site in a stainless steel.
sections, or change in the focus plane on a metallurgical micro-
Briefly, a material is exposed to a 10 wt% ferric chloride (FeCl3)
scope, depending on the size of the pits. Direct measurement of
solution for a relatively short time (24–72 h) at either ambient or
pit depth using optical profilometry is attractive in that pit
elevated (usually 50 C) temperature. At the end of the test, the
depths and distributions can be obtained rapidly. All line-of-sight
sample is examined for weight loss and localized attack (see
methods are unable to detect and characterize undercutting pits
ASTM G46 for a recommended practice for evaluating the extent
(i.e., those with “ink-bottle” shapes or those with lacy covers8).
of pitting corrosion). If pitting and crevice corrosion are of con-
The pitting factor (PF) is the ratio of the average of the 10 deep-
cern, artificial crevices can be applied by the use of polytetra-
est observed pits to the average metal penetration by uniform
fluoroethylene (PTFE) blocks held tightly to the sample surface
dissolution, with higher values indicating a greater susceptibility
by rubber bands (see ASTM G48). Ferric chloride exposure is
to pitting. Statistical methods also have been applied to the eval-
commonly used to assess the corrosion resistance of stainless
uation of pitting corrosion (see ASTM G16, Standard Guide for
steel weldments (typically per ASTM G48, method A).
Applying Statistics to Analyses of Corrosion Data, and Shibata
The basic concept behind this test is the application of a
and Takeyama9 and Aziz and Godard10). In terms of predictive
high potential using a chemical potentiostat in an acidic, concen-
capability, the use of extreme value statistics is attractive.10 Plot-
trated chloride solution. The ferric salt forms an Fe3þ/Fe2þ redox
ting the measured maximum pit depths for a large number of
couple with a potential of approximately þ0.45 V(SCE). The
small samples has been used to estimate the probability that a pit
high concentration of ferric ion allows the couple to provide a
of a specific depth will occur under the same conditions for a
large current without an appreciable change in potential
larger area.
(approaching an ideally nonpolarizable electrode). The cathodic
reaction (reduction of ferric to ferrous ion) occurs on the boldly
EXPOSURE ENVIRONMENTS exposed passive surface of the material under test. Thus, the
Two general types of environments are used in coupon testing redox couple serves the role of the chemical potentiostat. The
for pitting corrosion: those that simulate service conditions and high potential in turn nearly guarantees that the pitting potential
those that seek to accelerate the pitting process. Tests in simu- will be exceeded, especially in such a concentrated Cl- solution
lated (or actual) service environments are extremely valuable due (and even more so if the test temperature is raised to 50 C).
to their direct applicability.11,12 Because time is often of the The low pH of the solution (typically about 1.3) inhibits repassi-
essence, the long exposure times required usually limit the use of vation and lowers the stability of the passive film. Thus, the
such tests to (1) confirmation of decisions made on the basis of FeCl3 test is a test of the resistance of an alloy to propagation
accelerated laboratory tests, and (2) corrosion monitoring. The of localized corrosion for most alloys, because their pitting
aim of testing in accelerating environments is usually alloy rank- potentials are well below þ0.45 V(SCE). More highly alloyed
ing or screening. Thus, little information is gained on the materials can resist initiation in this solution, however, the time
expected rate of attack in the actual application. The relative sus- of the test can be extended to a period of many days or to the
ceptibility of different alloy compositions or the effects of heat increased temperature.
treatments, welding, or other processing can be assessed rapidly This popular test does have a number of limitations. Few
and quantitatively. industries operate in 10 wt% FeCl3. Thus, the relation of the
A variety of accelerated exposure tests have been developed results of this test to material performance in real service envi-
to aid engineers in material selection for corrosion resistance. ronments that are profoundly different is questionable, and in
This section reviews some of those that are useful for localized fact, reversals in alloy ranking can occur. For nickel-base materi-
corrosion resistance. In addition to a brief description of the test, als, the use of a ferric ion solution is also of questionable value.
the scientific reasoning behind it is presented, along with com- Despite these limitations, the FeCl3 test will continue to be an
ments concerning the limits of its applicability and alterations to important tool in alloy development and screening for historical,
improve the utility of the test for a specific application. An if for no other, reasons.
PITTING 3
The FeCl3 test details can be modified and still fall within limited solubility in water, oxygen reduction is usually under
the spirit of the requirements of the published method. The mixed or is fully diffusion controlled for most alloys, particularly
exposure time and temperature can be altered, as can the surface those undergoing stable pitting. The thin electrolyte layer present
finish. As mentioned, surface finish can have important impact during wet/dry cycling increases the rate of delivery of oxygen to
on the localized corrosion behavior. For example, it can affect the surface by reducing the diffusion boundary layer thickness
the geometry of occluded sites and, in some cases, it can alter the from about 0.08 cm,15 which is characteristic of a stagnant solu-
surface area for cathodic reactions. Thus, it is important that the tion, to the thickness of the solution layer, which is often
surface finish be chosen with care to simulate the expected con- between 25 and 100 microns.16 In addition, the concentration of
ditions of the application. aggressive ionic species increases dramatically during drying
periods to the point of saturation.
ASTM B117, Standard Practice for Operating Salt Spray (Fog) Although reams of salt spray data exist, their use must be
Apparatus, and ASTM G85, Standard Practice for Modified approached with care. As with FeCl3, few industries actually
Salt Spray (Fog) Testing operate in continuous salt spray (coastal regions and ships being
Probably the most widely used test for pitting resistance is salt notable exceptions). A number of industries have found that the
spray. ASTM B117, Standard Practice for Operating Salt Spray standard salt spray testing not only fails to reproduce the damage
(Fog) Apparatus, describes the experimental arrangements to be observed in service but also is not particularly accelerating. Thus,
used and mandates the use of 5 wt% sodium chloride (NaCl) at a the auto industry has developed a more complicated cyclic test,
slightly elevated temperature (35 C). The test chamber allows including an increase in the number of test intervals, known as
the solution to be sprayed within its confines, creating a salt fog GM 9540.17 The reasons for the discrepancies between service
environment around the coupons. Such a constantly moist, salty experience and these laboratory tests are not clear, and users of
environment is quite aggressive. the test should bear them in mind.
ASTM G85, Standard Practice for Modified Salt Spray (Fog)
Testing, describes modifications to ASTM B117 involving a variety Coupon Exposures after Salt Loading
of solution chemistries and exposure regimens that can be used, As salt spray environments often do not to reproduce damage
including acetic acid-NaCl solution, acidified synthetic sea water, morphologies and rates seen in-service on alloys, coupon expo-
NaCl solution with SO2 gas added, and a 0.05% NaCl þ 0.35% sures under controlled relative humidity and temperature with a
ammonium sulfate [(NH4)2SO4] solution. In addition, a variety known loading density of salt have been used more recently.
of cycles (wet/dry) are described that have been found to be Multiple methods are used to deposit known salt-loading densi-
more aggressive than the constant moisture of ASTM B117. In ties on the surface of the alloys, including a mixture of ethanol
general, a spraying period is followed by a longer time at high and saturated salt solutions18–20 and inkjet printing.21–23 When
relative humidity during which the sample can partially dry. using ethanol, a whitish layer is seen on the surface of the alloy
Standards such as ASTM G85, however, lack a quantitative speci- and the error in loading density is within 2 lg/cm2.20 When a
fication for relative humidity during dwell periods, which can be salt printer is used, the deposition of the salt is much more precise,
strongly affected by the type of test chamber used. Because rela- as seen in figure 1, with an error in loading of 60.1 lg/cm2.22
tive humidity controls both equilibrium salt concentration as In both cases, the type of salt and corresponding loading
well as water layer thickness, localized corrosion rates as well as density can be changed to match the environment of interest.
corrosion damage morphology also will be affected by relative After printing, the samples are put into controlled environments
humidity levels.13,14 for the desired time of exposure. Akin to ASTM G85, cycles of
This cyclic type of exposure represents a more aggressive relative humidity can be included in testing to mimic atmo-
condition for most alloys than does constant, full immersion. spheric conditions. In general, these exposure tests have a smaller
Although still the subject of some debate, the generally accepted water-layer thickness than accelerated tests in ASTM standards
explanation involves the increased kinetics for oxygen reduction and have the possibility to increase the diffusive flux of oxygen
within the thin electrolyte layer that is present. Because of its to the surface.
FIG. 1 (A) printed droplet pattern on steel coupon, (B) detail of droplet pattern immediately after printing, and (C) detail of crystal pattern
immediately after printing.
Droplet Exposures stabilization as a parameter to quantify pitting resistance. That

Along with controlled deposition of salt-loading density, pitting said, such changes must be introduced with care to ensure that
can be studied under the small defined droplets of salt solutions. the mechanism of attack in the accelerated test is the same as
Micro-pipettes are used to place a small amount of liquid (on the that in the actual service environment. Decreased time required
order of microliters) onto the surface of an alloy and result in a for the testing should be balanced against the decreasing rele-
droplet with a diameter in the range of a few millimeters. After vance of the results, and the consequential increase in the uncer-
deposition, the samples can be placed under relative humidity tainty in their interpretation. In addition, results from
and temperature control and left for a period of time.24,25 Electro- accelerated tests are useful for material selection, but not for life
chemical measurements can be made inside the droplets using prediction, as no means currently available can connect the rates
micro-electrodes to gain insight into the localized corrosion proof pitting corrosion observed in these tests to other environ-
cess in thin electrolyte layers.26 The size and concentration of the ments. This situation can be contrasted with crack growth testing
salt in the drop is highly dependent upon the relative humidity for which the similitude of the stress intensity factor, K, has been
in which the coupon is exposed in and can affect pitting that is repeatedly demonstrated. This similitude allows results from lab-
seen on the surface.25 The droplet can change size and volume oratory scale test samples to be applied to service structures if
through exposures or experimentation, and further affect the the stress and flaw size and shape are known.
results.26 This needs to be considered when interpreting experi-
mental results. A further consideration of droplet testing is the
effect of the area for cathodic reduction reactions. When electro- Electrochemical Tests
chemical reactions are occurring under the droplet, both the
The main advantage of electrochemical testing is the opportunity
anode and the cathode must be contained in the droplet and
to investigate corrosion phenomena in the solution of interest
thus can affect results from exposure testing.
rather than in a (possibly) more aggressive and (probably) less
relevant environment. In addition, a great deal of information
ASTM G69, Standard Test Method for Measurement of can be gained about the dependence of the phenomena on exter-
Corrosion Potentials of Aluminum Alloys nal variables in a short time. Finally, the determination of critical
Aluminum alloys are highly susceptible to localized corrosion, potentials for initiation and propagation of localized corrosion
including pitting. For many years, ASTM G69, Standard Test can be useful in design decisions. For example, the use of mixed
Method for Measurement of Corrosion Potentials of Aluminum potential theory can allow for prediction of the protection (either
Alloys, has been used to determine the so-called solution poten- anodic or cathodic) criteria, as well as provide information on
tial of aluminum (Al) alloys. The test solution described in the galvanic couples to avoid.
ASTM G69 is a strongly oxidizing, near-neutral pH chloride
solution. The oxidizing power originates in the 3 g/L (0.09 M) SPECIMEN MOUNTING
hydrogen peroxide that is added. In the 1 M NaCl, virtually all One of the main challenges associated with electrochemical test-
precipitation-hardened Al alloys will undergo stable pitting. The ing for localized corrosion resistance is sample mounting. It can
solution potential measurement is made over a period of 1 h. It be extremely difficult to mount a sample with an insulated elec-
represents a mixed potential between the passive portions of the trical contact and a controlled exposed surface area without
surface on which peroxide reduction is occurring and the pitting introducing a crevice at the sample or mount interface. Because
sites. Thus, the potential depends on (1) the cathodic kinetics of crevice corrosion will occur at lower potentials than pitting, the
peroxide reduction, (2) the pit dissolution kinetics, and (3) the sample invariably begins to be attacked at the crevice, leading to
number and size of the pits. As these characteristics vary from an underestimation of the resistance of the sample to pitting.
alloy to alloy as well as with time, quantitative interpretation of Some may argue that for the same reason, this type of testing is
the solution potential is challenging. Mixed potential theory can not overly conservative, as in service, one wants to know the
be used to demonstrate that the solution potential cannot be potential at which any localized corrosion can occur, not just pit-
used to rank the resistance of Al alloys to stable pitting. Nonethe- ting. The flaw in this argument is that most crevices formed dur-
less, it has been used as a type of quality control test to probe ing sample preparation are not reproducible either in position or
batch-to-batch variations within a given alloy. This solution is geometry, making comparisons extremely difficult. In addition,
also specified in ASTM G110, Standard Practice for Evaluating there may be applications in which crevice corrosion is not the
Intergranular Corrosion Resistance of Heat Treatable Aluminum failure mode of concern, but pitting is. Such testing with crevices
Alloys by Immersion in Sodium Chloride þ Hydrogen Peroxide present would lead one to choose a more resistant (and therefore
Solution. more expensive) alloy than one actually would need.
A number of suggested solutions have been made for sam-
ALTERATION OF TEST METHODS ple mounting, including the use of “knife-edge” Teflon washers,27
When considering how to accelerate a test, the two most com- various mounting compounds and procedures,28 the use of wire
monly applied methods are to increase the temperature and/or loops,29 and flag geometries.30 One experimental design even
increase the concentration of aggressive species (e.g., Cl or Hþ). includes a crevice area that is continually washed with deionized
Either can be effective, and some of the electrochemical tests water.31 All of these solution have limitations, and one must choose
described next use the strong temperature dependence of pit the most appropriate method for the particular alloy-environment
PITTING 5
combination. The knife-edge PTFE washer, in combination with solutions, it has been proven to be successful over typical flat cell
what has been known as the Stern-Makrides assembly (fig. 2), has mounting techniques in limited applications.
been used successfully in a number of applications in which a tight The cell designed by Ovarfort31,35 uses a slow flow (4 mL/min)
seal can be formed, which (1) prevents ingress of any electrolyte, or of deionized water into the creviced area to prevent the accumu-
(2) causes the voltage drop into the crevice to be so high as to pre- lation of dissolution products inside the occluded area, the
vent any polarization of the creviced surface away from Ecorr. hydrolysis of which leads to crevice corrosion. The design has
Because the latter is unlikely to occur, the prevention of ingress is been applied successfully to the study of the pitting of a wide
critical. This prevention of solution ingress is closely related to the variety of stainless steels at both ambient and elevated tempera-
quality of the surface finish both in terms of its fineness (i.e., final ture.31,35 This cell, however, can be used only for flat samples. In
polishing step particle size) and its uniformity. One large scratch addition, one must be careful to ensure that the deionized water
can allow capillary action to draw an electrolyte into an otherwise- flow is uniform throughout the crevice. If a dead spot were to
impervious crevice and start the crevice corrosion initiation pro- develop, crevice corrosion likely would be initiated. Details of the
cess. This is the prime reason for the failings of this type of cell can be found in Annex X2 of ASTM G150, Standard Test
approach. In addition, because of the cost of the PTFE washers, Method for Electrochemical Critical Pitting Temperature Testing
many experimenters tend to try to reuse them. After the knife edge of Stainless Steels and Related Alloys.
is deformed once, however, it will not form a watertight seal again, One example of the effect of crevices is shown in figure 3 for
thus allowing crevice corrosion to occur. a 18Cr-8Ni stainless steel in a solution in which propagating
Other methods also have been used to prevent crevice cor- crevice corrosion will not occur (1 N sulfuric acid [H2SO4]).28 In
rosion with varying levels of success. Electroplaters tape can be this case, the higher passive current densities are observed for
used as a standalone method32,33 or in combination with a gasket the insulating materials that perform poorly. In a Cl- containing
or PTFE washer. Without the presence of the electroplaters tape, solution, this would translate into a lower Ebd. As can be seen
crevice corrosion would occur, whereas when masked with tape, from figure 3, some mounting materials perform well in this
crevice corrosion was not present. This was signified by a higher solution, although note that these results cannot be extrapolated
breakdown potential when an anodic polarization was applied in to other solutions. For example, the alkyd-varnish is used in elec-
taped samples compared with non-taped samples.32 Other lac- troplating to mask off areas that should not be plated. Although
quers and epoxies also have been used widely to mask off certain it works well in acid solutions, it performs poorly in neutral or
areas; however, detailing all types of masks used is beyond the
scope of this work. More recently, when a sample has a rough
finish, such as printed additively manufactured alloys, quick set-
ting epoxy can be used as a masking technique. In such applica- FIG. 3 Polarization curves of stainless steel in 1N sulfuric acid
tions, the epoxy fills rough features present on the surface and using different specimen mounting methods: (1) Stern-
helps prevent solution ingress.34 Although this method has not Makrides compression gasket, (2) heat-cured epoxy,
been extensively tested across multiple materials systems and (3) alkyd-varnish, (4) phenol-formaldehyde,
28
(5) polymethyl methacrylate, and (6) cold-cured epoxy.
FIG. 2 Stern-Makrides electrode assembly: (A) glass tub that

protects threaded steel rod from solution, (B) PTFE
gasket, and (C) specimen. For more details, see ASTM G5,
Standard Reference Test Method for Making
Potentiodynamic Anodic Polarization Measurements.
basic solutions, especially on materials with passive films, such as individual phases, such as those on duplex steals, and different
stainless steel. regions of the alloy.41 As with many of the newly developed tech-
If mounting cannot be accomplished, three other niques, limited validation is present in literature, and it is impor-
approaches can be used. The first is the use of a wire loop elec- tant to understand the effects that advanced techniques have on
trode, as shown in figure 4A. Stockert, Hunkeler, and Bohni29 the underlying physical and chemical structure of the material
have used this approach to study pitting without the complica- through all processing cycles.
tions of crevice corrosion. This approach works extremely well if
one can get the material in wire form, but there is always the
CYCLIC POLARIZATION
concern of metallurgical differences between material in wire
By far, the most common electrochemical test for localized cor-
form and that in plate or tube form, which are more likely to be
rosion resistance is cyclic polarization. ASTM G61, Standard Test
used in engineering applications. A related approach is the use of
Method for Conducting Cyclic Potentiodynamic Polarization
a flag electrode configuration, as shown in figure 4B. This works
Measurements for Localized Corrosion Susceptibility of Iron-,
well with plate material by minimizing the shaft size and thereby
Nickel-, or Cobalt-Based Alloys, has been developed to allow
minimizing any effects of the waterline. If localized corrosion at
experimenters to test their equipment and procedures on sys-
the waterline continues to be a problem, deaeration of the solu-
tems that are well characterized. The potential is scanned from
tion and the air space above it can be of help. When deaerating,
Ecorr (or slightly below it) in the anodic direction until localized
a baffle should be placed between the sample and the bubbler to
corrosion initiates as indicated by a large increase in the mea-
prevent oscillations of the waterline. Note that flag electrodes can
sured current density. At this point, the direction of the scan is
suffer edge attack that is not indicative of the behavior of the flat
reversed, and the current decreases until it changes polarity (i.e.,
surface. Thus, post-test inspection of the location of the attack
becomes cathodic). Representative scans are shown in figure 5
and careful interpretation of the results are important, as is the
for Type 304 SS and Hastelloy C-276. Conventional wisdom
case for all electrochemical testing.
states that Ebd (the breakdown potential) is the potential above
Suter and Bohni36 developed a third approach to delineation
which stable pits are initiated, whereas Erp (the repassivation
of the surface area of interest. By using a microcapillary attached
potential) is the potential below which pits repassivate. The
to a conventional optical microscope, they were able to define
breakdown potential is usually defined as the potential at which
small areas of stainless steel surfaces and generate polarization
there is a large increase in the measured current, whereas the
curves. The area probed is defined by the diameter of the capil-
repassivation potential is the potential on the reverse scan at
lary with results demonstrated for capillaries between 2 and
which the measured anodic current becomes zero (i.e., the cur-
1,000 microns.37 The cell is of particular use when the behavior
rent changes polarity). Thus, the higher the value of Ebd, the
of a particular microstructural feature is of interest,38–40 as the
more resistant is the alloy to the initiation of localized attack.
design allows the matrix contribution to be minimized. Another
The higher Erp, the more easily the alloy can repassivate. At
method used to probe local areas on an alloy surface was devel-
potentials between Ebd and Erp, sites that have initiated can prop-
oped by Policastro et al. in which selective masking by photoli-
agate. On the basis of this argument, one would favor an alloy
thography was used to make electrochemical measurements on
that had both a high Ebd and a high Erp.
Examples of the range of data that can be expected are
shown in the standard. The scatter in the data is apparent, espe-
FIG. 4 (A) Wire loop configuration for electrochemical testing, cially in the forward scan. This scatter points out the statistical
and (B) flag electrode configuration for electrochemical nature of the nucleation of pitting. The average Ebd of Type 304
testing. SS was found to be approximately þ0.15 V(SCE), whereas the
average Erp was found to be approximately -0.21 V(SCE). The
reverse scans are much more reproducible, because the local
chemistry controls the repassivation. Another example of the
inherent scatter in Ebd is shown in figure 6 for three variants of
Type 304 SS in 1,000 ppm NaCl.42 The large variation in Ebd arises
despite the fact that all of the samples of each type were from the
same heat of material and were tested under identical conditions.
Numerous attempts have been made to use the amount of
hysteresis in the cyclic scan as a measure of localized corrosion
susceptibility, with varying degrees of success. In this approach,
the larger the hysteresis, the more likely a localized corrosion site
will propagate once initiated. In the presence of a well-defined
crevice, a good correlation has been found and the relative crev-
ice corrosion susceptibility of alloys can be obtained. Wilde43
demonstrated this for Hastelloy C, Inconel 825, and Carpenter
20Cb3 in seawater where the amount of hysteresis correlated
well with the amount of weight loss (because of crevice
PITTING 7
FIG. 5 Representative cyclic potentiodynamic polarization curves (ASTM G61). The average Ebd for Type 304SS was approximately þ0.15
VSCE while the average Erp was approximately -0.21 VSCE.
specimens tested. An example of the differences that one can

FIG. 6 Cumulative probability distributions of pitting breakdown observe is shown in figure 7. In the absence of crevices, the Fe-
potentials for three Type 304 stainless steels in 1,000 ppm 30Cr-3Mo alloy performs well in 1 M NaCl, with a high Ebd
NaCl with different sulfur contents: high sulfur (h) and a small hysteresis. Microscopic examination showed the
42
commercial purity (~), and high purity (*). attack occurred only at the grain boundaries. When a crevice
was intentionally applied, the alloy performed poorly. The pos-
sible problems in comparing one specimen that had a crevice
with another that did not are obvious; incorrect conclusions
concerning the relative resistance of two materials could easily
be reached. Independent of the mounting method used, one
should always examine the specimen for localized attack after
the test is completed. At a minimum, a microscopic examina-
tion of likely creviced areas should be performed. Some samples
should be broken out of their mounts for more thorough
examination.
Although the interpretation of breakdown and repassivation
potentials remains controversial, progress toward a consensus is
being made. The large scatter in the breakdown potential is
thought to be due to the sensitivity of pit initiation to the initial
conditions. Its dependence on scan rate is most likely the result
of the time dependence of the localized corrosion site chemistry
corrosion) in a two-year exposure to seawater. There is not a development. In addition, it is now generally accepted that
linear correlation, however, so local penetration rates could not corrosion-resistant designs should not use Ebd as the important
be predicted, but the test has been used successfully for alloy parameter, but should use the appropriate value of Erp, because
selection. In studies that have attempted to explore the relative this is the potential below which pits should repassivate. Under
pitting susceptibility of alloys, it has been found that compari- these circumstances, the determination of the proper value of Erp
sons are valid only if no crevices are present on any of the becomes the focus.
Type 317L, their results indicate the convergence of Ebd and Erp at
FIG. 7 Cyclic polarization curve for Fe-30Cr-3Mo alloy in a single potential of þ0.2 V(SCE). This “unique potential” can be
dearated 1 M NaCl for specimens (a) without a crevice (), interpreted as the potential below which the smallest pit will nei-
43
with a crevice (~). ther initiate nor grow. Quantifying the size of the “smallest” pit
remains an important task. This work is important support for the
hope of eventually developing quantitative, engineering-relevant
criteria for material selection against pitting.
One of the historical controversies with regard to Erp as a
“material property” are the results of Wilde43 in which the repassi-
vation potential was shown to depend to some extent on the
amount of localized dissolution that has been allowed to occur,
and, therefore, depends on both the scan rate and the current at
which the scan is reversed. The more attack that has been allowed
to occur, the more negative is the Erp. Other data on stainless
steels, however, show a limiting value for large pits (0.05- to 0.5-
mm deep),45,46 complementing the work of Thompson and Syr-
ett,44 in which a limiting value also was found for small pits.
Despite these problems, polarization testing is useful for com-
paring alloys with respect to propagation of localized corrosion,
although its use gives little information on the initiation time that
is necessary for accurate lifetime prediction. One alloy may have
Thompson and Syrett44 attempted to address the problem of
superior resistance to propagation, but have much inferior resis-
the proper pitting potential by performing a variety of electro-
tance to initiation, and thus result in a shorter application lifetime.
chemical tests on Type 317L and Alloy 825 in simulated flue gas
desulfurization environments to determine Ebd and Erp as a func-
tion of the extent of pitting damage, characterized in terms of the GALVANOSTATIC MEASUREMENTS
time during which localized attack was allowed to occur. In terms Controlled current tests for pitting are seeing increased popular-
of cyclic polarization, this time would be inversely proportional to ity. Galvanostatic measurements involve the application of a
the sweep rate on the reverse portion of the scan, with lower series of small, step changes in the applied current. The potential
sweep rates leading to greater attack. As shown in figure 8 for is followed as the current is increased as described in ASTM
G100, Standard Test Method for Conducting Cyclic Galvanostair-
case Polarization. In some cases, more reproducible values for
Erp can be obtained galvanostatically in some systems, notably
FIG. 8 Critical potentials (Ebd and Erp) for Type 317L stainless
aluminum in inhibited water.47 Potential oscillations at constant
steel exposed to a simulated flue gas desulfurization
current can sometimes occur, which, while of scientific interest,
environment as a function of the time during which
can make interpretation of the results difficult, as the choice of
localized corrosion was allowed to propagate before
potential becomes almost arbitrary.
repassivation occurred. Symbols denote different
methods used to determine values: cyclic polarization
(filled and open squares and triangles); constant potential
POTENTIOSTATIC MEASUREMENTS
tests (filled and open circles and diamonds).
44 By far the most common electrochemical tests used is cyclic
polarization. Nonetheless, potentiostatic measurements can be
powerful tools in evaluating pitting behavior. Ideally, potentio-
static tests would be conducted over long time periods to avoid
being fooled by long initiation times. Potentiostaircase tests
can be performed in lieu of potentiodynamic tests, however, at
equivalent potential scan rates, the results should be identical.
Unfortunately, long-term potentiostatic testing is extremely
time-consuming and expensive. In addition, the time frames
involved usually are still very short when compared to the pro-
jected life. Thus, a number of approaches have been developed
for accelerating the process of initiation.
Mechanical scratching is favored by some as a means by
which a bare surface can be created. In this technique, one is
ascribing no importance to initiation time. The surface is held at
a constant potential and then a portion of it is scratched, usually
with a diamond-tipped stylus. The current is monitored with
time. For potentials below Erp, the surface will repassivate rather
PITTING 9
FIG. 9 Scratch test current-time curves for a specimen held FIG. 10 Schematic E(t) and I(t) for electrochemical scratch
potentiostatically above the repassivation potential (Erp) method for determining the repassivation potential.
and below Ebd.
rapidly, as shown in figure 9. Just above Erp, the surface will try
to repassivate, but will fail, and the current eventually will
increase. The closer the potential to Erp, the longer is the time
before the current increases. Thus, in most cases, the Erp mea-
sured by this method is not conservative, as usually no more
than 10 min is spent at any one potential. If one had waited long
enough at the potential used just before the measured Erp, local-
ized corrosion might have occurred. This, however, does not
denigrate its utility as a screening test. One problem with
scratching tests of this type is the dependence on the weight of
the scratch. For instance, when scratching by hand, the Erp
decreases with increasing damage. A mechanical system
improves the reproducibility. A more difficult problem concerns
the site of pitting. In many cases, pitting occurs at inclusions or
second-phase particles of one type or another. Such inclusions
are usually present at small volume fractions, so the probability scratch” the specimen surface. A related method is described in
of scratching across one (or more) with a fine diamond tip is ASTM F746, Standard Test Method for Pitting or Crevice Corro-
extremely small. This paucity of sites can lead to erroneously sion of Metallic Surgical Implant Materials, for determining the
high values of Erp, which reflect the pitting susceptibility of the pitting and crevice corrosion susceptibility of materials used in
matrix material, but ignore the susceptibility of the weakest link, medical implants.
the inclusions. In another electrochemical test that focuses on pit propaga-
In addition, purely electrochemical methods can be used to tion, the potential is scanned at 10 mV/s to a potential E1 between
produce a bared surface. In one technique, the entire exposed Ebd and Erp, where it is held to determine the background passive
surface is activated by a large positive voltage excursion, which is current density. After 10 min, the potential is scanned anodically
followed by a voltage step back to (or toward) Ecorr. In this way, past Ebd until the current density is 10 mA/cm2, at which time
any potential pitting sites are initiated, and the test measures the the potential is stepped back to E1. The current is then moni-
ability of the material to resist propagation and to repassivate. tored for 10 min, after which the potential is held at Ecorr for
One version of this test (fig. 10) involves a step to þ2 V for 3 s 5 min to repassivate the pits. Finally, the potential is stepped
followed by a step back to Ecorr, during which time the current is back to E1 and the current is monitored to ensure that the back-
monitored. The potential is held there for 5 min before it is again ground current has not changed appreciably. The amount of
stepped to þ2 V for 3 s to reinitiate localized corrosion. At this charge passed during the propagation stage is compared to the
point, the potential is stepped back to a potential 50 mV above pitted area (determined by optical microscopy) to determine an
Ecorr, and the current is monitored for 5 min. The process is average pit penetration rate. This test is known as the Pit Propa-
repeated until the current does not decay upon the step in the gation Rate (PPR) Test.48
negative direction. In this way, an estimate of Erp can be made, Sehgal et al.49 and Frankel et al.50 developed a means of test-
with better estimates resulting from the use of smaller incre- ing pit propagation using thin foils. The geometry of the foil
ments in the test potential (e.g., 25 mV instead of 50 mV). This restricts the dissolution to two spatial dimensions, allowing opti-
method is essentially using the potentiostat to “electrochemically cal measurements of changes in diameter to be related to the
measured current, thereby establishing an accurate rate of pit prop- at the pit surface required for propagation is also needed, limit-
agation as well as conditions under which such pits repassivate. The ing the direct application of this parameter.52
method has been applied to sputtered aluminum (Al) thin films50
as well as Al alloys.49 The primary experimental challenge is the cre- CRITICAL TEMPERATURE TESTS
ation of foils that are sufficiently thin to produce a stable, two- Although ASTM tests use temperature to accelerate attack dur-
dimensional pit. While sputter deposition is an excellent method, ing exposures, temperature also can be used in combination with
the production of thin foils of engineering alloys provides more of a electrochemical techniques. One example of this is the determi-
challenge, although not always an insurmountable one. nation of critical pitting temperatures (CPT)35,60,61 for alloy
Along with two-dimensional dissolution in foils, insights development or selection, or both. An anodic potential is applied
into pit propagation and repassivation can also be made through to an electrode at low temperature (room temperature or below)
electrochemical measurements on artificial pits formed by in the solution of interest, and the temperature slowly increases
embedding wire (usually on the order of a 50-lm diameter) in to determine the temperature at which initiation of localized cor-
an insulating material restricting the geometry to one spatial rosion occurs, as signified by an increase in the current above
dimension.52,53 By leaving a cross-section of the wire exposed to some criterion. Such a method allows for a quantitative ranking
solution, a potentiostatic anodic hold will allow for the entire of materials in terms of resistance to pitting. Note that CPT does
interfacial area to be active. Dissolution of the wire is in one not represent an intrinsic material property but rather a statisti-
dimension; therefore, modeling the effects of mass transfer is cally distributed value that is dependent on material surface con-
straight-forward as given by Galvele’s original formulism.53,54 dition, test exposure area, and test environment.59
These one-dimensional (1D) electrodes can be used to measure ASTM G150 describes in detail how to perform such experi-
conditions for pit propagation, namely, the pit stability product, ments. The solution prescribed is 1 M NaCl, the suggested applied
(ix), where i is the current density and x is the pit depth. A criti- potential is þ700 mV(SCE), and the starting temperature is deemed
cal value of ix describes the current density needed to continue to be 0 C, with the temperature being increased at l C/min. The
propagation at any given depth, x; Erp also can be measured with CPT is defined as the temperature at which the current exceeds 100
1D electrodes, as limiting values for Erp are reached at sufficient lA/cm2 and remains so for more than 1 min. The test method
depth45,55 (charge passed) as seen in figure 11,51 further comple- clearly states that alternative potentials can be used if they are
menting the work of Thompson and Syrett.44 These Erp values within the range for which the CPT is potential independent.
are not affected by the dissolution products created during the Salinas-Bravo and Newman62 developed variation on the
1D pit growth because of the small amount of charge needed, as critical pitting temperature test for welded stainless steels in
compared with macro-sized electrodes. Artificial pit electrodes which a large, unwelded specimen was coupled to a welded sam-
can be used to gain insights into pit propagation and repassiva- ple using a zero resistance ammeter (ZRA). The unwelded speci-
tion in different alloys55,56 as well as to quantify solution and men polarizes the welded sample to a positive potential. As the
temperature effects.57–59 Measurements for pit stability generally temperature is raised, the galvanic current between the two
are made under the presence of a salt film; however, pitting has remains low until the CPT is reached. At that point, the welded
been shown to occur when a salt film is not present on the sur- sample undergoes stable pitting and a large current is observed.
face of a pit, thus a critical value of the fraction of saturation The attractiveness of this test is that it probes the inherent gal-
vanic couple that is the essence of localized corrosion: the large,
passive cathode, and the small, active pit.
FIG. 11 Repassivation potential of one-dimensional electrodes in
51
comparison to CPP experiments. ELECTROCHEMICAL NOISE
Electrochemical noise has seen increased interest as a tool for
both corrosion science and corrosion engineering. By carefully
monitoring the galvanic current between two nominally identical
electrodes or the corrosion potential of a single electrode, meta-
stable pitting can be detected. The localization of the dissolution
inherent in localized corrosion implies a separation of the anodic
and cathodic reactions that constitute the corrosion couple. This
physical separation of reactions distinguishes localized corrosion
from uniform corrosion in which it is traditionally thought that
the anodic and cathodic sites are in proximity to one another.
The majority of the anodic (oxidative dissolution) reaction
occurs inside the localized corrosion site, whereas the majority of
the cathodic (reduction) reaction occurs on the boldly exposed
surface. Thus, a galvanic couple is created. The spatial separation
of the processes necessitates the passage of current between the
two sites. This passage of current leads to the various electro-
chemical noise signals measured.
PITTING 11
Under open circuit conditions, bursts of dissolution at local- which can be collected as a function of time. The AE signals have
ized corrosion sites require the generation of bursts of cathodic been correlated to the number of pits that are present on the surface
current from the surrounding boldly exposed surface. This of the alloy66 along with other uses detailed in work by Wu, Jung,
increased demand typically causes a decrease in the measured and Byeon.67 This technique can be sensitive and allows for detec-
open circuit potential. Localized corrosion sites are typically very tion of very small perturbations; however, it is also a downfall of
small (<100 lm diameter). The current densities inside these the technique as deconvolution from ambient vibrations can be
cavities during transient bursts, however, can be on the order of rather difficult. There are many sources of vibrations on the surface
1 A/cm2. These rates are possible because of the extremely of a material during corrosion, including the following: (1) bubbling
aggressive environments that develop inside localized corrosion from H2 evolution, (2) initiation events caused by passive film rup-
sites. Thus, even though the sites are geometrically small, they ture, and (3) pit propagation. Along with these problems, it is likely
can influence the electrochemical potential of the much larger that an area under study could have multiple pitting events at dif-
boldly exposed surface on which the electrode kinetics are far ferent stages of the pitting process and therefore convolute the AE
slower. This difference in relative current densities on separated signal.
anodes and cathodes is what accounts for the ability to detect the
electrochemical noise associated with localized corrosion. When SCANNING TECHNIQUES APPLIED TO LOCALIZED
the potential of the surface is controlled with an external device, CORROSION
the same burst of dissolution requires the device to supply a burst Although a detailed overview of scanning techniques is beyond
of current, which can be recorded. Usually, these bursts are tran- the scope of this chapter, a quick summary of advantages and
sient, with temporary repassivation of the localized corrosion site disadvantages to each technique along with the capabilities will
occurring and allowing the system to return to the previous be outlined. Various scanning techniques are commonly used to
steady-state condition. On a metal surface of appreciable size (>1 investigate localized corrosion scenarios, including scanning
cm2), there can be many localized corrosion sites. They will usually Kelvin probe (SKP), scanning Kelvin probe force microscopy
propagate independently, so that a series of current (or potential) (SKPFM), scanning vibrating electrochemical technique (SVET),
fluctuations is observed because of the summation of the signals and scanning electrochemical microscopy (SECM). SKP is char-
from the individual sites. These fluctuations are referred to as acterized by measuring two-dimensional distributions of the
“electrochemical noise.” Because electrochemical noise often can contact potential difference between the tip and the surface of
be observed under open circuit conditions, it has been hailed as interest. The SKP can be combined with atomic force micros-
the only truly noninvasive electrochemical method. Several meth- copy to create an SKPFM and results in simultaneous mapping
ods for in-operando corrosion monitoring based on these concepts of the surface topography as well as the potential difference.68
are overviewed in ASTM G199, Standard Guide for Electrochemical The resolution of these techniques varies and SKPFM can pro-
Noise Measurement. Changes in the noise signal are often taken as duce measurements on the order of nanometers, while SKP gen-
an indication that conditions are favorable for pit initiation to erally is limited by the tip size and distance between the tip and
occur. Thus, if one is monitoring a process stream, corrective the sample. Because of the small resolution, SKP and SKPFM are
action can be taken. Numerous data analysis procedures for elec- useful in determining the propensity for pit initiation sites.
trochemical noise signals have been proposed for the identification SVET measures in solution to map electrochemical currents
of pitting conditions, some of which are described in ASTM G199. above the surface of corroding metals and allows for the determi-
The theoretical basis for these analysis approaches is often not well nation of local cathodic and anodic regions of interest. SVET has
defined, and the reliability can be highly variable depending on a much lower spatial resolution than SKP and SKPFM at
approach and the conditions of the system being monitored.63,64 about 100–200 lm and has a current density resolution around
Relatedly, another disadvantage of noise monitoring is that it does 1 lA/cm2.69 The user should be aware that when using these
not give sufficient information about what level of this metastable methods for in-situ measurements, the solution often is stirred,
pitting is acceptable. For example, there may be literally millions of causing mixing of the localized solution and can change diffu-
metastable pits forming and repassivating in a vessel wall, but only sion. SECM electrolysis current that flows at a microelectrode
one needs to penetrate completely for a leak to develop. It may not immersed in solution is moved above an alloys surface and is
be possible to differentiate between conditions that will allow that used to characterized electrochemical processes.70 Considering
to develop and those in which the extent of pitting is negligible. all scanning techniques, localized corrosion is characterized by a
Experience and correlations with coupon exposures are critical fac- stochastic process which can occur on short timescales. When
tors in the use of noise for localized corrosion monitoring. A guide scanning a surface in the presence of an electrolyte, it is possible
has been provided by Huet and Ngo to improve measurements and that these events are either missed or are in the stages of initia-
data analysis for electrochemical noise measurements.65 tion or repassivation and could affect the results.
ACOUSTIC EMISSION MONITORING OF CORROSION

Acoustic emission (AE) testing is a nondestructive technique aimed
Predictive Capabilities
toward understanding localized corrosion as it occurs. The basics of With the previous caveats in mind, the study of metastable pit-
AE involve the detection of micro-signals from growing corrosion ting can be used to assist in lifetime prediction studies. If pitting
damage by converting very small surface displacement to a voltage, is truly a stochastic phenomenon, then one can apply statistics to
allow prediction of the likelihood of pit propagation, given suffi- information concerning localized corrosion susceptibility. Although
cient information. The information needed is (1) the probability none of the methods is perfect or a panacea, when used judiciously
that a pit will nucleate under a given set of conditions, and (2) and in combination, a better picture of the localized corrosion pro-
the probability that once a pit nucleates, it will survive (i.e., cess can be gained, even in complicated solutions. This allows for
become stable). Such information could be used to estimate com- more informed decisions on alloy selection, process alteration, or
ponent lifetimes, which then could be used to make design deci- failure analysis. Although prediction of localized penetration rate
sions based on the consequences of a failure. For example, a 3% remains a goal of electrochemical testing, applications of statistics
chance of perforation may be acceptable for an easily shutdown to the process appear promising.
and repaired vessel if it allows a cheaper alloy to be used, but
such a probability would not be acceptable for a critical compo- ACKNOWLEDGMENTS
nent in an inaccessible submersible. Sandia National Laboratories is a multimission laboratory managed
Analyses of these current and potential transients caused by and operated by National Technology and Engineering Solutions of
metastable pits can provide information regarding the control- Sandia, LLC., a wholly owned subsidiary of Honeywell Interna-
ling factors and their dependence on environmental, metallurgi- tional, Inc., for the U.S. Department of Energy’s National Nuclear
cal, and applied potential conditions. For example, Pride, Scully,
Security Administration under contract DE-NA0003525. This doc-
and Hudson71 characterized the metastable pitting behavior of
ument is SAND2019-13965 B.
high-purity Al and aged Al-2%Cu. They found that the fre-
quency of pitting events was proportional to both the applied
potential and the chloride concentration. The rate of pitting also References
was found to decrease with increasing exposure time. These
1. Z. Szlarska-Smialowska, Pitting Corrosion of Metals (Houston,
kinds of analyses can serve as the basis for the pitting prediction
TX: National Assocation of Corrosion Engineers, 1986).
methodologies described next.
Shibata and Takeyama9 and Williams, Westcott, and 2. G. S. Frankel, “Pitting Corrosion of Metals. A Review of the
Fleischmann72 have applied such statistical arguments to pitting Critical Factors,” Journal of the Electrochemical Society 145
of stainless steel. To develop these models, a large amount of (1998): 2186–2198.
data that can be treated as an ensemble must be gathered. In 3. J. Soltis, “Passivity Breakdown, Pit Initiation and Propagation of
other words, variations in results from test to test are expected, Pits in Metallic Materials: Review,” Corrosion Science 90 (2015):
even for nominally identical tests. This variation is used to 5–22.
develop the cumulative probability curve for pitting under a cer-
4. G. S. Frankel, T. Li, and J. R. Scully, “Perspective—Localized
tain set of conditions. Both groups used multiple specimen test- Corrosion: Passive Film Breakdown vs Pit Growth Stability,”
ing apparatus to gather up to 12 data points for critical Journal of the Electrochemical Society 164 (2017): C180–C181.
potentials and metastable pit nucleation rates simultaneously.
The results for one set of 30 tests are shown in figure 6.42 This 5. R. Baboian, ed., Corrosion Tests and Standards: Application and
Interpretation, 2nd Edition (West Conshohocken, PA: ASTM
shows that the breakdown potential Ebd follows a distribution.
International, 1995).
Thus, there is a 20% chance that the breakdown potential of
commercial 304 SS will be below þ160 mV(SCE) in 1,000 ppm 6. W. H. Ailor, ed., Handbook On Corrosion Testing and Evaluation
NaCl. The argument is that there was nothing “wrong” with (New York: Wiley, 1971).
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variation reflects the stochastic nature of the pitting process. Journal of the Electrochemical Society 103 (2007): 375–390.
Qualitatively similar data have been developed for Al alloys and
their constituent second-phase particles.73 8. P. Ernst, N. J. Laycock, M. H. Moayed, and R. C. Newman, “The
The development of commercially available multipotentiostats Mechanism of Lacy Cover Formation in Pitting,” Corrosion
Science 39 (1997): 1133–1136.
has made measurements of pitting conditions and the underlying
factors more tractable. Lunt et al.74 used an array of nominally iden- 9. T. Shibata and T. Takeyama, “Stochastic Theory of Pitting
tical electrodes to characterize the strengths and extent of the types Corrosion,” Corrosion 33 (1977): 243–251.
of interactions that occur among active pits. In addition, such
10. P. M. Aziz and H. P. Godard, “Influence of Specimen Area on the
instrumentation makes the determination of the statistical distribu- Pitting Probability of Aluminum,” Journal of the Electrochemical
tion of pitting potentials through the testing of a large number of Society 102 (1955): 577–579.
specimens much less time intensive, as multiple electrodes (up to
100)75 can be independently tested simultaneously. 11. Standard Guide for Conducting Corrosion Tests in Field
Applications, ASTM G4-01 (2014) (West Conshohocken, PA:
ASTM International, approved November 1, 2014), 1–10, http://
doi.org/10.1520/G0004-01R14
Conclusion
12. Standard Practice for Conducting Atmospheric Corrosion Tests
This chapter provided a brief overview of the exposure tests used to on Metals 1, ASTM G50-10 (2015) (West Conshohocken, PA:
determine localized corrosion susceptibility and introduced a vari- ASTM International, approved November 1, 2015), 1–11, http://
ety of electrochemical techniques that can provide important doi.org/10.1520/G0050-10R15
PITTING 13
13. M. B. Parker and R. G. Kelly, “Improved Atmospheric Corrosion 29. L. Stockert, F. Hunkeler, and H. Bohni, “Crevice-Free
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15
Chapter 2 | Crevice Corrosion
Mariano Iannuzzi,1 Edgar Hornus,1 and Mobin Salasi1
Introduction become susceptible in alkaline environments free of aggressive spe-

cies in which a passive film is thermodynamically stable.9
Crevice corrosion is defined in ASTM G193, Standard Terminol-
ogy and Acronyms Relating to Corrosion, as “the localized corro-
CREVICE GEOMETRY
sion of a metal or alloy surface at, or immediately adjacent to, an
A crevice is formed when two surfaces, at least one being metal-
area that is shielded from full exposure to the environment
lic, are in proximity and are immersed in an electrolyte that can
because of close proximity of the metal or alloy to the surface of
promote crevice corrosion. Examples of materials that can cause
another material or an adjacent surface of the same metal or
crevice corrosion include metals, wood, plastics, ceramics, rubbers,
alloy.”1 Crevice corrosion affects most metals and alloys and is
glasses, concrete, asbestos, waxes, sand deposits, marine growth,
among the most damaging forms of corrosion. Crevice geome-
and coatings.3,10–12 Figure 1 illustrates an idealized crevice. As seen
tries can be found on a wide range of structures and compo-
in figure 1, the crevice geometry is described by the opening or gap
nents, including flanges, threaded connections, and lap joints, as
(g) and the length (L), measured as the distance from the crevice
well as under deposits and damaged coatings.2
mouth.3 The gap has to be wide enough to allow the ingress of the
Metals and alloys that develop a passive film are prone to
solution, but sufficiently tight to promote the formation of an
crevice corrosion. In contrast, those that do not form a surface
occluded environment within the cavity. Openings between 0.1
film tend to corrode uniformly outside the occluded region
and 100 lm have been found to cause crevice corrosion.2 Crevice
because of the ready access to the oxidizing species that support
corrosion rarely occurs in wide (e.g., >3 mm) grooves or slots.
the cathodic reactions.3 Stainless steels, especially those with little
Thus, the crevice is divided into two regions: the external surface
to no molybdenum, some nickel-based alloys, and aluminum
that is freely exposed to the environment and the shielded or crev-
alloys are particularly susceptible to crevice corrosion.4 More-
iced area exposed to a stagnant solution.
over, materials that have been shown to be highly resistant to pit-
The gap in a real crevice is not a fixed value. Indeed, at the
ting corrosion, such as titanium (Ti) and Ti-based alloys, suffer
microscale, the two mating surfaces have a series of ridges and
crevice corrosion in specific environments.5,6
asperities, as shown by the surface profiles in the call-out in figure 1.
As will be discussed, pitting and crevice corrosion mechanisms
The surface profiles seen in figure 1 correspond to an ASTM A480,
have many similarities. Researchers have argued that for many
Standard Specification for General Requirements for Flat-Rolled
material-environment combinations, the same mechanism is at
Stainless and Heat-Resisting Steel Plate, Sheet, and Strip, surface fin-
play.7 Although some authors suggest that crevice corrosion is a
ish no. 1 with a peak-to-peak distance of approximately 15 lm.13 As
particular form of pitting corrosion, all pits are crevices as “pits can-
a result, a real crevice has a complex and distributed geometry that
not be stable until a crevice-like cavity develops.”8 It is important to
cannot be defined rigorously, resulting in “a wide range of crevice
emphasize that crevice corrosion resistance is not a property of a
gaps, including areas of direct, intimate contact.”2
material. In this regard, the response of a particular alloy system to
a given environment determines the crevice corrosion susceptibility.
For example, iron and carbon steels do not suffer crevice corrosion OBJECTIVES
in strong acids because they do not develop a passive film but rather Today, a large number of accepted tests are available to study
crevice corrosion phenomena. The different methodologies can
be used to compare and rank alloys, conduct quality control,
assess the effects of changes in manufacturing routes and alloy
1
Curtin Corrosion Centre, Curtin University, GPO Box U1987, Perth WA 6845,
composition on crevice corrosion resistance, and determine criti-
Australia
The authors acknowledge the previous authors of this chapter, Narsi Sridhar,
cal temperatures and potentials and induction times.
Darrell S. Dunn, C. S. Brossia, and Gustavo A. Gragnolino, Southwest Research This chapter describes the various standard test methods
Institute, San Antonio, TX. available to the corrosion specialist as well as adaptations to
DOI: 10.1520/MNL202NDSUP20190034
FIG. 1 Geometry of crevice corrosion. In the sketch, the horizontal scale is arbitrary.
study specific crevice corrosion parameters and prevention strat-

egies (e.g., the use of inhibitors). The focus is on test methods Me ! Mezþ þ ze ; and (1)
developed by the ASTM Committee G-1 on corrosion of metals,
O2 þ 2H2 O þ 4e ! 4OH
(2)
but other procedures also are included. Although the test princi-
ples have been applied to many alloy systems, the scope of the Initially, these reactions occur inside and outside the crevice.
chapter is on stainless steels and nickel-based alloys. After a given time, oxygen is depleted inside the cavity because
of restrictions imposed by convection within the occluded sur-
face. The dissolution of the metal continues within the crevice,
CREVICE CORROSION MECHANISMS
resulting in excess of metal cations (e.g., iron [II], chromium [III],
Differential Aeration and Chloride Concentration aluminum cations). As the corrosion process continues, the con-
It was realized early on that the metals and alloys that were easily centrated metal cations within the stagnant cavity hydrolyze
passivated were also those that appeared more susceptible to crev- according to equation (3), which results in the formation of
ice corrosion.14 Mears and Evans10 and Uhlig15 were the first to pro- hydrogen ions (Hþ).18–20 The excess of metal cations is necessar-
pose that oxygen depletion within the crevice was the main driving ily balanced by the migration of anions, such as chloride ions
force leading to the destabilization of the passive film inside the (Cl), from the bulk into the cavity, which ensures charge neu-
cavity. A mechanism solely based on concentration cells, however, trality. As a result, the concentration of metal chlorides increases
has failed to explain many experimental observations.16 inside the crevice.
In the 1950s, Rosenfeld and Marshakov17 pioneered crevice
corrosion experimental methods. The authors suggested that Mezþ þ H2 O ! MeOH ðz1Þþ þ Hþ : (3)
crevice corrosion occurred through a combination of (1) deple-
tion in oxygen (or a corrosion inhibitor) in the crevice, (2) local The formation of a local acidic environment increases the metal
acidification, and (3) shift in the potential to more negative val- dissolution rate in the crevice, producing more protons, and fur-
ues, where active dissolution would take place. Many of the mod- ther increasing the Cl concentration. This process is often
ern crevice corrosion principles are based on these findings by referred to as autocatalytic. Concurrently, the oxygen reduction
Rosenfeld and Marshakov. reaction accelerates on the outer surface to counteract the
It is now well established that the mechanisms that drive a increased metal dissolution rate within the cavity, cathodically
growing crevice are identical to those promoting a growing pit.8 protecting the external surface.3 Active metal dissolution occurs
In this regard, when a passive metal or alloy (e.g., an austenitic when the crevice solution concurrently has (1) a sufficiently low
stainless steel, such as UNS S30400), partially covered by a non- pH and (2) a high concentration of Cl.21 The pH at which the
metallic surface is exposed to aerated seawater (pH ¼ 8.0), the passive-to-active transition takes place is referred to as depassi-
electrochemical reactions are the dissolution of the metal and the vation pH (pHd).21 Oldfield named the solution that leads to the
reduction of dissolved oxygen, equations (1) and (2).3 depassivation of the alloy within the crevice gap “critical crevice
CREVICE CORROSION 17
solution” (CCS).22 The formation of the CCS represents the transi-

tion from the initiation to the propagation stage. Although this FIG. 2 (A) Unidirectional pit and (B) crevice model.
model phenomenologically explained most experimental observa-
tions, it failed to rationalize the existence of a critical potential,
above which crevice corrosion develops.9 In this regard, the primary
limitation of Oldfield and Sutton’s model is that it considered that
the dissolution of cations (and their consequent hydrolysis) was
proportional to the passive current density, ipass. Because ipass is
constant over a broad potential range, the model is unable to
account for the existence of critical potentials, both initiation and
repassivation potentials. Moreover, Oldfield and Sutton’s descrip-
tion cannot consider the effect of inhibitive species (e.g., fluorides),
which increase the passive current density of UNS Alloy 22 (UNS
N06022) in hot chloride environments.23
The Critical Acidification Model

Galvele18 and later Oldfield and Sutton21,24 were the first to con-
sider the transport of species in and out of pits and crevices.
These models have since been improved and expanded to pro-
vide, in some instances, not just conceptual observations but also
(A)
numerical solutions.20,25,26 Galvele proposed that because crevice
corrosion is believed to be the result of localized acidification,
crevice corrosion could be described by the critical “xi” parame-
ter (referred to as pitting or crevice stability product) used in his
mathematical framework.9 In the pitting or crevice stability
product, x represents the diffusion path and i the current density
of a pit or crevice, as shown in figure 2.18 Localized corrosion
propagates stably above a critical xi value, which is constant for
a given material in a specific electrolyte. According to Galvele
and later Newman,8 pitting and crevice corrosion are similar (B)
from an electrochemical point of view; the only difference being
the geometric characteristics of the sample (i.e., a different diffu-
sion path). Accordingly, the critical potential for stable crevice
explains why crevice corrosion occurs much more readily than
propagation (ECrit) can be described as follows:
pitting.34

ECrit ¼ ECorr þ g þ U þ Einh (4) As discussed by Galvele, Wood et al. provided a clear experi-
mental demonstration of the correlation between pitting and crev-
where: ice corrosion.37 In their pioneering work, the authors conducted
ECorr ¼ corrosion potential in a simulated crevice electrolyte, potentiostatic experiments on freely exposed and creviced UNS
g ¼ polarization needed to reach the critical xi value, S30400 stainless steel samples. The crevice was formed using glass
U ¼ electrical potential induced by the migration of the aggres- microscope covers, leading to g values between 50 and 150 lm. The
sive anions to the crevice (or the bottom of a pit), and samples were exposed to 5 wt% sodium chloride (NaCl) (pH ¼ 8.0)
Einh ¼ contribution of the presence of inhibitors in the solution.16 at room temperature. Wood et al. found that at þ600 mVSCE, pit-
However, Einh cannot always be experimentally separated ting corrosion initiated not only on the outer surface but also inside
from other factors.27,28 The validity of equation (4) has been first the crevice. In contrast, when new samples were polarized at þ400
confirmed by Newman et al.29 and studied in numerous investi- mVSCE, the attack occurred exclusively inside the crevice. Crevice
gations.27,30–35 The different parameters in equation (4) can be corrosion started as individual pits that spread laterally as the attack
measured experimentally by conducting anodic polarization progressed, leading the authors to the idea that crevice corrosion is
experiments in crevice-like solutions.32–34,36 The effects of alloy- “lateral pitting” within the crevice gap.
ing elements on the crevice corrosion resistance are reflected in Today, it is accepted that the accelerated attack within the
changes in ECorr and g.34,35 Equation (4) also explains why certain crevice can manifest as uniform dissolution, pitting, or both.24
metals and alloys are susceptible to crevice corrosion but not to Figure 3 illustrates three common forms of corrosion attack
pitting. Indeed, g can be used as a measure of the crevice corro- occurring inside a crevice on different stainless steels. Stockert
sion resistance of an alloy.30–34 In this regard, the larger the value and Boehni,38 and later, Laycock, Stewart, and Newman,8 sug-
of g, the broader the range of potentials in which crevice corro- gested that pit nucleation within crevices occurs even at small
sion would be exclusively observed. For stainless steels and nickel applied potentials, resulting in measurable current noise. The
alloys, the values of g range from þ470 to þ1,000 mV, which current and, hence, the dissolution rate increase sharply above
FIG. 3 Different crevice attack morphologies: (A) pitting corrosion inside the crevice gap on UNS S30403 in 0.1M NaCl at 60 C, (B) pitting
and general dissolution with the crevice gap on UNS S31600 in 0.1M NaCl at 30 C, and (C) uniform crevice attack on UNS S31603
in 6 wt% FeCl3 at 20 C.
(A) (B)
(C)
the ECrit, and stable pit propagation takes place and leads to the potential drop and, thus, the potential inside the crevice will be
formation of metal-chloride salts. lower (i.e., more negative) than at the surface. In systems that
exhibit an active-passive behavior in the bulk electrolyte, the
OHMIC POTENTIAL DROP ohmic potential drop in the crevice can stabilize pit growth by
The passage of current from the external surface to the crevice decreasing the local potential into the active range.39 This mecha-
through a solution of finite conductivity results in an ohmic nism, proposed by Pickering, does not apply to a system in
which an active-to-passive transition does not occur. Indeed, the procedure, and the recommended assessment, among other
in systems that show spontaneous passive behavior, a decrease in experimental considerations. For more details, consider some of
potential has a negative effect on crevice corrosion stability. the excellent works cited in this chapter.21,22,24,56–59
STAGES OF CREVICE CORROSION

THE CREVICE FORMER
The crevice corrosion process, then, can be summarized in four
Before describing the various crevice corrosion test methods, it is
stages, as follows: (1) oxygen consumption within the crevice,
necessary to discuss the use of crevice formers, in particular, the
(2) increase in Hþ and Cl in the crevice, (3) stabilization of a
multiple-crevice assembly (MCA) as a means to rank and evalu-
critical Hþ concentration above a threshold xi value, and
ate crevice corrosion resistance. Described by Anderson in the
(4) propagation. The first stage is key for carbon and low alloy
late 1970s, MCAs were first introduced to study crevice corro-
steels in alkaline solutions, which suffer corrosion by differential
sion of stainless steels in seawater.60 Today, MCAs are used not
concentration cells,40 but it is of less importance for passive
only on stainless steels, but also nickel, titanium, and aluminum
alloys. Conversely, the second stage is crucial to explain the
alloys in virtually any process environment.58,61,62
depassivation of passive alloys. In this regard, the migration of
An MCA is composed of several grooves and plateaus—
chlorides supports the reduction in pH resulting in an acidic
typically between 12 and 20 slots—with a depth of approximately
solution of lower pH than predicted only by cation hydrolysis,
0.5 mm. The purpose of the serrations is to create several crevice
because a high concentration of chlorides results in a higher
initiation sites within a single specimen, which should allow for
activity coefficient for protons (Hþ).41,42
statistical analysis with a few replicate tests.58 MCAs are com-
Given the similarities between pitting and crevice corrosion
monly made of polytetrafluoroethylene (PTFE), polychlorotri-
discussed earlier, it is reasonable to conceptually adapt the
fluoroethylene (PCTFE), polyvinylidene difluoride (PVDF),
Li-Scully-Frankel (LSF) framework to describe crevice corro-
ceramic, and PTFE tape-covered ceramic. The contact area of
sion.43–46 Thus, the state of a crevice can be fully described in
each crevice contact and the total contact area are important var-
terms of a critical potential (ECrit), a critical temperature (TCrit),
iables that need to be reported. Figure 4A illustrates the various
and an induction time. The existence of ECrit has been discussed.
parts of a typical MCA that complies with ASTM G48, Standard
Temperature has a strong influence on localized corrosion phe-
Test Methods for Pitting and Crevice Corrosion Resistance of Stain-
nomena.47 Experimentally, pitting and crevice corrosion are
less Steels and Related Alloys by Use of Ferric Chloride Solution.63
observed only above specific temperatures (referred to as critical
In figure 4A, the bolts and nuts are made of highly corrosion-
pitting or crevice temperature, CPT and CCT, respectively) that
resistant materials, typically titanium grade 2 (UNS R50400) or a
are usually defined within a narrow 1–2 C range.48–50 The length
nickel-based alloy, such as UNS N10276 or UNS N06022. The
of time required to develop a critical crevice solution with a par-
bolts and nuts are electrically insulated from the test specimen
ticular crevice geometry, that is, a given “x” in the xi stability
using, for example, PTFE tape or a polymer insert.64
product, is referred to as induction time. In this regard, the
It has long been recognized that the tightness of a crevice
induction time can be seen as a measure of the effective crevice
former has a profound effect on the crevice corrosion severity,
corrosion resistance of an alloy. Crevice corrosion occurs at
which in the laboratory is usually controlled by the applied tor-
lower temperatures and in less time (a shorter induction period)
que. Akashi, Nakayama, and Fukuda studied, among other varia-
than pitting corrosion.47,51
bles, the effect of torque on the crevice repassivation potential
A detailed discussion of the different crevice corrosion
(ER,Crev).65 The authors found that if the torque was “too low”
mechanisms is outside the scope of this chapter. More informa-
(i.e., below 0.98Nm) ER,Crev moved toward higher potentials,
tion on localized corrosion models and mechanisms can be
indicating a less severe crevice. For torque values between 0.98
found in the excellent reviews by Betts and Boulton,3 Pickering,52
and 3.9 Nm, however, ER,Crev became stable and reproducible.
Frankel et al.,53 Frankel,54 and Newman.55
Presently, ASTM G48 recommends a torque of 0.28 and 1.54
Nm for nickel alloys and stainless steels, respectively. However,
Test Methods to Assess Crevice researchers have used torque values from 0.28 to 9.5 Nm with
varying degrees of success.33,66
Corrosion Resistance Shan and Payer investigated the effect of the crevice former
Different classification schemes could be used to group crevice material (i.e., polymer versus ceramic) as well as the influence of
corrosion test methods. Herein, the tests are divided into two the surface finish of the MCA.66 The authors used potentioki-
main groups: (1) immersion or nonelectrochemical and (2) elec- netic and potentiostatic test methods and evaluated PTFE,
trochemical testing. Electrochemical methods, in turn, are PCTFE, ceramic, and PTFE tape-covered ceramic crevice for-
further classified as tests with and without external polarization. mers on UNS N06022 (Alloy C22). Results showed that PTFE
Likewise, methods that use an external polarization are subdi- tape-covered MCAs produced systematic and reproducible crev-
vided into potentiostatic and potentiokinetic methods. Table 1 to ice corrosion of Alloy C22 in all tests. In contrast, as-fabricated
Table 4 summarize the most common standard and custom crev- ceramic crevice formers were not sufficiently severe. The severity
ice corrosion techniques. The tables are organized based on the increased as the MCA was polished to 1,200 US-grit before
categories described previously. Tables 1 to 4 illustrate the uses, assembly. Polymeric PTFE and PCTFE MCA were also less
exposure conditions, the type of crevice assembly, the duration, severe than the PTFE tape-covered formers, possibly because of
TABLE 1 Comparison of Nonelectrochemical Test Methods to Evaluate Crevice Corrosion Resistance
Method Summary
ASTM G48 Method B Uses • Pitting and crevice resistance in chloride environments.
(rubber band) • Rank alloy performance.
• Applicable to stainless steels and nickel-base alloys.
Exposure conditions • Electrolyte: 6 wt% FeCl3 (unadjusted pH approx. 1.0–2.0)
• Recommended test temperatures:
• 22 6 2 C
• 50 6 2 C
• Other values could be used.
Crevice assembly • Cylindrical TFE-fluorocarbon blocks.
• Fluorinated O-rings or rubber bands (low S).
Test duration • 72 h (recommended).
• Variations are allowed, which depend on the alloy composition.
• Periodic extractions are possible (could lead to variations in the rate of attack).
Assessment • Visual inspection (ASTM G46 suggested).
• Weight loss to 0.001 g or better accuracy.
ASTM G48 Methods D & F Uses • Determine the critical crevice temperature (CCT).
• Nickel-base and chromium-bearing alloys: Method D.
• Stainless steels: Method F.
• It can be used to rank alloy performance.
Exposure conditions • Electrolyte: 6 wt% FeCl3 þ 1 wt% HCl (pH adjusted approx. 1.0).
• Start temperature (nearest 5 C):
• Method D: (1.5 %Cr) þ (1.9 %Mo) þ (4.9 %Nb) þ (8.6 %W) – 36.2.
• Method F: (3.2 %Cr) þ (7.6 %Mo) þ (10.5 %N) – 81.0.
• Minimum Temperature: 0 C
• Maximum recommended temperature: 85 C.
Crevice assembly • Multiple-crevice assembly (MCA)
• TFE-fluorocarbon segmented washers.
• Different materials and geometries are allowed.
• Torque
• Method D: 0.28 Nm (40 in-oz).
• Method F: 1.58 Nm (14 in-lb).
Test duration • Method D: 72 h.
• Method F: 24 h.
Assessment • Visual assessment (could follow ASTM G46): Crevice corrosion is present if local attack >0.025 mm
(0.001 in) in depth.
• Weigh loss.
ASTM G78 Uses • Determine the crevice corrosion susceptibility in seawater and other chloride environments.
• Applicable to iron- and nickel-base alloys.
• It can be used to assess the crevice induction time.
• It can be used to determine the critical crevice temperature.
Exposure conditions • Seawater, natural waters, and chloride-containing aqueous electrolytes.
• Temperature: User-defined and maintained within 6 2 C.
Crevice assembly • Many different configurations are allowed, for example, MCA (various geometries and materials),
O-rings, gaskets, strips, coatings (for complex geometries).
Test specimens • Flat, cylindrical, and complex geometries are allowed.
• Specimens should maintain a constant bodily exposed to shielded area ratio.
Test duration • 30 days (recommended).
• Sampling at different time intervals is allowed.
Assessment • Visual assessment:
• Maximum crevice depth.
• Affected area.
• If using MCA, the number of segments showing crevice corrosion.
• Weight loss.
TABLE 2 Comparison of Electrochemical Test Methods with No External Polarization to Assess Crevice Corrosion Resistance
Method Summary
Corrosion Potential Monitoring • The initiation of pitting and crevice corrosion in stainless steels and nickel-based alloys leads to a sharp decrease
in the corrosion potential (ECorr).
• ECorr monitoring can be used to determine induction times.
• If done as a function of temperature, ECorr monitoring can be used to determine critical temperatures.
• Standards such as ASTM G48 and G78 can be modified to include open circuit potential (OCP) monitoring.
ECorr measurements during ASTM G48 testing can provide a better pass/fail criterion than visual inspection alone.
• Because it is nondestructive, ECorr measurements provide a means for field monitoring.
Zero Resistance Amperometry (ZRA)– • The remote crevice assembly consists of a creviced sample connected to a noncrevice specimen through a
Remote Crevice Assembly zero-resistance ammeter.
• The ZRA measures galvanic current and couple potential.
• It simulates a real crevice setting.
• The initiation of crevice corrosion is associated with a sharp increase in current.
• ASTM G71 can be used as a guide.
• There is no agreement on a critical current value to define crevice initiation.
ZRA–Electrochemical Noise • Similar to the remote crevice assembly except that it uses two creviced coupons.
• Electrochemical current noise is recorded and analyzed over time.
• The start of the crevice attack leads to an increase in current (it can be positive or negative depending on the
specimen where the attack initiates).
• ASTM G199 can be used as guidance.
TABLE 3 Comparison of Potentiostatic Electrochemical Test Methods to Assess Crevice Corrosion Resistance
Method Summary
Chronoamperometry • Chronoamperometry consists of measuring current (or current density) as a function of time at a constant applied potential.
• It can be performed using creviced or crevice-free specimens.
• Chronoamperometry is primarily used to determine induction times.
• When performed at different temperatures, it can be used to determine critical temperatures.
• It can also be used to determine the critical repassivation temperatures (TR, Crev) by reducing the temperature after crevice initiation.
ASTM F746 Uses • Assess the pitting or crevice corrosion resistance of metals and alloys for surgical implants.
• Determine the critical potential, ECrit, to initiate pitting, crevice, or both.
• Laboratory screening.
Exposure conditions • Electrolyte: Phosphate Buffered Saline (PBS) solution (7.3 < pH < 7.5).
• Temperature: 37 6 1 C
Test specimen • Cylindrical coupons: 6.35 mm in diameter and 20 mm in length.
• Surface preparation: 600-grit SiC paper.
Crevice assembly • Tapered PTFE collar (3.18 mm width).
• Force-fit to 10mm from the base of the cylinder
Procedure • Step 1: Measure the corrosion potential for 1-h, referred to as E1.
• Step 2: Stimulation
• The purpose is to initiate localized corrosion.
• The applied potential, EApp, is set to þ800 mVSCE.
• The duration depends on the current response:
-2
• If i instantly > 500 :Acm decrease potential to E1.
-2
• If current generally increases, but i < 500 :Acm , decrease EApp to E1 after 20 s.
• If after 15 min, there is no sharp increase in current, terminate the test.
• Step 3: Repassivation
• Decrease EApp so that EApp ¼ E1.
• If no repassivation, ECrit ¼ E1.
• If repassivation occurs:
• After stimulation the new EApp ¼ E1 þ 50 mV.
• Repeat until no repassivation after stimulation.
(continued)
TABLE 3 (continued)
Method Summary
Assessment • ECrit (pitting or crevice)

• Visual examination.
Modified ASTM G150 Uses • Determine the potential independent pitting (or crevice) temperature.
• Predict the conditions resulting in stable crevice propagation.
• Applicable to stainless steels from UNS S31600 to S31254, but could be extended to other alloys.
Exposure conditions and • Electrolyte: Deaerated, 1 M NaCl (unadjusted pH).
procedure • Temperature: Start at 0 C, ramp at 1 C/min.
• Potentiostatic polarization:
• þ700 mVSCE (recommended).
• Other values are possible.
• A test at þ800 (orþ 600) mVSCE can be performed to determine changes in CPT
Test specimen • Modified to include creviced coupons.

-2
Assessment • CCT (CPT) defined as the temperature at which i > 100 :Acm for 60 s.
• Visual confirmation.
TABLE 4 Comparison of Potentiokinetic Electrochemical Test Methods to Assess Crevice Corrosion Resistance
Method Summary
Modified ASTM G61 Uses • Determine the relative susceptibility to localized corrosion (pitting and
crevice corrosion).
• Determine critical potentials, for example, ECrev and ER,Crev if using crevice
formers.
• If done at different temperatures, determine the critical crevice temperature,
often referred to as electrochemical critical temperature.
• Check one’s experimental technique and instrumentation.
• Applicable to Iron, nickel, and cobalt-base alloys, but it could be used for
other passive alloys.
• It shall not be used to correlate with the rate of propagation.
Exposure conditions • Electrolyte: Deaerated 3.56 wt% NaCl (neutral pH), but other solutions can
be used.
• Temperature: 25 6 1 C (recommended), but it can be done at different
temperatures.
Test specimens • Modified to include creviced specimens.
Procedure • Step 1: 1-h corrosion potential stabilization.
• Step 2: Potentiokinetic polarization:
• Scan rate: 0.6 V/h (0.168 mV/s).
2
• Scan reversal at i ¼ 5 mAcm .
• Stop test once hysteresis loop closes or once reaching ECorr.
Assessment • ECrev and ER,Crev (or EP and ERP without crevice former).
• Hysteresis, DE ¼ ECrev – ER,Crev.
• Visual confirmation.
ASTM G192 Tsujikawa- Uses • Determine ER,Crev for corrosion-resistant alloys.
Hisamatsu Electrochemical • It is understood that an alloy will not develop crevice corrosion below ER,Crev
(THE) test or PD-GS-PS under the tested conditions (i.e., electrolyte composition, pH, temperature).
• It can be modified to determine the crevice repassivation temperature
(TR,Crev).
• Applicable to any corrosion-resistant alloy, but developed for UNS N06022.
(continued)
TABLE 4 (continued)
Method Summary
Exposure conditions • Electrolyte:

• It can be used with any electrolyte.
• Developed using 1 M NaCl (unadjusted pH).
• Temperature:
• 90 C (UNS N06022).
• Lower temperatures can be used for less resistant alloys.
Procedure • Step 1 – Potentiodynamic polarization:
• 0.6V/h (0.168 mV/s).
-2
• Until a preset current is reached (2 :Acm for UNS N06022)
• Step 2 – Galvanostatic period
• The preset current is kept constant for 2 h.
• E versus t is recorded.
• The goal is to develop and grow crevice attack (if any develops).
• Step 3 – Potentiostatic polarization
• The potential is decreased by 10 mV internals.
• The duration of each step is 2 h.
• I versus t is recorded at each step.
Assessment • ER,Crev is defined as the highest potential for which the current does not
increase as a function of time.
• ER,Crev and visual confirmation.
PD-GS-PD technique • The PD-GS-PD technique is a simplification of the THE test.
• Step 3 is replaced by a potentiodynamic polarization step.
• ER,Crev is defined as a crossover potential.
• It can be used to determine TR,Crev.
the relaxation of the polymers by creep at the elevated tempera- Alloy 22 (UNS N06022) at high pressure, high temperature, or
ture range of the tests. Figure 4B illustrates a typical PTFE tape- both. The crevice electrode consists of a PTFE crevice former of
covered MCA on an Alloy C22 sample. a known area centered and pressed between two flat coupons—
In Europe, research was undertaken as part of the CREV- one cut from a plate of the metal or alloy of interest and the
CORR project—funded by the European Community between other cut from a thick polysulfone plate. The crevice assembly is
the years 2000 and 2003 under the Competitive and Sustainable formed by tightening the plates using corrosion-resistant bolts
Growth Programme—to develop a crevice corrosion qualifica- and nuts. The tightness is adjusted with the help of a PTFE
tion test for stainless steels used in marine environments.67 The “feeler,” as described by the authors, using open-faced
outcome of the CREVCORR project is presented in detail in the wrenches.72 The approach was used by He, Noël, and Shoesmith
European Federation of Corrosion (EFC) Publication No. 60 to construct corrosion damage functions74 as well as to deter-
“Methodology of Crevice Corrosion Testing for Stainless Steels in mine the influence of temperature on crevice corrosion suscepti-
Natural and Treated Seawaters.”68 Regarding the type of crevice for- bility.72 Many other nonstandard methods have been used by
mer, the CREVCORR project concluded that a spring-loaded crev- researchers to create artificial crevices for different purposes. For
ice assembly, referred to as disc spring multiple crevice assembly a more in-depth explanation, consult the work by Oldfield22 and
(DSMCA), was the most suitable artificial crevice former.69 The Kain.62
DSMCA uses a flat polyvinylidene chloride (PVDC) crevice former
and employs disc springs to maintain a constant force instead of
constant torque during testing, which is especially critical in long-
Nonelectrochemical Test Methods
term immersion tests at elevated temperatures.70 Figure 4C details Nonelectrochemical immersion tests involve immersing a crev-
the CREVCORR crevice configuration. The CREVCORR project iced specimen for different lengths of time in solutions that often
also adapted the DSMCA configuration to evaluate stainless steel contain anions that promote crevice corrosion such as chlorides
pipes. Finite-element modeling was employed to quantify the and, in some instances, an oxidizing agent that facilitates the ini-
clamping force distribution and the uniformity of the crevice condi- tiation of crevice corrosion (e.g., Fe3þ cations). The crevice cor-
tion within the crevice former.71 rosion resistance, then, is determined based on mass loss and
He, Noël, and Shoesmith72 and Jakupi, Noël, and Shoe- visual observations. Visual characterizations include crevice
smith73 developed a single crevice array to study crevice corro- depth, number of crevice sites, location of the crevice attack
sion of highly resistant alloys, including titanium grade 2 and within the cavity, and the corrosion morphology.
FIG. 4 Different types of MCAs: (A) serrated MCA and Ti Gr. 2 bolts and nuts compliant with ASTM G48, (B) assembled PTFE tape-covered
ceramic MCA, and (C) a CREVCORR DSMCA setup.
(A) (B)
(C)
ASTM G48 is the most commonly used standard to assess (FeCl3; equivalent to 10 wt% FeCl36H2O) solution (unadjusted
pitting and crevice corrosion resistance of stainless steels and pH ¼ 1.0 to 2.0),75 designed to produce localized corrosion of
nickel-based alloys and to provide a quantitative ranking of crev- UNS S30400 (type 304) stainless steel at room temperature.
ice corrosion resistance. The current version of ASTM G48 The relative performance of alloys in 6 wt% FeCl3 correlated
(2011, reapproved in 2015) has six text methods. Methods A, C, well with their performance in natural seawater at ambient
and E cover pitting corrosion resistance, whereas Methods B, D, temperature76 and strongly oxidizing, low-pH, chloride-
and F describe different techniques to assess crevice corrosion containing environments,22 but exceptions also have been
susceptibility. Additionally, ASTM G78, Standard Guide for Crev- reported.11,22,77,78
ice Corrosion Testing of Iron-Base and Nickel-Base Stainless The standard recommends 22 6 2 and 50 6 2 C for the
Alloys in Seawater and Other Chloride-Containing Aqueous Envi- evaluation, but other values could be used depending on the
ronments, details guidelines to evaluate the crevice corrosion expected corrosion resistance of the alloy. The artificial crevice is
resistance of iron- and nickel-based alloys in seawater and other formed using two TFE-fluorocarbon blocks, 12.7 mm in diame-
chloride environments. ter and 12.7 mm in height, secured by fluorinated O-rings or
Although ASTM G48 Methods B, D, and F and ASTM G78 rubber bands that should be low in sulfur (i.e., <0.02%). The
are discussed in detail in the following sections, for a comprehen- surface roughness of the crevice formers is not specified. A 25 by
sive description, consult the latest versions of these standards. 55 mm test specimen is recommended as the standard size, but
other dimensions are allowed. According to the standard, both
ASTM G48 METHOD B: THE RUBBER BAND TEST the surface finish and the thickness of the coupons can influence
ASTM G48 Method B is used to assess the pitting and crevice the results. The standard also recommends storing the samples
corrosion resistance of stainless steels and nickel-based alloys in air for 24-h after grinding or pickling and before testing to
to chloride-containing environments. The procedure involves restore the naturally occurring passive film. Figure 5A illustrates a
immersing a creviced specimen in a 6 wt% iron (III) chloride typical test specimen before exposure.
FIG. 5 ASTM G48 Method B (A) type 304 stainless steel creviced specimen before exposure and (B) crevice corrosion attack after
immersion in 6 wt% FeCl3.
(A) (B)
After assembling the crevice formers, the coupons are critical crevice temperature (CCT) of a material. In the standard,
immersed in the electrolyte for 72 h, but other exposure times the CCT is defined as the minimum temperature, in degrees Cel-
also are permitted. The standard, likewise, allows for sample sius, to produce crevice attack at least 0.025-mm deep on the
removal and inspection; nevertheless, care should be exercised bold surface of a specimen beneath the crevice former, ignoring
because sample withdrawals could lead to variations in the rate edge attack. The methods also can be used to rank alloy perfor-
of attack. After the predetermined exposure duration, the sam- mance, aid in materials selection, and the design of new
ples are removed from the solution, visually inspected, and materials.56,80–83
weighted with a minimum accuracy of 0.001 g. ASTM G46, Stan- Methods D and F involve immersing creviced samples in
dard Guide for Examination and Evaluation of Pitting Corrosion, acidified 6 wt% FeCl3 þ 1 wt% hydrochloric acid (HCl; pH
can be used to characterize the extent of the attack. adjusted to pH ¼ 1.0) for a period of time. Both methods use
The rubber band method is inexpensive, easy, fast to assem- TFE-fluorocarbon MCA, and various geometries and construc-
ble, and produces useful comparative results in a short time. The tion materials are allowed. Method D recommends a torque of
ASTM G48 Method B technique, however, has a few disadvan- 0.28 Nm, whereas Method F suggests 1.58 Nm for stainless
tages and limitations. For example, as shown in figure 5B, in cer- steel. Authors also have reported, however, that applied torque
tain alloys, particularly the less alloyed materials, such as type values between 2 and 8 Nm were required to produce the most
304 stainless steel, crevices can initiate at the contact point reproducible crevice corrosion results when evaluating highly
between the rubber bands and the specimen. Indeed, similar corrosion-resistant nickel alloys.84 The recommended duration
approaches were used in classical corrosion lectures to demon- of the immersion is 72 h (Method D) and 24 h (Method F). The
strate that stainless steels could be “cut in half” with a rubber length of the tests has been evaluated by interlaboratory testing.
band.16 Likewise, the test is invalid if either rubber band or The initial temperature of the test solution may be estimated
O-ring breaks during testing, and the compressive pressure using the empirical expressions shown in equations (5) and (6). The
exerted by the rubber band onto the crevice formers is not uniform minimum temperature is 0 C and the maximum 85 C because of
and can be difficult to replicate. Moreover, DeForce has shown that the thermal degradation of the ferric chloride electrolyte.
the type of rubber band used affects the results.79 According to the
author, “specifying the rubber band elasticity (or rubber content) Method D: ð1:5 %CrÞ þ ð1:9 MoÞ þ ð4:9 %NbÞ
(5)
can improve the repeatability of ASTM G48 Method B.” Last, þ ð8:6 %WÞ 36:2:
although the mass loss is recorded after testing, there is currently
Method F: ð3:2 %CrÞ þ ð7:5 MoÞ þ ð10:5 %NÞ
no acceptance criterion. Producers and end-users have commer- (6)
cially accepted criteria, such as a maximum of 0.038 mm crevice þ ð8:6 %WÞ 81:0:
depth and 0.2 mg/cm2 mass loss. In all cases, the user and the ven-
A chief limitation of equations (5) and (6) is that the empirical
dor should agree on the pass or fail criteria.
expressions consider the effects of bulk composition alone, with-
out taking into account the influence of alloy microstructure. For
ASTM G48 METHODS D AND F: CREVICE example, sensitized and properly annealed stainless steels will
CORROSION TEMPERATURE have identical CCT values according to equation (5), yet the
ASTM G48 Methods D (nickel- and chromium-bearing alloys) actual CCT will be drastically lower in the sensitized samples
and F (stainless steels) overcome some of the limitations of the given the local depletion of chromium and molybdenum adja-
rubber band technique and allow the determination of the cent to, for example, chromium carbides.85,86 Likewise, the
expressions fail to capture the complex and intricate effects of regard, the difference between CCT and CPT was about 20 C for
alloying elements. Moreover, the equations were obtained by the low-PRE alloys (i.e., PRE ¼ 24) and increased to approxi-
regression analysis using a limited set of alloys.86 Interestingly, mately 50 C for UNS S31254, which has a PRE of about 43. A
alloy C-276, which has a nominal composition of 15.5 wt% chro- conclusion that can be drawn from Garner’s work is that the
mium, 16 wt% molybdenum, and 4 wt% tungsten, would have a more highly alloyed corrosion-resistant alloys (CRAs) can be
predicted CCT ¼ 51.85 C, whereas the more corrosion resistant susceptible to crevice corrosion while maintaining an excellent
alloy C22 (22 wt% chromium, 13% molybdenum, and 3 wt% pitting corrosion resistance, as discussed previously in this chap-
tungsten) should have a CCT of approximately 47 C. ter. Recently, Klapper et al.92 produced a comprehensive compi-
Testing shall begin at the nearest increment of 5 C, esti- lation of CPT and CCT values for a broad range of nickel alloys
mated based on equations (5) or (6). The temperature shall be with PRE values ranging from 25 to approximately 70. Klapper
recorded and maintained within 61 C during testing. Only one et al.’s results agree well with the work by Garner, with CCT val-
specimen is permitted per test vessel. The samples are removed ues for alloys with a PRE of 25 being 40 C lower than CPT. The
at the end of the exposure, rinsed with deionized water, and difference between CPT and CCT increased to more than 80 C
scrubbed with a nylon brush under running water to remove for alloys with a PRE between 68 and 70. Likewise, the crevice
loosely adhered corrosion products and are dried using com- corrosion induction time is typically shorter than that of pitting
pressed air or nitrogen gas. corrosion.24,93 Consequently, the duration of pitting tests is lon-
The specimens are then visually inspected after cleaning, ger than a crevice test in the same environment. Last, CPT values
and the weight loss is measured with a precision of 0.001 g. The are more reproducible than CCT (i.e., 2.5 vs. 10 C).47,70,94
recommendations of ASTM G46 can be followed to quantify the
crevice attack. During the visual examination, the location of Precision and Bias in Critical Temperature Tests
the crevice attack shall be determined, as well as the number of
As detailed in ASTM G48, the precision of Methods D and F for
MCA sites showing signs of crevice corrosion. A full characteri-
measuring the pitting and crevice corrosion resistance was deter-
zation includes the determination of the greatest depth of attack.
mined in an interlaboratory test program in which seven labora-
As per ASTM G48, crevice corrosion is considered to be present
tories carried out triplicate tests on four materials. The results of
if the local attack is 25 lm or higher in depth, but the standard
these tests are given in Table 5. Results were consistent among
does not give any weight-loss acceptance criterion.
laboratories, and there were no statistically significant variations
The CCT obtained by ASTM G48 must be interpreted with
between the materials in either repeatability or reproducibility.95
caution. Although CCT values are well defined within a narrow
range of temperatures, the CCT is not a property of a material,
but rather a function of the experimental methodology. The test ASTM G78: CREVICE CORROSION SUSCEPTIBILITY
technique, the composition of the environment, the resulting
IN SEAWATER
corrosion potential in the solution, and the presence of inhibiting
ASTM G78 is used to determine crevice corrosion susceptibility
species all influence CCT results. Indeed, high chloride concen-
in seawater and other chloride environments. The scope of the
trations, and corrosion potentials, and long exposure times tend
standard is on iron- and nickel-based alloys, but it can be applied
to result in lower CCT.87
to other alloy systems. The standard suggests a multitude of dif-
Researchers have shown that the critical pitting temperature
ferent crevice former geometries, including MCA of various
(CPT) and the CCT follow a similar trend with alloy composition,87
designs, O-rings, gaskets, strips, and coatings, if testing complex
which traditionally has been captured in the pitting-resistant equiv-
geometries. Specimens could be flat or cylindrical or have intri-
alent (PRE) expression. Different expressions have been proposed
cate shapes and be made of different polymers—including trans-
to define the PRE of stainless steels and nickel alloys, and a detailed
parent acrylics—ceramics, glass, metals, wood, and rubbers.
discussion is outside the scope of the current chapter. For more
Specimens shall maintain a constant boldly exposed (crevice-
information, the work of Malik et al.,87 Lorentz and Medawar,88
free) to shielded (crevice) area ratio to ensure reproducible
and Jargelius-Pettersson89 can be consulted. Presently, various inter-
results that are not restricted by the cathode area.
national standards, such as NORSOK M-00190 and ISO 21457,91
The exposure temperature is user-defined, and it shall be
respectively, define PRE as follows:
maintained within 2 C and recorded during testing. As with
ASTM G48, tests at different temperatures can be used to deter-
PRE ¼ %Cr þ 3:3 %Mo þ 16 N, (7)
mine the CCT. The recommended immersion time is 30 days.
PRE ¼ %Cr þ 3:3 ð%Mo þ 0:5 WÞ þ 16 N. (8) Sampling at different time intervals is permitted. A test program
can be designed to quantify the crevice induction time by care-
In equations (7) and (8), the concentrations are given in fully planning frequent extraction intervals.
weight percent. Qualitatively, the higher the PRE, the better the After immersion, the specimens are visually inspected to
localized corrosion resistance of an alloy. Garner showed that determine the maximum crevice depth—measured to the nearest
both the CPT and the CCT of various stainless steels and nickel 0.01 mm—and the affected area. When using MCA, the number
alloys correlated well with their respective PRE, that is, CCT of segments showing crevice corrosion also should be reported.
increased with the degree of alloying, especially their molybde- In addition, samples shall be weighed after exposure to deter-
num content.76 CCT values also were lower than CPT. In this mine weight loss.
TABLE 5 Results of the Second Interlaboratory Test Program
Method E, CPT Critical Pitting Corrosion Temperature (8C) Method F, CCT Critical Crevice Corrosion Temperature (8C)
Alloy/Laboratory UNS S31603 UNS S31803 UNS S44735 UNS N08367 UNS S31603 UNS S31803 UNS S44735 UNS N08367
a a a a a a
1 15/15/ 30/30/30 85/85/85 75/ 0/0/0 15/ / 30/ / 30/30/30
2 10/a/a 25/25/a 80/80/80 75/75 0/0/0 15/15/15 30/30/30 25/25/25
3 0/0/0 25/25/a 80/80/80 70/70/a 0/0/0 20/20/20 35/35/35 30/30/a
a a a a
4 15/15/ 30/30/30 75/ / 75/75/ 0/0/0 20/20/20 20/20/20
5 15/15/15 20/a 80/80/80 70/70/70 0/0/0 20/20/20 35/35/35 30/30/30
6 40 75 0/0/0 15 35 25
7 15/15/15 35/35/35 >85/>85/>85 75/75/75 0/0/0 25/25/25 35/a/a 30/30/30
Note: Minimum temperature ( C) to produce an attack at least 0.025-mm (0.001-in.) deep on the bold surface of the specimen. Edge attack ignored.
a
Test run but no attack observed.
NATURAL VERSUS SYNTHETIC SEAWATER electrolyte measured under open-circuit conditions versus a refer-
It is common to use either a 3.5 wt% NaCl solution or the ASTM ence electrode.1 At ECorr, the rate of the sum of the anodic reactions
D1141, Standard Practice for the Preparation of Substitute Ocean equals that of the cathodic reactions and, thus, the net current is
Water,96 artificial seawater composition to simulate natural sea- zero. Other experiments with no applied polarization employ a
water in the laboratory. Although these methods reproduce the zero-resistance ammeter to measure the current flow between two
chemical concentration of natural seawater, they do not take into working electrodes, which can be identical or dissimilar.
account the influence of microorganisms and biofilm formation Tests conducted under an applied current or potential can be
that takes place in natural environments. The establishment of used to quantify critical potentials. Critical potentials include the
biofilms has been shown to increase the corrosivity of seawater pitting and crevice potentials (EP or ECrev, respectively) as well as
drastically.97–99 Indeed, the corrosion potential increases to about critical repassivation potentials (ER or ER,Crev, depending on
þ300 mVSCE upon the development of a biofilm.100 This increase whether the experiments are performed using artificial crevices).
in potential is often enough to polarize stainless steels above the Potentiostatic tests (i.e., experiments under a fixed potential) also
critical pitting or crevice potential, depending on the PRE of the can provide information regarding the induction time, s. Addition-
alloy.100,101 ally, the critical pitting or crevice temperatures can be obtained
A second objective of the CREVCORR program discussed when multiple electrochemical tests—either at ECorr or employing
earlier was to develop alternative synthetic seawater chemistry an external polarization—are performed at different temperatures.
that would better simulate the effect of biofilms during labora- This section describes conventional approaches that have
tory testing.102 On the basis of comprehensive electrochemical been implemented by researchers to quantify localized corrosion
measurements, the CREVCORR project proposed two possible resistance, rank alloy families based on performance, and study
synthetic seawater compositions. The so-called Chemical localized corrosion mechanisms.
Method uses 3.5 wt% NaCl with the addition of 1 mM hydrogen
peroxide (H2O2) and 1 mM gluconic acid (C6H12O7). The Bio-
chemical Method involves adding glucose oxidase (GOD) (100 ELECTROCHEMICAL TEST METHODS WITH NO
U/L) and 20 mmol/L glucose to either 3.5 wt% NaCl or a simpli- EXTERNAL POLARIZATION
fied version of the ASTM D1141 composition (i.e., NaCl 24.53 Corrosion Potential Measurements
gL1, MgCl2 5.20 gL1, Na2SO4 4.09 gL1, CaCl2 1.16 gL1, Oldfield and Sutton showed that the initiation of crevice corro-
KCl 0.695 gL1, NaHCO3 0.201 gL1) referred to as simplified sion of stainless steels is accompanied by a sudden decline in
ASTM-type seawater.102 Appendix D of the EFC Publication No. ECorr from values within the passive region to low values around
60 details a proposal for an ISO standard specification for syn- the critical potential (i.e., ECrev). The authors showed that the ini-
thetic biochemical ocean or seawater. Nevertheless, the standard tial drop was associated with the formation of micro-pitting
has yet to be published.103 within the crevice gap, followed by pit coalescence and spreading
into a well-developed crevice attack.24 Haugan et al., for example,
recently used ECorr to determine induction times of different
Electrochemical Test Methods super-duplex stainless steels (SDSS) as a function of temperature
Electrochemical methods are powerful tools to obtain not only a when exposed to natural seawater.70 Because they are nonde-
comparative ranking of localized corrosion performance but also structive, ECorr measurements also could be used to assess the
quantitative information regarding pitting and crevice mechanisms. risk of localized corrosion of immersed structures in real-time
Tests can be conducted without an external polarization at the so- during field monitoring and, as suggested by Dunn, Cragnolino,
called corrosion potential (ECorr) or under different polarization and Sridhar,104 to model the long-term performance of
profiles. ECorr is the potential of a corroding surface in a given corrosion-resistant alloys.
Standard test methods such as ASTM G48 and G78 can be The remote crevice assembly simulates a real crevice in
adapted to include ECorr monitoring to indicate the initiation of which the crevice-free sample acts as a net cathode and the crev-
localized corrosion.105 Figure 6 shows the ECorr of UNS S32750 ice sample as the net anode. As with any test method based on
immersed in 6 wt% FeCl3 (pH ¼ 1.10) as a function of time during zero-resistance amperometry (ZRA), both the magnitude and
a stepwise increase in temperature. The temperature was increased the direction of the current flow carry information about the cor-
by 5 C increments every 24 h if the ECorr remained within typical rosion process. For this reason, it is crucial to define a sign con-
passive potentials, that is, approximately 0.68 VSCE. The sudden vention. In this regard, it is common to connect the two working
drop in potential at 75 C marked the initiation of localized electrodes so that a positive current represents the flow of elec-
corrosion, which was confirmed visually after testing. In this trons from the creviced to the crevice-free specimen.109
example, the CPT was defined as 75 C. Others have suggested The remote crevice assembly is sensitive to the early stages
the use of ECorr monitoring during ASTM G48 testing, as an of crevice corrosion, and it has been used to quantify crevice cor-
additional pass/fail criteria, which may be especially relevant in rosion initiation and propagation,110 to model crevice corrosion
quality control test methods, such as ASTM A923, Standard of UNS N06625,111 and to determine the effect of biofilms on
Test Methods for Detecting Detrimental Intermetallic Phase in crevice corrosion of corrosion-resistant alloys.112 More recently,
Duplex Austenitic/Ferritic Stainless Steels,106 and to detect sensi- Martin, Lucas, and Hogan113 adapted the remote crevice assembly
tized microstructures.107 technique to study the crevice corrosion resistance of Ni-Cr-Mo
alloys exposed to seawater.
The Remote Crevice Assembly Visual inspection after exposure is paramount to correlate
First used by Lee,108 the remote crevice assembly implies cou- the observed current trends with the degree of crevice corrosion.
pling a creviced specimen to a crevice-free coupon, both made of Likewise, although there is no international standard regulating
the same material. The galvanic current flow between specimens the methodology and no consensus on a critical current value to
is, then, recorded using a zero-resistance ammeter. The coupled define the initiation of crevice corrosion, ASTM G71, Standard
potential is monitored concurrently with the net galvanic current Guide for Conducting and Evaluating Galvanic Corrosion Tests
as a function of time. The area of the noncreviced sample should in Electrolytes,114 can be used as a guide.
be larger than that of the creviced coupon to ensure the cathodic
Zero-Resistance Amperometry and Electrochemical Noise
reactions are primarily sustained on the crevice-free side. The
Salinas-Bravo and Newman115 and Garfias116–119 popularized the
choice of area ratio depends on the intended application, and
use of ZRA to determine critical pitting temperatures of stainless
experiments can be conducted with different anode-cathode
steels. Later, others employed electrochemical noise (EN) analy-
ratios to study the possible effects of the cathode area. For
sis to investigate the crevice corrosion resistance of stainless
instance, in a low-conductivity solution, such as the case of con-
steels under simulated high-pressure high-temperature oil and
densed water films, the area ratio is expected to be small (e.g.,
gas environments.109
2:1). In contrast, in full-immersion tests in seawater, the ratio
As with the remote crevice assembly, ZRA and EN measure
can be quite high (e.g., 300:1).100
the current flow between two working electrodes. Unlike the
remote crevice assembly, ZRA and EN require two identical
creviced specimens. During ZRA and EN testing, the start of
FIG. 6 ECorr of UNS S32750 as a function of time during crevice corrosion leads to an increase in current—which can be
immersion in 6 wt% FeCl3 (pH ¼ 1.1) and a stepwise either positive or negative depending on the electrode that first
increase in temperature. The duration of each step was developed crevice attack—and a drop in coupled potential. A
24 h. The sudden drop in ECorr marks the initiation of change in sign indicates a reversal in the net anodic or cathodic
localized corrosion. behavior versus the defined sign convention. Figure 7A shows the
coupled current and potential of creviced UNS S32760 speci-
mens in 6 wt% FeCl3 (pH ¼ 1.10) as a function of temperature
during ZRA testing. In this case, the temperature was increased
at 0.2 C/min. The initiation of crevice corrosion was defined as a
sustained current above 5 lA after Salinas-Bravo and Newman.115
In this case, the critical crevice temperature, TCrev, was 41.8 C.
Herein, the nomenclature TCrev is used instead of CCT to indi-
cate the critical temperature was determined using electrochemi-
cal means rather than as per ASTM G48.
Unlike ZRA, EN requires a more sophisticated analysis of the
results. In this regard, the data can be analyzed in the time domain
(i.e., as recorded) or transported to the frequency domain using, for
example, a fast Fourier transformation (FFT) algorithm or the max-
imum entropy method (MEM). Once transformed into the fre-
quency domain, Power Spectral Density (PSD) plots can be
constructed to analyze EN current and potentials as well as to
FIG. 7 ZRA testing of UNS S32760 in 6 wt% FeCl3 (pH ¼ 1.1) (A) current and potential as a function of temperature and (B) crevice
corrosion attack.
(A) (B)
obtain the EN impedance. For a detailed overview of the EN analy- current steps wherein the time duration and current incre-
sis, consult the work by Cottis120 as well as ASTM G199, Standard ments or decrements are equal for each step.
Guide for Electrochemical Noise Measurement.121 • Potentiodynamic or potentiokinetic polarization—a technique
As with the remote crevice assembly technique, visual wherein the potential of an electrode with respect to a reference
inspection after exposure is required to correlate the observed electrode is varied at a selected rate (e.g., 0.6 V/h) by the applica-
current trends with the degree of crevice corrosion, figure 7B. tion of a current through the electrolyte. When the potential is
The ASTM G199 standard can be used as a guide. scanned in a direction so that EApp ECorr, the result is an
anodic polarization curve (i.e., an E-i diagram). Anodic polariza-
ELECTROCHEMICAL METHODS EMPLOYING AN
tion diagrams are used to determine (e.g., EP and ECrev). ASTM
APPLIED POLARIZATION
G59, Standard Test Method for Conducting Potentiodynamic
The techniques for evaluating crevice corrosion that employ an
Polarization Resistance Measurements, describes a method to
applied polarization involve holding or incrementally changing,
conduct potentiokinetic anodic polarization measurements on
either in steps or at a fixed scan rate, the potential or current.
stainless steels and nickel alloys, which also can be applied to
Some of the more common test methods, as defined in the
other alloy families.122
ASTM G193 standard, are as follows:
• Cyclic potentiodynamic polarization—a technique in which the
• Potentiostatic polarization—a technique used to maintain a applied potential is scanned forward from some low value, typi-
constant electrode potential. The current response is mea- cally ECorr, to a high value until reaching a predefined current
sured as a function of time. Different samples can be exposed density (e.g., 5 mA/cm2) or potential and then is scanned back-
at different applied potentials (EApp). ward to a predetermined potential or current value. The reverse
• Galvanostatic technique—a technique wherein an electrode is scan continues until the hysteresis loop closes or until a new
maintained at a constant current in an electrolyte. The result- corrosion potential is reached. The method is described in
ing electrode potential is recorded as a function of time. Dif- ASTM G61, Standard Test Method for Conducting Cyclic Poten-
ferent samples can be exposed at different applied currents or tiodynamic Polarization Measurements for Localized Corrosion
current densities (IApp or iApp, respectively). Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys.
• Potentiostaircase or potentiostep technique—a potentiostep These techniques are often used alone or combined with varying
technique for polarizing an electrode in a series of constant other environmental factors, such as temperature, pH, and chloride
potential steps wherein the time duration and potential incre- concentration, as discussed previously. It is important to emphasize
ments or decrements are equal for each step. Nevertheless, that, for a given environment, critical potentials and temperatures
when studying crevice corrosion, the duration of each step are not a property of the metal or alloy, as they are influenced by
can be varied. experimental parameters, such as potential and temperature scan
• Galvanostaircase or galvanostep technique—a galvanostep rate,14,123,124 and the selected current at scan reversal.125 These and
technique for polarizing an electrode in a series of constant other methods are described in more detail in the next section.
POTENTIOSTATIC ELECTROCHEMICAL TEST corrosion starts and repassivates. In their earlier work, Steinsmo
METHODS et al. applied a þ600 mVSCE potential to simulate chlorinated
Chronoamperometry seawater and a temperature scan rate of 4 C/24h; a technique
Chronoamperometry involves applying either a constant potential often referred to as cyclic thermammetry.128 In the case of UNS
or a series of potential steps and recording the resulting current or N08367, the authors observed an approximately 50 C difference
current density as a function of time. Tests can be performed using between TCrev and TR, Crev. The difference between TCrev and
creviced and crevice-free specimens. Chronoamperometry is pri- TR,Crev (shown in fig. 8) was about 8 C, which was much lower
marily used to estimate induction times.126,127 Nevertheless, chro- than the values reported by Steinsmo et al. for other corrosion-
noamperometry can be used to determine critical temperatures (i.e., resistant alloys.101 The difference in the case of UNS S39274 was
TPit or TCrev) when done as a function of temperature. Repassiva- attributed to the influence of tungsten.
tion temperatures also can be obtained if the temperature is reduced ASTM F746: Pitting or Crevice Corrosion of Metallic Surgical
after pitting or crevice corrosion initiation. Implant Materials
Figure 8 shows current density as a function of time of a ASTM F746, Standard Test Method for Pitting or Crevice Corro-
creviced UNS S39274, that is, a high-W SDSS, immersed in natu- sion of Metallic Surgical Implant Materials, is used to assess the
ral seawater during a stepwise increase in temperature followed pitting and crevice corrosion resistance of surgical implant mate-
by a stepped decrease in temperature. The applied potential was rials.129–131 The localized corrosion resistance is determined based
þ300 mVSSE to simulate the effect of naturally occurring bio- on the critical potential, ECrit, to initiate pitting, crevice corro-
films.100 During the forward ramp, the temperature was held for sion, or both. The primary purpose of the specification is to per-
15 days at each step. If no increase in current was observed, the form a laboratory screening of materials. Tests are conducted in
temperature was increased by 5 C. The ramping continued until phosphate-buffered saline (PBS) solution—8.0 gL-1 NaCl, 0.2
an apparent increase in current was observed. The critical crevice gL-1 KCl, 1.44 gL-1 Na2HPO4, and 0.24 gL-1 KH2PO4—with a
temperature, TCrev, was adapted after Steinsmo et al.,101 as the tem- pH between 7.3 and 7.5. The temperature of the electrolyte is set
perature step at which the current density exceeded 25 lA/cm2 to 37 6 1 C to simulate the temperature of the human body. The
for at least 4 h. This value was chosen because it corresponded standard employs cylindrical specimens that are 6.35 mm in
to a marked deviation from the passive current density. Once diameter and 20 mm in length. The crevice assembly consists of
the current density was reached, the temperature was then an inert tapered PTFE collar, 3.18 mm in width. The collar is
decreased in a 7-day period at 2.5 C steps, until a stable passive force-fit into the specimen from the base of the cylinder. Figure 9
behavior was observed. The repassivation temperature was arbi- illustrates the ASTM F746 crevice setup.
trarily defined as the temperature at which the current density The procedure has three steps. Step 1 involves the measure-
dropped below the 25 lA/cm2 threshold and stable passive ment of a stable corrosion potential for 1 h, referred to as E1.
current density values were observed. Step 2 is the stimulation step. The purpose of the stimulation
Figure 8 and the work of Steinsmo et al.101 illustrate well the step is to initiate localized corrosion. The applied potential is set
hysteresis that exists between the temperature at which crevice at EApp ¼ þ800 mVSCE, whereas the duration depends on the
FIG. 8 (A) Current density and temperature as a function of immersion time of UNS S39274 in natural seawater at an applied potential of
EApp ¼ þ300 mVSSE and (B) visual appearance after 110 days of exposure.
(A) (B)
other values can be used. A test at þ600 or þ800 mVSCE can be

FIG. 9 ASTM F746 crevice assembly (A) exploded view and performed to determine changes in the critical temperature.
(B) assembled working electrode. During testing, the temperature is ramped at 1 C/min. The
potential-independent CPT or CCT is defined as the temperature
at which i > 100 lA/cm-2 for 60 s. Visual confirmation is
required at the end of the test to verify the presence of pitting
and crevice corrosion. Figure 10 illustrates a modified ASTM
G150 test using a PTFE MCA on UNS S32750. The applied
potential was þ700 mVSCE, and the CCT varied between 61 C
and 65 C.
POTENTIOKINETIC ELECTROCHEMICAL TEST

METHODS
Modified ASTM G61: Cyclic Potentiodynamic Polarization
ASTM G61 is arguably the most common electrochemical tech-
nique used to determine the relative susceptibility to localized
corrosion, namely, pitting or crevice, of stainless steels as well as
cobalt- and some nickel-based alloys. ASTM G61 focuses on
crevice-free specimens, but the standard can be modified to
study creviced samples. The crevice former is often an MCA that
complies with, for example, ASTM G48. The analysis of the E-i
(A)
diagrams provides information about the critical crevice and
crevice repassivation potentials, ECrev and ER,Crev (EP and ER if
using crevice-free samples). Likewise, the critical crevice temper-
ature and critical repassivation temperature (TCrev and TR,Crev,
(B) respectively) can be obtained when multiple experiments are per-
formed at different temperatures. When done on crevice-free
current response. If the current density instantly increases above specimens, the standard can be used to check one’s experimental
þ500 lA/cm2, the potential is immediately decreased to E1. If technique and instrumentation.
the current generally increases but i < þ500 lA/cm2, the poten- As per ASTM G61, experiments are performed in deaerated
tial is reduced to E1 after 20 s. The test is terminated if there is 3.56 wt% NaCl (neutral pH) at 25 6 1 C, but other environ-
no sharp increase in current density after 15 min. ments and temperatures can be used. The test is divided into two
Step 3 is the repassivation step. In Step 3, the applied potential steps. First, the working electrode is exposed at the corrosion
is decreased to EApp ¼ E1. If no repassivation is observed, that is, potential for 1 h until a stable ECorr is obtained. The
the current remains above the passive current density, ECrit is
defined as ECrit ¼ E1. If repassivation occurs, the process is repeated.
The new applied potential in Step 3, after the new stimulation step,
is set as EApp ¼ E1 þ 50 mV. The sequence is continued until no FIG. 10 An example of i versus temperature curve of UNS S32750
repassivation occurs in Step 3. The assessment entails the quantifi- in 1 M NaCl as per ASTM G150.
cation of ECrit and a visual confirmation after testing.
Modified ASTM G150: Potential-Independent Critical

Temperature
ASTM G150, Standard Test Method for Electrochemical Critical
Pitting Temperature Testing of Stainless Steels and Related Alloys,
is used to determine the so-called potential-independent critical
pitting temperature. The tests can be modified to determine the
potential-independent critical crevice temperature by employing
creviced specimens, as described in ASTM G48 or G78 (fig. 4).
ASTM G150 also can be used to predict the conditions that would
result in stable crevice propagation. The test method applies to
stainless steels from UNS 31600 to S31254, but it could be
extended to other alloy families. Tests are performed in deaer-
ated 1 M NaCl (unadjusted pH). The technique implies applying
a fixed potential and measuring the current response as a func-
tion of time. The recommended potential is þ700 mVSCE, but
potentiodynamic polarization commences immediately after the and ER,Crev.70 For creviced specimens, hysteresis, DE, is defined
1-h stabilization step. The potential is scanned at 0.6 V/h (0.168 as follows:
mV/s) in the forward direction until reaching a current density
DECrev ¼ ECrev ER,Crev , (9)
threshold of 5 mA/cm2. Once the current density threshold is
met, the direction of the scan is reversed until the hysteresis loop When evaluating crevice-free samples—where hysteresis is
closes or once reaching a new ECorr. Data are plotted in an E-i defined as DE ¼ ER EP—it is accepted that alloys with large DE
diagram, where the current density i is presented in logarithmic values are more susceptible to localized corrosion than those
scale. with small hysteresis loops.14
There are different ways to determine pitting, crevice, and Figures 11A and 11B show two potentiokinetic E-i curves of
repassivation potentials from E-i diagrams. According to Sridhar UNS S32750 in 3.56 wt% NaCl at two different temperatures. Each
and Cragnolino,125 EP can be measured at the inflection point of diagram presents two repetitions to illustrate the test-to-test vari-
the E-i plot, while ER is defined as the potential, in the backward ability. The E-i curves shown in figure 11A and figure 11B were
scan, where the current density reaches 2 lA/cm2. A similar con- obtained at 30 C and 60 C, respectively. In Figure 11A, the sharp
vention can be applied to tests using MCAs to determine ECrev increase in current was associated with the transpassive region and,
FIG. 11 Cyclic anodic polarizations of creviced UNS S32750 samples in 3.56 wt% NaCl at (A) 30 C and (B) 60 C. (C) The critical crevice
repassivation temperature is shown in the E versus T diagram.
(A) (B)
(C)
thus, the potential was labeled ETrans. The transpassive region repre- galvanostatic (GS) step starts after reaching the current density
sents the “region of an anodic polarization curve, more positive threshold. In the GS period, the pre-set current is kept constant
than the passive potential range, in which there is a significant for 2 h, while the potential is recorded as a function of time. The
increase in current density (increased metal oxidation) as the poten- goal of the GS step is to develop and grow crevice attack if any
tial becomes more positive.”1 In contrast, a large hysteresis loop was develops. After the 2-h GS period, the potential is decreased at
obtained at 60 C, figure 11B. The forward scan in figure 11B also 10 mV intervals. The duration of each step is 2 h and the current
reached high positive values, but crevice corrosion occurred upon is recorded versus time. ER,Crev is defined as the highest potential
scan reversal as confirmed visually. The high DE value suggested for which the current does not increase with time. The presence
that the driving force for crevice corrosion was large.46 Figure 11C and extent of crevice corrosion are verified using visual inspec-
presents an E versus temperature plot, constructed from a series of tion after testing.
cyclic anodic polarization curves performed at different tempera-
tures. The critical crevice repassivation temperature, TR,Crev, was Precision and bias in ASTM G192 testing
56 C. Figure 11C also illustrates that the critical temperature has a Under some testing conditions, results from this method may be
well-defined value, as suggested by Brigham and Tozer,47,48 which comparable to results from ASTM G61. The current Tsujikawa
in this case was within 5 C and limited by the temperature interval and Hisamatsu electrochemical (THE) test method is meant to
chosen for the tests. be a complement to ASTM G61. The THE test method may pro-
duce crevice corrosion in conditions in which cyclic potentiody-
Precision and bias in ASTM G61 testing namic polarizations have limitations caused by transpassive
ASTM G61 shows the precision of the test method based on dissolution.
interlaboratory testing. An investigator’s data should fall within Results of an interlaboratory program showed that the over-
the range of 62 standard deviations because this includes 95% of all crevice repassivation potential for alloy C22 in 1 M NaCl at
all data, provided random variations are the only source of error. 90 C was -107 mVSSE, and the standard deviation was 10.0 mV.
No information is available on the repeatability when one labora- This low standard deviation suggests that the measurement of
tory conducts several identical tests. Crevice corrosion under the repassivation potential using the PD-GS-PS test method is
gaskets may lead to erroneous results. Researchers have found highly reproducible. For more details, ASTM G192 should be
that the scatter in EP and ECrev is much larger than the scatter in consulted.
ER and ER,Crev.104,132,133 For example, the limited experimental
data suggest a scatter in ER,Crev for type 316L stainless steel, and Potentiodynamic-Galvanostatic-Potentiodynamic Technique
UNS N09925 of about 100 mV.104 Although the THE technique circumvents the limitations of the
ASTM G61 method for highly corrosion resistant alloys that
ASTM G192: Tsujikawa-Hisamatsu Electrochemical Technique would otherwise present transpassive dissolution before crevice
Adapted from the work of Tsujikawa and Hisamatsu on stainless corrosion, the method is time consuming and challenging to
steels, ASTM G192, Standard Test Method for Determining the automate.136,139 For this reason, Mishra and Frankel developed a
Crevice Repassivation Potential of Corrosion-Resistant Alloys simplified version of ASTM G192 that replaces the PS step by a
Using a Potentiodynamic-Galvanostatic-Potentiostatic Tech- PD polarization.137 In the so-called PD-GS-PD technique, the
nique,134 is a complex technique that involves potentiodynamic, potential is first scanned at 0.6 V/h (0.168 mV/s) until the prede-
galvanostatic, and potentiostatic steps.135 The test has been used fined current density threshold. The threshold current density
to study the crevice84,136,137 and pitting138 corrosion susceptibility then is applied for 2 h to promote the initiation and propagation
of highly alloyed nickel alloys. ASTM G192 is used to determine of crevice corrosion. After the 2-h GS step, the potential is
the ER,Crev of corrosion-resistant alloys. It is understood that an reverted at a scan rate of 0.6 V/h (0.168 mV/s) until the hystere-
alloy will not develop crevice corrosion below ER,Crev under sis loop closes. The ER,Crev is defined as a crossover potential.
the tested conditions (i.e., electrolyte composition, pH, and The PD-GS-PD method has been used successfully not only
temperature). Although ASTM G192 was developed for alloy on nickel alloys64,84,139–142 but also stainless steels with varying
C22, it applies to any corrosion-resistant alloy. The standard degrees of corrosion resistance.32,33 Figure 12 illustrates an E-i plot
suggests the use of a PTFE tape-covered ceramic MCA and a tor- as well as the E versus time curve recorded during the GS step of
que of 3.4 Nm. The test can be modified to measure the critical UNS N06059 (alloy 59) in 10 M Cl at two different tempera-
crevice repassivation temperature, TR,Crev, if done at various tures, as indicated. As seen in figure 12, crevice corrosion did not
temperatures. occur at 40 C, as suggested by the lack of a positive hysteresis
The tests can be done in any electrolyte, although the loop, which was later confirmed visually (not shown). Crevice
method was developed using a deaerated 1 M NaCl. The recom- corrosion was evident at 90 C, and the hysteresis loop was about
mended test temperature for alloy C22 is 90 C, but lower tem- DE ¼ 200 mV. Figure 12C shows the extent of the crevice attack
peratures can be chosen for less corrosion-resistant metals and after PD-GS-PD testing.
alloys. The procedure has three steps, as follows. The potentiody-
namic (PD) step commences after a 1-h ECorr stabilization Crevice Corrosion Repassivation by Cooling
period. During the PD step, the potential is scanned in the for- Hornus et al.30 recently adapted the PD-GS-PD technique to
ward anodic direction at 0.6 V/h (0.168 mV/s) until a pre-set study crevice repassivation by cooling. The authors named the
current is reached (e.g., 2 lA/cm2 for alloy C22). The technique PD-GS-PD-(PS þ Cooling), which was designed to
FIG. 12 PD-GS-PD test of UNS N06059 in 10 M Cl- solution at 40 C and 90 C (A) E versus I curve, (B) potential versus time during the GS
step, and (C) crevice corrosion attack after testing at 90 C.
(A) (B)
(C)
determine TR,Crev values of nickel alloys. First, the temperature polarization at a given cooling rate of, for example, 3.33 C/h or
of the electrolyte is set to 90 C. After reaching the desired initial 33.3 C/h, until the current reaches typical passive current density
temperature, the procedure involves five steps. Step 1 (PD) con- values. The TR,Crev is determined once i ¼ 1 lA/cm2. Figure 13
sists of an anodic potentiodynamic polarization at 0.6 V/h (0.168 illustrates Step 5 applied to UNS N06625 (alloy 625) and
mV/s) until the anodic current density reaches 20 lA/cm2. In N10362 (alloy Hybrid B-C1) in 0.1 M NaCl at two different cool-
Step 2 (GS), the applied current is set at 20 lA/cm2 for 4-h. ing rates. In this example, the TR,Crev of alloy Hybrid B-C1 was
Given that the current drops instantaneously upon removal of approximately 60 C while that of alloy 625 was approximately
the GS, Step 3 involves a potentiodynamic polarization at 35 C.
0.06 V/h (0.0168 mV/s) until the current density reaches Although applying the PD-GS-PD-(PS þ Cooling) tech-
20 lA/cm2. In Step 4 (PS), the last potential of Step 3 is applied nique to, for example, stainless steels and nickel alloys with
for at least 2 h to produce sufficient crevice corrosion to obtain a relatively low PRE (e.g., PRE <4080) might be excessively com-
conservative TR,Crev value. Likewise, Step 4 was designed to plicated, the method can be used to quantify the critical crevice
ensure a relatively low current density so that the drop in current repassivation temperature of highly corrosion-resistant nickel
during Step 5 can be attributed to the cooling effect exclusively. alloys, which cannot be done using other conventional tests
Last, the temperature is decreased while holding the PS methods.
ACKNOWLEDGMENTS
FIG. 13 PD-GS-PD-(PS þ Cooling) Step 5 applied to UNS N06625 We thank Dr. Ke Wang, Cristian Torres, and Adam Cianfrini for
and N10362 applied potential and cooling rates as
their support in producing the figures for this publication.
indicated.
Terms and Definitions

CCS Critical crevice solution
CCT Critical crevice temperature, as determined by ASTM G48
CPT Critical pitting temperature, as determined by ASTM G48
CRA Corrosion-resistant alloy
DSMCA Disc spring multiple crevice assembly
EApp Applied potential
ECrev Critical crevice potential (crevice initiation potential)
ECrit Critical potential as defined by the critical acidification
model
ECorr Corrosion potential
E*Corr Corrosion potential in a simulated crevice electrolyte.
Eihn Overpotential to reflect the contribution of the presence of
inhibitors in the solution
EN Electrochemical noise
Depassivation pH and the Critical Crevice Solution EP Critical pitting potential (pitting corrosion initiation)
As proposed by Oldfield and Sutton, the depassivation pH ER Repassivation potential
(pHd) is defined as the pH at which a metal or alloy does not ER,Crev Crevice repassivation potential
exhibit any passivity.21,24 The pHd value is associated with the FFT Fast Fourier transformation
critically acidic environment that develops inside a crevice, as g Crevice gap
discussed earlier. In this regard, Oldfield and Sutton referred to I or i Current or current density
the solution that causes the permanent breakdown of the pas- IApp or iApp Applied current or current density, respectively
sive film within a crevice and the rapid propagation of the ipass Passive current density
attack as critical crevice solution (CCS).21,24 According to the L crevice length measured as the distance from the crevice
mouth
authors, the CCS is defined in terms of pH (i.e., the pHd) and
MCA Multiple-crevice assembly
chloride concentration. The pHd and CCS can be obtained
MEM Maximum entropy method
experimentally using polarization curves in crevice-like envi-
PBS Phosphate-buffered saline
ronments as a function of solution pH and chloride concentra-
pHd Depassivation pH
tion. Malik et al.87 and Okayama et al.,143 for example,
PCTFE Polychlorotrifluoroethylene
determined the CCS of a considerable number of CRAs of
PRE Pitting resistant equivalent
increasing PRE. Polarization experiments can be performed
PSD Power spectral density
adapting ASTM G5 and G61 or by monitoring the potential of a
PTFE Polytetrafluoroethylene
specimen under galvanostatic conditions, while simultaneously
PVDC Polyvinylidene chloride
decreasing the pH by the addition of HCl. There are, however,
PVDF Polyvinylidene difluoride
no broadly accepted standard procedures to determine CCS.
SCE Saturated calomel electrode
SSE Silver/silver chloride electrode
Conclusion TCrev Critical crevice temperature measured using electrochemical
methods
This chapter summarized the most common electrochemical and
TCrit Critical temperature (either pitting or crevice)
nonelectrochemical methods to study crevice corrosion. Other
TPit Critical pitting temperature measured using electrochemical
approaches, such as multi-microelectrode array testing and electro-
methods
chemical methods that can quantify local electrochemical reactions
TR,Crev Critical crevice repassivation temperature measured using
with high spatial resolution, were not covered. It is important to electrochemical methods
emphasize that the choice of methodology depends on the problem x Diffusion path
being study. In this regard, all techniques have advantages and dis- xi Galvele’s pitting or crevice stability product
advantages that need to be considered carefully. Indeed, often ZRA Zero resistance amperometry
short-term accelerated laboratory tests should be combined with Polarization needed to reach the critical xi value
long-term exposure evaluations to validate critical parameters, such U The electrical potential induced by the migration of the
as induction times, crevice propagation rates, and critical tempera- aggressive anions to the crevice
tures. The ample literature cited herein can be consulted for more s Induction or incubation time
detailed discussions on crevice corrosion mechanisms.
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41
Chapter 3 | Galvanic
Harvey P. Hack,1 Carol Glover,2 and Jason Lee3
Basic Principles oxygen reduction occurring primarily in acids
ELECTROCHEMICAL REACTIONS O2 þ 4Hþ þ 4e ! 2H2 O, and (4)

To be able to properly design and interpret results from galvanic oxygen reduction occurring primarily in bases or neutral water
corrosion (also called bimetallic corrosion) tests, it is necessary
to have some appreciation of the electrochemical theory behind O2 þ 2H2 O þ 4e ! 4OH : (5)
galvanic corrosion. Metal corrosion consists of at least two reac-
The first of these cathodic reactions generates hydrogen gas and
tions. The first is the metal going into solution in the electrolyte:
is readily observed when zinc or iron are placed in certain strong
M ! Mnþ þ ne : (1) acids. The last two cathodic reactions use oxygen molecules that
are dissolved in the water. Other reduction reactions not illus-
For iron in steel corroding in water at room temperature, this trated include metal ion reduction, such as electroplating.
reaction would be All of these reactions generate or consume electrons and,
therefore, involve the flow of a current. For this reason, they are
Fe ! Fe2þ þ 2e : (2) called electrochemical reactions, and their rates are influenced by
externally applied currents, such as those that control electrode
Because the metal is transformed from an atom with no net
potentials. For example, if electrons are forcibly removed from
charge to an ion in solution with a net positive charge, this type
the anodic corrosion reaction, then the reaction will occur more
of reaction is called an oxidation reaction, and it generates elec-
rapidly. Removing electrons also causes the potential of the cor-
trons. Oxidation reactions require a net increase in charge of the
roding metal, as measured relative to a device with a stable
metal or ion. The presence of oxygen is not required for an oxi-
potential called a reference electrode, to become more positive.
dation reaction to occur. The oxidation reaction involved in the
This is plotted in figure 1. The relationship is illustrated as a
corrosion process is also called the anodic reaction.
straight line, where potential is plotted against the log of the
Because electrons are generated by the oxidation reaction,
reaction rate. This straight-line relationship was first noted by
and because there can be no net accumulation of charge in these
Tafel,1 and the slope of the line honors him by being called the
reactions, another reaction must be occurring that consumes
Tafel slope. Anodic reactions usually have a positive Tafel slope.
these electrons. This is the cathodic or reduction reaction, and it
Ideal reactions frequently yield these straight lines, but in prac-
always results in some species reducing its charge as it gains elec-
tice, it is common to see curved lines. The process of changing
trons. The three common reduction reactions in water follow:
potential by applying a current is called polarization.
hydrogen reduction, occurring primarily in acids
The cathodic reactions also can be plotted on the same type
2Hþ þ 2e ! H2 ðgasÞ, (3) of graph. Adding electrons to the hydrogen reduction reaction
(or to any cathodic reaction) will increase the rate of that reac-
tion and shift the potential in the negative direction. This is
shown in figure 1 as another straight line with a negative Tafel
slope. Electrochemical reactions generate or consume electrons,
1
Northrop Grumman Corp., 895 Oceanic Dr., Annapolis, MD 21409, USA and therefore, the rate of a reaction is equivalent to the electron
http://orcid.org/0000-0001-9887-2285
2
current generated or used up by that reaction.
Center for Electrochemical Science and Engineering, University of Virginia, 395
McCormick Rd., Charlottesville, VA 22904, USA http://orcid.org/0000-0002-
9220-622X
GALVANIC SERIES
3
U.S. Naval Research Laboratory, 1008 Balch Blvd., Stennis Space Center, MS Because no charge can accumulate on any metal surface, the
39529, USA http://orcid.org/0000-0002-1079-433X electrons generated by the anodic reaction all must be used up
DOI: 10.1520/MNL202NDSUP20190008
FIG. 1 Evans diagram for iron in an acid. FIG. 2 Galvanic series of various metals in flowing seawater at
2.4–4.0 m/x for 5–15 days at 5–30 C. Source: Redrawn
21
from original in Isaacs, taken from ASTM G82, Standard
Guide for Development and Use of a Galvanic Series for
−
Predicting Galvanic Corrosion Performance.
2e
+
2+
Fe
Æ
Potential
Fe
ECorr 2H +
+2
e−
iCorr Æ
H
2 (g
as
)
Log Reaction Rate, i
by the cathodic reaction. This can occur as shown in figure 1 only

where the anodic and cathodic reaction lines cross. At this point,
the rate of the anodic reaction, the corrosion rate, equals the rate
of the cathodic reaction—in this case, hydrogen generation. This
rate is called the open-circuit corrosion rate, abbreviated icorr.
The potential at which the lines cross is called the open-circuit
corrosion potential, abbreviated Ecorr. This type of plot is called
an Evans diagram, after U. R. Evans, a pioneer in corrosion
and electrochemistry. Any corroding metal should, under open-
circuit conditions, exist at Ecorr corroding at a rate icorr, which
can be predicted from the Evans diagram. The value of Ecorr will
depend on the position of the curves. The anodic curve for metal
dissolution is a function of the type of metal and the charge it
receives when it goes into solution. The cathodic curve is a func-
tion of the type of cathodic reaction, the type of surface on which
that reaction takes place, the concentration of reacting species,
and other factors, most of which depend on the environment in
which the metal sits.
Each metal and environmental combination, therefore,
exists at a unique potential. For a given environment, the poten- positive metal is called galvanic corrosion. The galvanic series
tials of various materials can be listed in a form called a galvanic allows for the prediction of which of the metals in contact (i.e.,
series. Galvanic series can be expressed either as a graph giving the galvanic couple) will suffer increased corrosion.
the numerical values of the potentials of the materials in the
given environment, as in figure 2, or as a list in order of increas- MIXED POTENTIAL THEORY
ing or decreasing potential without the specific values, as in It is tempting to say that the farther apart two metals are in the
figure 3. The galvanic series is important because it helps to pre- galvanic series, the more corrosion will occur on the more nega-
dict what happens when two metals are placed in electrical con- tive material, or anode. Unfortunately, the galvanic series cannot
tact in that environment, called a galvanic couple. For a galvanic be used to predict the corrosion rate that may occur. To predict
couple to exist, there must exist at least two metals with different the rate of galvanic corrosion, kinetics of the anodic and cathodic
corrosion potentials, a metal path for electrons to flow between reactions of both materials in a particular environmental expo-
them, and an ionic path through the electrolyte to complete the sure condition must be understood. This can be done by consid-
electronic circuit. The metal that is more negative in the galvanic ering an Evans diagram of both metals involved. This approach
series will have a driving force to lose electrons to a metal that is is called Mixed Potential Theory.
in electrical contact that is more positive in the series. This will In figure 4, Evans diagrams are shown for two materials of
cause the corrosion rate of the more negative metal to increase equal surface area that have different potentials on the galvanic
when the electrical connection is made. This increase in corro- series in an acid: iron and zinc. The anodic material, zinc
sion of the more negative metal upon contact with a more with the more negative Ecorr, Zn, corrodes uncoupled at a rate of
GALVANIC 43
FIG. 3 Galvanic series of various metals exposed to seawater. FIG. 4 Evans diagram for iron and zinc in acid.
Source: Taken from ASTM G82, Standard Guide for
Development and Use of a Galvanic Series for Predicting
Galvanic Corrosion Performance.
Potential
Log Total Reaction Rate, I
coupled potential, Ecouple. The mixed potential of the couple is

shown as a dotted line in figure 4. The points at which the indi-
vidual reaction lines cross the mixed potential define the rates
of those reactions. The zinc corrosion rate has increased from
Icorr, Zn to Icoupled, Zn. This increase is the galvanic corrosion
rate. The iron corrosion rate has decreased from Icorr, Fe to
Icoupled, Fe. This decrease, caused by forcing the metal to act as a
cathode, is called cathodic protection and is an important cor-
rosion control method.
EFFECTS OF ANODE–CATHODE AREA RATIO

The axis labeling shifted between figure 1 and figure 4. Figure 1
expressed the reaction rate as lower case i, the reaction current
per unit area, which is appropriate for considering single metals.
Figure 4 was forced to switch to total reaction current I, because
it is the total current (summation) from both metals that must
be considered. The effect of changing the relative areas of the
anode and cathode is illustrated in figure 5. If the exposed surface
area of the cathode is small, then the original Evans diagram for
the cathodic material must have the current densities multiplied
by a small area to obtain total currents. This makes the lines shift
far to the left in figure 5, and results in only a small increase in
Icorr, Zn. The cathodic material, iron with the more positive Ecorr, anodic corrosion rate, Icoupled, anode, small cathode, over Icorr, anode. If
Fe, corrodes uncoupled at a rate of Icorr, Fe. When these metals the exposed surface area of the cathode is large, then the original
are electrically connected, electrons can flow between them, Evans diagram for the cathodic material must have the current
changing the behavior of each coupled metal. Because there are densities multiplied by a large area to obtain total currents. This
four reactions to consider, and because electrons can now flow makes the lines shift far to the right in figure 5, and results in a
freely between all four reactions, the charge balance must be large increase in anodic corrosion rate, Icoupled, anode, large cathode,
handled differently than for the individual metals. All of the over Icorr, anode. This illustrates the area ratio effect in galvanic
electrons generated by the anodic reactions must be consumed corrosion. A small anode and large cathode result in a large
by the cathodic reactions. Therefore, the sum of the anodic anodic corrosion rate, whereas a large anode and small cathode
reactions is plotted as a dashed line with a positive Tafel slope, are far more desirable.
and the sum of the cathodic reactions is plotted as a dashed line
with a negative Tafel slope. These two sum lines intersect where FLOW RATE
all charges balance, and the potential at this intersection is Changing the electrolyte flow rate can have significant effects on
defined as the mixed potential of the galvanic couple, or the reaction kinetics, shifting the curves in the Evans diagram,
FIG. 5 Effect of cathodic area on couple current. FIG. 6 Effect of flow on diffusion-limited current density.
Large Cathode
Small Cathode
Un
aff
ec
ted
by
Diffu
Potential
sio
Potential
n
ICoupled, Anode, Large Cathode

ICoupled, Anode, Small Cathode
Diffusion Controlled,
ICorr, Anode Low Flow
Diffusion Controlled,
High Flow
Log Total Reaction Rate, I
iL, Low Flow iL, High Flow
and therefore, can dramatically influence galvanic corrosion rate. Log Current Density
The direction of the effect can be predicted only using Evans dia-
grams, however.
If the cathodic reaction is oxygen reduction rather than FIG. 7 Effect of passivity on anodic polarization curve.
hydrogen reduction, then oxygen must be supplied to the metal
surface by diffusion in order to react. Diffusion can be a slow
process relative to the electron exchange, and this can make the Flim Breakdown or
cathodic line in the Evans diagram deviate from a straight line. Oxygen Generation
Oxygen diffusion occurs through a relatively stationary boundary
layer, which becomes thinner as flow increases. Diffusion rate
therefore increases with flow, and the maximum rate of the oxy-
gen reduction reaction, iL, increases with flow. This is shown in
Potential
figure 6. When the diffusion-limited cathodic curve is present in Passivity Caused by

Protective Corrosion Product
a galvanic couple, the total cathodic current will increase with
increasing flow, causing the corrosion rate of the anode to
increase with increasing flow.
Flow also can have an effect on the anodic reaction. Many
materials exhibit passivity, which causes the anodic reaction to
deviate dramatically from a straight line. This is caused by the
corrosion products formed during the anodic reaction becoming No Protective Corrosion Product
firmly attached to the metal surface, blocking the reaction from
proceeding further. The anodic line in the Evans diagram will be
straight until the corrosion product forms, after which the cur-
Log Current Density
rent will rapidly drop even though potential is still increasing.
The low current will persist until the potential becomes suffi-
ciently positive to break down the corrosion product or to pro-
erosion corrosion, or can increase removal of certain less-
duce oxygen directly from water by electrolysis. In either event,
adherent corrosion products.
the current will then rise sharply. This is shown in figure 7. Some
of the most protective passivating corrosion products are on
stainless steels. These films form more readily in the presence of MEASURED CURRENTS
oxygen, and so are enhanced by flow. This leads to the situation Much of the current that flows between reactions in a galvanic
shown in figure 8, where increasing flow increases oxygen deliv- couple will flow between the anodic and cathodic metals, but
ery, which increases the amount of protective corrosion prod- some also flows within these metals. Internal current is not
ucts, lowering the anodic currents. This can cause corrosion directly measurable, although it can be inferred from other test
rates in a galvanic couple to decrease with increasing flow, oppo- methods that use external current that can be measured. Measur-
site to the oxygen effect on the cathodic reaction discussed previ- able external currents can be predicted from the Evans diagrams
ously. Flow also can increase the corrosion rate, as in the case of as follows. When a metal is corroding by itself, as in figure 9, the
GALVANIC 45
externally applied current will follow a shape called a polariza-

FIG. 8 Effect of flow on passivity. tion curve, shown in figure 9.
Galvanic corrosion rate can be roughly predicted by super-
imposing the polarization curves of the anodic and cathodic
materials. This is shown in figure 10. When the open-circuit
potentials of the anode and cathode are relatively far apart, more
than roughly 120 mV depending on the slopes of the curves, this
High Flow Low Flow prediction is fairly accurate. The polarization curves for the
anodic and cathodic materials are multiplied by their respective
wetted surface areas and placed on the diagram. The intersection
Potential
of the anodic curve for the anodic material with the cathodic
curve for the cathodic material provides an indication of the gal-
vanic corrosion rate, Igalvanic, and the exact coupled potential,
Ecouple. This technique does have limitations. For example, it
does not account for any change in reaction rates that may occur
over time.
CURRENT AND POTENTIAL DISTRIBUTIONS

As stated earlier, for galvanic corrosion to occur, there must exist
at least two metals with different corrosion potentials, a metal
Log Current Density path for electrons to flow between them, and an ionic path
through the electrolyte to complete the electronic circuit. The lat-
ter is sometimes not considered, but it contributes to the nonuni-
corrosion current is icorr, which flows entirely between anodic formity of galvanic current and potential on large structures.
and cathodic sites in the metal and cannot be measured. All elec- Figure 11 shows two metals electrically connected in an elec-
trons produced by the anodic reaction are consumed by the trolyte that has a significant resistivity, such as tap water. Current
cathodic reaction. If an external source, such as a power supply I1 must travel through some small electrolyte resistance R1 to go
or another metal electrically connected to the first, removes elec- the short distance from the anode to the cathode, experiencing a
trons, then the anodic reaction will increase to supply more elec- voltage drop according to Ohm’s law of I1R1. Current I2 must
trons, and the cathodic reaction will decrease to use fewer travel farther, through an increased resistance R2, and therefore
electrons. The externally applied anodic current will be the dif- will be smaller than I1. The voltage drop here is I2R2. The largest
ference between the anodic and cathodic reaction currents.
At very positive potentials, the cathodic current will be negligi-
ble, and the applied current will roughly equal to the anodic cor-
rosion rate. At very negative potentials, the anodic current will FIG. 10 Rough prediction of galvanic current from overlapping
be negligible, and the applied current will roughly equal the polarization curves.
cathodic current. At Ecorr, the external current will be zero. The
FIG. 9 Creating polarization curves from Evans diagrams.

Potential
Externally Applied
Anodic Current
ECouple
Potential
ECorr IGalvanic
iCorr
Externally Applied
Cathodic Current
Log Current Log Current

FIG. 11 Effect of distance on IR drop and current density.
distance is traversed by current I4, through the largest resistance area ratio, electrolyte resistivity, and geometry. Sometimes it is
R4, and therefore will be the smallest current and undergo a volt- important to know which reactions control or limit galvanic cor-
age drop of I4R4. The falloff of current (and corrosion rate) as rosion rates. The polarization curves in figure 12A illustrate how a
distance from the second metal increases is a common method diffusion-limited cathodic reaction will control the rate of gal-
for recognizing galvanic corrosion. Although current decreases vanic corrosion. Changing the shape of the anodic polarization
with distance, the product of current times resistance will curve, for example, by the use of an anodic inhibitor, has no
increase with distance. The largest voltage drop in this example effect on galvanic corrosion rate determined by the curve inter-
would be I4R4 and the smallest would be I1R1. The voltage drops section, whereas changes in the cathodic diffusion-limited cur-
are shown in figure 11. The presence of an IR drop not only rent result in equivalent changes in galvanic corrosion rate.
decreases the current on the anodic and cathodic materials, but Similarly, galvanic corrosion of passive materials, as shown in
also causes the anode to be at a different potential than the cath- figure 12B, is frequently under anodic control, with the shape of
ode. The potentials will be closest to Ecouple, where the anode and the cathodic polarization curve making little difference unless it
cathode are closest, and will shift toward Ecorr for each material intersects the active-passive nose of the anodic curve. Mixed con-
as separation distance increases. This creates a potential distribu- trol as in figure 12C is also possible.
tion over the structure that can be measured.
Testing Techniques
FACTORS CONTROLLING GALVANIC CORROSION
Any factor that controls corrosion of a single metal may control EXPOSURE OF GALVANIC COUPLES
galvanic corrosion by its effect on one or more of the reaction The most obvious method of testing for galvanic corrosion is to
lines on the Evans diagram. In addition to flow and pH, these construct a couple between the materials of interest and place it
factors include temperature, electrolyte composition, surface in the environment of interest. Material condition, environment,
condition of the metals, thermo-mechanical and potential his- and geometry should simulate the application as closely as possi-
tory of the surfaces, and many more too numerous to mention. ble. Care should be taken during assembly to ensure adequate
Factors unique to galvanic corrosion include anode-to-cathode electrical connection, and this connection should be checked
GALVANIC 47
FIG. 12 Type of control of galvanic corrosion reactions: (A) cathodic control; (B) anodic control; and (C) mixed control.
(A) (B) (C)
Potential
Potential
Potential
Log Current Log Current Log Current
before, after, and occasionally during the exposure using an Conditions as in Atmospheric Corrosion Testing; and ASTM G92,
appropriate ohmmeter. In some cases, it may be possible to elec- Standard Practice for Characterization of Atmospheric Test Sites.
trically isolate the individual metals from each other and connect The relative geometry of the parts of interest in the galvanic
them through an external wire, which can be used to measure couple also can influence corrosion behavior. In low-conductivity
galvanic current during exposure. For small specimens, it is per- environments, the distance of separation of the dissimilar metals
missible to use a 1-X resistor in the line to measure voltage drop will affect galvanic corrosion rate. Even in high-conductivity
and calculate current. Where currents are larger or where corro- environments, it is difficult for galvanic current to travel into
sion potentials are close for the materials involved, use of a zero- long narrow crevices or through narrow tubes. The relative
resistance ammeter may be more appropriate for current mea- wetted surface areas of the dissimilar metals will dramatically
surement. The potential of the couple usually can be monitored influence galvanic corrosion rate. In atmospheric exposures,
during the exposure using a suitable reference electrode. More geometry can control water trapping and drainage as well as
detail on electrochemical potential measurement can be found in thermal mass, which controls dew retention.
ASTM G215, Standard Guide for Electrode Potential Measure- Ensuring adequate electrical contact between the dissimilar
ment, and detail on galvanic corrosion testing in electrolytes can metals in a galvanic couple can be difficult. Pressure contact,
be found in ASTM G71, Standard Guide for Conducting and Eval- such as between two plates bolted together, is subject to corro-
uating Galvanic Corrosion Tests in Electrolytes. In vitro testing sion products forming between the plates and wedging them
information can be found in ASTM F3044, Standard Test apart. Attachment of wires by soldering or brazing will work
Method for Evaluating the Potential for Galvanic Corrosion for with some materials, but the use of drilled and tapped holes for
Medical Implants. screw attachment or through holes for bolting may be required
Important material factors to consider when simulating a for others. In some cases, spot welding can be used for electrical
galvanic corrosion situation include chemical composition, ther- attachment. Finally, a wire may be inserted into a drilled hole
mal history, and surface condition. Changes in these parameters and the hole then peened closed around the wire, although this
may change the corrosion behavior of a material when it is not method is not reliable over long exposure periods. Whatever
in a galvanic couple without affecting its galvanic corrosion connection method is used, the connection area and wire are
behavior, or changes may affect its galvanic corrosion behavior subject to corrosion, which can affect both the electrical contact
without a significant effect on its corrosion properties when it is and the performance of the galvanic couple being tested. For this
used alone. reason, coatings frequently are used on the connection area,
Any environmental factor that can influence corrosion also although coatings may result in crevice corrosion. When electri-
can affect galvanic corrosion. Environmental factors to consider cal contact is maintained by physical contact of the dissimilar
when designing a test include major chemical components, dis- metals, periodic measurement is desirable to ensure that electri-
solved gases, minor constituents, organic materials, biological cal continuity is maintained. If continuity is checked frequently
organisms and activity, temperature, flow, and electrical conduc- relative to the length of the exposure, then it will be possible to
tivity. In atmospheric galvanic couples, atmospheric factors adjust the materials to regain this continuity without significantly
such as time-of-wetness, orientation relative to prevailing winds, affecting the results. This should be done without disassembly or
sunlight exposure, height above ground, and other unique gross movement, such as by tightening tensioning bolts.
atmospheric conditions also should be considered. Some impor- Mounting of galvanic couples for testing should be done
tant atmospheric factors affecting corrosion are discussed in carefully using insulator materials to avoid the possibility of estab-
ASTM G33, Standard Practice for Recording Data from Atmo- lishing electrical continuity with the mounting device or test
spheric Corrosion Tests of Metallic-Coated Steel Specimens; chamber. Mounting techniques include gasketed seals, rod mount-
ASTM G50, Standard Practice for Conducting Atmospheric Cor- ing, epoxy mounting, press-fit, partial immersion, full immersion,
rosion Tests on Metals; ASTM G84, Standard Practice for Mea- and others. The mounting technique chosen is related to the type
surement of Time-of-Wetness on Surfaces Exposed to Wetting of corrosion expected, the electrical connection method, the type
of exposure desired, the presence or absence of water-line effects, with a zero-resistance ammeter or by voltage drop across a 1-X
and the materials chosen. shunt resistor. This type of testing is described in ASTM G71.
Duration of exposure is extremely important in galvanic Galvanic current also can be measured by measuring potential
corrosion testing. In many galvanic couples, the amount of cor- gradients in the electrolyte near the materials of interest. This is
rosion is highly variable with time. Initial high corrosion rates discussed in the section “Scanning Electrochemical Testing:
may fall dramatically, initial low rates may suddenly increase, Scanning Vibrating Electrode Technique.”
and the relationship between anodic and cathodic materials can Determination of a galvanic series involves placing the
even reverse with time. For these reasons, the duration of the test materials of interest from the galvanic couple individually in the
exposure should be of sufficient length to ensure that the corro- environment of interest and monitoring their electrochemical
sion processes have reached steady state if long-term perfor- potential over time. The material with the more electronegative
mance is being evaluated. Test duration should be similar to potential will become the anode and suffer accelerated corrosion
service duration for short-term service. In atmospheric testing, when placed in a galvanic couple. Galvanic series are extremely
the season of the year when exposure is initiated may influence useful during the materials selection process to ensure that the
the test. Multiple exposures of different time periods may be anodic areas are large compared to the cathodic areas in complex
used to give corrosion rate information as a function of time. structures. The galvanic series is influenced by all of the environ-
Exposures can be conducted on full-scale components or on mental variables described earlier, so the series should be used
scaled-down or simplified geometries. Full-scale components only if it is developed in the environment in which the galvanic
have a number of advantages, including not needing to consider couple will see service. One disadvantage of the galvanic series is
details of geometry and ease of relating the results to service per- that it is frequently misapplied. A series developed in one envi-
formance. Full-scale component testing, however, may be ronment cannot be used to predict performance in another envi-
impractical or too expensive, in which case scale modeled com- ronment. A second disadvantage of the galvanic series is that it
ponents may have to be used. If scale modeling is used, then does not predict rate. Separation in potential between dissimilar
details of scaling laws must be understood before designing the materials does not relate to the rate of corrosion in a couple.
test. For example, when galvanic corrosion current distribution More details of the development and use of galvanic series are
is important, the conductivity of the electrolyte may need to be given in ASTM G82, Standard Guide for Development and Use of
scaled by the same factor as the physical size. This procedure, a Galvanic Series for Predicting Galvanic Corrosion Performance.
called Dimension and Conductivity Scaling (DACS), involves the Insight into galvanic corrosion behavior can be gained by
use of an electrolyte of one-tenth conductivity for a one-tenth- overlaying polarization curves, as described earlier. The determi-
scale model. DACS scales only primary current distribution, nation of polarization curves is, therefore, an important method
which is controlled by the IR drop in the electrolyte. Secondary for galvanic corrosion testing, although it may miss important fac-
and tertiary current distribution are influenced by polarization tors that long-term testing may better capture. These curves can
behavior of the material involved, and are best approximated by be obtained galvanostatically, potentiostatically, or potentiody-
the use of full-conductivity electrolytes. Both types of current namically. Galvanostatic testing is typically used for determining
distributions cannot be modeled simultaneously, so a decision the efficiency of sacrificial anodic materials, such as is done in
must be made as to which is most important. Small structures in ASTM G97, Standard Test Method for Laboratory Evaluation of
highly conductive electrolytes generally should be tested in full- Magnesium Sacrificial Anode Test Specimens for Underground
conductivity electrolytes, whereas DACS should be used primar- Applications, or NACE SP0387, Metallurgical and Inspection
ily for large structures in low-conductivity electrolytes. To date, Requirements for Cast Sacrificial Anodes for Offshore Applications.
DACS has been used primarily for ship cathodic protection sys- The most common method of obtaining polarization curves
tem design. More information on scaling can be found in previ- is potentiodynamically. Potentiodynamic testing is described in
ously published work.2–5 Chapter 8, “Electrochemical Tests.” For galvanic corrosion, the
scan rate for these tests should be as slow as possible, since long-
ELECTROCHEMICAL TESTS term polarization behavior usually is sought when predicting
Accelerated testing to get a result in a shorter time period than long-term galvanic corrosion behavior.
would be possible naturally should be avoided whenever possible Potentiostatic polarization curve generation is advantageous
because the mechanism of galvanic corrosion can change if the for situations in which polarization is time dependent and pre-
rate is altered significantly. For this reason, electrochemical tests diction of long-term galvanic corrosion performance is desired.
frequently are chosen to evaluate galvanic corrosion perfor- This involves exposing a series of individual specimens of each
mance. The sensitivity of these tests allows for obtaining results material at a variety of different potentials for a duration suffi-
fairly quickly without accelerating the corrosion process. cient to ensure steady-state behavior. The steady-state current at
Electrochemical galvanic corrosion tests can be placed into each potential is obtained, and polarization curves are con-
three categories: sensitive galvanic current measurement, gal- structed from the potential–current data pairs.
vanic series determination, and polarization curve measurement. Using electrochemical tests to predict galvanic corrosion
Sensitive current measurement involves an ordinary galvanic performance has the same caveats as any other type of predictive
couple exposure, but with current between the dissimilar metals testing. Conditions must be as close as possible to those being
forced to flow through an external wire where it can be measured modeled. This includes not only solution chemistry and flow,
GALVANIC 49
but also the surface condition of the samples. Polished samples which galvanic interactions take place to about 0.5 cm, which in
can behave quite differently from samples with more representa- turn means that the effective area ratio of anode to cathode in an
tive surface conditions and corrosion products developed by atmospheric exposure is almost always about 1:1. The limited
preexposure. electrolyte also makes electrochemical measurements impracti-
More detail on using electrochemical tests for galvanic cor- cal. If atmospheric aerosols are heavy, such as may be the case in
rosion can be found in work by Scully6 and Baboian.7 coastal conditions, the effective area ratio may not be 1:1 because
of the thickness and conductivity of the surface moisture.
PROBES FOR GALVANIC CORROSION TESTING IN Atmospheric corrosion typically occurs only during a small
PRODUCTION ENVIRONMENTS percentage of the total exposure time, typically when the surfaces
Galvanic probes can be used in a production environment to are wet from precipitation, dew, or fog, or when hygroscopic
monitor corrosion. The use of such probes is detailed in NACE compounds on the surface absorb moisture during periods of
TM0416, Test Method for Monitoring Atmospheric Corrosion high humidity. For this reason, atmospheric corrosion occurs
Rate by Electrochemical Measurements, and NACE 1C187, Use slowly, and long exposure durations are usually necessary. Most
of Galvanic Probe Corrosion Monitors in Oil and Gas Drilling tests typically involve minimum durations of 1 to 3 years, with
and Production Operations. Atmospheric time-of-wetness can 20 years maximum exposure not unusual. Tests of shorter dura-
be determined using a galvanic corrosion probe as detailed in tion than 1 year not only have so little corrosion as to make eval-
ASTM G84. uation of mass loss difficult but also suffer from the effects of
seasonal variation of corrosion rate.
COMPUTER MODELING Finally, the time that a specimen is wet depends on sunlight
Although not a laboratory testing technique, computer modeling heating, prevailing winds, and specimen geometry. Specimen
is an increasingly important tool in understanding and predicting orientation, therefore, is much more critical in atmospheric gal-
galvanic corrosion performance. As noted, exposure of scaled vanic corrosion testing. Standard orientations are specified in
components of a galvanic couple leads to scaling problems in that ASTM G50 as 30 to the horizontal facing south or the nearest
the primary current distribution cannot be scaled at the same time source of corrodent (the sea).
as the secondary and tertiary current distributions. Computer Three standardized atmospheric galvanic corrosion tests are
modeling is usually best for making accurate predictions of the the plate test, the wire-on-bolt test, and the disk test. The plate
distribution of galvanic corrosion over a structure in which solu- test, described in ISO7441, Determination of Bimetallic Corrosion
tion IR drop and polarization behavior both control current distri- in Outdoor Exposure Corrosion Tests, consists of a large plate of
bution. Computer models require the geometry of the structure to the anodic material sandwiched between two small plates of the
be an input. Additional inputs include the electrolyte conductivity cathodic material that are held together with nonmetallic or
and the polarization behavior of the surfaces of all materials, insulated bolts. Sometimes the crevice area between the plates is
which usually are obtained from laboratory testing. Although coated with an organic material. The two possible configurations
finite element analysis and finite difference analysis have both are shown in figure 13. Typical exposure durations are 1 to
been used to predict the distribution of galvanic currents on struc- 20 years. At the end of this time, the anodic plate may be evalu-
tures, the boundary element technique is becoming the computer ated metallographically, visually, by mass loss, or by material
tool of choice. This technique requires only that the surfaces of property loss (typically using tension testing). The advantages of
the structure be defined, whereas the other methods require that this test are that materials usually are available in plate form, and
the volume of the electrolyte be divided into a three-dimensional a wide range of analyses can be used on the exposed panels. The
grid, which is a time-consuming and difficult process for complex disadvantages include the need to know which material is the
structures. The disadvantage of the boundary element method is anode beforehand, the long exposure duration, the difficulty of
that, at present, some commercially available software for per- maintaining electrical continuity between panels, and the possibil-
forming this analysis is not user-friendly. ity of confusing crevice effects with galvanic effects. At one time,
ASTM also had a standard for this test method, but dropped this
ATMOSPHERIC TESTS standard because of these disadvantages and lack of use.
Unlike galvanic corrosion testing in electrolytes, galvanic corro- The wire-on-bolt test, described in ASTM G116, Standard
sion testing in the atmosphere has a limited number of test varia- Practice for Conducting the Wire-on-Bolt Test for Atmospheric
bles, making it easier to conduct standardized tests. Galvanic Corrosion, has been used with standard materials as an
Three factors that are different in atmospheric testing from atmospheric corrosivity test under the names of the CLIMAT
most other galvanic corrosion testing are the presence of a lim- and ATCORR tests. This test consists of wrapping a 1.0-m length
ited amount of electrolyte, the need for a long duration of expo- of wire of the anodic material around a threaded bolt or rod of
sure, and the importance of specimen orientation. Because the cathodic material. Post-test evaluation typically is done only
rainwater and dew are fairly poor electrical conductors, and by mass loss. Because the wire diameter is much smaller than the
because they usually are present only as thin layers on the surfa- 0.5-cm galvanic interaction distance in the atmosphere, the effec-
ces of materials exposed to the atmosphere, there is a large IR tive anode-to-cathode area ratio is well below 1:1, making this a
drop between the anode and the cathode in any atmospheric cor- fast test. A typical exposure duration is 90 days. The short dura-
rosion exposure. This drop limits the effective distance over tion is a significant advantage to this test. The disadvantages
FIG. 13 Plate test assembly for galvanic corrosion testing (redrawn and simplified from ISO7441).
include materials needing to be in wire and threaded rod form,

the beforehand knowledge of which material is the anode, and FIG. 14 Components for making wire-on-bolt atmospheric
the seasonal variations in exposures of such short duration. A exposure assemblies. Source: Taken from ASTM G116.
diagram of the sizes and forms of the components needed to

construct an assembly is given as figure 14, and a completed
assembly is shown as figure 15.
The disk test, described in Baboian8 and Blum9 and in the
now-discontinued ASTM G149, Standard Practice for Conducting
the Washer Test for Atmospheric Galvanic Corrosion (withdrawn
2004), consists of a set of four washers of alternating anodic and
cathodic materials of graduated sizes bolted together with an insu-
lated bolt. Only the center two washers are used for the analysis.
A cross-sectional assembly view is shown in figure 16. The duration
of this test is usually 1 to 20 years. Post-test evaluation usually con-
sists only of mass loss. Advantages to this test are that material is
usually easy to find, the anodic material need not be known before-
hand, and it is easy to set up and evaluate. The disadvantages
include the long test duration and the lack of information available
on corrosion morphology or mechanical property degradation.
COMPUTATIONAL MODELING OF GALVANIC

PROCESSES
Computational corrosion models are either empirical or funda-
mentally deterministic. Models derived from empirical data are
inherently linked to the precision and accuracy of the data.
Deterministic models are based in the fundamental physics of
multivariable processes and therefore are more robust than
empirical models. Modeling of corrosion processes allows for the
GALVANIC 51
Finite difference modeling involves dividing the region of

FIG. 15 Schematic of completed wire-on-bolt assemblies interest into a grid of points, expressing the governing differen-
mounted for exposure. Source: Taken from ASTM G116. tial equations as difference equations at each point, and solving
the difference equations to determine an approximate solution of
the governing equations. Finite difference methods are simple to
code, but clumsy when applied to complex geometries. They
most often are used for the temporal aspect of a model. Bound-
ary element models translate the differential equations across the
geometry volume into integral equations over the surface enclos-
ing the volume and solve these integral equations by dividing up
the surface into elements. Boundary element models are most
useful when the geometry of interest has a low surface-to-volume
ratio. Finite element models divide the region of interest into
simple geometric shapes (such as triangles), build equations for
the value of the variable of interest at each node on each shape,
and then solve the equations for all of the nodes simultaneously.
Finite element models have the advantage that they can represent
complex geometries. Much of the recent modeling efforts have
utilized finite element analysis because of its wide availability in
commercial multiphysics frameworks.
As corrosion models add complexity, they become more dif-
ficult to solve and require increased computational processing
power, speed, and memory. Therefore, assumptions are made to
FIG. 16 Cross section of disk test assembly for atmospheric simplify the governing equations that described the underlying
galvanic corrosion. physics. The goal is to remove factors that do not play a strong
Stainless Steel Bolt role in the underlying corrosion mechanisms, but not to eliminate
Stainless Steel Washer
too many factors causing the model to lose its predictive behavior.
Bakelite Washer
Metal A Washer The simplifying assumptions commonly made in corrosion mod-
Metal B Washer els fall into five different categories, as defined by Stewart:12
Metal A Washer
Metal B Washer
• Elimination of some thermodynamic variables: Most experi-
Bakelite Washer Bakelite Bushing ments are performed at a constant temperature and pressure,
Stainless Steel Washer and the effects of changes to these are often ignored.
• Simplifying chemistry effects: Dilute solution theory is usually
Stainless Steel assumed; the diffusivity and mobility of a species is indepen-
Lock Washer
dent of its concentration. The precipitation and accumulation
of corrosion products is often ignored.
Galvanized Angle Support • Simplifying potential effects: As described earlier, the diffu-
sion potential is usually ignored in most models and charge
neutrality is maintained by specific species.
separation of parameters that cannot be separated in practice • Ignoring some temporal effects: Whereas changes of species
(i.e., virtual experiments). Each parameter can be individually concentration over time may be accounted for, the changes in
probed in computational experiments while holding other electrode kinetics or generation rates with time are often
parameters to defined values. ignored. The use of a single electrochemical polarization
Models of corrosion processes have been developed that behavior is often used throughout a model. Some models also
incorporate a range of chemical and electrochemical reactions assume chemical reactions are in equilibrium at all times or
with the complex interactions of diffusion and migration. The also called steady state.
models often are expressed as differential or other nonexplicit • Simplifying geometry: Models assume that electrodes and the
mathematical equations.10 Numerical methods are used to solve overlying electrolyte have ideal dimensions. This is often not
a wide range of partial differential equations based on discretiza- the case, however, of practical systems that often have varia-
tion methods, including the following: (1) finite difference analy- tions in geometry throughout.
sis, (2) boundary element analysis, and (3) finite element
analysis. The governing equations are based on primary, second- Modeling of galvanic corrosion processes requires the follow-
ary, and tertiary current distribution equations.11 The mathemati- ing: (1) dissimilar alloys; (2) electrical contact, either directly or
cal treatment of the different solver routines is beyond the scope by a secondary, grounding path between the dissimilar alloys;
of this work but an overview is provided. and (3) an electrolyte. Early galvanic corrosion modeling of alloy
surfaces covered by thin electrolytes generally assumed that only film of salt solution. The model solved the LaPlace equation for
the anodic reaction occurred on a single galvanic member and secondary current distribution with electrochemical boundary
that the cathodic reaction transpired on the other member of the conditions adapted from experimentally determined polarization
couple.13–15 When galvanic couples contain more than two indi- curves. The model also incorporated thin film resistances mim-
vidual members, however, there may be anodic and cathodic icking the resistive nature of the MgRP as a heterogeneous struc-
contributions from more than one member of the couple. Kinet- ture of metallic Mg particles embedded in an epoxy matrix. The
ics generally are assumed to follow linear or Butler-Volmer model was validated with a microarray of AA2024 and Mg elec-
behavior, but this may not be the case in a number of practical trodes exposed to salt solution in humid atmosphere. The model
cases in which experimentally determined polarization curves correctly predicted the potential distribution of the galvanic cou-
may be more appropriate. ple interface as a function of electrolyte thickness and solution
Most recently, computational galvanic corrosion models conductivity. The model also predicted that the inherent resistiv-
have been employed to examine the corrosion and protection ity of the MgRP would regulate the cathodic protection throwing
of aluminum. Mizuno and Kelly16 modeled the galvanic interac- power over the AA2024 surface.
tion between aluminum-magnesium alloy AA5083 and AISI Computational modeling is a powerful tool used to examine
4340 steel under atmospheric exposure conditions. The model galvanic systems. Modeling can be used to guide the design of
geometry consisted of co-planar steel and aluminum electrodes structures to minimize galvanic corrosion or to predict the life-
covered by a thin electrolyte with a thickness determined from time of structures exposed in corrosive environments such as
relative humidity and salt loading. A finite element solver was seawater. Using computer models to predict the magnitude of
used to calculate the potential distribution over the electrodes galvanic corrosion or the current demand for cathodic protection
based on the tertiary current distribution governing equations. systems in seawater or other electrolytes requires accurate polari-
Electrochemical boundary conditions were determined by zation data for the materials involved.20 Polarization curves for
experimental measurements in the form of polarization curves. most structural materials in seawater are exposure-time and
The model was validated by correctly predicting that the maxi- scan-rate dependent, however, thus complicating long-term gal-
mum degree of intergranular corrosion damage of sensitized vanic corrosion predictions.20
AA5083 would occur at 90% relative humidity when coupled to Because of the need for assumptions to make computa-
AISI 4340 steel. tional models useful, care must be taken to verify and validate
Murer et al.17 modeled galvanically coupled co-planar 99.9% the results after model convergence. Verification can include
aluminum and solid solution aluminum-4% copper electrodes model result comparisons to an analytically solvable system
under thin film atmospheric conditions. Electrochemical bound- while validation often requires a proof-of-concept laboratory
ary conditions were determined from experimentally measured experiment. In addition, convergence criteria and geometry
polarization curves through microcapillary and bulk solution mesh density interplay between model accuracy and computa-
electrochemical cells. The model framework was based on the tion time. Specifically for galvanic models, which most often
finite element method with potential distributions solved operate under open-circuit conditions, the requirement that the
through either secondary (LaPlace equation) or tertiary (Nernst- total anodic and cathodic currents sum to zero is a valid verifi-
Plank equation) current distribution governing equations. The cation step.
model was validated against a bimetallic electrode probed by the
scanning vibrating electrode technique (SVET). The authors Evaluation of Test Results
concluded that the model (regardless of current distribution
type) qualitatively predicted the experimentally obtained SVET EXPOSURE OF GALVANIC COUPLES
measurements. The model was too overly dependent on the If the different materials can be disassembled after testing, then
input boundary conditions, however, to be used as a predictive mass loss measurements can be performed. In some cases, loss of
model of microgalvanic coupling. strength also may be of interest. If disassembly is not possible, the
Liu et al.18 examined the galvanic interactions of AA7075 specimens still may be examined for pitting, cracking, color, and
anode and austenitic stainless steel 316L cathode under thin extent of corrosion products and, in some geometries, thickness
films conditions. The finite element model solved the LaPlace loss. Mass loss of an assembly may be useful if corrosion of the
governing equation describing the secondary current distribution cathode was minimal. After exposure, destructive techniques such
of the system. Simulated thin film electrochemical boundary as metallographic examination may provide information about the
conditions were determined from the cathodic kinetics generated extent and morphology of corrosion. Useful standards for cleaning
experimentally by use of a rotating disk electrode. The model samples after immersion and evaluating mass loss, pitting, and deg-
predicted that under thin film conditions, ohmic drop through radation in properties are ASTM G1, Standard Practice for Prepar-
the electrolyte was the controlling factor for the total galvanic ing, Cleaning, and Evaluating Corrosion Test Specimens; ISO8407,
current (corrosion) of the system. Corrosion of Metals and Alloys – Removal of Corrosion Products
King et al.19 used the finite element method to examine the from Corrosion Test Specimens; ASTM G46, Standard Guide for
throwing power of sacrificial metallic coatings in the cathodic Examination and Evaluation of Pitting Corrosion; and ASTM G71.
protection of AA2024. The geometry was co-planar electrodes of Applying the results of a set of measurements designed to generate
AA2024 and magnesium rich primer (MgRP) exposed to thin a galvanic series is described in ASTM G82.
GALVANIC 53
ELECTROCHEMICAL TESTS occurring on each metal of a galvanic couple. As such, the effi-
When the potentials of two materials in a galvanic couple are ciency of a sacrificial anode supplying current to a cathodically
widely separated, the majority of the corrosion is driven by the protected surface can be discerned by differentiating between the
external cathode, in which case Faraday’s law can be used to cal- current available for cathodic protection or galvanic corrosion
culate the galvanic corrosion rate from the galvanic current mea- and “self-corrosion.” Likewise, the distance over which a sacrifi-
sured between them. This calculation can be done by the cial anode can afford protection, termed the “galvanic throwing-
procedures in ASTM G102, Standard Practice for Calculation of power,” can be studied by mapping or profiling across an
Corrosion Rates and Related Information from Electrochemical extended length of a cathodically protected surface.29 Methods
Measurements. for using SVET for the study of dissimilar metal interfaces will
Overlaying of polarization curves of the different materials in be discussed in detail.
a galvanic couple must be done by first converting the current The SVET is completely nonperturbing to the corrosion
densities into total currents by multiplying the polarization curves occurring on the metal surface and to the experimental conditions,
by the exposed wetted surface area for each material. The curves and thus it enables quantification of corrosion activity over peri-
then may be overlaid, and if IR drop is not important, then the ods of several days. The size, shape, and spatial distribution of
couple current and potential may be predicted. If the coupled anodic (positive) current and cathodic (negative) current above a
potential deviates by more than 50–100 mV from the open-circuit corroding surface can be measured and a time-resolved data series
potential of the anode, then the current may be converted by Fara- can be built up to map the progression of electrochemical pro-
day’s law into a corrosion rate. If the coupled potential deviates by cesses. A vibrating platinum microdisc electrode, typically 5 lm to
less than 50–100 mV from the open-circuit potential of the anode, 150 lm in diameter, is scanned over the surface in a series of lines
then it is conservative to add the open-circuit corrosion rate of the as shown in figure 17A. The probe is held at a fixed height (typi-
anode to the corrosion rate calculated from Faraday’s law to get cally 100 lm) above the corroding metal (fig. 17B). In a localized
the total anodic corrosion rate. Neither of these methods is exactly corrosion cell, ionic current flow passes from spatially separated
accurate, but both will give a reasonable approximation to the true sites of cathodic and anodic activity in the electrolyte solution and
corrosion rate of the anode in the couple. electrons flow through the metal from anode to cathode. This is
If the polarization curve for the anode is known, then the represented schematically in figure 17C where lines of ionic current
coupled potential may be measured to predict corrosion perfor- flux and electron flow direction are shown. An ohmic potential
mance. The couple current is the current on the anodic material gradient is generated that can be represented as lines of iso-
polarization curve at the measured coupled potential. The corro- potential normal to the ionic current flux lines (fig. 17C). The
sion rate may be calculated from the couple current determined vibrating probe measures the peak-to-peak electrochemical poten-
in the same way as in the previous paragraph. tial difference (Vpp) between two points in the electrolyte perpen-
dicular to the metal surface, shown as points a and b in figure 17C.
A matrix of individual data points is collected over the corroding
SCANNING ELECTROCHEMICAL TESTING:
metal surface and each data point is used to build a current den-
SCANNING VIBRATING ELECTRODE TECHNIQUE
sity distribution map.
SVET is a well-established tool for in situ assessment of localized Calibration is necessary to convert the SVET peak-to-peak
corrosion phenomena in full immersion conditions.21–25 The output voltage signal (Vpp) to current flux density along the axis
technique is particularly useful for the study of galvanic corro- of probe vibration (jz). These are related as follows:
sion and has been used extensively to study the interface between

dissimilar metals.26–30 A major advantage of the SVET for this Vpp ¼ jZ App =j , (6)
application is the ability to measure local internal currents
FIG. 17 A series of schematics showing: (A) the scanning vibrating Pt probe moving over a metal surface in a series of line scans, (B) the
probe at a fixed scan height above a metal surface, (C) ionic current flux emanating from a dissolving metal surface and the
corresponding iso-potential lines, and (D) the point-current-source calibration method.
where:
j ¼ solution conductivity, and FIG. 18 Representation of SVET-derived current density line
App ¼ the peak-to-peak amplitude of vibration. profiles across the full length and interface of Metal 1 and
A quantity G may be defined as the SVET calibration factor, Metal 2 at Time 1 and Time 2.
where:
G ¼ j/App.
G must be obtained for the specific electrolyte solution of

interest and is not linked to the metal being tested. It is recom-
mended that calibration is carried out before every experiment.
The most common method for obtaining G is by a “point cur-
rent source” method,26,31,32 as demonstrated in figure 17D. An
applied external galvanostatic current (iapplied) of known value is
set up in the solution and the area that encompasses the emanat-
ing current is mapped with the SVET probe at a fixed probe
height, z. An even current distribution over the surface of a
hemisphere is assumed, and applied current density is calculated
by dividing iapplied by the surface area of a hemisphere (2pz2). corrosion occurring on one or both of the predominantly
The maximum Vpp can be obtained from the resulting Vpp distri- anodic or cathodic metals within the couple can be observed. In
*1 *1
bution map. G is then obtained by taking the gradient when figure 18, the labeled anode and cathode pictured on Metal 1
plotting the maximum Vpp versus iapplied/(2pz2) for a range of demonstrate areas of local internal corrosion activity at Time 2.
positive and negative iapplied. G is applied to equation (6) to A reduction in the overall anodic and cathodic current is typical
obtain jz. when some of the current is being supplied to local internal
The maximum test area for a commercial SVET is approx- activity, or “self-corrosion,” as shown at Time 2 (when compared
imately 30 mm 30 mm and test samples must be adjusted with Time 1) on Metal 1 and Metal 2, respectively.
accordingly, adhering to DACS where necessary. To study a Data from individual current density distribution maps can
galvanic couple the two metals of interest should be electrically be converted into time-dependent net anodic (Jat) and cathodic
connected either through direct contact or through an external (Jac) current density values through area-averaged numerical
wire connecting them at the back. The most common sample integration.35 Compiling all Jat values from an experiment and
set-up for SVET experiments is by mounting in resin, because plotting against immersion time enables an estimate of the cor-
the technique requires a smooth, flat surface to ensure a con- rosion rate. For a galvanic corrosion cell in which two metals
stant probe height when scanning the area of interest. Most have been electrically connected, as described here, data from
commercial instruments are capable of measurement over pla- each metal can be integrated separately to monitor the overall
nar surfaces only; however, height mapping is possible with currents and local internal currents of each. This is particularly
some in-house instruments.33 Scan resolution can be calculated useful for the study of galvanic sacrificial protection systems as
using Vpp measured during the calibration and is quantified as “self-corrosion” can be monitored. For any freely corroding sur-
follows: face, Jat should be equal to Jct and figure 19 represents an ideal
scenario in which the sum of the measured anodic current is
Vpp =FWHM, (7) equal to the sum of the measured cathodic current in accordance
with mixed potential theory,
where:
where:
FWHM ¼ full-width at half-maximum signal peak height (lm)
and has been shown to be:
RIanodic ¼ RIcathodic.
FWHM ¼ 1.533 z.32
In reality, discrepancies exist between SVET-derived Jat and
Evaluation of Test Results for a Dissimilar Metal Interface Jct measurements (this is discussed next). Figure 19 illustrates a
Data can be plotted either as a series of current density distribu- scenario in which local internal corrosion activity occurs
tion maps or as a series of line profiles across the length of the (beyond 10 h) and cathodic activity can be observed on the pre-
coupled metals, the latter is shown in the plot given in figure 18. dominantly anodic Metal 1. Because of the previous equation,
This plot is a representation of data typical of that shown in pre- the amount of anodic activity on Metal 1 supplying cathode*1
vious publications.20,29,34 As described earlier in this chapter, the rather than Metal 2 can be discerned.
current (both anodic and cathodic) is at a maximum at the inter- As with the zero-resistance ammeter experiments described
face between the two coupled metals and gradually diminishes in this chapter, area-averaged current density values can be con-
with increasing distance from the interface because of the verted into mass loss by applying Faraday’s law to obtain metal
increased resistance. Line profiles enable inspection of the pro- dissolution (taken from Jat values) or H2 evolution and O2 reduc-
gression of the current density over time and any localized tion (taken from Jac values).
GALVANIC 55
FIG. 19 Representation of area-averaged integrated SVET-derived anodic and cathodic current density data as a function of time extracted
individually for Metal 1 and Metal 2.
Limitations the galvanic couple. To study the breaking strength of a piece of

The SVET has some limitations, and it is typical for comple- metal, a standard mechanical pull test such as that found in
mentary measurements to be made to verify quantitative data, ASTM E8, Standard Test Methods for Tension Testing of Metal-
such as gravimetric or volumetric measurements. The technique lic Materials, may be used. To study the effect of galvanic corro-
provides only an estimate of current density data as each scan sion on breaking strength, the same test may be used on pieces
can take several minutes depending on the size of the exposed of metal after exposure to the environment of interest, both
area to be mapped. The very nature of the scanning probe with and without galvanic coupling to a second material. Sub-
means that data for the whole surface is not recorded instanta- tracting the strength of the metal with galvanic coupling from
neously. A further limitation of the SVET is low detection effi- that without it will give the effect due to galvanic corrosion.
ciency in cases in which the spacing between anodes and Two guidelines for galvanic corrosion testing are published by
cathodes is so small that the current flux lines pass below the ASTM: ASTM G71 and ASTM G82. Specific test standards for
plane of scan of the vibrating probe.27 For localized corrosion atmospheric galvanic corrosion can be found in ASTM G116
with large-spaced anodes and cathodes, however, SVET detec- and ISO7441, as described earlier.
tion efficiency is high.
Another laboratory method for measuring potential distri-
butions in the vicinity of a galvanic interface is the multielectrode
Additional Information
technique, described in ASTM G217, Standard Guide for Corro-
sion Monitoring in Laboratories and Plants with Coupled Multi- Additional information and details of galvanic corrosion testing
electrode Array Sensor Method. are available in the standards referred in this chapter and in
Hack.36,37 Additional information on the theory of galvanic corro-
ATMOSPHERIC TESTS sion is available in several publications.38–48 A good series of
articles summarizing galvanic corrosion theory and application in
Only mass loss information is obtained from the standard atmo-
various industries is available in the edited volume, Galvanic Cor-
spheric galvanic corrosion tests, with the exception of the plate
rosion, ASTM STP978.49 Galvanic corrosion testing descriptions
test. The plate test specimens also can be evaluated by metallog-
are written at the level of a corrosion technician following Hack.37
raphy, visual examination, probe-type attack depth gages, or
mechanical tests, such as tensile strength.
References
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Evolution,” Zeitschrift fur Elektrochemie und Angewandte
Laboratory testing for galvanic corrosion involves so many var- Physikalische Chemie 50 (1905): 641–712.
iables that it is difficult to write a single standardized test. For
2. H. P. Hack, “Scale Modeling for Corrosion Studies,” Corrosion 45,
this reason, there are no standardized laboratory testing proce-
no. 7 (July 1989): 601–606.
dures specifically for galvanic corrosion. If another form of cor-
rosion is being studied, then a slight modification to a 3. D. J. Tighe-Ford, J. N. McGrath, and L. Hodgkiss, “Design
standardized test for that corrosion form may be used. For Improvements for a Ship’s Cathodic Protection System Using
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Prevention and Control 32, no. 5 (October 1985): 89–91.
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a wire between the specimen and a second material to create Protection,” Sea Technology, September 1981, 25–30.
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21. H. S. Isaacs, “The Localized Breakdown and Repair of
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22. M. J. Franklin, D. C. White, and H. S. Isaacs, “A Study of Carbon
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23. H. Krawiec, V. Vignal, and R. Oltra, “Use of the Electrochemical
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ASTM International, 1956). 25. Z. P. Cano, J. R. Kish, and J. R. McDermid, “On the Evolution of
Cathodic Activity during Corrosion of Magnesium Alloy AZ31B in
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27. G. Williams, A. J. Coleman, and H. N. McMurray, “Inhibition of
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Cathodic Focusing” (PhD thesis, University of Virginia, plexing Compounds,” Electrochimica Acta 55, no. 20 (August
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and Current Distributions over Coplanar Electrodes Using SVET Study of the Galvanic Corrosion of Zinc Coupled with Iron,”
Polarization Parameters,” Journal of the Electrochemical Society Corrosion Science 49 (2007): 4568–4580.
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29. B. Kannan, C. F. Glover, H. N. McMurray, G. Williams, and J. R.
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Thin Electrolyte Layer Galvanic Cells,” Journal of the AA2024-T351 in Full Immersion: A Galvanic Throwing Power
Electrochemical Society 136 (1989): 3229–3236. Investigation Using a Scanning Vibrating Electrode Technique,”
Journal of the Electrochemical Society 165 (2018): C27–C41.
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Techniques,” Corrosion Science 52 (2010): 2819–2826.
16. D. Mizuno and R. G. Kelly, “Galvanically Induced Intergranular
Corrosion of AA5083-H131 under Atmospheric Exposure Condi- 31. S. Böhm, H. McMurray, S. Powell, and D. Worsley,
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17. N. Murer, R. Oltra, B. Vuillemin, and O. Neel, “Numerical
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Journal of the Electrochemical Society 164 (2017): C845–C855. McMurray, “The Use of 3D-SVET for the Examination of Plasti-
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GALVANIC 57
35. G. Williams and H. N. McMurray, “Pitting Corrosion of Steam 43. R. Baboian, “New Methods for Controlling Galvanic Corrosion,”
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(West Conshohocken, PA: ASTM International, 1976), 5–19. ASTM International, 1988).
59
Chapter 4 | Hydrogen Damage
Kevin Nibur1 and Brian Somerday2
Introduction initial step for hydrogen uptake is the production of atomic

hydrogen at the gas–surface interface. This production of atomic
Hydrogen embrittlement affects virtually every common struc- hydrogen is catalyzed by transfer of electrons from the structural
tural alloy to some degree. Some alloys, notably high-strength metal to the hydrogen molecule (H2), leading to dissociative
steels, are rendered virtually useless by even small concentrations chemisorption as described by the following reaction:1
of hydrogen, whereas other alloys, for example, certain austenitic
stainless steels, remain quite sound even with large concentra- H2 ð g Þ ¢ Hads þ Hads , (1)
tions of dissolved hydrogen. Only sensitive testing methods may
detect a degradation of mechanical properties. The variety of where:
mechanical test methods discussed in the chapter can be broadly Hads ¼ atomic hydrogen adsorbed on the surface.
broken into two categories: those intended to detect only the Once adsorbed hydrogen is produced, it can enter the sub-
presence or absence of hydrogen embrittlement and those surface region via interstitial sites between the host metal atoms.
intended to quantitatively measure the mechanical properties of This subsurface absorbed hydrogen can penetrate further into
a material intentionally exposed to hydrogen. the bulk by diffusion through interstitial sites, as described in an
The primary way in which hydrogen alters mechanical proper- ensuing section.
ties is by facilitating crack initiation and growth. The influence of The concentration of absorbed hydrogen resulting from
hydrogen on fatigue crack growth is covered in the chapter on cor- exposure to H2 gas is quantified from the relationship:2,3
rosion fatigue; this chapter emphasizes the influence of hydrogen
Es 1=2
on quasistatic test methods. Proper selection of test methods and CL ¼ Sf 1=2 ¼ So exp f , (2)
RT
interpretation of the results requires an understanding of hydrogen
uptake and transport, trapping, hydrogen-metal interactions, and where:
hydrogen’s impact on failure mechanisms. CL ¼ the concentration of hydrogen in interstitial lattice sites,
S ¼ the solubility (and So is the preexponential factor),
Es ¼ heat of solution,
Hydrogen Uptake, Transport, R ¼ the gas constant,
and Trapping T ¼ absolute temperature, and
f ¼ hydrogen fugacity.
HYDROGEN UPTAKE The fugacity is related to gas pressure through the following
Hydrogen can enter structural metals during exposure to expression:3
hydrogen-containing or -generating media in gaseous or aqueous
Pb
form. Prominent sources of hydrogen uptake into structural met- f ¼ P exp , (3)
als include molecular hydrogen gas and water in either the vapor RT
or liquid phase. where:
This section first considers hydrogen uptake from gaseous P ¼ pressure, and
species, focusing on molecular hydrogen as an example. The b ¼ a constant in the Abel-Noble equation of state.
1
As the deviation from ideal gas behavior becomes more pro-
Hy-Performance Materials Testing, LLC, Bend, OR, USA http://orcid.org/
nounced at higher pressure, fugacity is the more appropriate
0000-0003-0920-3157
2
Somerday Consulting LLC, 118 Rehoboth Rd., Wayne, PA 19087, USA http:// parameter to describe hydrogen uptake in equation (2). At lower
orcid.org/0000-0002-5238-7281 pressure f ! P, and the relationship between CL and P in equa-
tion (2) becomes the more familiar Sievert’s law.
DOI: 10.1520/MNL202NDSUP20190031
In aqueous solutions, atomic hydrogen is produced on the where:

structural metal surface through electrochemical reactions. In ko ¼ the rate constant for hydrogen transfer from the oxide to
acidic solutions, the reduction of protons yields surface-adsorbed the metal, and
hydrogen, as described by the following reaction: km ¼ the rate constant for hydrogen transfer from the metal to
the oxide.
H þ þ e ¢ Hads : (4) Here, kabs and kdes are rate constants for hydrogen absorption
and desorption, respectively, at the oxide surface exposed to the
Atomic hydrogen also can be produced in basic solutions by
environment. When considering bulk hydrogen uptake into struc-
the reduction of water—that is:
tures or laboratory test specimens, equation (8) applies assuming
H2 O þ e ¢ OH þ Hads : (5) that the oxide is continuous on the surface. It is possible, however,
for such oxide barriers to become locally breached, particularly
Similar to the case of hydrogen gas, the surface-adsorbed when the structure or test specimen is subjected to stress. In this
hydrogen can then migrate into subsurface lattice sites. The case, locally elevated plastic strain can mechanically rupture the
resulting lattice hydrogen concentration can theoretically be oxide at specific sites, allowing hydrogen uptake at these locations,
quantified from the following relationship:1 following equations (2) and (6).
hads kabs
CL ¼ , (6) HYDROGEN TRANSPORT
1 hads kdes
Once hydrogen enters the subsurface region, it can then diffuse
where: into the bulk via interstitial lattice sites. The essential parameter
hads ¼ the surface coverage of adsorbed hydrogen atoms, for characterizing this hydrogen transport process is the lattice
kabs ¼ the rate constant for subsurface hydrogen absorption, and diffusion coefficient, DL. The magnitude of the lattice diffusion
kdes ¼ the rate constant for subsurface hydrogen desorption. coefficient depends on the activation energy barrier between
Strictly, this relationship can be derived only when the adjacent interstitial sites (Ed), the frequency factor (Do), and tem-
hydrogen diffusion flux into the bulk is relatively low.1 In princi- perature according to the Arrhenius relationship:1–3
ple, equation (6) also applies to hydrogen uptake in gaseous
Ed
media, but equation (2) is more practical because the parameters DL ¼ Do exp : (9)
RT
So and Es are readily determined experimentally.
The lattice hydrogen concentration resulting from exposure The flux of hydrogen from the surface into the bulk depends
to gaseous and aqueous media (e.g., equations (2) and (6)) can on the lattice diffusion coefficient, as demonstrated through
be amplified by applied stress. The fundamental concept is that Fick’s first law:
an imposed triaxial stress (i.e., mean normal stress) expands the
volume of interstitial lattice sites, allowing a higher fraction of dCL
J ¼ DL , (10)
these sites to accommodate hydrogen. The magnitude of this dx
effect is a function of mean normal stress (rm) and the partial
where:
molar volume of hydrogen in solution (VH), as follows:2,3
flux, J ¼ moles of hydrogen atoms transported through a unit

rm VH area during a unit time, and dCL/dx is the hydrogen concentra-
CLr ¼ CL exp , (7) tion gradient.
RT
Fick’s first law applies to steady-state conditions (i.e., time-
where: independent hydrogen concentration gradient), and the for-
CLr ¼ the stress-modified lattice hydrogen concentration. mulation in equation (10) presumes one-dimensional hydrogen
The mean stress can be elevated near features, such as transport. As an example, these conditions are designed to pre-
notches and cracks, leading to higher lattice hydrogen concentra- vail in experiments to measure hydrogen permeation through
tions at these locations. thin membranes.
The expressions for lattice hydrogen concentration in equa- In the case of an evolving hydrogen concentration gradient
tions (2) and (6) tacitly presume that no barriers to hydrogen from the surface into the bulk (i.e., nonsteady state), the penetra-
uptake exist on the surface of the structural metal. One such barrier tion depth of hydrogen can be quantified assuming a constant
that realistically forms on the surface of structural metals in both subsurface concentration and one-dimensional diffusion:
gaseous and aqueous media is an oxide film. In gaseous media, it is pffiffiffiffiffiffiffiffi
essential to recognize that oxide films can form even in high-purity x ¼ K 2 DL t , (11)
environments, for example, oxide films can result from only part-
per-million concentrations of oxygen in hydrogen gas.4 When oxide where:
films are present on the surface, the lattice hydrogen concentration x ¼ the penetration distance for a specific hydrogen concentra-
is reduced according to the following expression:1 tion level in the gradient extending from the surface,
t ¼ time, and
hads kabs ko factor, K ¼ parameter dependent on the hydrogen concentration
CL ¼ , (8)
1 hads kdes km level.
HYDROGEN DAMAGE 61
For example, at the level equal to 15% of the surface con-

centration, K is approximately unity so that the penetration dis- FIG. 1 Calculated total hydrogen concentration (CL þCT on
pffiffiffiffiffiffiffiffi 2
y-axis) versus temperature for iron. The lattice hydrogen
tance for this concentration is x ¼ 2 DL t .
concentration is established from exposure to hydrogen
HYDROGEN TRAPPING gas at 545 Pa pressure. The total hydrogen concentration
As described in the previous section, hydrogen atoms are trans- is calculated for two trap site densities: NT ¼ 9 1015 sites/
ported in structural metals by diffusion through interstitial lattice cm3 (dashed line) and 1 1017 sites/cm3 (dotted line). The
sites. The characteristic volume of these interstitial sites is suffi- solid line is the calculated lattice hydrogen concentration.
2
ciently restricted such that occupation by hydrogen perturbs the Source: Reprinted by permission from Hirth.
neighboring host metal atoms. This displacement of the host
metal atoms from their equilibrium positions raises the local
stored elastic energy. As a result, it is energetically favorable for
hydrogen to reside at microstructural sites that have more free
volume than interstitial sites. Such lower-energy sites exist at
metallurgical features, such as vacancies (point defects), disloca-
tions (line defects), and interfaces (surface defects), and are col-
lectively referred to as hydrogen traps.
One consequence of hydrogen trapping at defects is that the
total hydrogen concentration in a structural metal can exceed
the lattice concentration. The fraction of a particular trap site
type occupied by hydrogen (hT) is quantified as follows:1–3

hT hL Eb
¼ exp , (12)
1 hT 1 hL RT
where:
hL ¼ the fractional occupancy of lattice sites, and
Eb ¼ the binding energy of hydrogen to the trap site.
The binding energy is the difference in potential energy for
hydrogen residing at an interstitial site versus the trap site. Each
type of trap site (e.g., point defect, line defect, surface defect) has This manifestation of hydrogen trapping is characterized by the
a characteristic binding energy. The fractional occupancy terms, effective diffusion coefficient, Deff. The magnitude of Deff relative
hL and hT, are related to hydrogen concentrations through the to DL depends on the fraction of trap sites occupied by hydrogen,
density of lattice sites or trap sites, that is, CL ¼ hLNL and hT, according to the following expression:5
CT ¼ hTNT, where NL and NT are the densities (sites/volume) of
CL
lattice sites and trap sites, respectively. The total hydrogen con- Deff ¼ DL : (13a)
CL þ CT ð1 hT Þ
centration in a structural metal is then the sum of lattice site and
trap site concentrations. The relationship in equation (12) pre- Similar to equation (12), the relationship in equation (13a)
sumes equilibrium between hydrogen in lattice sites and hydro- presumes that hydrogen populations in lattice sites and trap sites
gen in trap sites, that is, the rate of hydrogen entering traps from are in equilibrium. A practical simplification of equation (13a)
lattice sites equals the rate of hydrogen escaping traps into lattice results at low trap occupancy (hT 1), that is:1,5
sites.

For a structural metal in which a lattice hydrogen concen- CL NT Eb 1
tration is established through exposure to a gaseous or aqueous Deff ¼ DL ¼ DL 1 þ exp (13b)
CL þ CT NL RT
environment (e.g., equations (2) or (6)), figure 1 illustrates how
the total hydrogen concentration can vary as a function of tem- Although Deff is typically less than DL, equations (13a) and
perature.2 In this figure, the total hydrogen concentration (13b) illustrate two cases in which Deff approaches DL. In equa-
(CL þ CT) is calculated for iron with two different trap site densi- tion (13a), one circumstance in which Deff ! DL occurs when
ties (NT ¼ 9 1015 sites/cm3 and 1 1017 sites/cm3). For the trap sites become fully occupied by hydrogen (hT ! 1). Such
parameters selected in the calculations displayed in figure 1, the extensive trap site occupancy can result from hydrogen environ-
trends demonstrate that total hydrogen concentration is domi- ments that induce high lattice hydrogen concentrations (e.g.,
nated by trapped hydrogen at lower temperature. As temperature equations (2), (6), and (12)). The diffusion coefficients Deff and
increases, the trapped hydrogen concentration effectively DL similarly converge as temperature increases (equation (13b)).
decreases to zero, and the total hydrogen concentration is dic- This trend is attributed to the reduced effectiveness of hydrogen
tated solely by lattice hydrogen. trapping at higher temperature (equation (12)). Equivalently, the
Although trapping can enhance hydrogen uptake, it can dwell time of hydrogen in trap sites is reduced as temperature
have the concomitant effect of hindering hydrogen transport. increases.
Implications of Hydrogen Uptake, temperature and decreases with increasing temperature. As the
temperature continues to increase, CT may increase again. This
Transport, and Trapping on behavior results from the opposing influences of temperature
Embrittlement and lattice concentration on trapped hydrogen concentration, as
reflected in equation (12).
Hydrogen accumulates in structural metals at localized stress
The concentration and distribution of hydrogen in a test
fields (equation (7)) and hydrogen traps (equation (12)), and
specimen exposed to the closed-system boundary condition is
activation of hydrogen embrittlement often is associated with a
more complicated and often is not intuitive. Although the total
critical hydrogen concentration at such locations. For this rea-
hydrogen concentration in the test specimen (CH) must always
son, the manifestation of hydrogen embrittlement for compo-
be the sum of the trapped and lattice concentrations, that is,
nents in service and in materials testing is sensitive to variables
that affect these local hydrogen concentrations. For both assess- CH ¼ C T þ C L , (14)
ing in-service component performance and interpreting materi-
als testing results, temperature is one of the most prominent under the closed-system boundary condition this total concen-
variables influencing hydrogen embrittlement, and its effects can tration, CH, is assumed to be fixed by the initial hydrogen-
be rationalized based on hydrogen uptake and trapping. For precharging step. Precharging is often conducted at an elevated
example, hydrogen embrittlement diminishes at elevated temper- temperature to exploit the faster diffusivity and larger CL, which
ature, and this trend has been linked to decreasing hydrogen reduces the necessary precharging time and increases CH, respec-
concentrations in stress fields and traps as temperature increases. tively. As the specimen is cooled from the precharging tempera-
Conversely, because these hydrogen populations increase as ture to the test temperature, CH is assumed to remain constant.
temperature decreases, it may be expected that hydrogen Test procedures often involve a short elapsed time between pre-
embrittlement is always exacerbated at lower temperature. The charging and mechanical loading to enforce this assumption.
equilibrium relationships between hydrogen concentration and Figure 1 demonstrates that hydrogen resides predominantly in
temperature (equations (7) and (12)), however, are satisfied lattice sites at elevated temperature, so during the precharging
only when transport kinetics are sufficiently high to supply step, most hydrogen occupies these sites. As the specimen cools,
hydrogen to these sites. Thus, there is a temperature-dependent hydrogen will redistribute between lattice and trap sites accord-
interplay between the hydrogen concentration relationships ing to Equations (2), (6), (7), and (12) but further constrained by
and hydrogen transport kinetics (e.g., equations (9) and (11)), equation (14).
such that hydrogen embrittlement is often most severe at near- When a test specimen microstructure contains multiple
ambient temperatures. trap types, hydrogen preferentially redistributes from lattice sites
Another aspect that affects hydrogen concentrations in to trap types with high binding energy, Eb (equation (12)), dur-
stress fields and traps that must particularly be considered for ing cooling. If such high binding energy trap types are also pre-
materials testing methods is the environmental boundary condi- sent in high density (NT), these sites significantly deplete the
tions. Specifically, the nature of hydrogen environment exposure lattice hydrogen, because the total concentration is fixed accord-
(continuous versus discontinuous) coupled with temperature ing to equation (14).6 Moreover, high binding energy trap types
variations can dictate the hydrogen concentrations in stress fields may not be the locations for activating hydrogen embrittlement,
and traps, which in turn determines the severity of hydrogen so their primary function is only to limit CL. In this case, the lim-
embrittlement. Two different sets of boundary conditions are ited remaining lattice hydrogen concentration cannot sufficiently
common to most testing methods associated with hydrogen populate other trap types with lower binding energy, which may
embrittlement. First, the open-system boundary condition serve as locations for hydrogen embrittlement but cannot
applies when a test specimen is concurrently exposed to the develop sufficiently high CT to activate it.
hydrogen containing or generating environment and subjected The practical importance is that variations in material
to mechanical loading. Second, the closed-system boundary con- microstructure may greatly influence the hydrogen concentra-
dition applies when a test specimen is first exposed to a hydrogen tion and distribution present during test methods subject to
containing or generating environment to precharge the specimen closed-system boundary conditions, potentially leading to sub-
with hydrogen, and then it is removed from the hydrogen envi- stantially different results compared with those from otherwise
ronment and subsequently subjected to mechanical loading. similar tests conducted under open-system boundary condi-
The temperature-dependent concentration and distribution tions.7 Moreover, without carefully considering all of the differ-
of hydrogen in a test specimen exposed to the open-system ent contributions to hydrogen trapping (e.g., number of trap
boundary condition are described by equations (2), (6), (7), and types and their respective values of Eb and NT), there is no way
(12). Figure 1 illustrates one example of relationships between lat- to anticipate how test results from the two different types of
tice and trapped hydrogen concentration as a function of tem- boundary conditions will compare. When such details are not
perature for an open system and demonstrates some important fully understood, the boundary conditions selected for testing
aspects of these relationships. Most notably, the lattice concen- should match, as closely as possible, the service conditions for
tration of hydrogen (CL) in metals is small at lower temperature the application the test is designed to assess.
and increases rapidly at elevated temperature, whereas the Note that the closed system condition (fixed total hydrogen
trapped hydrogen concentration (CT) is typically largest at lower concentration) is an idealization that may be tenuous for certain
HYDROGEN DAMAGE 63
structural metals. For example, assuming that a fixed total hydro- fields at these incompatibility points then drive the formation of
gen concentration is established at elevated temperature, it may microcracks, where the nucleation site is likely associated with
not be retained when hydrogen environment exposure is discon- defect structures in the deformation bands. Although the forma-
tinued and temperature is lowered. In structural metals such as tion of microcracks at deformation band intersections may be
ferritic and martensitic steels, the diffusion coefficient for hydro- uniquely associated with hydrogen exposure, hydrogen-
gen is relatively high so that hydrogen egress from the metal is enhanced strain localization alternately can accelerate more con-
likely, particularly for modest section sizes and slower rates of ventional microcrack formation mechanisms. For example,
temperature change. In such situations, the total hydrogen con- hydrogen-enhanced strain localization can expedite stages of the
centration at the lower temperature may be less than the concen- microvoid coalescence mechanism commonly manifested in
tration introduced at the higher temperature. ductile structural metals.16 From a physics perspective, the com-
mon characteristic of the hydrogen embrittlement mechanisms
described earlier is the need to accumulate deformation to acti-
Physics and Micromechanical vate microcracks. This leads to the deduction that the strain-
Elements of Hydrogen controlled micromechanical framework17,18 is most appropriate
for quantitatively modeling these types of microcrack formation.
Embrittlement As an alternative to the deformation-dominated forms of
For materials testing characterized by either the open- or closed- hydrogen embrittlement, one of the archetypal signatures of
system environmental boundary condition, hydrogen in the test hydrogen embrittlement is microcrack formation along grain
specimen concentrates at stress fields and trap sites and interacts boundaries. In this mechanism, it is widely accepted that hydro-
with defects at these locations to accelerate material failure. The gen segregates to trap sites on grain boundaries.19,20 This hydro-
key serial elements in the failure process include deformation, gen population then weakens the cohesive strength of the
microcrack formation, and crack growth. Details of the physics interface, leading to microcrack formation. Although there is evi-
and micromechanics of these material responses are described in dence that trapped hydrogen at grain boundaries is required for
this section to provide a foundation for the formulation and microcrack formation,21 hydrogen-enhanced strain localization
interpretation of materials test methods. may condition these interfaces for failure. Here, one notional
Structural metals sustain some amount of deformation role for hydrogen-enhanced localized deformation is to create
before microcrack formation. The extent of deformation that strain incompatibilities and modify the defect structure at grain
precedes microcrack formation is an important contribution to boundaries.14,15,22 Elevated stresses and augmented trapped
measured fracture resistance. Numerous theoretical and experi- hydrogen associated with strain compatibilities and modified
mental results have demonstrated that hydrogen facilitates the defect structure promote conditions for microcrack formation.
nucleation and motion of dislocations.8–11 These hydrogen- Given these characteristics, the stress-controlled micromechani-
dislocation interactions can be reflected through modified mate- cal framework18,23 may be the most germane for modeling inter-
rial properties, such as yield strength and strain hardening, but granular microcrack formation.
arguably the most important manifestation that affects material As a final category of hydrogen embrittlement mechanisms,
failure is strain localization. Several aspects of hydrogen- the mechanistic ingredients of trapped hydrogen and hydrogen-
dislocation interactions can promote strain localization. In mate- related strain incompatibilities invoked earlier can cause micro-
rials with metallurgical characteristics that induce some degree cracks to form at other interfaces as well (e.g., phase boundaries).24
of strain localization, hydrogen concentrates in these regions of Such hydrogen-assisted microcrack formation associated with
localized deformation because it becomes trapped at the disloca- phase boundaries is often described by the term “quasi-cleavage,”
tions. Hydrogen then enhances the mobility of these dislocations, but arguably, this is a misnomer because cleavage seldom operates
which further localizes the deformation.12 In materials that are in hydrogen embrittlement failures.23,25 Generally, these “quasi-
not metallurgically conditioned toward strain localization, cleavage” fracture mechanisms are poorly characterized; how-
hydrogen still can induce localization by inhibiting cross-slip of ever, the role of plastic strain is consistently evident.17,22 For this
dislocations.9,10 Localized deformation resulting from any mate- reason, quantitative models for this type of microcrack forma-
rial characteristic or environmental effect contributes to material tion may be based on the strain-controlled framework.18,22
failure by promoting strain incompatibilities. These strain Although the physics and micromechanics of hydrogen
incompatibilities are associated with the impingement of defor- embrittlement are more easily conveyed by describing micro-
mation bands on metallurgical features, such as interfaces and crack formation, materials test methods are not interrogating
boundaries. microcrack formation but rather macroscopic crack extension.
Hydrogen-enhanced strain localization can activate or Microcrack formation, however, is the fundamental element in
accelerate microcrack formation through several mechanisms. macroscopic crack extension given that the repeated nucleation
One mechanism that is most directly linked to strain localization and coalescence of microcracks constitutes crack extension.
is microcrack formation at the intersection of deformation Thus, the physics and micromechanics of hydrogen embrittle-
bands.13–15 The essential role of hydrogen in this mechanism is to ment described previously equally pertain to crack extension.
promote localized deformation bands, which can then intersect Most important, the difference between strain- and stress-
and create strain incompatibilities at these junctions. The stress controlled crack extension is critical to the proper selection and
interpretation of materials test methods that assess hydrogen developed by considering microcrack formation, the concepts in
embrittlement. The implications of strain-controlled versus the underlying micromechanical frameworks can be applied sim-
stress-controlled crack extension for materials test methods can ilarly to model crack growth resistance. One subtlety that is
be revealed by detailing the following micromechanical modeling imperative to recognize in the case of strain-controlled crack
frameworks. growth is that the strain field evolves as a function of crack
The fundamental differences between stress- and strain- extension. This characteristic of the strain field results because
controlled fracture mechanisms have been quantified through plastically deformed material is transferred from the high-stress
two similar micromechanical models promulgated by Ritchie. region ahead of a loaded crack tip to the crack wake, where it
These models describe the relationship between the remotely then unloads elastically. This wake of plastically deformed mate-
applied driving force necessary for microcrack formation ahead rial imparts a residual strain field that interacts with, and alters,
of an existing macroscopic crack (e.g., the critical value of the the stress and strain fields ahead of the crack tip. This interaction
linear elastic stress intensity factor, Ki) and the associated frac- has a negligible effect on the crack tip stress fields but can signifi-
ture resistance expressed as a local stress18 or strain26 quantity. cantly alter the crack tip strain fields.28 Because the crack tip
The stress-controlled micromechanical framework (fig. 2A) stip- strain fields can be affected significantly by the plastic crack
ulates that microcracks form at the driving force level Ki when a wake, these fields are a function of crack growth history. Specifi-
critical value of local stress (r*f) is achieved over a critical length cally, a stationary crack with no plastic wake has a strain field
scale ahead of the crack tip (l*), such that: described by Hutchinson29 and Rice and Rosengren,30 in which
the strain (e) varies with distance from the crack tip (r) as
ð1þnÞ=2
Ki / rf =ðro Þð1nÞ=2 l1=2 (15) follows:
e / ðJ=r Þ1=2 : (17)

where:
ro ¼ the yield stress, and Once the crack begins to extend, this relationship between e
n ¼ the strain-hardening exponent. and r transitions toward that of a crack propagating under steady
Similarly, the strain-controlled micromechanical framework state conditions:28
(fig. 2B) stipulates that microcracks form at the driving force
level Ki when a critical value of local strain (e*f) is achieved over e / InðJ=r Þ: (18)
a critical length scale (l*) ahead of the crack tip, such that:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Compared with equation (17), equation (18) represents a
Ki / ef l ro E, (16) weaker strain singularity at the crack tip, thus at a given relative
distance ahead of the crack tip, the strain magnitude will dimin-
where: ish as the crack extends. As a consequence, because the local cri-
E ¼ the elastic modulus. terion for strain-controlled fracture (cf. fig. 2B, e ¼ e*f at r ¼ l*)
Although the quantitative models for fracture initiation does not change, the driving force level (remotely applied J or K)
resistance reflected in Equations (15) and (16) were strictly associated with each successive crack growth increment must
FIG. 2 Schematic of the fracture criteria for (A) stress-controlled fracture and (B) strain-controlled fracture. Source: Reprinted from Ritchie
27
and Thompson.
HYDROGEN DAMAGE 65
increase continually. In the limit as crack extension approaches a stationary crack (equation (17)) to that of a steady-state pro-
steady state, the crack growth resistance (expressed as remote pagating crack (equation (18)). In contrast to strain-controlled
driving force, J or K) can be quantified by coupling the strain fracture, stress-controlled fracture is defined by crack tip stress
field given by equation (18) with the fracture criterion illustrated fields that are not significantly modified during crack extension.
in figure 2B (i.e., e ¼ e*f at r ¼ l*), as follows:23 Hence, the driving force is not dependent on crack growth history
pffiffiffiffi and the R-curve has an ideally zero slope (fig. 3A).
KR Aro l exp B f ef =e0 : (19) The evolution of crack growth resistance during crack
extension (i.e., the positive slope of the R-curve) is a distinguish-
where: ing characteristic of strain-controlled fracture and must be
KR ¼ the predicted crack growth resistance at steady state, recognized in applying materials test methods. The microme-
eo ¼ the yield strain, and chanical models in equations (16) and (19) further illustrate that
A and B are undefined constants. the local fracture strain, e*f, governs the disparity between Ki and
Because the plastic wake does not notably alter the crack tip KR (e.g., for a fixed value of eo, lowering e*f reduces the slope of
stress fields, the crack growth resistance, KR, under stress- the R-curve). Because e*f dictates the slope of the R-curve, it is
controlled conditions is nominally the same as the resistance to essential to revisit the physics of strain-controlled hydrogen
microcrack initiation, that is: embrittlement mechanisms presented earlier. In particular,
although the local fracture strain, e*f, is a continuum quantity, its
ð1þnÞ=2
KR ¼ Ki / rf =ðro Þð1nÞ=2Þ lð1=2Þ , (20) magnitude is related to the severity of hydrogen-induced strain
localization. Furthermore, the potential for hydrogen to reduce
which is simply equation (15) applied to crack extension. e*f through strain localization requires that deformation accumu-
The micromechanical modeling results in equations (16), lates in the presence of hydrogen—that is, the sequence of
(19), and (20) are manifested in materials testing through crack hydrogen exposure and deformation is essential. Such history
growth resistance curve (R-curve) constructions (fig. 3). The con- dependence contrasts to stress-controlled hydrogen embrittle-
ventional crack growth resistance curve concept was born in the ment, in which reduced critical fracture stress, r*f, is only a func-
ductile fracture domain, in which fracture mechanisms (e.g., tion of the instantaneous hydrogen concentration.
microvoid coalescence) are well accepted as strain-controlled. In summary, the physics and micromechanics of hydrogen
According to the fracture testing of ductile metals, it is well embrittlement and their connection to crack growth resistance
established that the crack growth resistance (as characterized by curve behavior have implications for materials test methods.
remotely applied J or K) varies as a function of crack extension First, the applied driving force (J or K) needed to initiate a
(Da). The fundamental reason for such a relationship is con- microcrack may be different from that needed to sustain crack
nected to the evolution of the crack tip strain field, as embodied extension when fracture is strain-controlled and the crack
in equations (16) and (19). The crack growth resistance will growth resistance curve exhibits a positive slope. In particular,
gradually evolve from that described by equation (16) to that of measurements of fracture resistance from materials test methods
equation (19) as the crack grows toward steady state. (Practically, associated with propagating cracks may be higher than measure-
most materials test methods do not allow sufficient crack exten- ments that characterize microcrack initiation. Second, because
sion to reach steady state conditions.) For any value of e*f greater strain-controlled hydrogen embrittlement is history dependent,
than eo, equations (16) and (19) show that KR is always greater materials test methods must consider the sequence of deforma-
than Ki, demonstrating that the crack growth resistance increases tion accumulation and hydrogen exposure. It is evident from
(fig. 3B) as the crack tip strain field gradually evolves from that of these two summary points that characterization of strain-
controlled hydrogen embrittlement is more complex than char-
acterization of stress-controlled hydrogen embrittlement.
FIG. 3 Schematic crack growth resistance curves (R-curves).
(A) flat R-curve representative of a material exhibiting
ideal stress-controlled fracture and (B) rising R-curve
Testing Methods for Prevention
typical of higher toughness materials exhibiting strain- of Hydrogen-Related Failures
controlled fracture.
Components manufactured from high-strength steel, including
high-strength fasteners and certain aircraft components, must be
Crack growth resistance (J, K)
Crack growth resistance (J, K)
free of internal diffusible hydrogen and often must be coated to

prevent corrosive reactions that could generate hydrogen. A vari-
ety of standard test methods are available through ASTM to
ensure hydrogen embrittlement is precluded following plating
procedures. ASTM F1113, Standard Test Method for Electrochemi-
cal Measurement of Diffusible Hydrogen in Steels (Barnacle Elec-
trode), and ASTM F326, Standard Test Method for Electronic
Crack extension Crack extension Measurement for Hydrogen Embrittlement from Cadmium-
(A) (B) Electroplating Processes, describe methods for directly
monitoring the hydrogen uptake from plating baths; however, hydrogen redistribution will influence the extent of embrittle-
this chapter will address only mechanical test procedures. ment so that the loading rate from one step to the next may be
Two ASTM standards, ASTM F519-18, Standard Test as, or more, important than the duration of the step hold. The
Method for Mechanical Hydrogen Embrittlement Evaluation of rate of load increase between steps is not addressed by these
Plating/Coating Processes and Service Environments, and ASTM standards. Similar active-loading methods using slow rising dis-
F1940-07a, Standard Test Method for Process Control Verification placement may be expected to yield similar results, and possibly
to Prevent Hydrogen Embrittlement in Plated or Coated Fasten- greater degrees of test acceleration because the rate of strain
ers, are intended to detect critical levels of hydrogen that may accumulation is consistently slow during such testing.
result from processing (e.g., plating or other chemical exposure)
of high-strength steel fasteners and components. These standards
are not intended to evaluate hydrogen embrittlement resulting Quantitative and Qualitative
from environmental exposure. In both standards, AISI 4340 steel
quenched and tempered to high strength (specified as 260–280 Measurements of Hydrogen
ksi in ASTM F519, and 50–52 HRC in ASTM F1940) is selected Embrittlement Susceptibility
as a material that is highly susceptible to hydrogen embrittle-
Numerous applications require materials that maintain struc-
ment. Test specimens fabricated from the high-strength 4340 are
tural integrity while exposed to hydrogen environments,
to accompany the product during the processing steps of interest.
including hydrogen pressure vessels, power generation equip-
Following processing, these witness specimens are subjected to
ment, oil and gas infrastructure, rocket engines, and many
mechanical testing procedures that evaluate the presence of dam-
others. Design and selection of materials for these applications
aging concentrations of hydrogen. These specimens serve as the
require knowledge of the impact of hydrogen on the mechani-
conceptual canary in the coal mine to indicate whether the proc-
cal properties of a given material. Many of the test methods
essing steps are leading to hydrogen uptake in the parts. Inherent
designed to assess the performance of alloys that are intention-
to these test methods is the assumption that the high-strength
ally exposed to hydrogen result in qualitative assessments of
4340 material used for the test specimens has hydrogen embrit-
relative embrittlement. It has been demonstrated (e.g., ISO
tlement susceptibility that equals or is more severe than the
DTR 1078331) that different qualitative assessment tests will not
material used for the components being screened. ASTM F519 is
necessarily provide the same quantitative metric. In other
targeted to aerospace applications, whereas ASTM F1940 is tar-
words, each specific test method may need to be calibrated
geted to automotive applications.
against a set of known criteria (i.e., service experience that has
A variety of specimen geometries are allowed by ASTM
demonstrated a set of alloys known to perform acceptably and
F519; the specimens are stressed to an initial force or deflection
a set known to perform unacceptably in the presence of hydro-
(typically 75% of notched tensile strength) and held statically for
gen). ASTM G142-98(2016), Standard Test Method for Determi-
a predetermined period (typically 200 h). The absence of failures
nation of Susceptibility of Metals to Embrittlement in Hydrogen
within this duration indicates that the process has not resulted in
Containing Environments at High Pressure, High Temperature,
damaging levels of hydrogen uptake. Alternatively, in some cases,
or Both; ASTM G129-00(2013), Standard Practice for Slow
ASTM F519 may allow the use of notched bend specimens tested
Strain Rate Testing to Evaluate the Susceptibility of Metallic
under stepwise increasing displacement (referred to as incremen-
Materials to Environmentally Assisted Cracking; and ASTM
tal step loading, or ISL) rather than constant displacement.
F1459-06(2017), Standard Test Method for Determination of the
ASTM F1940 allows only for notched bend specimen testing
Susceptibility of Metallic Materials to Hydrogen Gas Embrittle-
under stepwise increasing displacement. Both ASTM F519 and
ment (HGE), are designed to measure the relative susceptibility
ASTM F1940 suggest that the ISL technique yields results that
of an alloy to hydrogen embrittlement.
are comparable to sustained load test techniques but in signifi-
cantly shorter times.
Hydrogen embrittlement of such high-strength steels occurs RELATIVE SUSCEPTIBILITY
through intergranular fracture with low crack growth resistance. Tensile Testing
As such, it is reasonable to consider this as a stress-controlled Tensile testing remains one of the most common methods for
fracture mechanism, and static loading methods seem appropri- assessing material properties because of the relative simplicity of
ate. As discussed in the section “Physics and Micromechanical the specimens and test procedures. Hydrogen embrittlement will
Elements of Hydrogen Embrittlement,” hydrogen-enhanced manifest as a reduction of the tensile ductility. If this reduction
strain localization has been shown to condition grain boundaries in ductility is large enough, it will result in a reduction of the ten-
for failure. Thus, even nominally stress-controlled fractures may sile strength as well. When hydrogen causes a reduction of ten-
involve a critical contribution of hydrogen-enhanced plasticity. sile ductility, it also will result in a reduction of other mechanical
Speculatively, the use of the ISL test method may allow hydrogen properties, such as fracture toughness and low-cycle fatigue resis-
to redistribute to the high-stress region of the notch concomi- tance. For this reason, tensile tests serve as a valuable indicator
tantly with the application of strain, facilitating hydrogen- of relative susceptibility to hydrogen embrittlement. The absence
enhanced strain localization and accelerating the failure process. of any degradation in tensile properties, however, does not nec-
Critically, the rate of strain accumulation relative to the rate of essarily mean that hydrogen embrittlement is not present and
HYDROGEN DAMAGE 67
may still be realized through fracture or fatigue tests (e.g., Harris two rupture pressures is presented in the form of the embrittle-
and VanWanderham32 and Stoltz33). ment index. This test method is relatively straightforward to per-
Tensile tests conducted in hydrogen-containing or -generating form, and the equipment generally is less complicated than that
environments usually exhibit surface cracking; specimen failure needed for other types of materials testing in hydrogen gas.
occurs when one of these surface cracks propagates through the Extensive results have been collected using this test method
gage section.16,34 This sequence of events leading to fracture is for pressure vessel steels, and these results have been compared
usually different in inert environment in which failure is often with service history data of hydrogen storage cylinders for many
associated with the formation of a plastic instability (necking) decades.31 Materials that exhibit a burst pressure in hydrogen
followed by microcracking in the interior of the specimen. Some that is at least 50% of the burst pressure measured in helium cor-
combination of both mechanisms may be present in materials relate with steels that have reliable service history. This test
that exhibit moderate resistance to hydrogen embrittlement or necessitates that hydrogen pressure continuously increases dur-
when the applied strain rate is too high for hydrogen uptake and ing the test, so specimens with higher rupture pressures also will
transport to keep pace with damage formation mechanisms. be exposed to higher hydrogen pressure. In addition, the stress
Increasing levels of hydrostatic stress enhance hydrogen embrit- and strain state at the location of rupture (which is claimed to be
tlement,33,35 as expected from equation (7); consequently, a triaxial stress state) cannot be applied easily to design parame-
notched tension specimens may be more sensitive to hydrogen ters, so this test does not provide any other information about
embrittlement. the behavior of the material beyond the embrittlement index.
ASTM G142 provides a standard test method for conducting
tensile tests in gaseous hydrogen. This standard issues guidance QUANTITATIVE FRACTURE MECHANICS
on the testing apparatus, gaseous hydrogen test environment, Most failures resulting from hydrogen embrittlement are the
test specimen geometry, and loading rates. Specifically, it recom- result of subcritical crack growth. Fracture mechanics-based test
mends specimen geometries for smooth and notched tensile methods are necessary to directly measure the effect of hydrogen
specimens. ASTM G142 further recommends displacement rates on subcritical crack growth and, in many cases, offer a preferred
for testing that, for the specified geometries, correlates to a strain way to assess susceptibility to hydrogen embrittlement. ASTM
rate of 7 10-5 1/s for smooth specimens and that is 10 times provides several fracture mechanics–based standards, some of
faster for notched specimens. It is unclear why a faster rate which are specific to environment assisted cracking. Standards
would be suggested for the notched specimen because the strain for measuring conventional fracture toughness (e.g., KIc and JIc)
is localized and magnified by the presence of the notch. As such, are not specific to environment assisted cracking but provide
even for the same applied displacement rate, the effective strain valuable procedures that can be adapted to assess the effects of
rate at the notch root will be much higher than that in a smooth hydrogen on subcritical crack growth.
specimen. It is reasonable to suggest that testing the notched ten-
Sustained Load Fracture Threshold Test Methods
sile specimens at a slower displacement rate may be appropriate.
ASTM E1681-03(2013), Standard Test Method for Determining
CSA CHMC1, for example, references ASTM G142 for the slow
Threshold Stress Intensity Factor for Environment-Assisted Crack-
strain rate tensile test parameters, but it recommends a strain
ing of Metallic Materials (superseded), and ASTM G168-17, Stan-
rate of 1 10-5 1/s for smooth specimens and notched specimens
dard Practice for Making and Using Precracked Double Beam
should be tested at a displacement rate that corresponds to 1/10
Stress Corrosion Specimens, describe generally similar test proce-
the rate that would produce a strain rate of 1 10-5 1/s in the
dures for either constant displacement or constant load testing of
smooth tensile specimen.
precracked specimens in a variety of test environments. Both of
ASTM G129 is a standard practice that provides a method of
these standards describe procedures for applying either a con-
presenting the property measured in an embrittling environment
stant load or constant displacement to the test specimens either
relative to the corresponding property measured in air or in a
before or after immersion in the test environment. The specimen
nonembrittling environment. Procedures are broadly described
is held in the environment for some period of time during which
for testing smooth, notched and fatigue precracked fracture
crack extension may or may not occur. The presence or absence
mechanics specimens. The methods described in ASTM G129
of crack extension at various applied K levels can be used to
have been applied widely and provide a consistent way to present
identify the threshold stress intensity factor below which crack
and compare the relative degree of hydrogen embrittlement
extension does not occur. Both standards can be used to assess
based on the particular measured property. This practice is appli-
crack growth velocity and the threshold stress intensity factor for
cable to all alloys, environments, and test types.
crack arrest if proper instrumentation is applied.
Disk Pressure Testing ASTM E1681 and ASTM G168 differ primarily with regards
Another ASTM standard that provides a method to evaluate the to the specified specimen geometry; ASTM E1681 allows use of
relative susceptibility of a given material to hydrogen embrittle- any properly characterized fracture mechanics specimen and
ment is ASTM F1459. This method subjects a thin disk of mate- provides specific guidance for either tension loaded compact
rial, which is securely clamped into a fixture, to pressurized gas specimens (either compact tension or the modified bolt loaded
on one side only. The gas pressure is gradually increased until compact specimen) or bend-loaded notched beam specimens.
the disk ruptures. This rupture pressure is recorded with hydro- ASTM G168 specifies only the use of double cantilever beam
gen gas as well as helium or other inert gas, and the ratio of these (DCB) specimens. The DCB specimen is known to induce a
positive T-stress*36 ahead of the crack tip (e.g., Hadj Meliani,

Matvienko, and Pluvinage37), and positive T-stress has been FIG. 4 Post-test image of a wedge-loaded DCB specimen
shown to destabilize straight, in-plane crack paths under mode I previously exposed to hydrogen gas showing deflection
25
loading.38 The result is that cracks tend to deflect away from the of the crack away from the crack plane.
crack plane in the DCB specimen (fig. 4). The use of side grooves
may help to constrain the crack to the desired plane; however,
the specimen generally must be limited to low K values to pre-
vent out-of-plane cracking.
Sustained load test procedures are relatively easy to execute
and have been shown to produce consistent and conservative
results when applied to high-strength steels in which the fracture
mode was intergranular and nominally stress-controlled.39 These
test procedures, however, are inherently flawed when applied to
material-environment combinations that promote strain-
controlled hydrogen embrittlement.23,25 As discussed in the sec-
tion “Physics and Micromechanical Elements of Hydrogen
Embrittlement,” two barriers cause sustained load test methods
to be nonconservative when the fracture mechanism is strain
controlled. First, concurrent hydrogen exposure and slow, active
deformation is necessary to stimulate hydrogen-induced strain-
controlled fracture mechanisms. Sustained load test procedures FIG. 5 The relationship between threshold stress intensity factor,
often involve load application before environmental exposure, K, and yield stress for a variety of low-alloy pressure
and when load is applied concurrent with environment exposure, vessel steels. Filled symbols represent the threshold for
the load application is rapid. Either scenario prevents or limits the onset of crack extension measured under slow rising
the strain-history dependence of strain-controlled hydrogen- displacement whereas open symbols represent the
enhanced microcrack formation. Second, constant displacement threshold for crack arrest measured under fixed
23
test methods are designed to identify the threshold stress inten- displacement.
sity factor (KTH) as the value of remote driving force at which a
small, but detectable, amount of crack growth occurs, or at which
a growing crack arrests. The first barrier generally prevents crack
growth from occurring unless the applied stress intensity factor
is elevated significantly above the threshold stress intensity fac-
tor. Large applied stress intensity factors necessarily overestimate
the threshold stress intensity factor for the onset of crack exten-
sion. The alternative is to measure the threshold stress intensity
factor for crack arrest. Testing approaches in which the threshold
stress intensity factor is identified based on crack arrest also
result in nonconservative measurements when the fracture
mechanism is strain controlled because the conditions for arrest
of a growing crack are described by equation (19) rather than by
equation (16). In other words, the crack will arrest at some posi-
tion along the R-curve, which is necessarily higher than the K or
J value associated with the onset of crack extension.40 Figure 5
demonstrates the large potential differences in measurements of
the threshold stress intensity factor for the onset of crack exten-
sion and crack arrest. Figure 5 also demonstrates that this differ-
ence diminishes as the critical strain for hydrogen assisted
fracture (denoted as eHf) decreases. As eHf decreases toward the
yield strain, the fracture mechanism essentially becomes stress
controlled and the difference between threshold measurements
diminishes.
Rising Displacement Fracture Threshold Measurement
ASTM E1820-20b, Standard Test Method for Measurement of Frac-
ture Toughness (superseded), and ASTM E399-20a, Standard Test
*The T-stress refers to the uniform stress acting parallel to the crack plane. When
Method for Linear-Elastic Plane-Strain Fracture Toughness of
the crack tip stress field is expressed as an infinite power series, with K represent- Metallic Materials (superseded), provide standard methods for
ing the amplitude of the first, singular term, T is the second term.
36
measurement of, respectively, the elastic-plastic and linear-elastic
HYDROGEN DAMAGE 69
fracture toughness. Neither of these standards are specific to the measurements to be valid. In addition, any specimen that can
hydrogen embrittlement or environment assisted cracking, but yield a valid measure of KIc from ASTM E399 generally also will
both may easily be adapted to environment-assisted cracking yield a valid measure of JIc from ASTM E1820; however, it is often
with little modification. In comparison with static-loading test the case that a specimen capable of yielding a valid measure of JIc
methods, rising displacement tests may produce lower values of cannot yield a valid measure of KIc.
the threshold stress intensity factor when the hydrogen embrit- Slow-rising displacement methods are the only fracture
tlement mechanism is strain controlled (e.g., fig. 5). Conversely, mechanics tests that address the history dependence of crack tip
rising displacement methods may produce nonconservative val- strain accumulation and therefore provide the only method to
ues when the applied loading rate is too high (e.g., Clark and accurately measure the threshold stress intensity factor for the
Landes39 and Nibur and Somerday41), because hydrogen uptake onset of crack extension when the hydrogen embrittlement
and transport kinetics may not be sufficiently accommodated. mechanism is strain controlled. In addition, these test methods
Rising displacement test methods utilizing slow, monotoni- are fully appropriate for stress-controlled hydrogen embrittle-
cally increasing crack opening displacement ensure that the pro- ment mechanisms as well. In either case, appropriate selection of
cess zone ahead of the crack tip is continuously exposed to loading rate remains necessary.
hydrogen throughout the formation of the crack-tip plastic zone.
The resulting threshold stress intensity factor will be dependent Rising Step Loaded Measurements
on the loading rate when the mechanical driving force is applied Intermediate between static and rising displacement test methods
at rates that truncate the kinetic processes associated with hydro- are the step loading methods described in ASTM F1624, Standard
gen uptake and transport. Below some critical loading rate, Test Method for Measurement of Hydrogen Embrittlement Thresh-
hydrogen uptake and transport are not limited and threshold old in Steel by the Incremental Step Loading Technique. Although
stress intensity factor measurements are independent of loading ASTM F1624 is often used to provide a pass-or-fail criterion
rate. Available data support this concept (fig. 6).41 Such critical for material qualification as an alternative to ASTM F519 or
values of loading rate depend on the specifics of the material ASTM F1940, this standard is included in the section on fracture
tested (e.g., the diffusion coefficient) and the severity of the envi- mechanics because it also purports to provide an alternative
ronment (i.e., surface hydrogen concentration) and need to be means of measuring the threshold stress intensity factor. This
identified empirically. standard specifies that a notched specimen is loaded in either
ASTM E1820 describes elastic-plastic fracture mechanics test- tension or bending through a sequence of displacement increases
ing procedures that yield a much broader range of applicability and followed by displacement holds. Crack growth is assumed to
validity compared with linear elastic fracture mechanics methods occur when load drop is observed during the hold period. The
described in ASTM E399. When compared with ASTM E1820, output of this standard is the threshold load, which is the highest
ASTM E399 requires some combination of larger specimens, higher load applied to the specimen before the determination of crack
strength material, and lower threshold stress intensity factors for extension. It is suggested that this threshold load may be
FIG. 6 Threshold stress intensity factor, K, for the onset of crack extension under rising displacement in hydrogen gas as a function of the
23 39 42 43
applied loading rate. Source: Data from Nibur et al., Clark and Landes, Xu, and San Marchi.
converted to a threshold stress intensity factor, but no guidance 4. J. H. Holbrook, H. J. Cialone, E. W. Collings, E. J. Drauglis,
for performing this calculation nor any relevant validity criteria P. M. Scott, and M. E. Mayfield, “Control of Hydrogen
are provided in ASTM F1624. Embrittlement of Metals by Chemical Inhibitors and
Coatings,” in Gaseous Hydrogen Embrittlement of
The most consequential difference between static and ris-
Materials in Energy Technologies, vol. 2, ed. R. P. Gangloff
ing displacement test methods is the sequence of hydrogen and B. P. Somerday (Cambridge: Woodhead, 2012), 129–153.
exposure and strain accumulation at the crack tip. The effective
loading rate utilized in ASTM F1624 is simply the average over 5. R. A. Oriani, “The Diffusion and Trapping of Hydrogen in Steel,”
Acta Metallurgica 18 (1970): 147–157.
the loading portion and hold portion of each step; the rate of
increase of displacement during the loading portion of the step 6. Z. S. Hosseini, M. Dadfarnia, K. A. Nibur, B. P. Somerday,
is not specified and is typically applied rapidly. The history R. P. Gangloff, and P. Sofronis, “Trapping against Hydrogen
dependence of strain-controlled hydrogen embrittlement neces- Embrittlement,” in Proceedings of the 2016 International
sitates that the rate of strain accumulation be sufficiently slow Hydrogen Conference: Materials Performance in Hydrogen
Environments, 71–80 (New York: ASME Press, 2017).
to accommodate the kinetics of hydrogen transport to and
within the evolving strain field. It is questionable whether the 7. K. A. Nibur, B. P. Somerday, S. Pillot, and R. P. Gangloff, “The Role
step loading profile fully accommodates these kinetic factors. In of VC Precipitates in Hydrogen Assisted Cracking of Vanadium
fact, direct comparisons between monotonically rising displace- Modified 21=4 Cr -1Mo Steel,” in Proceedings of the Twenty-Ninth
ment and step-wise increasing displacement using cathodically (2019) International Ocean and Polar Engineering Conference,
ISOPE-I-19-405 (International Society of Offshore and Polar
polarized Monel K-500 in sodium chloride solution at nomi-
Engineers, 2019).
nally equivalent loading rates (based on total time to reach the
final applied displacement) have shown the step load tests to 8. H. K. Birnbaum and P. Sofronis, “Hydrogen-Enhanced
produce much slower crack growth rates and higher threshold Localized Plasticity: A Mechanism for Hydrogen-Related
stress intensity factors. In addition, the fracture mechanism Fracture,” Materials Science and Engineering A A176 (1994):
191–202.
was intergranular when stressed under monotonically rising
displacement but was transgranular with microvoids when 9. I. M. Robertson, M. L. Martin, and J. A. Fenske, “Influence of
stressed using step loading procedures.44 These results strongly Hydrogen on the Behavior of Dislocations,” in Gaseous
suggest that crack tip strain rate during the active loading seg- Hydrogen Embrittlement of Materials in Energy Technologies,
ment plays a critical role in full development of the hydrogen vol. 2, ed. R. P. Gangloff and B. P. Somerday (Cambridge:
Woodhead, 2012), 166–206.
embrittlement mechanism.
ASTM F1624 identifies the threshold load based on the 10. D. Delafosse, “Hydrogen Effects on the Plasticity of Face
assumption that the onset of crack extension will correlate to a Centered Cubic (FCC) Crystals,” in Gaseous Hydrogen
load drop during the fixed displacement portion of the loading Embrittlement of Materials in Energy Technologies, vol. 2,
profile. Implicit to the discussion in the section “Sustained Load ed. R. P. Gangloff and B. P. Somerday (Cambridge: Woodhead,
2012), 247–285.
Fracture Threshold Test Methods” is the observation that sus-
tained crack growth at fixed displacement is likely to occur only 11. Y. Z. Chen, X. Y. Ma, X. H. Shi, T. Suo, C. Borchers, K. H. Zhang,
when the R-curve is flat. The presence of a rising R-curve indi- F. Liu, and R. Kirchheim, “Hardening Effects in Plastically
cates that the driving force must be continually increased to Deformed Pd with the Addition of H,” Scripta Materialia 98
maintain crack growth. For such cases, driving force values sig- (2015): 48–51.
nificantly greater than the true threshold for the onset of crack 12. Y. Liang, P. Sofronis, and N. Aravas, “On the Effect of Hydrogen
extension may be needed to maintain a measurable increment of on Plastic Instabilities in Metals,” Acta Materialia 51 (2003):
crack extension under constant displacement conditions.23,25 2717–2730.
Therefore, the use of load drop to indicate crack extension will
13. A. Gysler, G. Lütjering, and V. Gerold, “Deformation Behavior of
lead to overestimates of the threshold stress if the fracture mech- Age-Hardened Ti-Mo Alloys,” Acta Metallurgica 22 (1974):
anism is strain-controlled. 901–909.
14. K. A. Nibur, B. P. Somerday, D. K. Balch, and C. San Marchi, “The

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73
Chapter 5 | Microbiological Effects
Jason S. Lee1 and Brenda J. Little2
Introduction There are no credible reports of field failures caused by MIC of

titanium and high-nickel alloys. In addition, MIC has been
2010 U.S. Code § 2228, Office of Corrosion Policy and Oversight reported for metal matrix composites, polymers, paints and coat-
defines “corrosion” as “the deterioration of a material or its ings, ceramics, glass, sandstone, heritage stone works, sealants
properties due to a reaction of that material with its chemical caulks, concrete, and fabrics (e.g., tent materials). The industries
environment.”1 Similarly, National Association of Corrosion reporting MIC include oil exploration, refining, transportation,
Engineers (NACE) International provides the following defini- storage, and usage; conventional and nuclear power generation,
tion: “The deterioration of a material, usually a metal, that results chemical processing, paper production, and fire protection. MIC
from a reaction with its environment.”2 Microbiologically influ- has been evaluated as a potential problem in long-term nuclear
enced corrosion (MIC) is corrosion that is initiated or aggravated waste storage. MIC has been documented for materials exposed
by the direct or indirect activities of microorganisms. in water-containing liquids, including ultrapure, distilled, and
The term “microbiologically influenced corrosion” was first demineralized waters; natural waters, including marine, estua-
used by Pope et al.3 and in 1986 was adopted as the term of rine, and fresh; process chemicals; hydrocarbons, including crude
choice by NACE International. The debate at that time focused oils, and biofuels (i.e., fatty-acid methyl-ester [FAME] fuels);
on the difference between “influenced” and “induced.” soil; and human plasma, saliva, urine, and sewage.
“Influenced” was meant to convey multiple direct and indirect
effects and mechanisms, whereas “induced” was considered to
connotate direct effects. Over time, the word “influenced” has
been further interpreted to convey the notion that microorgan- Corrosion Mechanisms Related
isms can inhibit corrosion. to MIC
The following sections provide information about the
microbiological effects that lead to MIC. In all cases, the impact Corrosion reactions directly related to oxidations (anode) and
of microorganisms will be determined by the vulnerability of the reductions (cathode) and microbial processes require one- and
metal or material on which the microorganisms are growing and two-electron transfers (oxidation or reduction reactions). Micro-
the composition of the electrolyte. organisms can accelerate rates of partial reactions in corrosion
processes or shift the mechanism for corrosion. In all cases, MIC
involves a conversion of a metal oxide to a less protective layer
(e.g., a sulfide), removal of an oxide layer (e.g., metal oxide
Scope of the Problem
reduction or acid production), or localization of an anode or
Microorganisms produce localized attack, including pitting, deal- cathode. MIC is not caused by a single mechanism or group of
loying, enhanced erosion corrosion, enhanced galvanic corro- microorganisms.4 Instead, microorganisms from the three
sion, stress corrosion cracking, and hydrogen embrittlement. domains of life—that is, archaea (e.g., methnaogens), bacteria,
MIC has been documented for the following metals and alloys: and eucaryotes (e.g., fungi)—can influence corrosion through
carbon steel, low-alloy stainless steels (<6% molybdenum), cop- numerous mechanisms.
per and its alloys, nickel and copper alloys, and aluminum alloys. Archaea and bacteria are both procaryotes, lacking a
membrane-bound nucleus. Archaea are considered the oldest
1
Naval Research Laboratory, 1009 Balch Blvd., Stennis Space Center, MS 39529, species on Earth. Many are extremophiles, living in waters that
USA http://orcid.org/0000-0002-1079-433X
2
are either near boiling (90 C) or freezing (4 C) and at acidic
B. J. Little Corrosion Consulting, LLC, 6528 Alakoko Dr., Diamondhead, MS 39525,
USA http://orcid.org/0000-0002-9994-791X
pH (<2) or a combination of these extremes. In addition to suc-
The authors acknowledge the previous author of this chapter, Stephen C. Dexter, cess in extreme environments archaea, “exist in a wide variety of
University of Delaware, Lewes, DE. terrestrial, freshwater and marine habitats, sometimes in very
DOI: 10.1520/MNL202NDSUP20190005
high abundance.”5 Archaea can have the shape and size of bacte- causing microorganisms typically reflects their impact on MIC—
ria, but the two groups have unique biochemistries. Both bacteria for example, acid-producing bacteria (APB) (acid production)
and archaea can be obligate anaerobes, facultative anaerobes, or and sulfate-reducing bacteria (SRB) (sulfide production). These
aerobes, depending on the oxygen requirements for growth. designations are too simplistic to convey the complexity of
Eucaryotes have a membrane-bound nucleus. Most, but not all, microbial reactions within biofilms. For example, any consider-
eukaryotes require oxygen to survive (i.e., aerobes). ation of sulfide production must include sulfate-reducing archaea
In aquatic environments, microorganisms attach to solid sur- in addition to SRB and bacteria that can reduce thiosulfate to
faces. Immobilized (sessile) cells grow, reproduce, and produce sulfide. The more inclusive term for the microorganisms that can
extracellular polymeric substances (EPS), forming a structure for influence corrosion by sulfide production is sulfide-producing
microbial growth (i.e., biofilm). Many researchers have investi- prokaryotes (SPP). Other MIC mechanisms include oxygen con-
gated biofilm formation on a variety of substrata, and this chapter centration cells, metal concentration cells, ammonia production,
does not attempt to summarize that body of literature.6–8 The rate metal oxidation and deposition, metal reduction, dealloying, and
of biofilm formation depends on the characteristics of the substra- consumption and alteration of corrosion inhibitors.
tum and properties of the aqueous medium (e.g., nutrients, flow, To clarify mechanisms for the impact of microorganisms,
temperature) and many other environmental factors. Over time, several investigators have invented additional terms. For exam-
biofilms form on all substrata exposed to aqueous environments. ple, Enning and Garrelfs14 defined two types of MIC (i.e., chemi-
For many years, biofilms were studied as the preferred habitat for cal and electrical) to describe corrosion damage to iron substrata
bacteria, allowing the microorganisms to remain stationary within by SRB. They described chemical microbially influenced corro-
an EPS matrix, protected from biocides and desiccation. During sion (CMIC) as indirect through a corrosive chemical agent (i.e.,
the 1990s, bacterial biofilms were studied in detail and many hydrogen sulfide) formed by SRB as a dissimilatory product
molecular details were elucidated.9 During that period, references from sulfate reduction with organic compounds or hydrogen.
to “multispecies” biofilms referred to multiple species of bacteria They concluded that other SRB can attack iron by withdrawal of
within a biofilm. Biofilms can be formed by a single bacterial or electrons (electrical microbially influenced corrosion, EMIC),
archaeal species, but it is now well established that natural biofilms directly by metabolic coupling. Gu15 defined three categories of
are mixed communities of archaea and bacteria in varying abun- MIC to distinguish mechanisms (i.e., Types I, II, and III). Gu
dances,10 suggesting that multispecies biofilms can have represen- defined Type I MIC as caused by electrogenic bacteria. The
tatives from multiple domains. mechanism is based on the assumption that electrogenic bacteria
Biofilm formation is not limited to aqueous environments. can form pili for electron transfer and energy distribution. The
All microorganisms require water for growth. Fungi and other authors claim that electrogenic microorganisms can use carbon
microorganisms, however, can survive in humid atmospheric steel or other non-noble metals as electron donors because the
environments (relative humidity >65%) within atmospheric bioreduction potentials of the ions of these metals can form thermo-
films. Aqueous and atmospheric biofilms have several properties dynamically favorable redox reactions when coupled with the
in common. Microorganisms within biofilms tend to stratify for reduction of an oxidant (e.g., sulfate and nitrate). The supposi-
survival. In oxygenated waters, stratification can be related to tion is that electrogenic microorganisms use electrons released
oxygen concentrations required for growth or survival. Anae- from elemental metal oxidation and reduce the oxidant intracel-
robes are found in anaerobic niches within biofilms, while the lularly. Gu defined Type II MIC as corrosion caused by metabo-
aerobes remain at the oxygen-containing water–biofilm inter- lites, such as acids, secreted by APB.16 Copper MIC caused by
face.11 As the rate of aerobic respiration increases, the oxygen SRB is also classified as Type II MIC. According to Gu, Type III
within the depths of the biofilm decreases. Similarly, biofilms in MIC is caused by microorganisms that secrete enzymes or other
atmospheric exposures tend to be multidomain, including algae, corrosive chemicals and degrade nonmetallic materials contain-
fungi, and bacteria, forming mutualistic communities with algae ing organic carbon as one of the components. More recently, Gu
located on the outermost layers of biofilms exposed to ultraviolet et al.17 identified two main types of anaerobic MIC, namely,
radiation, whereas bacteria and fungi are located within the inner extracellular electron transfer MIC (EET-MIC) and metabolite
layers of the biofilm.12 MIC (M-MIC). The definitions established by Gu et al.15–17 and
Microorganisms within aqueous and atmospheric biofilms Enning and Garrelfs14 have not received widespread acceptance.
maintain environments at the biofilm solid interface that are rad- The electron transport mechanisms for both EET-MIC and
ically different from the bulk in terms of pH, dissolved oxygen, EMIC are not well described. Blackwood18 questioned mecha-
and organic and inorganic species. Consequently, microorganisms nisms for “direct electron” transfer across cell walls (7.5-10 nm)
in biofilms produce reactions not predicted by thermodynamic and suggested that electron transfer is more likely mediated by
arguments based on the chemistry of the bulk medium. Micro- redox intermediates that reside within or on the walls of the
bial colonization can change material surface properties, increas- microorganisms.
ing or decreasing the susceptibility to corrosion. Mechanisms It is obvious that not all materials have the same vulnerabil-
and rates of corrosion are microorganism-material-environment ities and that some specific vulnerabilities can be predicted. For
specific. example, SRB are routinely listed as causative microorganisms
Causative organisms and possible mechanisms for MIC for MIC. Sulfide can react with some metal oxides to produce
have been described in many reviews.13 The list of possible MIC- metal-sulfide corrosion products. The susceptibility of the oxide
MICROBIOLOGICAL EFFECTS 75
conversion to a sulfide can be predicted.19 The McNeil and The relationship between nutrients and MIC is complicated
Odom19 model predicts that titanium and some stainless steels and largely ignored in laboratory experiments. Although oxyan-
will be immune to sulfide and MIC by SPP, whereas carbon steel ions can serve as nutrients or electron acceptors (e.g., nitrates,
and copper alloys will be vulnerable. Similarly, Kovach and Red- phosphates, sulfates), they also can be corrosion inhibitors. Both
man20 predicted that austenitic stainless steels containing more maintenance and inhibition of localized corrosion require spe-
than 6% molybdenum were immune to MIC, despite their exten- cific ratios of aggressive:inhibiting ions. For example, Webster
sive use in applications in which lower alloys (i.e., 304 and 316L) and Newman28 demonstrated that an anion ratio of [Cl-]: R [all
were vulnerable. other anions] of 5:1 was required to consistently produce corro-
Researchers at the State Research Center for Microbiology, sion in laboratory experiments with SRB and a creviced stainless
Moscow, Russian Federation21 demonstrated that environmental steel (Fe-15Cr-10Ni).
conditions (e.g., electrolyte composition) determined the specific Critical pitting potentials are the potentials below which pit-
microbiological effects on corrosion processes—not the microor- ting and crevice corrosion are not stable. Increasing Cl- (an
ganisms. They demonstrated that a single consortium of micro- aggressive anion) shifts the critical pitting potential to more
organisms could both accelerate and inhibit corrosion of carbon active (negative) values. Conversely, the potential is shifted to
steel based on the composition of the electrolyte in which they more noble (positive) values by inhibiting anions (e.g., chlorate
were growing. Because of this possibility, there are reports of the (ClO4–), SO4–2, NO3–, phosphate (PO4–3), NO2–, and hydroxide
same microorganism both causing and inhibiting corrosion of (OH–). Kehler, Ilevbare, and Scully22 developed equations that
the same material. Consequently, lists of causative microorgan- can be used to predict the corrosiveness of a particular medium/
isms are not useful in the absence of specific information regard- electrolyte to specific metals in the absence of microorganisms.
ing media composition and an evaluation of aggressive:inhibiting Concentrations and types of anions required for corrosion inhi-
anions and electron donors:acceptors.22,23 Changes in these ratios bition in Cl–-containing media are metal-specific. For example,
can dramatically affect the outcome of laboratory experi- sulfates can inhibit Cl–-induced pitting of stainless steels but are
ments.24,25 For example, Shewanella ssp. frequently are cited in aggressive toward mild steel. Furthermore, inhibitor anions must
lists of MIC-causing bacteria. The mechanism most frequently be maintained in certain minimum concentrations to be fully
cited for their involvement is reduction of Feþ3 oxides.26 Philips effective. In many service applications, excursions in solution
et al.27 demonstrated that a Shewanella isolate (4t3-1-2LB) could chemistry, temporary loss of inhibitor, or transient increases in
accelerate corrosion using metallic iron (Fe0) as the sole electron temperature may give rise to localized corrosion in an otherwise
donor and fumarate as the electron acceptor. The authors did inhibited system.29 Below the critical concentration, inhibitive
not suggest that their observations are applicable to all Shewa- anions may stimulate breakdown of the oxide films. Microbial
nella ssp. and they provided a careful description of the experi- activities alter anion ratios through metabolism and respiration,23
mental conditions and medium composition required for their concurrently altering the corrosivity of the electrolyte.
observations.
Corrosion mechanisms requiring microbial growth must
account for nutrients, electron donors, and electron acceptors
Standards for MIC
required to support the mechanism. The nutritional requirements There are many motivations for standardized MIC testing in
of a microorganism include carbon, hydrogen, oxygen, nitrogen, both laboratory and field applications. In the laboratory, testing
sulfur, phosphorus, potassium, magnesium, iron, calcium, and is used to evaluate the vulnerability of a specific material to a nat-
manganese, and traces of zinc, cobalt, copper, and molybdenum. ural source water containing a natural microflora. Alternatively,
Microorganisms use assimilatory and dissimilatory pathways to a range of materials could be ranked as to susceptibility for spe-
process nutrients and electron acceptors. Assimilatory pathways cific MIC mechanisms in artificial media with an inoculum of
are methods for moving a nutrient into the cell and using it for microorganisms (pure or mixes cultures). There are no specific
biosynthesis of macromolecules. Dissimilatory pathways use elec- standards, however, for MIC laboratory testing. Published
tron acceptors to generate energy. Bacteria and archaea have sev- experiments have been completed using different test media and
eral possible electron donors, including organic molecules, electrolytes at differing temperatures with either pure cultures
hydrogen, carbon monoxide, ammonia, nitrite, sulfur, sulfide, and or laboratory-specific consortia. Most important, few experi-
ferrous iron. If oxygen is available, it is used as the terminal elec- ments have considered aggressive anions–inhibiting anions or
tron acceptor, because it generates the greatest Gibbs free energy electron donor–electron acceptor relationships. Interlaboratory
change and produces the most energy. In the absence of oxygen, data cannot be compared. Laboratory experiments are routinely
several electron acceptors can be used (e.g., sulfate [SO4–2], nitrate conducted in nutrient-rich media inoculated with specific
[NO3–], nitrite [NO2–], iron[III] [Feþ3], chromium[VI] [Crþ6], microorganisms. Few researchers verify the identity of the micro-
and manganese[IV] Mnþ4). Not every donor-acceptor combina- organisms at the conclusion of the experiment. Many experiments
tion is thermodynamically possible. The redox potential of the are conducted in the absence of abiotic controls (i.e., media
acceptor must be more positive than that of the donor. Environ- controls).
mental conditions differ from standard conditions used to The motivations for field testing for MIC typically are
describe redox potentials. The carbon requirements can be met by related to diagnosing a failure or controlling MIC by establishing
organic carbon or carbon dioxide (CO2). pigging intervals or scheduling biocide additions. NACE
International has approved the following test methods for field unstable RNA.34 Bernstein et al.39 observed that about 80% of all
applications: TM0106-2016, Detection, Testing, and Evaluation of mRNAs of Escherichia coli had half-lives between 3 and 8 min.
Microbiologically Influenced Corrosion (MIC) on External Surfa- PCR can be used to synthesize and amplify a specific section
ces of Buried Pipelines;30 TM0194-2014, Field Monitoring of Bac- of DNA (e.g., 16S rRNA). Following PCR, the amplified regions
terial Growth in Oil and Gas Systems;31 and TM0212-2018, are sequenced and used to identify microorganisms in a sample.
Detection, Testing, and Evaluation of Microbiologically Influenced Design of PCR primers requires prior knowledge about the
Corrosion on Internal Surfaces of Pipelines.32 These three test microorganisms in the sample and amplification bias also has
methods, designed specifically for oil and gas pipelines, do not been reported. A further limitation is that no single variable
consider recent additions to products transported in oil pipelines region of 16S rRNA gene can identify all microorganisms in a
(e.g., FAME biodiesel and ethanol). The test methods rely on community. Quantitative information about specific micro-
quantification of specific groups of microorganisms, especially organisms requires quantitative PCR (qPCR). Eid, Duncan, and
bacteria, or some constitutive property of bacteria (e.g., DNA or Tanner40 further demonstrated that “monitoring to single SRB-
ATP). There are no NACE International-approved MIC test specific genes such as dsrAB or aprBA or to one SRB genus or
methods for pipelines in other industries (e.g., drinking water species via a technique such as qPCR may be of less utility in
distribution systems). detecting microbial communities associated with MIC than
measurements that target more than one group or gene.” They
concluded that simply quantifying the number of Deltaproteo-
Diagnosing bacteria (e.g., SRB) or even Desulfomicrobium using targeted
The microorganisms responsible for MIC cannot be identified by qPCR “would not be sufficiently predictive.”
characterization and quantification of microorganisms in the bulk Extracellular DNA (e-DNA), occurring outside of living
medium or electrolyte.33 Kotu, Mannan, and Jayaraman34 provided organisms, may account for the largest fraction of total DNA in
a chronological review of the following techniques to investi- some environments and can include molecules in dead cells as
gate microorganisms directly associated with corrosion prod- well as organic and inorganic aggregates adsorbed onto mineral
ucts or corrosion sites: culture, hybridization, polymerase chain matrices.41 e-DNA undermines the assumption of a direct link
reaction (PCR), sequencing, and metabolomics. The molecular between a characterized DNA pool and the actual living micro-
microbiological methods (MMMs; i.e., hybridization, PCR, and bial cell abundance and diversity in a sample. Makama et al.42
sequencing) do not rely on cultivation of microorganisms for recently demonstrated e-DNA in corrosion products on carbon
diagnosing MIC. Instead, MMMs detect a microbial constitu- steel exposed to sterilized natural seawater. The authors con-
ent, such as DNA, RNA, or protein-based markers.35 cluded that in a marine environment corrosion deposits on
Culture techniques and MMM, related to identification or ferrous alloys could harbor bacterial e-DNA. They stressed,
enumeration of microorganisms associated with corrosion prod- “Care must be exercised when using DNA profiling as a sole
ucts, have demonstrated the microbial diversity in MIC. For tool in demonstrating the involvement of biofilms in carbon
example, Rajasekar et al.36 reported a phylogenetic analysis of steel corrosion.”42
16S ribosomal RNA (16S rRNA) sequences in samples removed Metabolomics (i.e., identification and characterization of
from pitted, diesel-transporting, and naphtha-transporting car- microbial metabolism products [metabolites]) has been advo-
bon steel pipelines. They identified Serratia marcescens, Bacillus cated as a method to provide information on the functionality of
subtilis, Bacillus cereus, Pseudomonas aeruginosa, Klebsiella oxy- microbial species involved in MIC.34 Kotu, Mannan, and Jayara-
toca, Pseudomonas stutzeri, Bacillus litoralis, Bacillus sp., Bacillus man34 suggested that identification of key metabolites (e.g.,
pumilus, Bacillus carboniphilus, and Bacillus megaterium. The amino acids, fatty acids, carboxylic acids, and their derivatives)
dominant species varied between the two pipelines, but SRB produced by microorganisms, in addition to information about
were not detected in the samples from either of the pipelines community structure, could provide biomarkers for MIC. Boni-
operated under aerobic conditions. Many of these specific micro- fay et al.43 used a combination of metabolomics and metagenom-
organisms are not typically associated with MIC. The authors ics (16S rRNA gene qPCR and sequencing of 16S PCR products)
concluded several types of bacteria may be involved in MIC in to demonstrate the fundamental differences between samples
industrial facilities and that prolonged addition of corrosion from two crude oil production pipelines. The pipelines had simi-
inhibitor or biocide resulted in the dominance of the biocide- lar backgrounds but were experiencing different rates of corro-
resistant spore-forming Bacillus sp. sion. The rates were generalized as high and low. Deposits from
All culture techniques underestimate the natural microbial the pipeline with the high-corrosion (HC) rate contained SRB
population37,38 and can produce both false positives and false neg- and archaea, whereas samples from the pipeline with low-
atives. There are also inherent limitations to culture techniques corrosion (LC) rates were dominated by pseudomonads. The
and MMM. Hybridization techniques, for example, fluorescence abundance of alkylsuccinates and benzylsuccinates, diagnostic
in situ hybridization (FISH) and DNA arrays, require probes for anaerobic hydrocarbon degradation, was an order of magni-
designed to bind DNA or RNA from specific microorganisms— tude greater in HC samples compared with LC samples. The
that is, one can identify only those microorganisms for which authors concluded that the differences in metabolic activity and
probes have been developed. In addition, DNA arrays require microbial community organization could be used to explain the
“sufficient amounts” of nucleic acids, especially for detection of differences in corrosion rates. Beale et al.44 reviewed multiple
“omic” approaches for studying MIC, including metabolomics. Dissimilatory microbial sulfate reduction produces large
The approaches demonstrate the possibility for the identification sulfur isotope fractionation in which the resulting sulfide is defi-
of metabolic networks characteristic for MIC. cient in the heavy isotopes (33S, 34S, and 36S) relative to the most
Eckert and Skovhus concluded, “A multidisciplinary process abundant isotope 32S.50,51 Grengg et al.52 reported sulfur isotope
for establishing the significance of microbiological data (particu- fractionation of up to 13% between sulfate in waste water and
larly from molecular methods) in regard to MIC threat identifica- newly formed gypsum (CaSO42H2O) in a concrete sewer sys-
tion, mitigation and monitoring has yet to be clearly established. tem. In sewer systems, microbial sulfate reduction produces sul-
As a result, MMMs will not be embraced by oil and gas asset oper- fides that are oxidized by sulfur oxidizing bacteria to sulfuric
ators until their significance relative to corrosion management and acid (H2SO4) that reacts with the concrete to produce gypsum.
asset integrity are made more transparent.”35 Kotu, Mannan, and Little, Wagner, and Jones-Meehan53 demonstrated sulfur isotope
Jayaraman identified two fundamental problems with all identifi- fractionation in sulfide corrosion deposits resulting from activi-
cation and enumeration techniques for diagnosing MIC: “all the ties of SRB within biofilms on copper surfaces. 32S accumulated
microorganisms identified at a specific MIC impacted location in sulfide-rich corrosion products, and 34S was concentrated in
need not contribute to the observed corrosion at that location.”34 the residual sulfate in the culture medium.
Furthermore, “it is not possible to directly correlate relative abun- There is no simple diagnostic test for identifying MIC ver-
dance of microorganisms to a causative role in MIC.”34 sus abiotic corrosion.54 Diagnosing MIC requires a combination
Care also must be taken when analyzing electrochemical, of microbiological, metallurgical and chemical analyses. The fol-
metallurgical, and chemical data during MIC diagnostics. Elec- lowing are required for an accurate diagnosis of MIC:13
trochemical polarization influences the distribution, number,
• Samples of surface deposits from corroded and unaffected
and types of bacteria associated with the surface. Anodic sites
areas that have not been altered by collection or storage.
attract microorganisms in the absence of MIC.45 In addition,
MIC does not produce a macroscopic, unique metallographic • Identification of a corrosion mechanism that is consistent
feature or pit morphology. Metallurgical features previously with the corroded material and the environment to which it
thought to be unique to MIC, for example, hemispherical pits in has been exposed.
300 series stainless steel localized at welds or tunneling in carbon • Identification of microorganisms capable of growth and
steel, are consistent with some mechanisms for MIC, but also maintenance of the corrosion mechanism in the particular
can be produced by abiotic reactions.46 environment.
Two microbiological effects on corrosion products can be • Demonstration of an association of the microorganisms with
used as diagnostic tools for MIC—unique mineralogy and isotope the observed corrosion.
fraction. McNeil, Jones, and Little47 evaluated corrosion product
mineralogy using X-ray diffraction data, thermodynamic stability The changes introduced by the presence of microorgan-
diagrams (Pourbaix), and the simplexity principle for precipitation isms, independent of corrosion-causing reactions, have been
reactions. They concluded that some sulfides under near-surface largely ignored. Electrochemical techniques cannot separate
natural environmental conditions could be produced only by the biotic and abiotic reactions contributing to the electro-
microbiological activity. Tetragonal mackinawite (FeS1- x) pro- chemical parameters being measured. Abiotic control experi-
duced by SRB from iron and iron oxides was identified as a miner- ments should accompany biotic experiments. It is difficult,
alogical fingerprint for MIC by SRB (with some exclusions, e.g., however, to maintain a sterile control in nutrient-rich media
industrial water). Alteration of mackinawite depends on Fe2þ con- used to grow microorganisms. Dexter55 recommended the fol-
centration in the electrolyte. If Fe2þ in the electrolyte is low, mack- lowing three approaches for maintaining an abiotic control: use
inawite alters to greigite (Fe2þFe3þ2S4), an alteration that is not an artificially prepared water instead of a natural water as the
observed in nonbiological systems. When Fe2þ is high, mackina- electrolyte,56 treat the electrolyte to control microbial growth,57
wite is accompanied by green rust 2, a complex ferrosoferric oxy- or manipulate the surface of the working electrode by periodi-
hydroxide. On continued exposure to SRB and continued sulfide cally removing the biofilm.58 All of these recommendations can
production, mackinawite alters to greigite, smythite, and pyrrho- have unintended, unmeasured electrochemical consequences.
tite. Pyrite (FeS2) is not a typical iron corrosion product, but SRB For example, Eid, Duncan, and Tanner40 demonstrated that 50
can produce pyrite from mackinawite in contact with elemental ppm glutaraldehyde, a common oil field biocide, in an abiotic
sulfur. Abiotic aqueous synthesis of these minerals, with the possi- experiment was 3.6 times more corrosive than an identical
ble exception of pyrite, requires hydrogen sulfide (H2S) pressures experiment inoculated with SRB. Furthermore, in addition to
higher than those found in shallow waters. Using a similar colonizing the working electrode, microorganisms colonize the
approach, McNeil and Little48 reported that djurlelte, spionkopite, Luggin capillary, potentially isolating the reference electrode,
and the high-temperature polymorph of chalcocite were mineral- and the counter electrode.
ogical fingerprints for SRB-influenced corrosion of copper-nickel
alloys. Fredrickson et al.49 indicated that electron donor and
acceptor concentrations influenced the microbial reduction of
Monitoring
hydrous ferric oxide and the resulting suite of iron minerals There are no industry standards for monitoring MIC. Monitoring
formed as a result of the reduction. techniques have been designed to collect background information
and detect modifications in operating systems that are indicative 5. E. F. DeLong, “Oceans of Archaea,” ASM News 69, no. 10 (2003):
of MIC.13 For example, devices can monitor heat-transfer resis- 503–511.
tance, fluid friction, and galvanic current because of biofilm for- 6. W. G. Characklis and K. C. Marshall, Biofilms (New York: Wiley,
mation. Weight loss, an indication of general corrosion, can be 1990).
monitored by periodic removal of witness coupons from operat-
ing systems. Electrochemical techniques, including electrochemi- 7. H. M. Lappin-Scott and J. W. Costerton, Microbial Biofilms
(Cambridge: Cambridge University Press, 1995).
cal noise and linear polarization, are available in commercial
instrumentation to provide real-time corrosion rate information. 8. M. Ghannoum and G. A. Toole, Microbial Biofilms (Washington,
Linear polarization devices measure the polarization resistance DC: American Society of Microbiology, 2004).
(Rp) of a material in a specific environment where the inverse of
9. M. van Wolferen, A. Orell, and S.-V. Albers, “Archaeal Biofilm
Rp (Rp-1) is proportional to corrosion rate. Mansfeld et al.59 com- Formation,” Nature Reviews Microbiology 16 (2018): 699–713.
pared Rp-1 corrosion rate data with weight loss data for copper
alloys exposed in artificial and natural seawater, assuming that 10. S. Fröls, “Archaeal Biofilms: Widespread and Complex,”
the difference between the two media was the presence of a natu- Biochemical Society Transactions 41, no. 1 (2013): 393–398.
ral microflora in natural seawater. Corrosion in abiotic artificial 11. J. Larsen, K. Rasmussen, H. Pedersen, K. Sorensen, T. Lindgaard,
seawater was accurately predicted by the device—that is, the elec- and T. L. Skovhus, “Consortia of Bacteria and Archaea Causing
trochemical Rp-1 calculation matched measured weight loss. The Pitting Corrosion in Top Side Oil Production Facilities” (paper
calculations based on Rp-1 measurements, however, did not presentation, NACE Corrosion 2010, NACE International, San
match the actual weight loss in natural (i.e., biotic) seawater. Antonio, TX, March 14–18, 2010).
Those calculations were two to four times lower than the weight 12. J. S. Lee, B. J. Little, J. M. Sullivan, R. E. Stote, and K. A. Kuehn,
loss measurements. Differences in the absolute measurements “Biodegradation of Expeditionary Temporary Structures and
may not be significant for monitoring purposes. Materials in Tropical Environments” (paper presentation, 2017
Department of Defense, Allied Nations Technical Corrosion
Conference, Corrosion Policy and Oversight Office, Birmingham,
Conclusions AL, August 7–10, 2017).
Understanding the microbiological effects that result in MIC 13. B. J. Little, and J. S. Lee, Microbiologically Influenced Corrosion
(Hoboken, NJ: Wiley, 2007).
requires more than the identification of putative microorgan-
isms. The connection between specific microorganisms and 14. D. Enning and J. Garrelfs, “Corrosion of Iron by Sulfate-Reducing
metal vulnerabilities is determined by electrolyte composition Bacteria: New Views of an Old Problem,” Applied Environmental
(e.g., inhibiting anions:aggressive anions). Diagnosis of MIC Microbology 80 (2014): 1226–1236.
should begin with identification of a plausible corrosion mecha- 15. T. Gu, “Theoretical Modeling of the Possibility of Acid Producing
nism, followed by identification of the microorganisms associ- Bacteria Causing Fast Pitting Biocorrosion,” Journal of Microbial
ated with the corrosion products and confirmation that both and Biochemical Technology 6, no. 2 (2014): 68–74.
are consistent with the properties of the electrolyte. State-of-
16. T. Gu and D. Xu, “Why Are Some Microbes Corrosive and Some
the-art monitoring for MIC is based on detection of changes in
Not?” (paper presentation, NACE Corrosion 2013, NACE
electrochemical or microbiological data that may be an indica- International, Orlando, FL, March 17–21, 2013).
tor of MIC for a particular operating system. Identification of
specific minerals or isotope fractionation of elements within 17. Y. C. Li, D. K. Xu, C. F. Chen, X. G. Li, R. Jia, D. W. Zhang, W. Sand,
corrosion products can provide definitive evidence that the for- F. H. Wang, and T. Y. Gu, “Anaerobic Microbiologically Influenced
Corrosion Mechanisms Interpreted Using Bioenergetics and
mation of the corrosion product required a microbiological
Bioelectrochemistry: A Review,” Journal of Materials Science and
effect. Technology 34 (2018): 1713–1718.
18. D. Blackwood, “An Electrochemist Perspective of

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4. C. R. Woese and G. E. Fox, “Phylogenetic Structure of the
Prokaryotic Domain: The Primary Kingdoms,” Proceedings of the 21. V. B. Rodin, S. K. Zhigletsova, N. A. Zhirkova, N. V. Alexandrova,
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Composition as a Potential Method for Reversing International Biodeterioration and Biodegration 126 (2018):
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NACE Corrosion 2005, NACE International, Houston, TX,
April 3–7, 2005). 36. A. Rajasekar, B. Anandkumar, S. Maruthamuthu, Y. P. Ting, and
P. K. S. M. Rahman, “Characterization of Corrosive Bacterial
22. B. A. Kehler, G. O. Ilevbare, and J. R. Scully, “Crevice Corrosion Consortia Isolated from Petroleum-Product-Transporting
Stabilization and Repassivation Behavior of Alloy 625 and Alloy Pipelines,” Applied Microbiology and Biotechnology 85 (2010):
22,” Corrosion 57 (2001): 1042–1065. 1175–1188.
23. B. J. Little, “A Perspective on the Use of Anion Ratios to Predict 37. S. J. Giovannoni, T. B. Britschgi, C. L. Moyer, and K. G. Field,
Corrosion in Yucca Mountain,” Corrosion 59 (2003): 701–704. “Genetic Diversity in Sargasso Sea Bacterioplankton,” Nature
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24. J. S. Lee, R. I. Ray, and B. J. Little, “Comparison of Key West and
Persian Gulf Seawater” (paper presentation, NACE Corrosion 38. D. M. Ward, M. J. Ferris, S. C. Nold, and M. M. Bateson, “A Natural
2007, NACE International, Nashville, TN, March 11–15, 2007). View of Microbial Biodiversity within Hot Spring Cyanobacterial
Mat Communities,” Microbiology and Molecular Biology Reviews
25. J. S. Lee, R. I. Ray, and B. J. Little, “Influence of Experimental
62 (1998): 1353–1370.
Conditions on the Outcome of Laboratory Investigations Using
Natural Coastal Seawaters,” Corrosion 66 (2010): 15001–15006. 39. J. A. Bernstein, A. B. Khodursky, P. H. Lin, S. Lin-Chao, and
S. N. Cohen, “Global Analysis of mRNA Decay and Abundance in
26. B. J. Little, P. A. Wagner, K. R. Hart, R. I. Ray, D. M. Lavoie, K.
Escherichia coli at Single-Gene Resolution Using Two-Color Fluo-
Nealson, and C. Aguilar, “The Role of Biomineralization in
rescent DNA Microarrays,” Proceedings of the National Academy
Microbiologically Influenced Corrosion,” Biodegradation 9 (1998):
of Sciences 99 (2002): 9697–9702.
1–10.
40. M. M. Eid, K. E. Duncan, and R. S. Tanner, “A Semi-Continuous
27. J. Philips, N. van den Driessche, K. De Paepe, A. Prevoteau, J. A.
System for Monitoring Microbially Influenced Corrosion,” Journal
Gralnick, J. B. A. Arends, and K. Rabaey, “A Novel Shewanella
of Microbiological Methods 150 (2018): 55–60.
Isolate Enhances Corrosion by Using Metallic Iron as the Electron
Donor with Fumarate as the Electron Acceptor,” Applied and 41. A. Torti, M. A. Lever, and B. B. Jørgensen, “Origin, Dynamics, and
Environmental Microbiology 84, Article e01154-18 (2018): 1–19. Implications of Extracellular DNA Pools in Marine Sediments,”
Marine Genomics 24 (2015): 185–196.
28. B. J. Webster and R. C. Newman, “Producing Rapid Sulfate-
Reducing Bacteria (SRB)-Influenced Corrosion in the Labo- 42. Z. Makama, S. Celikkol, A. Ogawa, C. Gaylarde, and I. Beech, “The
ratory,” in Microbiologically Influenced Corrosion Testing, ed. J. R. Issue with Using DNA Profiling as a Sole Method for Investigating
Kearns and B. J. Little (Philadelphia, PA: ASTM, 1994), 28–41. the Role of Marine Biofilms in Corrosion of Metallic Materials,”
International Biodeterioration and Biodegration 135 (2018): 33–38.
29. A. Turnbull, D. Coleman, A. J. Griffiths, P. E. Francis, and L.
Orkney, “Effectiveness of Corrosion Inhibitors in Retarding the 43. V. Bonifay, B. Wawrik, J. Sunner, E. C. Snodgrass, E. Aydin,
Rate of Propagation of Localized Corrosion,” Corrosion 59 K. E. Duncan, A. V. Callaghan, A. Oldham, T. Liengen, and I.
(2003): 250–257. Beech, “Metabolomic and Metagenomic Analysis of Two Crude
Oil Production Pipelines Experiencing Differential Rates of
30. Detection, Testing and Evaluation of Microbiologically Influenced
Corrosion,” Frontiers in Microbiology 8, Article 99 (2017): 1–17.
Corrosion (MIC) on External Surfaces of Buried Pipes, NACE
Standard TM0106-2016 (Houston, TX: NACE International, 2016). 44. D. J. Beale, A. V. Karpe, S. Jadhav, T. H. Muster, and E. A.
Palombo, “Omics-Based Approaches and Their Use in the
31. Field Monitoring of Bacterial Growth in Oil and Gas Systems,
Assessment of Microbial-Influenced Corrosion of Metals,” Corro-
NACE Standard TM0194-2014 (Houston, TX: NACE International,
sion Reviews 34 (2016): 1–15.
2014).
45. B. J. Little, P. A. Wagner, K. R. Hart, and R. I. Ray, “Spatial
32. Detection, Testing, and Evaluation of Microbiologically Influenced
Relationships between Bacteria and Localized Corrosion” (paper
Corrosion on Internal Surfaces of Pipelines, NACE Standard
presentation, NACE Corrosion 96, NACE International, Denver,
TM0212-2018 (Houston, TX: NACE International, 2018).
CO, March 24–29, 1996).
33. T. P. Zintel, D. A. Kostuck, and B. A. Cookingham, “Evaluation of
Chemical Treatments in Natural Gas Systems versus MIC and 46. Y. Chung and L. K. Thomas, “Comparison of MIC Pit Morphology
Other Forms of Internal Corrosion Using Carbon Steel Coupons” with Non-MIC Chloride Induced Pits in Types 304/304L/E308
(paper presentation, NACE Corrosion 2003, NACE International, Stainless Steel Base Metal/Welds” (paper presentation, NACE
San Diego, CA, March 16–20, 2003). Corrosion 99, NACE International, San Antonio, TX, April 25–30,
1999).
34. S. P. Kotu, M. S. Mannan, and A. Jayaraman, “Emerging Molecular
Techniques for Studying Microbial Community Composition and 47. M. B. McNeil, J. M. Jones, and B. J. Little, “Mineralogical
Function in Microbiologically Influenced Corrosion,” International Fingerprints for Corrosion Process Induced by Sulfate-Reducing
Biodeterioration and Biodegration 144, Article 104722 (2019): Bacteria” (paper presentation, NACE Corrosion 91, NACE Interna-
1–11. tional, Cincinnati, OH, March 11–15, 1991).
35. R. B. Eckert and T. L. Skovhus, “Advances in the Application of 48. M. B. McNeil and B. J. Little, “Corrosion Mechanisms for Copper
Molecular Microbiological Methods in the Oil and Gas Industry and Silver Objects in Near-Surface Environments,” Journal of the
and Links to Microbiologically Influenced Corrosion,” American Institute for Conservation 31 (1992): 355–366.
49. J. K. Fredrickson, S. Kota, R. K. Kukkadapu, C. Liu, J. M. and J. B. Corrosion using Fe Isotopes,” Corrosion Science 49 (2007):
Zachara, “Influence of Electron Donor/Acceptor Concentrations 3759–3764.
on Hydrous Ferric Oxide (HFO) Bioreduction,” Biodegradation 14
(2003): 91–103. 55. S. C. Dexter, “Microbial Effects,” in Corrosion Test and Standards:
Application and Interpretation, ed. R. Baboian (West
50. B. A. Wing and I. Halevy, “Intracellular Metabolite Levels Shape Conshohocken, PA: ASTM International, 2005), 509–522.
Sulfur Isotope Fractionation during Microbial Sulfate
Respiration,” Proceedings of the National Academy of Sciences 56. S. C. Dexter, “Laboratory Solutions for Studying Corrosion
111 (2014): 18116–18125. of Aluminum Alloys in Seawater,” in The Use of Synthetic
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51. S. Ono, M. Sub Sim, and T. Bosak, “Predictive Isotope Model T. S. Lee (Philadelphia, PA: ASTM International, 1988),
Connects Microbes in Culture and Nature,” Proceedings of the 217–234.
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57. B. Little, S. Gerchakov, and L. Udey, “A Method for Sterilization of
52. C. Grengg, F. Mittermayr, A. Baldermann, M. E. Böttcher, A. Leis, Natural Seawater,” Journal of Microbiological Methods 7 (1987):
G. Koraimann, and M. Dietzel, “Stable Isotope Signatures within 193–200.
Microbial Induced Concrete Corrosion: A Field Study,” Procedia
Earth and Planetary Science 13 (2015): 68–71. 58. H.-J. Zhang and S. C. Dexter, “Effect of Biofilms on Crevice
Corrosion of Stainless Steels in Coastal Seawater,” Corrosion 51
53. B. J. Little, P. A. Wagner, and J. Jones-Meehan, “Sulfur Isotope (1995): 56–66.
Fractionation by Sulfate-Reducing Bacteria in Corrosion
Products,” Biofouling 6 (1993): 279–288. 59. F. Mansfeld, G. Liu, C. H. Tsai, H. Shih, and B. J. Little, “Evaluation
of Polarization Curves for Copper Alloys Exposed to Natural and
54. E. Hutchens, B. J. Williamson, M. Anand, M. P. Ryan, and R. J. Artificial Seatwater” (paper presentation, NACE Corrosion 92,
Herrington, “Discriminating Bacterial from Electrochemical NACE International, Nashville, TN, April 27–May 1, 1992).
81
Chapter 6 | Tribocorrosion
Jeremy L. Gilbert1
Basic Principles The general concern surrounding tribocorrosion is the loss

of metal from the surface as a result of tribological and electro-
REVIEW OF MECHANISMS chemical processes, and in particular when these two processes
Tribocorrosion is a conjoint mechanism of degradation of a interact synergistically.7 Corrosion in the absence of mechanical
metallic surface that involves surface mechanics associated with effects include oxide film formation (through the already extant
contact, loading, and motion (tribology) and the increased corro- film) and ionic dissolution (through the film; so-called passive dis-
sion that results from such mechanical perturbations. Tribology solution8). Both processes are typically very slow for intact passive
is the study of wear, friction, and lubrication, whereas tribocorro- films with current densities typically well below 10 nA/cm2. These
sion generally is focused on the enhanced corrosion processes passive corrosion processes are, therefore, of less concern.
that arise when surface mechanical processes are present.1–3 A When surfaces are tribologically impacted (contact, stress,
more inclusive concept around tribocorrosion is mechanically and motion), several mechanical events occur in tribocorrosion,
assisted corrosion,4–6 wherein enhanced corrosion can arise from including plastic deformation of the near-surface alloy, and
surface mechanical processes that are not limited to wear phe- mechanical removal of metallic materials and passive oxide
nomena only and can include other factors like stress corrosion films resulting from wear processes. The nature of the surface
cracking, corrosion fatigue, and strain-enhanced corrosion. contact between the two tribologically interacting bodies is
Tribocorrosion processes are focused primarily on passivat- one of multiple asperity-asperity contacts,9 in which case the
ing alloys that derive corrosion resistance from the kinetic bar- true area of contact, for metal-on-hard interactions, is driven
rier passive oxide films that spontaneously form on such alloy by the normal load and the hardness of the surfaces.10 That is,
surfaces. These include titanium and its alloys, stainless steels, the nominal microgeometry (i.e., roughness) of the contact-
cobalt-chromium alloys, and others (e.g., Al, Ta, W, Zr, Nb). ing surfaces has little initial effect on the true area of contact
Low-temperature, high-field-based passive oxide film growth is a and therefore of extent of abrasion; however, surface topogra-
central part of such tribocorrosion processes, as are the mechani- phy does affect the locations where contacting asperities inter-
cal factors that affect the adhesion and barrier effects of oxide act and the progression of contact as asperities are abraded
films, and the fracture and mechanical disruption of the oxides. over time.
Much of the research on tribocorrosion has been focused around In addition to the loss of material from a strictly wear-
medical devices and metallic biomaterials, including Ti, based phenomenon (without electrochemical processes), dra-
CoCrMo, and 316L stainless steel alloys, but these processes are matically enhanced electrode reactions involve increased
not limited to this field. currents as well as both charge transfer (Faradaic) and charging
Because tribocorrosion is composed of both surface (non-Faradaic) processes in the breached region and outside,
mechanical processes related to deformation, wear, and friction, at least until the oxide film reforms or repassivates, which can
and processes related to oxidation of metal surfaces when such take as little as 0.5 ms.11–15 During this brief period, both ionic
mechanical effects are present, it requires an understanding of dissolution from the bare metal surface and the film reforma-
both surface mechanics and electrochemistry. Both the mechani- tion (or repassivation) processes generate electrochemical cur-
cal and electrochemical elements of tribocorrosion will be rents that can be monitored and measured. The magnitude of
presented. these current densities, when scaled to the breached area, are
orders of magnitude greater than those present across intact
1
oxide films. These currents are a highly sensitive measure of
Clemson–MUSC Bioengineering Program, Medical University of South Carolina,
the electrochemical processes and can be used as a tool to
68 Presidents St., Charleston, SC 29425, USA; Dept. of Bioengineering, Clemson
University, 68 Presidents St., Charleston, SC 29425, USA http://orcid.org/ assess tribocorrosion. In addition, for nonpotentiostatically
0000-0002-7428-2851 controlled electrode surfaces, these reactions alter the electrode
DOI: 10.1520/MNL202NDSUP20190003
potential of the surface because of the burst release of electrons metal combine to form oxide. This includes the metal particle
from the oxidation processes. Thus, electrode potentials typi- surface as well as the metal substrate surface from which the
cally become more negative with tribocorrosion processes as metal particle comes. In addition, plastic deformation mecha-
corresponding reduction reactions increase to consume these nisms (e.g., dislocation motion) intersecting with the metal sur-
electrons. The balance in reactions is not instantaneous, how- face can introduce additional fresh metal (step ledges) for
ever, and therefore the capacitive and resistive character of the repassivation processes. The details of the surface mechanics will
surface will affect the potential drops observed.16 Factors be described in more detail.
including the surface impedance and total electrode area affect The second mechanism of mass loss is wear-based mass loss
the extent of potential change and the time course of the of the passive oxide film. This is also a mechanical process of
response.16 oxide removal or disruption from the surface. This releases oxide
debris that can accumulate as a solid particle (or agglomerated
particles), which can serve both as a lubricant and as an abrasive
MASS BALANCE DURING TRIBOCORROSION
within the tribocorrosion contact region. The lost passive oxide
When assessing material loss from a metal caused by tribocorro-
is replaced by new oxide film repassivation on the freshly
sion processes, both mechanical and electrochemical mecha-
exposed metal, the process of which generates currents that can
nisms contributing to mass loss and mass gain must be
be detected.
accounted for, as shown in equation (1):
The third mechanism of mass loss is the electrochemically
metal
Mloss ¼ Mwear oxide
þ Mwear oxide
þ Mions Mgrowth debris
Madhered : (1) based ionic dissolution of metal into metal ions into solution
beyond that which normally occurs through the intact oxide.
The first mechanism of mass loss is metal mass loss caused This is ionic dissolution through the instantaneously breached
by mechanical wear processes only (fig. 1). This mass loss is bare metal surface where the charge transfer kinetics are not lim-
purely mechanical, with no electrochemical process (or current ited (at least initially) by a passive oxide film. As the surface
or voltage dependent mechanism). It results in the generation of repassivates, the kinetics of ionic dissolution quickly return to
metal wear particles leaving the surface by way of the tribological the passive film-based kinetics, and therefore, ionic dissolution is
processes of abrasive, adhesive, and fatigue wear. Note, however, controlled and limited by the repassivation rate of the oxide film.
that for passivating alloys in an electrolyte, even the purely This mass loss is associated with charge transfer and currents
mechanical removal of metal must be accompanied by repassiva- across the interface (i.e., Faradaic processes).
tion of the freshly exposed metal surfaces. That is, wear of pas- The fourth mechanism is mass gain resulting from the Fara-
sive alloys in solution must include corrosion reactions (and daic process of metal repassivation, which involves the reaction
currents) associated with repassivation as oxygen from water and of metal with water to produce metal oxide (and hydrogen ions
FIG. 1 Schematic of tribocorrosion processes at an asperity-metal contact where an oxide film is being disrupted. Oxide debris, metallic
debris, and ions can be released, whereas oxide film can be repassivated and reformed and the metal subsurface material is
plastically deformed and damaged.
TRIBOCORROSION 83
and electrons). This mass gain of the surface, while small, occurs debris removed and generated during the abrasion and the film
because of the addition of oxygen anions to the metal cations to currents generated. This link between mechanical disruption
form the oxide (i.e., to repassivate the surface); see figure 1 and of the oxide and the film currents associated with reformation of
equation (1). This oxide formation is linked to the oxide film loss the oxide is an important one for using current as a means of
and will be nearly identical to, or of similar magnitude as, the assessing tribocorrosion processes.
oxide reformed. Here, then, the repassivation currents may be Finally, a term is added to account for any accumulated
reflective of the oxide film loss and is a direct measure of the debris (metal or oxide, or other) that occurs over the course of
oxide film reformed after disruption. Note that, while the mass the tribocorrosion process. For example, oxide debris may
gain per repassivation event is small, the cumulative effect can be adhere to the surface and accumulate, thus reducing the overall
significant. For example, a unit volume of titanium (Ti) con- mass loss into the solution from the tribocorrosion processes.
verted to titanium dioxide (TiO2) results in a volume of oxide The various mass terms in equation (1) (and their rates) are
that is 1.75 times the volume of the metal from which it came. not always independent, and indeed, they depend on the interac-
Thus, volume loss from the metal and volume of oxide debris are tion of tribology and electrochemistry. For example, the rate of
not the same and the difference is significant. metal mass loss will depend on the nature of the counterface
The third and fourth terms of equation (1) both consist of causing the abrasive, adhesive, or fatigue wear process. Genera-
Faradaic processes that are associated with anodic electrochemi- tion and accumulation of oxide debris may either enhance or
cal currents generated over and above the baseline currents, reduce such wear mechanisms as the debris acts either as high-
release of electrons into the metal, and changes in potential that hardness third-body wear particles or as a solid lubricant that
may arise as a result. Examples of ionic dissolution and film limits additional metal wear.
growth reactions that result in measurable anodic currents are The mass loss from ionic dissolution only represents the
shown in equations (2) and (3).13 increase of ionic dissolution present from bare metal surfaces
g arising from mechanical disruption of the passive film and expo-
Ti ! Ti4þ þ 4e Idiss ¼ io Að1 hÞeba , ð2Þ sure of the bare metal. As such, this is a tribologically enhanced
qnF dh ionic dissolution process. Similarly, current arises from repassi-
Ti þ 2H2 O ! TiO2 þ 4H þ þ 4e IFilm ¼ V : ð3Þ vation of exposed metal surface. Thus, when one develops a test
Mw dt
that measures currents (either potentiostatically, or with an
For ease of representation, these equations are shown for ammeter between abrading electrode and a second electrode), it
titanium The currents that result from these reactions are also is important to understand the relative contributions of ionic dis-
shown, where: solution and passive film formation to the measured current.
Idiss (equation (2)) ¼ the dissolution current; These currents, for example, cannot be used as a measure only of
io ¼ the exchange current density for ionic dissolution across a ionic loss because most of the current measured goes to oxide
bare metal surface (not the oxide); formation.
A ¼ the area of exposed metal where oxide is removed; In addition, these terms may be modified over time by
h ¼ the area (or volume) fraction of the abraded oxide area that local changes in solution chemistry where, for example, pro-
has reformed by repassivation; teins of other biologically derived chemical species may alter
g ¼ the over potential for ionic dissolution (i.e., the voltage the surface oxide properties creating oxide film defects, increas-
above the equilibrium half-cell potential for ionic dissolution ing passive dissolution reactions or increasing the oxidizing
across the bare surface); power of the electrolyte. Recent work has shown, for example,
ba ¼ the anodic Tafel slope for ionic dissolution across the bare that fretting-initiated crevice corrosion of 316L stainless steel
surface; could arise because of the fretting corrosion process generating
IFilm ¼ the film current that depends on the density, q, of the a local crevice solution chemistry within the fretting contact
oxide film, the charge per cation, n, Faraday’s constant, F, the region that leads to unstable crevice corrosion reactions.14
molecular weight of the oxide, Mw, and the volume of oxide Other effects of solution proteins on both the tribological and
reformed, V; and h ¼ the volume fraction of oxide formed at any electrochemical interactions may arise as well. Corrosion
instant after disruption, so the time derivative of h (i.e., dh/dt) is in vivo may occur in the presence of significant immune and
the rate of oxide fraction reformed.13 inflammatory cell reactions, where such biological processes
Note that the ionic dissolution current directly reflects metal and living systems may induce local changes in solution chem-
ions lost from the metal. Conversely, the oxide film currents istry and increase the corrosion rates of medical alloys15,16 and
reflect the currents associated with the formation of the oxide also may alter the tribocorrosion behavior of these alloys.17
over the previously breached surface and is related, in fact, to a Chemical species involved in reactive oxygen species generation
mass accumulation (resulting from the oxygen addition to the are of particular interest.18
surface; the fourth term in equation (1)). These oxide films are The Ambrose model of passive film repassivation13,19,20 pro-
removed in subsequent mechanical disruption processes and vides a framework around which one can assess the relative con-
reformed in essentially equal amounts. Therefore, although the tributions of film currents and ionic dissolution currents through
repassivation reactions increase the mass (and volume) of oxide bare metal. This model expresses the total current in terms of
film on the metal surface, they also reflect the amount of oxide both ionic and film currents and uses the concept of the fraction
of oxide reformed (h) starting from an instantaneously removed polarization resistance of the surface (reflecting the cathodic
oxide region. kinetics). Therefore, the area-dependent impedance (capacitance
and polarization resistance) of the electrode surface will affect
Itotal ¼ Idiss þ Ifilm , (4) the extent of the shift in electrode potential from the at-rest
g qnF dh open-circuit potential, where in the limit of large areas, the sur-
Itotal ¼ io Aeba ð1 hÞ þ Ah (5) face acts essentially as a potentiostatically held electrode.
Mw dt
Electrode potential also will affect the repassivation reac-
Experiments on mechanically controlled high-speed single- tions, including the thickness of the oxide reformed. Several
diamond asperity scratch tests of Ti and cobalt-chromium- studies have shown13,21,23,24 that the thickness of reformed oxide,
molybdenum (CoCrMo) alloys13,19,21 showed an exponential current after mechanical disruption depends linearly on the electrode
t
transient (Itotal ¼ Io e s ), where Io is the peak current above the potential. There is an onset potential (or passivating potential)
baseline current, and s is the time constant for the repassivation below which no oxide repassivation will occur.25 Thus, the nega-
response. The solution of this equation using the previous tive excursion in potential that occurs during tribocorrosion is
expression for the total currents follows: limited by this onset potential (i.e., the electrode potential cannot
fall below the onset potential) and thinner films form when the
t
h ¼ 1 es , (6a) potential is more negative and closer to the onset potential. This
is a consequence of the high-field growth model of Gunter-
g qnFV schulze and Betz.22
Io ¼ io Aeba þ : (6b)
Mw s It has been documented13,19,21 in single-asperity scratch or
pin-on-disk fretting corrosion tests25 that the tribocorrosion cur-
Thus, tribocorrosion currents (i.e., currents arising from rent increases roughly linearly with potential above the onset
film formation and ionic dissolution through the breached potential (for fixed mechanical and tribological conditions; e.g.,
region) can be assessed based on the parameters outlined. Note normal load and sliding speed). In some alloys (CoCrMo, and
that the volume of oxide, V, that reforms depends on the voltage 316L SS), however, changes in oxide film chemistry, resulting
above the onset potential, and the relative amount of ionic cur- from transitions in the Pourbaix diagram, lead to loss of passivity
rent to film current can be assessed by comparing the magnitude of the film. This occurs primarily in chromium(III) oxide
of the two terms in equation (6b). (Cr2O3)–dominant passive films, where above about 300 mV
Analysis of the Ambrose model shows, for example, that for versus silver/silver chloride (Ag/AgCl) in saline, the oxide film
a 0.5 ms time constant (typical for Ti/TiO2 repassivation), the begins to transform away from a passive film (Cr2O3) to a film
film current density (the second term), is 8.6 A/cm2 when the with higher valence Cr ions that are much less passive.26
film reforming is 2 nm thick.13 The film currents were signifi-
cantly larger than the ionic currents in the potential range
investigated. CONTACT MECHANICS AND TRIBOCORROSION
The contact mechanics associated with tribocorrosion need to be
clearly elucidated. Passive oxide films on metal alloy surfaces are
ELECTRODE POTENTIAL EFFECTS ON disrupted only when certain specific mechanical conditions hold.
TRIBOCORROSION For example, oxide disruption arises only when the contact
During tribocorrosion, the mechanical disruption of the passive stresses reach or exceed the underlying metal substrates surface
film induces highly energetic oxidation reactions resulting in a plastic deformation limit (i.e., hardness) or when the fracture
burst-like response of ionic dissolution and film repassivation. stress (or strain) of the oxide-metal interface is reached. That is,
This results in a buildup of electrons from the oxidation pro- for the oxide film to be disrupted by mechanical processes, the
cesses that are not instantly reacted (or consumed) by reduction alloy upon which the film has formed typically must experience
reactions. That is, the mixed-potential theory does not instanta- localized plastic yielding.27 Dislocation motion intersecting with
neously hold in the transient response period of oxide disrup- the metal surface will disrupt the oxide film and expose underly-
tion. These electrons build up capacitively on the surface, ing metal. Alternatively, the oxide film adhesive strength to the
causing electrode potential shifts of the surface that are not solely underlying metal must be reached. This, however, is again domi-
the result of a balance of anodic and cathodic currents.22 These nated by the hardness of the underlying alloy. As a result, during
potential shifts depend on several characteristics of the surface, tribocorrosion, the metal surface undergoing tribocorrosion pro-
including the capacitance of the surface, the reduction reaction cesses (i.e., wear, oxide film disruption and repassivation, and
kinetics, the surface area, and solution resistance. ionic dissolution) must be in contact with a counter surface that
The kinetics of electron transfer to consume these excess has specific relevant properties necessary to induce tribocorro-
electrons (i.e., reduction) may be limited compared with the sion, which include being capable of inducing localized plastic
kinetics of oxidation. Thus, a capacitive buildup of electrons at deformation of the passive oxide covered alloy. Materials with a
the metal surface will result and the electrode potential will hardness below the metal surface hardness typically will not
become increasingly more negative. The rate of consumption of induce oxide disruption; however, if such softer materials embed
these electrons by reduction reactions will be related to the area hard oxide particles, then these embedded particles may serve as
available for reduction, the solution resistivity, and the oxide film disruption counterfaces.
TRIBOCORROSION 85
In addition, the contact area between two surfaces, gener- the local topography. When these two surfaces slide relative to
ally, is much smaller than the nominal area available for contact one another, the sliding mechanics may rapidly become a com-
and can be, under some circumstances, only a percent or two of plex problem involving coulombic friction (if dry contact is
the nominal contact area. Thus, when the tribological conditions present) or fluid-film lubricated sliding, in which case the envi-
are such that a hard-on-hard junction (e.g., ceramic on metal, ronment between the two surfaces may become pressurized and
metal on metal) is present, then contact mechanics show that the carry a portion (mixed-film lubrication) or all (hydrodynamic
true area of contact is basically governed by the normal force lubrication) of the normal load. In some tribocorrosion condi-
across the contact area divided by the effective hardness of the tions (e.g., fretting), a dry or mixed lubrication layer is likely and
surfaces (the softer one dominating). That is, full hydrodynamic lubrication is unlikely.
In each of these regimes (dry contact, mixed lubrication,
F
Atrue ¼ , (7) hydrodynamic lubrication), the frictional interactions and the
H mechanics of surface film disruption can be affected. The Stri-
where: beck curve10 (coefficient of friction [COF] plotted against the
F ¼ the force across the interface, and product of the sliding velocity and viscosity divided by the nor-
H ¼ the effective hardness of the softer surface.10 mal load) shows significant transitions in the COF, with a low
This is an upper limit estimate of the contact area because, Stribeck number (low viscosity, slow speed, high normal force)
if elastic contact were present, the stresses in the contact region giving rise to Coulombic contact conditions and a “dry” COF. In
would be lower than the yield, and hence less area would be in these and other conditions of mixed lubrication, tribocorrosion
contact. conditions lead to significant effects.
Of course, this conveys that the details of the surface topog-
raphy (at least initially) do not affect the tribocorrosion response. Asperity Contact, Surface Roughness, and Friction
It also indicates that the local asperity-based contact stress The contact mechanics during tribocorrosion are inherently
reaches the hardness of the alloy (i.e., is very high locally) and related to asperity-asperity contact mechanics. Regardless of the
will induce oxide disruption with sliding because of plastic nominal shape of the contacting surfaces, the true area of contact
deformation. during tribocorrosion is dominated by the asperity-asperity
For example, when two Ti-alloy asperity-based surfaces interactions and local contact stresses. For most tribocorrosion
come in contact (fig. 2) with a load of 10,000 N, where the hard- conditions, the surfaces in contact are both high-hardness mate-
ness of the titanium is about 3 GPa (3000 N/mm2), the true area rials. As the tribocorrosion process continues, abraded debris
of contact will be 3.3 mm2 distributed about the area available. can remain in the contact region and alter the distribution of
How this area is distributed about the nominal area depends on stresses and the sliding interaction. It is typical that in long-term
FIG. 2 Asperity-asperity contact schematic. This shows how two randomly rough surfaces would engage (even at the nanometer scale)
and how the forces would be distributed over a small true area of contact. In addition, the concept of surface height distributions
and how it affects the contact engagement is shown.
fretting corrosion tests, the fretting currents diminish with advanced is the use of superposition of tribocorrosion events
cycles. This is thought to be the result of debris increasingly car- over time and the use of Duhamel integrals (or heredity inte-
rying the contact load and reducing the amount of oxide surface grals) to make predictions of both net current and net potential
abrasion taking place. changes during an arbitrary oxide abrasion process.22,28 In this
The surface roughness affects the location and distribution approach, oxide film removal and repassivation events are dis-
of contact regions. It is useful to conceptualize the surface as cretized into infinitesimal volume elements where the rate of
containing a distribution of contact that starts at zero above the removal of oxide is slow compared with the repassivation rate.
surface and increases with depth into the surface to 1 (or 100% Each infinitesimal disruption results in an exponential current
contact) when a hypothetical plane of intersection is drawn at transient related to repassivation, and these events are integrated
various depths (see fig. 2). The depth profile or differential distri- over time for some arbitrary oxide removal path. The net current
bution (DP; fig. 2) can be used to determine the true area of is then just the integral over time of these summed infinitesimal
contact. events.
Because tribocorrosion of hard-on-metal contacts occurs
only at sites where oxide film disruption occurs, it is the sum of ðt
dV
the diameters of all asperities in contact times the sliding speed I ðt Þ ¼ AT ðt ÞV ð0Þ þ AT ðt kÞ dk, (10)
dk
that determines the area disrupted per unit time: k¼0
dA X dd where:
¼ li , (8) AT ¼ the tribocorrosion admittance, which is a relationship
dt i
dt
between current generated and the volume of oxide abraded;
where: V ¼ the volume of oxide abraded and reformed;
li ¼ the diameter of the ith asperity, and I ¼ the current; and
dd/dt ¼ the sliding speed. k ¼ the integration variable for time.
For many cases, the sum of all asperity diameters for hard- AT, for the case in which the system is dominated by film
on-metal contacts can be approximated as follows: currents only, has the following form:
rffiffiffiffiffiffiffi
Io tk qnF io bg tk qnF tk
l ¼ 2 F , (9) AT ðt kÞ ¼ e s ¼ þ ea e s e s , (11)
pH V Mw s h Mw s
which is assumed to arise from a single small circular contact where:

area. q ¼ the density of the oxide,
The link between the contact mechanics during tribocorro- n ¼ the valence,
sion and the electrochemical currents arises from the relation- Mw ¼ the molecular weight of oxide, and
ship between abraded area and oxide film disruption and s ¼ the time constant for repassivation.
repassivation. Assuming these correspond to one another, then Note, the second term is very small compared with the first
the area abraded can be linked to the area repassivated (and the term over most of the potential range. Thus, for any path of vol-
associated film current is directly proportional to the abraded area). ume abrasion (dV/dk) the current associated with film formation
In addition, from equation (6), if the film currents are assumed to can be determined and is based primarily on the film currents. A
dominate (as they appear to do in many cases), then a link between similar type of equation can be developed for how the voltage of
the abraded area and the currents can be made. the electrode undergoing tribocorrosion currents, I(t), can cause
For example, if we used the previous example (i.e., 3.5 mm2 potential shifts. This heredity integral follows:
contact area), which corresponds to a nominal diameter of ðt
2.11 mm, with a sliding speed of 1 mm/s, and an oxide film dI
Eðt Þ ¼ Z ðt ÞI ð0Þ þ Z ðt kÞ dk, (12)
thickness of 2 nm, then a volume of oxide abraded per second of dk
k¼0
0.00422 mm3/s results. The charge per volume of oxide repassi-
vated (qnF/Mw), for titanium oxide is: 21,500 C/cm3 of oxide. where:
This results in a steady-state current of about 90 lA arising from E ¼ the potential away from resting potential,
such a process assuming the repassivation rate equals the rate of Z ¼ the time-based impedance response of the surface (which may
film removal. be modeled using, for example, a Randle’s circuit model), and
I ¼ the instantaneous current as a function of time.
Modeling Tribocorrosion Using Heredity Integrals Together, these equations for voltage and current can be
(Boltzmann Superposition) coupled and integrated over time.
A number of modeling approaches have been put forward to These integrals provide a means to explore the links
help understand tribocorrosion processes. These approaches between the mechanics, electrochemistry, and impedance behav-
typically focus on the oxide film currents based on Faraday’s ior of tribocorroding systems and could be adapted to more
law and have attempted to describe several aspects of the tribo- complex analyses (e.g., finite element approaches) to investigate
corrosion processes present.2,7 An alternative approach recently the overall and local responses to tribocorrosion processes.
TRIBOCORROSION 87
As an example of how this analysis can be used, figure 3 most of these parameters, which allow for in-depth assessment
shows the tribocorrosion currents generated from a known of performance. Each of these topics will be discussed in more
displacement-time movement of a pin on disk, where the area detail.
abraded was determined from the contact mechanics, and the
thickness was voltage based. The sliding-time behavior is a start- Electrochemical Conditions
stop cyclic process and the current transients are spike- During a tribocorrosion experiment, a number of parameters of
exponential decay responses. The theory fits the experimental both the mechanical and electrochemical systems need to be
results very well and is based on the vertical load, the sliding accounted for and dealt with. From the mechanical perspective,
speed, the hardness, the potential, and the charge per volume of such tribocorrosion experiments typically include a disk and a
oxide formed.28 pin or ball of some specified geometry (radius) and properties
(hardness). The normal load, sliding speed, and sliding distance—
whether it is reciprocating (oscillatory), linear track (including
Tribocorrosion Testing rotating), or cross patterned—may significantly affect the long-
The tribocorrosion tests currently in use span a range of applica- term results as debris entrainment and its effects may be very
tions and test conditions. They all, however, have some basic different. Solution conditions are another consideration. They
common instruments and measurements. These include both cor- include the oxidizing conditions, solution resistance, ionic
rosion testing and mechanical testing. For corrosion testing, cur- composition, temperature, presence of lubricants, proteins, and
rent and potential are the two primary tools of analysis and pH. In addition, whether the electrode potential is fixed (poten-
control of the electrochemical portion of testing. Controlled tiostatic testing using a three-electrode system) or is allowed to
potential (potentiostatic tests) and freely corroding tests can be shift with the test conditions will dictate some of the behavior.
performed (see fig. 4). Specific conditions for each are necessary For freely floating electrode potential tests, the area of the
(to be explored). In some instances, electrochemical impedance electrode (outside of the contact region) will affect the magni-
spectroscopy is used before and after tribocorrosion testing to tude of the electrode potential excursions experienced. Test
investigate changes in electrode performance. configurations for potentiostatic and freely corroding condi-
Solution conditions are also important. These include the tions are shown in figures 4A and 4B for potentiostatic and
overall solution chemistry as well as the local chemistry, which freely corroding configurations, and the basic mechanical
may change if crevices are present.14 and electrochemical set up for fretting corrosion is shown in
The mechanics of tribocorrosion tests have measurable figure 5.
parameters that include normal loads, friction loads, sliding dis- For potentiostatically controlled tests (fig. 4A), the role of
placements, contact geometry, and materials. These mechanics potential on the electrochemical and mechanical response can be
may involve fretting motions (cyclic displacements less than investigated directly. When the potential is held away from the
100 um) or other sliding motions. Additionally, measurements at-rest corrosion potential (or open circuit potential), then a
can be made on the surface damage, the released solid debris, the background current representing the sum of all reactions on the
ionic species released and adsorption or adhesion of tribocorro- intact surface will be present (e.g., net reduction currents, or net
sion products. Well-designed tribocorrosion experiments include oxidation currents). The tribocorrosion currents are then the
FIG. 3 An example of fretting corrosion currents for CoCrMo pin and disk tests. Shown are the sliding displacement-time plot, the
experimentally obtained currents under potentiostatic control, and the theoretically obtained currents using the values in table 1
and the sliding displacement-time behavior. Note the excellent fidelity of the theoretical currents to the experimental ones.
FIG. 4 Schematics of (A) potentiostatic three electrode tests and (B) freely corroding tests for tribocorrosion experiments. Measurements
or control of current and potential are possible in both.
FIG. 5 Schematic of a pin-on-disk fretting corrosion test system used from tribocorrosion testing under fretting mechanics. The test
samples, load cell, DVRT displacement sensor, piezoelectric actuator, and movement stage are shown.
deviation away from these background currents as they represent area effects, therefore, affect the measurements of potential and
the currents over and above those from nonabrading conditions. current, and make interpretation of the electrochemistry more
For the freely corroding setup (fig. 4B), tribocorrosion currents indeterminate.
and the shifting electrode potentials can be captured concur- Important results from potentiostatically controlled tribo-
rently. The currents and the potential will be affected by the sec- corrosion tests include the fact that there is a potential (defined
ond electrode area and intrinsic impedance. A larger second as the onset potential or passivating potential) below which no
electrode area will increase the currents (to a plateau) and anodic electrochemical currents are generated.13,21,25 This indi-
decrease the potential excursions, whereas a smaller second elec- cates that even with mechanical perturbation of the surface, there
trode area will reduce the measured currents and increase the is no driving force for oxide repassivation and therefore no
negative potential excursions measured. These second electrode increased anodic tribocurrents. Above the onset potential
TRIBOCORROSION 89
average, tribocorrosion currents increase linearly with potential Tribocorrosion tests may include variations in normal load,
with all other conditions held fixed (e.g., sliding speed, normal sliding speed (or frequency), sliding amplitude, presence or
force). These results imply that approximately linear increases in absence of a crevice geometry, variations in potential, solution
oxide thickness are associated with increasing electrode potential chemistry, and temperature. Short-term tests (with relatively few
above the onset potential. wear cycles) and long-term tests can be performed. When
For freely corroding tests, the potential of the test system reporting tribocorrosion experiments, all of the test parameters
will vary with the extent of the tribocorrosion taking place and described need to be defined and controlled or measured.
will depend on the remaining area of the electrode and its prop- Frictional Load-Displacement Plots
erties. This movable potential also will alter the driving potential Measurement of forces and displacements during tribocorrosion
for film formation, and as a result, the oxide thickness. helps us understand the mechanical conditions present. These
Solution Changes in Crevices include determination of the COF (lateral force divided by nor-
mal force). In addition, especially for cyclic type tribocorrosion
During tribocorrosion, especially under fretting crevice corrosion
tests (e.g., fretting corrosion tests), closed-loop friction load ver-
conditions where the interface between the two surfaces remain
sus sliding displacement plots can be obtained (see fig. 6), in
close and a crevice like geometry is established, alterations in the
which information like COF and work per cycle of load can be
solution chemistry within the crevice region may alter the results
determined (i.e., area inside the curve, or hysteresis energy). In
of the tribocorrosion processes. For example, the oxide film reac-
addition, the system compliance can be ascertained (i.e., the
tion (equation (3)) liberates hydrogen ions into the solution,
slope of the friction force versus sliding displacement reversal
thus altering the local pH in the contact region. In addition,
region) and the conditions of sticking can be determined.
release of cations locally within the crevice will attract chloride
To undertake such load and displacement measurements,
ions into the crevice as well. Tight crevices also raise the local
appropriately calibrated sensors are needed for displacement and
solution resistance, resulting in local voltage shifts. These solu-
load. These may include noncontact displacement sensors
tion changes and others (e.g., deaeration) may alter the stability
(DVRTs; fig. 4) and normal and lateral (or multi-axis) load cells.
of the oxide film within the crevice and alter the local electro-
All experimental setups must be carefully assessed for machine
chemical equilibrium potentials.
compliance to ensure that direct analysis of local loads and dis-
When the solutions are complex and contain additional
placements can be made.
molecules (e.g., proteins, other organic species), the triboelectro-
chemical interactions that may arise can be similarly complex.
There are reports29 of tribomixing in the surface where proteins
mix with tribocorrosion products (e.g., ions and oxides) and
Materials Characterization
become entrained and mixed with surface layers of the material. Post-Testing
This results in changes in chemistry of the surface and break-
SURFACE DAMAGE AND MATERIALS ASSESSMENTS
down of the proteins, otherwise altering the surface chemistry of
Tribocorrosion processes, whether they are fretting or sliding
the tribocorrosion-affected surface.
based, will result in progressive damage of the surface and near-
Mechanical Conditions of Testing surface alloy over time. The debris generated (e.g., metal particles,
The mechanical factors involved in tribocorrosion testing include oxide particles, ions, precipitated metal-organic complexes) can
the forces normal to and tangential to the interface, the COF, the remain within the tribocorrosion region or may migrate out-
sliding speed (frequency) and distance (amplitude), the lubrica- ward. Indeed, the surface of the alloy may undergo mixing and
tion regime (e.g., sliding speed, fluid viscosity, normal load), and
the surface properties of the materials in contact (e.g., modulus,
FIG. 6 Typical load-sliding displacement plots for fretting
hardness, ductility, fracture resistance). In addition, the test sys-
corrosion test for Ti-CoCrMo pin-on-disk combination.
tem compliance may affect load-displacement behavior, particu-
larly in cyclic reciprocating tests.
The basic schematic for tribocorrosion testing is shown in
figure 5. Tribocorrosion test systems need to control and measure
mechanical parameters and electrochemical parameters. For the
mechanics of the test, position sensors (e.g., differential variable
reluctance transducers, DVRTs), load cells that capture normal
and lateral forces, and movement actuators (e.g., piezoelectric
actuators) are needed. Typically, the movement control is
applied by waveform voltage generators or computer-based data
acquisition and control programs. Typical data captured includes
normal and tangential loads, displacements versus time, current
versus time, potential over time, etc. From these, parameters like
COF and work per sliding distance can be determined and corre-
lated on a cycle-by-cycle basis.
incorporation of solution constituents or oxides generated from reactions of bone cells and immune cells (e.g., macrophages) to
tribocorrosion. The local solution chemical environment, the the effects of tribocorrosion. These efforts may elucidate the
local adsorbed tribocorrosion debris layer, and the near-surface interplay between this material degradation mechanism and the
metal deformation state can all be altered from the tribocorro- biological impacts it can have on the living system.
sion processes.
It has been documented that a severely plastically deformed TRIBOCORROSION MAPS AND SYNERGY
surface layer up to 100 nm thick or more can develop from AND ANTAGONY
tribocorrosion processes, leading to a range of near-surface A number of efforts have attempted to describe the interplay
metallurgical effects.27,29–31 There are reports, for example, of between wear and corrosion using maps,33–35 in which the test
tribocorrosion-based mixed layers, in which metal, metal oxide, parameters (e.g., sliding speed, normal load, applied potential)
and organic materials (proteins) can interact and mix to create are plotted against one another and different modes of interac-
a surface tribochemical layer that is a consequence of the tion occur, including wear-passivation. Efforts at partitioning the
alloy, oxide, solution, and adsorbed species intermixing. In tribocorrosion processes into synergistic effects (wear assists cor-
addition, highly deformed alloy surface layers may result from rosion and corrosion assists wear) and antagonistic effects (wear
repeated asperity-asperity interactions. For some alloys, this hinders corrosion and corrosion hinders wear) have been pro-
results in a high dislocation density in the near-surface region posed. The challenge in these approaches is in how the various
resulting in subgrains and in high dislocation density entangle- terms are measured and partitioned. Indeed, it is often the case
ments. In other alloys, particularly those with low stacking that corrosion is based on measuring currents and the use of
fault energies (e.g., CoCrMo alloys), local surface plastic Faraday’s law. As pointed out, however, currents go to reform
deformation may result in crystallographic transitions (i.e., passive oxide films as well as toward ionic dissolution. Because
strain-induced transformations) from hexagonal close packed the passive oxide current is a formation current, it cannot go
to face centered cubic and back based on stacking faults. This toward corrosion-based material loss. It also reflects the oxide
may result in nano-crystalline grains (or highly deformed sub- that was abraded (by mechanical means), and thus it also
grains) developing near the surface, which may fracture or contributes to the corrosion-based loss. This shows the challenge
egress from the surface as nanoparticles by the mechanism of of using synergistic or antagonistic analyses, as discussed
fatigue wear. previously.36
For fretting crevice corrosion processes, the debris gener-
ated often will egress from the crevice, in part, but also will
adhere to the substrate metals in a zone near the site of genera-
Conclusion
tion. These forms of surface and near-surface damage and modi-
fication have been assessed primarily using analytical techniques, This chapter has defined the physics, chemistry, electrochemis-
including X-ray photoelectron spectroscopy, scanning electron try, and mechanics of tribocorrosion to provide insight into the
microscopy/energy dispersive spectrometry, Fourier-transform testing methods, parameters, and variations needed to under-
infrared spectrometry, and focused ion beam milling and trans- stand tribocorrosion. This mechanism couples a range of disci-
mission electron microscopy techniques. plines (e.g., tribology, metallurgy, electrochemistry, biology), each
of which contribute to the overall observed behavior at tribocor-
Coupling of Electrochemistry and Tribology
rosion contacts, notably in medically related implant interac-
In tribocorrosion processes, coupling effects exist between the
tions. Test methods to explore such phenomena need to have an
mechanics and the electrochemistry that may lead to interesting
ability to control and measure a range of mechanical factors and
observations that are, as yet, not fully explained. For example,
electrochemical factors to fully explore performance. Post-test
experiments recently conducted have shown that the COF of
analysis of damage is another important approach to explore the
fretting corrosion pin-on-disk tests of Ti and CoCrMo alloy
materials, transport, and electrochemical factors at play. Tribo-
combinations are highly sensitive to the electrode potential. The
corrosion is a complex, interdisciplinary phenomenon with sig-
COF of Ti-CoCr couples is around 0.2 at potentials near 0 V ver-
nificant consequences in a range of industries and disciplines
sus Ag/AgCl in phosphate buffered saline and rise to more than
beyond medical devices and biomaterials. It will continue to be
0.6 at -0.5 V and then fall again as the potential drops to -1V.
an important element in engineering design and materials per-
These variations are not seen for Ti-Ti couples (COF 0.6 to
formance analysis.
0.7) and are less extreme for CoCr-CoCr couples (COF
0.2–0.25).17 The mechanism for these variations is not fully elu-
cidated but likely reflects changes in the surface oxide chemistry,
thickness, and morphology. References
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31. N. Espallargas, A. Fischer, A. Igual-Munoz, S. Mischler, and 34. M. M. Stack, W. Huang, G. Wang, and C. Hodge, “Some Views
M. A. Wimmer, “In-Situ Generated Tribomaterial in Metal/Metal on the Construction of Bio-Tribo-Corrosion Maps for
Contacts: Current Understanding and Future Implications for Titanium Alloys in Hank’s Solution: Particle Concentration
Implants,” Biotribology 10 (2017): 43–50. and Applied Loads Effects,” Tribology International 44 (2011):
1827–1837.
32. G. M. Kubacki, T. Hui, and J. L. Gilbert, “Voltage and Wear Debris
from Ti-6Al-4V Interact to Affect Cell Viability during In-Vitro 35. M. M. Stack, “Mapping Tribo-Corrosion Processes in Dry and in
Fretting Corrosion,” Journal of Biomedical Materials and Aqueous Conditions: Some New Directions for the New Millen-
Research, Part A 106A (2018): 160–167, https://doi.org/10.1002/ nium,” Tribology International 35 (2002): 681–689.
jbm.a.36220
36. S. Mischler, “Triboelectrochemical Techniques and Interpretation
33. K. Sadiq, M. M. Stack, and R. A. Black, “Wear Mapping of CoCrMo Methods in Tribocorrosion: A Comparative Evaluation,” Tribology
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Analysis, Testing, and Environments
93
Chapter 7 | Metallographic Analysis
William L. Mankins1
A new door opened into the study of materials in the late-19th When sectioning, care should be taken to keep the sample
century (1863) when a British geologist named Henry C. Sorby cool. Elevated temperatures can promote phase transformations
learned to polish a piece of steel, etch it with acid, and examine it and exfoliation of surface deposits and scales. Heat can promote
under a microscope. Since that time, metallographic examina- volatilization of chemical species on the surface. Keeping the
tions have been performed on most every engineering metal sample cool may require slow cutting to avoid heat generation. If
developed. Metallographic examination is the preparation of samples must be cut using a torch, ensure that large areas are
specimens for microscopic evaluation and the study of micro- removed, thus leaving enough unaffected area for later saw cuts.
structures in relation to the physical and mechanical properties Recently, the plasma cutting torch has gained much acceptance
of a particular metal. An etching process reveals the microstruc- for use in obtaining samples in steels. The plasma torch transfers
ture of the metal. By preparing specimens through a process of very little heat to the steel, thus creating very small heat-affected
cutting (sectioning), grinding mounting, polishing, and etching, areas.
skilled metallurgists can examine metal samples on a micro- Cutting also may require the use of a coolant. One should
scopic level. Using various methods, alloys can be identified and be careful of liquid coolants, especially if chemical analysis of
material properties predicted. surface scales and deposits will be required. Introduction of cool-
Metallography is the study of the physical structure and ing liquids can contaminate areas of metallurgical interest. In
components of metals, by using microscopy. Metallographic addition, chemical species responsible for damage may dissolve
examination is a valuable tool in providing an understanding of and be washed away.
structure and property relationships in many metals. The true
value in these examinations cannot be obtained without an inti-
mate knowledge of metal thermodynamic phase equilibria, and Cutting (Sectioning)
the effects of environmental factors on that equilibria. Although
The preferred method of cutting metallographic samples utilizes
this knowledge can be gleaned from the numerous technical vol-
an abrasive saw with a blade of abrasive particles that do the
umes available, firsthand experience can be a far better teacher.
actual cutting. Rubber or resinoid bonded aluminum oxide or sil-
icon carbide particles of various grits account for the many cut-
Sample Selection ting blades that are available. Various commercially available
saws are designed for optimum cutting by saw blade selection,
The selection of samples can be very important to the outcome cutting speed, wet or dry cutting, and rate of cutting to ensure
of metallographic analysis. If the component is very large, it may that over-heating of the metal does not occur, which can alter
require sectioning to provide manageable metallographic sam- the microstructure and mechanical properties. If samples must
ples. The location for removal of metallographic samples should be cut with a torch, ensure that large areas are removed, thus
be considered carefully. Samples should contain areas represen- leaving enough heat-unaffected areas for later saw cuts. A caveat
tative of the corroded or fractured component. Samples of unaf- regarding cutting is an old carpenter’s saying: “Measure twice,
fected areas can reveal contrasting structures, thus distinguishing and cut once.”
damage. Sometimes multiple samples must be taken at different
orientations to understand the true nature of failure mechanism.
Procedures for Sample Preparation
1
Metallurgical Services, Inc., Huntington, WV, USA
PREPARING METALLOGRAPHIC SPECIMENS
The author acknowledges the previous author of this chapter, Richard L. Colwell, The surface of a metallographic specimen to be examined is pre-
Bechtel Corp., Houston, TX. pared by various methods of grinding, polishing, and etching.
DOI: 10.1520/MNL202NDSUP20190038
Saw cut small or irregular-shaped objects must be metallographi- polymer granules or powder, or both, are carefully added to the
cally mounted for grinding and polishing if automatic polishing cavity, with care being taken to not disturb the sample. Once suf-
equipment is used. Mounted samples also facilitate etching and ficient material has covered the sample, the ram portion end of
performing other metallographic tests and measurements. the cylinder is secured, and the cylinder is pressurized. Heat and
pressure cause the polymer to liquify and then set, thus encapsu-
FIXTURING AND MOUNTING lating the sample. Thermoplastic polymers should be allowed
Once a sample has been obtained, it can be prepared for metallo- to cool to near room temperature before releasing pressure. At
graphic examination. Preparation usually involves taking a rep- excessive temperatures above their glass transition, flow will
resentative sample of usable size and fixturing it for easy result, causing the polymer to pull away from the sample.
handling during grinding. The sample may be fixtured in a Another means of mounting specimens involves the use of
mechanical assembly by using a clamping load supplied by a clear lucite mounting compound, which allows the metallogra-
threaded fasteners. Most often the sample is sandwiched between pher to observe the location of cracks, pits, and other anomalies
two pieces of material of similar hardness. This sandwiching pro- in the mounted specimen, if further polishing and grinding are
motes good edge retention. One should be sure that the sand- necessary. When encapsulating samples, it is advisable, if possi-
wich material is nonreactive with the sample, especially in the ble, to remove any sharp corners, sharp protrusions, and burrs
presence of water and other fluids. To prevent a capillary draw from the sample edges. Their presence tends to concentrate
of fluid into the crevices inherent to the clamping fixture, paraf- stresses during polymer cool-down and can promote cracking.
fin can be used to fill the voids and gaps. Once cool, the sample can be handled easily during grinding and
Another fixturing technique involves the use of either ther- polishing.
moplastic, or thermosetting polymer granules and powders. These Another method of sample fixturing uses cold-set epoxy
powders and granules have different values of wearability. Mount- resins. This method is helpful when samples are large or when
ing resins with high wear resistance promote good edge retention, cutting affects the physical integrity of the sample. Samples can
but slow the material removal rate. Mounting polymers also can be mounted in mold release coated metal molds or plastic pre-
be transparent and electrically conductive. Conductive mounts are forms. Molds or preforms, or both, are then affixed (rubber
required to keep the sample from charging when examination cement; e.g., Seal-All) to an aluminum foil or polytetrafluoro-
using a scanning electron microscope is required. ethylene (PTFE; e.g., Teflon) covered flat surface. The sample
A systematic preparation method is the easiest way to is then placed on the flat foil or PTFE surface, in the preform,
achieve the true structure. Sample preparation therefore must with the side to be polished down. Mixed, bubble-free epoxy
pursue rules that are suitable for most materials. Different mate- resin is then poured over the sample, filling the mold. When
rials with similar properties (hardness and ductility) will respond using epoxy resins, it is helpful to have access to a bell jar and
alike and thus require the same consumables during preparation. vacuum pump. A few minutes under vacuum tends to draw any
For metals, hot compression mounting is widely used. Phe- air and gas bubbles out of the sample. The best method using liq-
nolics are popular because they are low cost, whereas the dia- uid resins involves introducing it to the sample while under vac-
llyphtalates and epoxy resins find applications in which edge uum. Upon venting to atmosphere, resin is actually forced into
retention and harder mounts are required. The acrylic mounting microcavities. The sample is then placed in the preform mold
compounds are used because they have excellent clarity. and resin is added to fill the mold.
For cold mounting, castable mounting resins are commonly The resin reaction is exothermic, raising the temperature sig-
used for electronic and ceramic materials. They are recom- nificantly and reducing the time required for the resin to cure, but
mended for brittle and porous materials. These mounting com- there are some drawbacks. If the temperature is too high, the resin
pounds typically have two component systems (1 resin and 1 can oxidize, causing discoloration, thus decreasing visibility of the
hardener). Mounting consumables include cold and hot mount- sample. More important, the amount of shrinkage is significantly
ing systems and mounting accessories. Mounting instruments higher for resins cured at temperatures above room temperature.
includes programmable hot mounting presses. This shrinkage can lead to cracking of the epoxy resin. Curing at
Formerly, phenolic thermosetting resins were used for high temperatures also can cause the epoxy to pull away from the
mounting specimens, but modern epoxy is becoming more pop- sample, which promotes staining during etching.
ular because reduced shrinkage during curing results in a better If metallographic examination of coatings, specifically oxide
mount with superior edge retention. A typical phenolic (bakelite) coatings, is required, the following special techniques are helpful
mounting cycle will compress the specimen and mounting media in preserving the integrity of the coating. The basis of coating
to 4,200 psi (28 MPa) and heat to a temperature of 300 F preservation involves reducing the shrinkage associated with the
(150 C). When specimens are sensitive to temperature, “cold curing resin. Blank mounts are made by filling bubble-free liquid
mounts” may be made with a two-part epoxy resin. Mounting a resin in 1.25-in.-diameter bakelite preforms. After a 24-h cure,
specimen provides a safe, standardized, and ergonomic way by two parallel saw cuts are made (approximately 7/8 in. apart)
which to hold a sample during the grinding and polishing through the sample, creating flats (fig. 1). Next, a thin slot is
operations. cut normal to the flats, halfway through the mount thickness.
Mounting involves inserting a specimen, with the side to be The ends of the slot are dammed up using cellophane tape. The
polished face-side down, into a heated mounting press. Next, sample is vacuum impregnated and then placed in the slot.
METALLOGRAPHIC ANALYSIS 95
purpose of grinding is to produce a flat or planar surface. Sec-

FIG. 1 Mountain arrangement for preserving oxide scales. ond, grinding involves removal of gross scratches and deformi-
ties from the surface. Finally, it is equally important, especially
for softer materials, to remove subsurface damage. During grind-
ing, abrasive particles actually cut microgouges in the sample
surface. While cutting, the material just beneath the surface of
the gouge is plastically deformed (cold worked). This work-
hardened material has a higher dislocation density and is there-
fore higher in internal strain energy than the material around it.
During etching, these higher energy areas are preferentially
attacked, thus leaving traces of scratches and etch pits. It is
important to not only remove the scratches observed but also
remove subsurface damage not visible.
During grinding, the metallographer should keep in mind
that increasing the pressure on the sample will result in greater
material removal rates, but it will not increase the amount of
subsurface damage.3 The maximum depth of subsurface damage
is independent of pressure.3
The smoothness of the sample cut surface will decide the
grit size of the grinding paper that initially is used. Traditionally,
grinding can start at grits as fine as 200 grit, depending on the
initial smoothness and flatness of the sample. Grinding should
start with the finest grit capable of rendering a flat specimen and
removing damage from sectioning. Coarse grinding should be
minimized to limit subsurface deformation. If a finer surface fin-
ish is required before polishing on a diamond past wheel, polish-
ing 600 grit or finer should be considered. Figure 2 shows the
relationship between scratch depth (roughness) and depth of
deformation in steels of various grit sizes.4 Additional grinding is
The sample is then shimmed up using thin stainless steel strips. performed using successively finer abrasives, typically using 320,
According to Hussey, Beaubien, and Caplan, “The strips mini- 400, and 600 grit abrasives sequentially. Rinsing of the ground
mize rounding and reduce the chance of separation at the surface with flowing water is imperative between grinding steps
specimen-resin interface by providing a preferential site for such to prevent loose abrasive particles from being carried onto the
separation, if any should occur”.1 Other methods are available next finer-grade grit paper, which will result in scratching by the
and the reader is advised to explore them. A good outline of larger particles from the coarser paper just used.
additional mounting methods and materials is given in Metallog- During grinding, the sample surface should be kept cool.
raphy Principles and Practice by G. VanderVoort (see chap. 2, Cooling usually is provided by use of water, alcohol, or other
60–93),2 and ASTM E3, Standard Guide for Preparation of Metal- organic compounds. Methanol or ethanol coolants are used to
lographic Specimens, sections 7 through 9.
FIG. 2 Depth of scratches (roughness) and subsurface
GRINDING deformation in steels as a function of abrasive grit size.
Caution: Before grinding, chamfer the sharp edges of the sample Note: 1 lm (micrometer ¼ 4 10-4 inches).
mounting material to prevent cutting the fingers of the person
doing the polishing, if hand polishing, and to prevent snagging of
the grinding or polishing media. Once the sample is fixtured prop-
erly, the surface should be ground smooth and flat. Grinding
traditionally is performed using silicon carbide papers, but some-
times diamond impregnated grinding media are used. Grinding
can be done manually with stationary abrasive papers, manually
using rotating abrasives, or automatically (usually encompassing
rotating abrasives, a counterrotating sample platen, and applying
downwards pressure of the sample onto the abrasive). The choice
between these methods depends on the number of samples
and economy.
Whatever method is used, the principle is basically material
removal. Material is removed for multiple reasons. The initial
inhibit leaching of water-soluble compounds from the sample or

oxide scales. TABLE 1 Polishing Cloth Types and Uses
POLISHING Cloth Recommended Uses

There are basically two methods of polishing metallographic Canvas Rough general polishing. Use with
samples: mechanical and electrolytic (electrochemical). Each will coarse grades of silicon carbide (SiC)
be discussed separately. and aluminum oxide (Al2O3).
Billiard Cloth (Sheared Virgin Rough general polishing of ferrous-
Mechanical Polishing Wool) based materials.
Subsequent to grinding and before polishing, the metallogra- Red Felt (Plucked Virgin Wool Rough or intermediate polishing.
pher’s hands and the sample should be thoroughly washed. Pile)
Washing keeps any residual grinding abrasives from contaminat- Cotton-Medium Nap Intermediate polishing. Commonly used
ing the polishing cloth. with diamond, Al2O3, and colloidal silica
The polishing operation is similar to grinding, but the size Cotton-Fine Nap Rough diamond polishing of soft metals.
of the polishing abrasives is considerably smaller than the size of Use with polishing grades ofAl2O3,
grinding abrasives. Again, the sample should be washed between chromium(III) oxide (Cr2O3), and silica.
each polishing step to inhibit abrasive carryover and contamina- Nylon Rough polishing with diamond. Helps
tion of the polishing cloths. Ultrasonic baths are highly recom- maintain flatness.
mended for cleaning during polishing. Ultrasonic waves promote Silk Use with diamond in rough polishing
superior cleaning by agitating small particles out of cracks and of extremely friable materials and rough
polishing of metals.
voids. However, metallographers beware: extended use can result
Woven Wool Rough and intermediate polishing of
in cavitation and pitting on the sample surfaces.
hard materials.
Typically, a sample will first be rough polished using a
Wool (Short Pile) Use in all final polishing stages.
6-lm or 3-lm diamond compound. Diamond abrasive can be
Rayon (Flock on Cotton Backing) Final polishing with diamond, Al2O3.
suspended in an oil-based slurry or paste. Choice of polishing
Rayon-Fine Superior final polishing with diamond,
cloth is a function of sample material hardness, polishing rate,
Al2O3, and colloidal silica.
desired edge retention, and relief. A typical listing of various pol-
Synthetic Velvet Intermediate and final polishing.
ishing cloths and their uses is presented in table 1.
Minimizes relief and edge rounding.
A diamond extender (i.e., fine cutting oil) is used during
Synthetic Velvet-Fine Use in vibratory polisher, especially with
polishing to minimize the use of expensive diamond polishing
soft materials.
compounds and to ensure a uniform distribution of the abrasive
Medium Napped Polyurethane Polishing oxide films. Use with cerium
over the polishing cloth. Initially, a small amount of diamond Cloth on Polyester oxide.
compound is distributed on the polishing cloth and polishing
Source: Courtesy of South Bay Technology, Inc., San Clemente, CA.
begins with the wheel revolving at about 100 to 300 rpm. This
oily compound allows diamond particles to adhere to the fibers
time is unattended. Vibratory polishing is very good at produc-
of the polishing cloths, removes abraded material, and permits
ing scratch-free samples for soft metals. Vibratory polishing is
dissipation of heat during polishing.
also useful for polishing samples having secondary phases in
Once the sample has been polished to 3 lm, a final step
addition to the matrix. Harder phases are more resistant to the
(fine polishing) usually involving either an alumina slurry or col-
abrading action of the polishing media and stand in relief on the
loidal silica slurry is used. The size of particles in these aqueous
polished surface. After polishing, samples should be washed,
slurries can be as small as 0.02 lm. Once finished with this step,
rinsed in alcohol (and acetone if an oily film is present), and
the sample is ready for examination as-polished or etching. All
blown dry to avoid staining.
samples should be examined in the as-polished condition to eval-
uate the quality of the polishing, and it is easier to identify very
small particles in the microstructure before etching. Procedures Electrolytic Polishing
such as inclusion measurements (ASTM E45, Standard Test Electrolytic polishing is a convenient way to polish metallic
Methods for Determining the Inclusion Content of Steel) require samples in the fine ground (600 grit) or machined surface condi-
assessments be conducted on as-polished samples. tion. This method requires formation of an electrical circuit in
which the sample is the anode (fig. 3). A suitable electrolyte flows
Vibratory Polishing across the surface or submerges the sample. The current density
Vibratory polishing is another method commonly used. is adjusted for the type of material and size of the polished sam-
Mounted samples are weighted down and allowed to randomly ple to facilitate suitable dissolution of metal ions from the to-be-
circulate on a cloth-covered vibrating platen. The platen holds polished surface. Typically, 30–50 V are applied to the circuit
an aggressive slurry of polishing abrasives and usually is covered and draw a current of 10–13 amperes. Polishing time is about
to avoid evaporation and splashing. The downside of vibratory 10–15 s. As the electrolyte washes over the sample, any perturba-
polishing is that it requires much more time than traditional tions in the surface (high-energy sites) are selectively dissolved.
mechanical or electrolytic polishing. Fortunately, this operating The result is a flat surface with no mechanical damage.
that have undergone plastic deformation will etch faster than

FIG. 3 Diagram of a simple electrolytic polishing cell. nonstrained, nondeformed material. In a multiphase material,
D.C.
one phase may be more reactive than another.
Similarly, grain orientation on polished surfaces can affect
the degree of etching. Close-packed orientations can etch slightly
VARIABLE RESISTOR
faster than lesser packed planes.
SWITCH Microscopic examination of etched samples under reflected
VOLTMETER light, will show variations in the amount of light reflected to the
AMMETER
eyepiece of the microscope as a function of the etching of more
or less anodic portion of the surface of the sample. Surface undu-
SPECIMEN lations created by etching, reflect light away at different angles.
CATHODE (ANODE) The “off-reflected” light cannot be reflected back through the
objective lens of the microscope and therefore appears as regions
of darkness (fig. 4).
COOLING BATH Some materials etch more easily than others. Grain bound-
ary delineation in aluminum alloys is perhaps one of the most
difficult tasks for a metallographer. In aluminum alloys, it is
ELECTROLYTE
sometimes necessary to experiment with many known etchants
to obtain the desired microstructural resolution. Certain alloys
Electrical circuit and arrangement of apparatus suitable for are designed for corrosion resistance and therefore are resistant
most electrolytic polishing operations. (Source: The Principles of
to typically used chemical etchants.
Metallographic Laboratory Practice by George L. Kehl,McGraw-Hill
Book Company, Inc., 1949) Table 2 lists a number of chemical etchants that have proved
useful for a limited number of the more popular engineering
alloys. Included are the microstructural characteristics highlighted
Although this method is easy to use, storage and use of by the etch.
potentially dangerous and poisonous electrolytes may limit its After chemical etching, samples should be rinsed in water
use. For example, some solutions of perchloric (HClO4) can (to terminate the chemical action of the etchant with the metal),
become explosive if allowed to evaporate to concentrated solu- followed by alcohol rinse to displace water from the surface
tions or perchlorate salts. (eliminate water staining) and blown dry to avoid further stain-
ing. Avoid touching the etched surface of the sample to protect
microstructural features or oxidation caused by “finger prints.”
Etching
Samples should be stored in desiccators to inhibit corrosion on
The final step in sample preparation is etching, which is a con-
the highly polished surfaces. If a desiccator is not available, use
trolled corrosion process. Etching exposes the polished surface of
of commercial clear-coat spray paints is recommended.
a mounted specimen to a suitable environment that reveals par-
Electrolytic etching is similar to chemical etching and is
ticular structural features of the material that are not observable
used to etch corrosion-resistant materials. The electrochemical
in the as-polished condition. After etching, the various surface
reaction is supplied by means of an externally applied potential.
constituents must be shown definitively with extreme clarity.
Etching is accomplished using the electrolytic cell used for elec-
Etching is performed to observe microstructural constituents,
tropolishing, as shown in figure 3. Typical operating parameters
including grain boundaries, twin planes, slip lines, and second-
phase particles. Etching also can reveal a material’s propensity
toward certain corrosion mechanisms, material defects, and
FIG. 4 Simplistic representation of the principle of chemical
service failures.
etching.
Safe laboratory work practices are important. A metallogra-
pher is useless without his or her eyes. Use proper protective equip-
ment (e.g., gloves, safety glasses) when using laboratory chemicals.
The basic types of etching mechanisms are chemical etch-
ing, electrolytic etching, staining, and optical etching. Chemical
etching uses the anisotropy (nonhomogeneity) in a material. The
reaction rates of the chemical etchant on a polished sample’s sur-
face depend on the energy state of the materials microstructure.
The higher the energy state of one region, the faster it will react,
and more etching (localized material removal) occurs.
In other words, some microstructural constituents are
anodic to others. Grain boundaries and twin boundaries are
more energetic (anodic) than the material in the center of a
grain. Likewise, regions under elastic tensile strain, or regions
TABLE 2 Typical Chemical Etchants
Alloy Chemical Etchants Uses
Aluminum and Al Alloys 0.5–25 g NaOH General purpose etch.

1 g zinc chloride Grain boundary delineation.
100 mL water Immerse up to 2 min.
1 mL HF (48%) Outlines microconstituents.
200 mL water Immerse for 30–40 s.
12.5 mL HNO3 (cone.) General purpose etch.
2.5 mL HF (48%) Grain boundary delineation.
85 mL water Immerse up to 1 min.
2 mL HF (48%) Modified Keller’s Rgnt.
3 mL HCl (cone.) General purpose etch for Al and Al alloys. Immerse 10-60 s.
20 mL HNO3 (cone.) Wash in warm water, blow dry.
175 mL water
Copper and Copper Alloys 10 mL NH4OH General purpose etch.
10 mL H2O2 (3%) Grain boundary delineation.
Can dilute up to 20 mL water Use fresh, swab, or immerse up to 1 min.
10 g (NH4)2S2Os General purpose etch.
90 mL water Grain boundary delineation. Immerse up to 1 min.
10 g Cr2O3 Swab or immerse up to 30 s.
4 drops HCl
75–100 mL water
Nickel and Nickel Alloys 20 mL HNO3 Aqua-Regia
60 mL HCl Grain boundary, carbide, and a contrast. Use fresh and underhood. Discard after use.
Swab or immerse up to 1 min.
3 parts glycerol Glyceregia.
2–3 parts HCl Popular etch. Use fresh and under hood. Discard after use.
1 part HNO3 Swab or immerse up to 1 min.
10 g CuSO4 Marble’s Reagent.
50 mL HCl Grain boundary delineation
50 mL water Swab or immerse up to 1 min.A few drops of H2SO4 increases etch activity.
Iron and Iron Alloys 2 mL HNO3 Nital.
98 mL ethanol Gives good pearlite-ferrite-grain boundary contrast in carbon and low-alloy steels.
Swab or immerse up to 1 min.
4 g picric acid Picral. Promotes good resolution of pearlite, bainite,
100 mL ethanol martensite, and carbides.
4–5 drops of zephiran Swab or immerse up to 1 min.
chloride (wetting agent)
100 mL picric acid (sat.) Reveals prior austenitic grain boundaries in martensitic steels.
1 g tridecylbenzene
Stainless Steel 1 part HNO3 General purpose etch for stainless steels.
1 part HCl Promotes grain boundary contrast.
1 part water Immerse in a gently stirred solution.
1 g picric acid Viella’s Reagent.
5 mL HCl Outlines carbides, c, and 5.
100 mL ethanol Immerse up to 1 min.
1 part glycerol Glyceregia for SSs.
3 parts HCl Reveals grain structure.
1 part HNO3 Outlines a and carbides.Use fresh and under hood. Discard after use.Swab or immerse up
to 1 min.
10 g oxalic acid Electrolytic etch (sample is anode). Use at 1–6 V at 0.1–1.0 A/cm2.
100 mL water Resolves O in 5–10 s. Resolves carbides in 15–30 s. Resolves grain boundaries in 45-60 s.
2 4 5
Note: See VanderVoort, Petzow, and the ASM Metals Handbook for extensive listing of etchants.
for electro-etching are as follows: about 100–200 lA, and about Optical etching is a nondestructive method. The term opti-
5–10 V, and an etching time of 5–10 s. If the sample is embedded cal etching is a misnomer. Optical methods do not involve etch-
in a polymeric mounting material, provisions for making electri- ing, but they are useful in showing microstructural features in
cal contact must be made (i.e., prepared mount, drilling through certain alloys. In this method, microstructural contrast, specifi-
the mount, removal from mount). cally crystallographic contrast of polished samples, is produced
A family of chemical etchants known as deposit etchants by using the Kohler principle of illumination (fig. 5). Modes of
works slightly differently than chemical etchants. Like electro- illumination including polarized light, differential interference
lytic etchants, deposit etchants promote dissolution of metal on contrast (Nomarski), and dark-field (DF) illumination can pro-
the polished surface. The dissolved metal ions react with agents duce vivid and sometimes colorful contrast. Microstructural
in the etchant solution, however, thus promoting precipitation metallurgy has made many technical advances created by metal-
of insoluble compounds on the sample surface. The relative lurgical microscopes utilizing the Kohler system with high-
thickness of the coating depends on the reaction rate, which intensity illumination sources, a complex system of diaphragms,
again is a variant depending on microstructure and chemical and combination lenses.5
composition. A digital microscope is a more recent development of typi-
Commercial electropolishing and etching equipment is also cal optical microscope that uses both optics and a digital camera
available and is useful for metallographic polishing and etching to supply an image to a computer coupled monitor. A digital
applications. Electrolytic processes do have some limitations. microscope with integral LED lighting differs from an optical
Alloy specimens that are multiphase, have cracks or voids, or microscope in that there is no means to observe the image
previously have been cold worked may be difficult or even through an eyepiece. The image is focused on the digital circuitry
impossible to polish or etch electrolytically. It may be necessary with the entire system designed for monitor imaging. Digital
to mechanically polish samples followed by a combination of microscopes provide digitally enhanced three-dimensional in-
chemical and electrolytic etches to delineate the actual micro- focus imagery from 20 to 6,000.
structures. Etching results are a product of the metallographer’s A comprehensive list of electrolytes for electrolytic etching
experience and patience. and chemical etchants can be found in VanderVoort,2 Petzow,4
Heat tinting is another type of deposit etch. Exposing a pol- and the ASM Metals Handbook.5 Instructions for the preparation
ished sample (not in a plastic mount!) to elevated temperatures of etchants and operating parameters for electrolytic polishing
in air causes oxidation. On the microscopic level, oxidation rates and etching are also referenced.
of microstructural constituents vary according to their reactivity
in a given environment. Metallographic Interpretation
The second type of etching is more of a staining operation In the preparation of metallographic samples, not only are good
than etching. Staining has been more involved with the identifi- hygiene and techniques required but also a good understanding
cation and differentiation of oxide films than in outlining micro- of the sample material and its properties. Most metallographers
structural constituents. have been surprised at least once by a structural anomaly that
FIG. 5 The Kohler principle of illumination.

turned out to be an artifact. Experience and an inquisitive nature piece of paper under one corner of the mount so that the plane-
are necessary for good metallographic interpretation. of-polish is no longer perpendicular to the optical axis.2
Bright- and dark-field microscopy. Scanning electron and transmission electron

Most light optical microscope (LOM) observations are con- microscopes.
ducted using bright-field (BF) illumination, where the image of If a specimen must be observed at higher magnification, it can be
any flat feature perpendicular to the incident light path is bright, examined with a scanning electron microscope (SEM) or a trans-
or appears to be white. But, other illumination methods can be mission electron microscope (TEM). When equipped with an
used and, in some cases, may provide superior images with energy dispersive spectrometer (EDS), the chemical composition
greater detail. DF microscopy is an alternative method of obser- of the microstructural features can be determined. The ability to
vation that provides high-contrast images and actually greater detect low-atomic number elements, such as carbon, oxygen, and
resolution than BF microscopy. In DF illumination, the light nitrogen, depends upon the nature of the detector used. But,
from features perpendicular to the optical axis is blocked and quantification of these elements by EDS is difficult and their
appears dark, whereas the light from features inclined to the sur- minimum detectable limits are higher than when a wavelength-
face, which look dark in BF, appear bright, or “self-luminous” dispersive spectrometer (WDS) is used. But quantification of
in DF. Grain boundaries, for example, are more vivid in DF composition by EDS has improved greatly over time. The WDS
than BF.2 system has historically had better sensitivity (ability to detect low
amounts of an element) and ability to detect low-atomic weight
Polarized light microscopy. elements, as well as better quantification of compositions, com-
Polarized light (PL) is very useful when studying the structure of pared with EDS, but it was more time consuming to use. Again,
metals with noncubic crystal structures (mainly metals with hex- in recent years, the speed required to perform WDS analysis has
agonal close-packed (hcp) crystal structures). If the specimen is improved substantially. Historically, EDS was used with the
prepared with minimal damage to the surface, the structure can SEM, whereas WDS was used with the electron microprobe ana-
be seen vividly in cross-polarized light (the optic axis of the lyzer (EMPA). Today, EDS and WDS are used with both the
polarizer and analyzer are 90 degrees to each other, i.e., crossed). SEM and the EMPA. A dedicated EMPA, however, is not as
In some cases, an hcp metal can be chemically etched and then common as an SEM.2
examined more effectively with PL. Tint etched surfaces show
visible thin films (such as a sulfide, molybdate, chromate, or ele- Design, resolution, and image contrast.
mental selenium film) to aid metallographic study. These epitax- Light microscopes are designed for placement of the specimen’s
ial features are grown on the surface to a depth at which polished surface on the specimen stage either upright or inverted.
interference effects are created when examined with BF produc- Each type has advantages and disadvantages. Most LOM work is
ing color images. Microstructural resolution can be improved done at magnifications between 50 and 1,000. With a good
with PL. If it is difficult to get a good interference film with good microscope, it is possible to perform examination at higher mag-
coloration, the colors can be improved by examination in PL nifications, for example, 2,000, and even higher, as long as dif-
using a sensitive tint (ST) filter.2 fraction fringes are not present to distort the image. The
resolution limit of the LOM will not be better than about 0.2–0.3
Differential interference contrast microscopy. lm. Special methods are used at magnifications below 50,
Another useful imaging mode is differential interference contrast which can be helpful when examining the microstructure of cast
(DIC), which usually is obtained with a system designed by the specimens where greater spatial coverage in the field of view may
Polish physicist Georges Nomarski. DIC converts minor height be required to observe features such as dendrites. In addition to
differences on the plane-of-polish, invisible in BF, into visible considering the resolution of the optics, one must also maximize
detail. The detail in some cases can be quite striking and very visibility by maximizing image contrast. A microscope with
useful. If an ST filter is used along with a Wollaston prism, color excellent resolution may not be able to image a structure, that is
is introduced. The colors are controlled by the adjustment of the there is no visibility, if image contrast is poor. Image contrast
Wollaston prism and have no specific physical meaning, how- depends on the quality of the optics, coatings on the lenses, and
ever, visibility may be better. DIC capabilities are integral com- reduction of flare and glare; however, it also requires proper
ponents of numerous commerically available LOM. specimen preparation and good etching techniques. So, obtain-
DIC has largely replaced the older oblique illumination (OI) ing good images requires maximum resolution and image
technique, which was available on reflected light microscopes contrast.2
before about 1975. In OI, the vertical illuminator is offset from
perpendicular, producing shading effects that reveal height differ- Quantitative metallography.
ences. This procedure reduces resolution and yields uneven illumi- A number of techniques exist to quantitatively analyze metallo-
nation across the field of view. Nevertheless, OI was useful to graphic specimens. These techniques are valuable in the research
detect if a second-phase particle was standing above or was and production of all metals and alloys and nonmetallic or com-
recessed below the plane-of-polish, and it is still available on a few posite materials. Microstructural quantification is performed on a
microscopes. OI can be created on any microscope by placing a prepared, two-dimensional plane through the three-dimensional
part or component. Measurements may involve simple metrology used to assess high-temperature damage of power-generating
techniques, for example, the measurement of the thickness of a equipment, chemical-processing units, heat exchangers, high-
surface coating, or the apparent diameter of a discrete second- pressure piping, or other areas where sample removal is not easy.
phase particle (e.g., spheroidal graphite in ductile iron). Measure- Field metallographic procedures follow the same procedures
ment also may require application of stereology to assess matrix used in standard metallography. The surface to be examined is
and second-phase structures. Stereology is the field of taking zero-, ground and polished with a series of progressively finer abrasive
one-, or two-dimensional measurements on the two-dimensional papers and diamond or silica polish is used to achieve a mirror-
sectioning plane and estimating the amount, size, shape, or distri- like scratch-free finish. Pre-mixed etchants are used to swab etch
bution of the microstructure in three dimensions. These measure- the localized area to be examined. Replication is a nondestructive
ments may be made using manual procedures with the aid of sampling procedure that records and preserves the topography
templates overlaying the microstructure, or with automated image of a metallographically prepared surface as a negative relief on a
analyzers. In all cases, adequate sampling must be made to obtain plastic film (replica). The replica permits the examination and
a proper statistical basis for the measurement. Efforts to eliminate analysis of the metallographically prepared surface on the LM
bias are required. Some of the most basic measurements include microscope or the SEM. Enhancement procedures for improving
determination of the volume fraction of a phase or constituent, replica contrast for microscopic examination are used and fre-
measurement of the grain size in polycrystalline metals and quently are necessary. ASTM E1351-01, Standard Practice for Pro-
alloys, measurement of the size and size distribution of particles, duction and Evaluation of Field Metallographic Replicas, covers
assessment of the shape of particles, and spacing between par- recognized methods for the preparation and evaluation of cellu-
ticles. Standards organizations, including ASTM International’s lose acetate or plastic film replicas which have been obtained
Committee E4 on Metallography and other national and interna- from metallographically prepared surfaces. This procedure
tional organizations, have developed standard test methods describes the evaluation of replicas to ensure that all significant
describing how to characterize microstructures quantitatively. features of a metallographically prepared surface have been
For example, the amount of a phase or constituent, that is, its duplicated and preserved on the replica with sufficient detail to
volume fraction, is defined in ASTM E562, Standard Test Method permit both LM and SEM examination with optimum resolution
for Determining Volume Fraction by Systematic Manual Point and sensitivity. Replication involves the application of the acetate
Count; manual grain size measurements are described in ASTM sheet on the etched surface to produce a replica of the surface
E112, Standard Test Methods for Determining Average Grain Size (see fig. 6) Before being applied to the surface, the acetate sheet
(equiaxed grain structures with a single size distribution) and must be softened using methyl-acetate solution or acetone caus-
E1182, Standard Test Method for Measurement of Surface Layer ing the acetate sheet to adhere to the surface. The softened ace-
Thickness by Radial Sectioning (Withdrawn 2002) (specimens tate sheet is pressed firmly onto the etched surface to be
with a bi-modal grain size distribution); ASTM E1382, Standard replicated. After drying, the acetate sheet is sprayed with a black
Test Methods for Determining Average Grain Size Using Semiau-
tomatic and Automatic Image Analysis, describes how any grain
size type or condition can be measured using image analysis
FIG. 6 Schematic representation of the replication process
methods. Characterization of nonmetallic inclusions using stan-
(Buehler).
dard charts is described in ASTM E45, Standard Test Methods
for Determining the Inclusion Content of Steel (historically,
ASTM E45 covered only manual chart methods and an image
analysis method for making such chart measurements was
described in ASTM E1122, Standard Practice for Obtaining JK
Inclusion Ratings Using Automatic Image Analysis (Withdrawn
2006). The image analysis methods are currently being incorpo-
rated into ASTM E45). A stereological method for characterizing
discrete second-phase particles, such as nonmetallic inclusions,
carbides, and graphite, is presented in ASTM E1245, Standard
Practice for Determining the Inclusion or Second-Phase Constituent
Content of Metals by Automatic Image Analysis.
Nondestructive Field Metallography

Field metallography is nondestructive in situ testing of metallur-
gical conditions of metallic components that are in service
wherein the removal of the equipment is either impractical or
impossible. This method of nondestructive metallographic test-
ing permits field evaluations without the need to remove equip-
ment from service or production. Metallographic replication is
paint to provide an opaque surface to the film and surface con- Susceptibility of SCC is highly dependent on the metals
trast before peeling the tape from the component surface. The stress state. Tensile stresses, either applied or residual, above a
replica tape is carefully affixed to a glass slide using double-stick threshold value (alloy or heat dependent), are required for SCC
adhesive tape. cracking to occur. Chemical etching of metals can sometimes
Care must be taken in handling the fragile replicas. An ace- provide clues into a metal’s thermomechanical history. Indica-
tate tape thickness of 20–25 lm is suggested for replication. The tions of plastic deformation (deformation twins, slip lines), and
contrast of the replica is further improved by applying carbon or thus knowledge of exceeding of material yield strength, can be
metallic coating to the replica through a vacuum deposition revealed through etching.
sputtering process. Metallic coated replicas will provide excep- Some stainless steels6 can be made susceptible to IGSCC by
tional spatial resolution. exposure to elevated temperatures 1021 F (550 C) < T < 1963 F
The process of acetate sheet replication can be substituted (800 C). At these temperatures, carbon atoms migrate to grain
using a silicone-rubber elastomer coating two-part replication boundaries where they combine with chromium atoms to precip-
process. Commercially available replicating equipment is ideal to itate chromium carbides (see fig. 8). Because chromium atoms
measure surface roughness in tribological applications or during are tied up as carbides, they are not available for matrix corro-
the analysis of fracture surfaces of large components. Silicone- sion resistance, and the near-grain boundary regions are locally
based systems provide ideal surfaces and where replicas of low depleted in chromium. The 18Cr-8Ni austenitic stainless steels
volume are required. The total time for the preparation of a sili- with various modifications in composition are known for corro-
cone replica is less than the time needed to prepare an acetate sion resistance. When these alloys are heated in the temperature
replica and the silicone replica is not as fragile when being han- range 800 F to 1500 F (425 C to 815 C), for extended periods of
dled. Once the replicas are prepared, observation procedures are time, they become sensitized, or susceptible to intergranular cor-
quite similar. Extracted replicas are normally examined with an rosion. This depletion renders grain boundary regions suscepti-
optical microscope at magnifications of 50 to 1,000 with BF ble to corrosion, and the alloy is then termed “sensitized.” The
illumination. degree of sensitization is a function of temperature and time at
temperature. The commonly accepted explanation for this
behavior is the chromium impoverishment or chromium deple-
Metallographic Examination and tion theory. The addition of chromium in the amount of about
Evaluation of Corrosion Mechanisms 12% or more to ordinary steel imparts stainless steel characteris-
tics and corrosion resistance.
STRESS CORROSION CRACKING In the specified temperature range, carbon migrates (dif-
The nature of stress corrosion cracking (SCC) can be directly fuses) to the grain boundaries and precipitates out of solid solu-
observed by metallographic examination. The distinction tion as Cr3C (in 304SS). Chromium is removed from solid
between intergranular (IGSCC) and transgranular cracking solution, producing metal with lowered chromium content in
(TGSCC) is best revealed by etching materials to reveal grain the areas adjacent to the grain boundaries. Calculations show the
boundaries (fig. 7). In addition, the magnitude of crack branch- composition of these carbides are approximately 93% chromium
ing and crack initiation sites are best revealed by metallographic and 7% carbon, so the area within the grains where chromium is
examination. diffused from solution creates a wide corrosion-sensitive band.
FIG. 7 Transgranular stress corrosion cracking (left) and intergranular stress corrosion cracking (right) in 304 stainless steel (200).
can be performed easily using charts A, B, and C in ASTM G46,

FIG. 8 Schematic diagram illustrating carbide precipitation. Section 7.2.1. (figs. 8 and 9). These charts characterize a sample’s
(A) Microstructure of 18Cr-8Ni stainless steel; white area pit density, pit size, and pit depths. Metallographic evaluation of
is austenite of 18-8 composition, white particles in grain pitting is done with the sample in the as-polished condition.
boundaries are chromium carbides, and shaded areas are These data are convenient ways of relating and illustrating the
chromium-depleted areas. (B) Differences in chromium severity of pitting to the lay person. It is sometimes helpful to
content caused by carbide precipitation; cross-hatching reassess a sample after additional grinding and polishing. Mate-
represents a low-chromium area, which can be severely rial removal can eliminate overly conservative measurements
corroded. caused by the three-dimensional (3D) travel path of corrosion
pits.
Another way to quantify the extent of pitting is to examine
the pitted surface of an as-polished sample under a laboratory
microscope. By measuring the vertical distance using the microme-
ter focus knob, focusing on the top surface of the sample and the
bottom of the pit, depth can be measured and determined. Care
must be exercised because, as seen in figure 10, pits may not be per-
pendicular to the surface of the sample. Pits may be a continuous
path or undercut beneath the surface. An erroneous perceived pit
bottom may result in a conservative depth measurement.
DEALLOYING (SELECTIVE LEACHING)

Dealloying is a corrosion mechanism in which one element in a
multielement system is selectively leached from the matrix by
action of a fluid system. Two alloy systems that are widely
known for dealloying are cast iron (graphitic corrosion) and
copper-zinc (Zn > 15 wt.%) brasses. In gray cast irons (in the
presence of sulfate reducing bacteria, salt water, or weak acids),
alpha iron is anodic to graphite and corrodes, leaving behind a
porous mass of graphite and iron sulfates. In brasses, zinc is
The illustration in figure 8A shows chromium as low as 5% at the FIG. 9 ASTM G46 pitting chart for density, size, and depth.
grain boundary carbide. This produces a chromium gradient
which increases to 18% which is the chromium content of the
alloy. The chromium-impoverished area of the sensitized layer
extends to a width where the chromium is at least 12% and cor-
rosion resistance is restored.
In many cases, a prediction of the susceptibility of austenitic
stainless steels to IGSCC can be obtained by a simple electrolytic
etch test (ASTM A262, Standard Practice for Detecting Sus-
ceptibility to Intergranular Attack in Austenitic Stainless Steels,
Practice A).
Pitting
Metallographic examination can be quite useful in determining
severity of pitting and also can be used to qualify materials for
use in specific environments. A procedure for metallographic
preparation of pitted samples is cited here, quoting ASTM G46,
Standard Guide for Examination and Evaluation of Pitting Cor-
rosion, Section 5.1.5: “Select and cut out a representative portion
of the metal surface containing pits and prepare a metallographic
specimen in accordance to the recommended procedures in
ASTM E3. Examine microscopically to determine whether there
is a relation between pits and inclusions or microstructure, or
whether the cavities are true pits or might have resulted from
metal dropout caused by intergranular corrosion, dealloying,
etc.” Evaluation of the metallographic samples of pitted materials
FIG. 10 ASTM G46 pitting chart showing variations in pit shapes. FIG. 12 SEM-EDS utilizing an X-ray dot map shows a reduction in
zinc concentration across a de-zincified (de-alloyed)
interface in an a-b brass alloy (5000).
differences over the examined area. Depending on computer capa-

bilities and software, some systems can map out the concentra-
tions of up to 16 elements simultaneously.
selectively leached from the matrix, leaving behind a porous CORROSION DUE TO PHASE CHANGES
mass of copper.7,8 Dealloying severely reduces the mechanical (r—SIGMA-PHASE FORMATION IN CR-NI-FE
properties causing complete failure of the affected components. AND FE-CR ALLOYS)
Metallographic examination can confirm visual indications of Exposure of certain alloys to elevated temperatures can produce
dealloying (fig. 11). deleterious embrittling phase changes within the alloy. These
The zinc-rich grain boundary phase (the dark areas appear- phase changes sometimes can lead to corrosive attack of the
ing in the grain boundaries at the bottom of fig. 11), can be seen to alloy. Corrosion can occur if the phase change alters the forma-
have dissolved in the top of the photomicrograph leaving grainy tion of protective oxide barriers on the surface. Examples of this
copper. Complete dealloying has occurred leaving nearly pure mechanism include sensitization of stainless steels (see fig. 8) and
copper after dissolving the zinc. Not only will the microstructure sigma-phase (r) formation. Sigma-phase formation occurs in
appear changed as one element is selectively leached from the nickel-chromium-iron and chromium-iron alloys containing a
matrix, but also changes in microchemistry can be observed. Deal- minimum of 16.5% Cr exposed to temperatures between 1100 F
loying can be observed optically or by analyzing the polished and 1700 F (593.3 C and 926.7 C) over long periods of time.9
specimen in an SEM (see fig. 12). Backscattered electron images Sigma phase is an iron chromium–rich phase that precipitates
will show contrast in regions of varying atomic number. Another along austenitic grain boundaries and delta ferrite9 high-
SEM method that graphically displays differences in microstruc- temperature grain boundary precipitates (fig. 13). Test results
tural elemental composition is the digital X-ray line scan or X-ray have shown that austenitic stainless steels exhibiting precipitated
dot map. The line scan can show variations in elemental composi- sigma phase undergo significant intergranular corrosion in boil-
tion along a line (fig. 12). The dot map shows compositional ing 65% HNO3 and in hot concentrated sulfuric acid solutions.
FIG. 13 Photomicrograph showing (sigma phase r) precipitate

FIG. 11 Photomicrograph showing selective dezincification of the (dark phase in austenitic grain boundaries) of a 310-type
continuous alloy phase in an a-b brass (200). stainless steel (500).
Sigma-phase formation also results in the loss of room tempera-

ture base metal ductility. FIG. 14 As-polished photomicrograph showing diffusion of
Sigma-phase formation can be assessed easily by metallo- Pb/Sb into steel (500).
graphic examination. One of the most definitive ways of deter-
mining the presence of sigma phase is by using a 45% aqueous
potassium hydroxide solution as an electrolytic etch. Sigma pre-
cipitates are revealed as distinct reddish-brown islands in the
austenitic matrix.
GENERAL CORROSION
In conditions in which general corrosion occurs, metallographic
samples can be used to verify the extent of metal loss through
microscopic measurements of sample thickness. The reduction
of thickness coupled with weight loss information provides a
checks and balances program into the analysis and reveals any
corrosion rate differences caused yt anisotropy. system densities, cracks can be revealed easily on X-ray film,
even when they are not visible on the surface.
LIQUID METAL EMBRITTLEMENT
Liquid metal embrittlement (LME) is not a common corrosion HIGH TEMPERATURE CORROSION—METAL
mechanism. Only a small number of lower melting point liquid DUSTING
metals can cause LME in any given alloy system. LME is an Metal dusting of heat-resistant alloys (Ni-Cr-Fe) occurs in carbo-
inter- and intragranular cracking mechanism produced by a liq- naceous atmospheres at temperatures above 800 F (426.7 C),
uid metal on the surface of a sensitive solid metal in the presence with very high activity in the temperature range of 1450 F to
of a tensile stress, either applied or residual. The mechanism 1550 F (787.7 to 843.3 C) and above 1700 F (926.6 C). In
occurs only above a threshold stress value and has an incubation metal dusting environments, a black “sooty” residue (graphite)
period. Table 3 shows a few of the solid and liquid systems exhib- usually covers the surface in most of the wasted areas. The resid-
iting LME. More alloys systems exhibiting LME are tabulated in ual metal is usually thinned and contains multiple rounded pits.
the ASM Metals Handbook.10 The original austenitic matrix transforms to a brittle ferromag-
Metallographic examination can assist in identifying LME. netic material and can be checked with a simple magnet. Metal-
Liquid metal penetration can be observed readily in mounted, lographic examination reveals an inward diffusion layer of gross
unpolished samples (fig. 14). carburization and grain “pop out.”
Etching for grain boundaries, however, can distinguish
between inter- and intragranular cracking. In addition, SEM/
SULFIDATION
EDS analysis, as discussed in the section covering dealloying, can
Metallographic examination of metals that have exhibited wast-
positively identify the presence of foreign metals at grain bound-
age because of sulfidation usually show a two-layer scale, the
aries within a matrix. Care should be taken when trying to iden-
upper layer (surface) being red, the lower being black and shiny.
tify mercury using SEM/EDS. High vacuum and electron beams
A few drops of aqueous hydrochloric acid on the deposit can
promote evaporation of mercury. Low kilovolt settings (less than
release a noticeable H2S odor and verify the presence of sulfides.
10 kV) should be used over wide areas to inhibit burning off
In addition, creation of a “sulfur print” can verify sulfidation
highly volatile mercury. In addition, mercury X-ray energy peaks
damage. A sulfur print is produced as follows: A metallographi-
(M) and sulfur (Ka) peaks are easily mistaken for each other.
cally mounted cross-section sample of thinned metal with sur-
Wet chemical spectroscopy is perhaps the best method for abso-
face scale is sanded to a 120 grit finish. Next, wash (immerse) a
lute identification of liquid metal species.
piece of black and white photographic paper in 2–3% sulfuric
Radiography can be used as a check for LME in large struc-
acid. Wipe away excess acid with a clean sponge. The sample is
tures. By virtue of the large difference in liquid and solid metal
placed on the photographic paper for a few seconds. The paper
is then stopped (acid neutralized) and fixed (using photographic
TABLE 3 Solid and Liquid Systems Exhibiting
fixer, sodium, or ammonium thiosulfate, which removes excess
unexposed silver halide and a shiny image) as in normal circum-
stances. An image of the sulfide distribution on the sample will
Solid Metal Liquid Metals Promoting Embrittlement
appear.9
Aluminum alloys Mercury, gallium, sodium, indium, tin
Brass (70/30-Cu/Zn) Mercury, lithium bismuth
OXIDATION
Iron or steel Lithium
Oxidation, perhaps the most visible of all corrosion mechanisms,
Nickel copper alloys Mercury, lead
is responsible for consuming a significant amount of mainte-
Stainless steels Zinc, cadmium
nance dollars. Metallography of oxidized metals can provide
Ni-Cr-Fe alloys Lead
information about the type of reaction. Types of oxidation
reactions (general, internal [subsurface], intergranular) can be dif- German name) forms at high temperatures (>565 C, 1100 F)
ferentiated by microexamination. Knowing the oxide scale thick- adjacent to the steel surface. Magnetite is an intermediate layer
ness and composition can provide data on time-temperature and hematite is the outer layer. Usually a layer of mixed hematite
exposure by knowing the oxidation rate laws of the material. In and magnetite is observed.
addition, knowledge of the mass ratio of oxide species in the scale An etchant containing 0.5% selenic acid (H2SeO4) and 4%
can determine exposure temperature. hydrochloric acid (HCl) in ethanol can produce a nice contrast
Metallographic examination of different phases within oxide between the oxide phases on polished samples after immersion
scales has proven difficult, but some techniques are available. For at room temperature.11 Selected dyes have also been used with
example, in steels, the scales formed at high temperature gener- various degrees of success. The reader is encouraged to read for
ally are composed of three layers: iron oxide (FeO), hematite further information on dying oxide scales.12
(Fe2O3), and magnetite (Fe3O4). The formation of these three
oxides can be described by the following reactions: THERMAL BARRIER COATINGS
Thermal barrier coatings (TBC)13 produced by Electron Beam
Fe þ 12O2 ¼ FeO Physical Vapor Deposition (EB-PVD) are primarily applied to
3Fe + 2O2 ¼ Fe3 O4 critical hot section turbine components. EB-PVD TBC for tur-
2Fe3 O4 þ 12O2 ¼ 3Fe2 O3 bine applications exhibit a complicated structure of porous
ceramic columns separated by voids that offers mechanical com-
The mineralogical names are used to emphasize their spe- pliance. Currently, there are no standard evaluation methods for
cific physical and chemical properties. Wüstite (from the evaluating EB-PVD TBC structure quantitatively. A proposed
FIG. 15 SEM-backscattered scanning electron images of the same sample taken at different positions with respect to the coating thickness.
13
Images (A) 150, (B) 96, (C) 64, and (D) 11 lm from the TBC/TGO interface (500). Source: Kelly et al.
metallographic method for preparing samples and evaluating References

(TBC) techniques quantitatively by measuring the structure is
1. R. J. Hussey, P. E. Beaubien, and D. Caplan, “Metallography of
discussed. TBC samples were produced and evaluated with the
Oxide Scales on Metals,” Metallography 6 (1973): 27–36.
proposed metallographic technique and digital image analysis
for columnar grain size and relative intercolumnar porosity. 2. G. VanderVoort, Metallography Principles and Prentice
Incorporation of the proposed evaluation technique will increase (New York: McGraw-Hill, 1984).
knowledge of the relationship between processing parameters 3. L. E. Samuels, Metallographic Polishing by Mechanical Methods
and material properties by incorporating a structural link. Appli- (Materials Park, OH: ASM International, 1982).
cation of this evaluation method will directly benefit areas of
quality control, microstructural model development, and 4. G. Petzow, Metallographic Etching (Materials Park, OH: ASM
reduced development time for process scaling.
Modern hot section turbine components are composite 5. ASM Metals Handbook, 9th ed., Vol. 9 (Materials Park, OH: ASM
systems composed of a metallic structural component, metallic International, 1985).
bond coat, thermally grown oxide (TGO) of the bond coat, and
6. Robert J. Radebaugh, Stainless Steel (Materials Park, OH: ASM
a ceramic TBC. The rationale for the layered system design is International, 1990).
to reduce thermal conductivity, increase adhesion of the
ceramic top layer, reduce sharp changes in thermal expansivity 7. H. J. Uhlig, Corrosion Handbook (New York: Wiley, 1948).
mismatch, improve oxidation resistance, and reduce the diffu-
sion rate of corrosive products to the structural members. TBC 8. L. L. Shreir, ed., Corrosion, Vol. 1 (London: Newnes-Butterworths,
1977).
produced by either EB-PVD, or thermal spray processes, have
been used to protect metallic components in the hot sections of 9. D. J. Gaertner, “Characterization of Sigmatized Austenitic
a turbine successfully for more than two decades. TBCs pro- Stainless Steels,” Materials Performance (January 1985): 18–24.
duced by the EB-PVD method typically are described as
10. W. R. Warke, ASM Handbook, 10th ed., Vol. 11 (Materials Park, OH:
columnar in nature and offer high lateral mechanical compli- ASM International, 2002).
ance because of the high aspect ratio voids between columns,
whereas similar coatings produced by thermal spray techniques 11. B. Chicco and T. Heijkoop, “Metallographic Reagent for the
offer lower thermal conductivity and lateral compliance Characterization of Oxide Scales on Iron and Steel,” Praktische
Metallographie 20 (1983): 321–326.
because of lamellar formation and discontinuous porosity. Per-
formance of either coating for a particular engineering applica- 12. B. Chicco, “Dye Adsorption—A New Technique for the Color
tion is inevitably determined by the coating microstructure Metallography of Oxide Scales on Steels,” Metallography 14
dictated by the coating method and process parameters. (1981): 319–328.
Understanding the relationships between process parameters 13. M. Kelly, J. Singh, J. Todd, S. Copley, and D. Wolfe, “Metallographic
for a coating system, coating microstructure, and performance Techniques for Evaluation of Thermal Barrier Coatings Produced
is essential. by Electron Beam Physical Vapor Deposition,” Materials
Characterization 59, no. 7 (July 2008): 863–870.
109
Chapter 8 | Electrochemical Tests
John R. Scully,1 Carol F. Glover,1 and Raymond J. Santucci2
Introduction where:
n ¼ number of electrons transferred, equivalents/mol, and
Several textbooks and symposia proceedings cover the applica- F ¼ Faraday’s constant, 96,484.6 coulombs/equivalent.
tion of electrochemical methods in corrosion testing.1–16 This Monitoring this current provides the means of assessing the
chapter highlights many of the commonly used laboratory meth- kinetics of the corrosion process, not just the thermodynamic
ods after presenting a brief review of thermodynamics and tendencies for corrosion nor merely the mass of metal loss regis-
kinetic aspects of electrochemical reactions that describe corro- tered after the test. There are three typical half-cell reactions by
sion processes. Techniques discussed include Tafel extrapolation, which a metal (M) may be oxidized in water:
polarization resistance, electrochemical impedance spectroscopy
(EIS), electrochemical noise (EN) resistance, use of rotating MðsÞ ¼ Mnþ ðaqÞ þ ne ðsÞProduction of metal cations, (2)
disks, and cylinders to study aspects of corrosion affected by
solution flow, polarization methods for assessing susceptibility MðsÞ þ nH2 O ¼ MðOHÞn þ nH þ ðaqÞ þ ne ðsÞ
to localized corrosion, scratch repassivation, potential-step Oxide or hydroxide formation, or ð3Þ
repassivation, EN applied to pitting, potentiodynamic repassi-
MðsÞ þ nH2 O ¼ MOH ðaqÞ þ 2nHþ ðaqÞ
vation techniques for assessing sensitization, the barnacle elec-
trode and permeation methods for hydrogen concentration þ ne ðsÞ Anion production: (4)
analysis, and methods for evaluating anodized layers and coat-
ings on metals. In all cases, metal atoms in the solid (s) metallic state (in
the electronic conductor) are converted to an oxidized state.
ELECTRODE REACTION THERMODYNAMICS These species remain either on the metallic surface or are ejected
AND KINETICS IN CORROSION into the aqueous (aq) solution (the ionic conducting phase).
Metallic corrosion is usually an electrochemical process. Electro- Typical cathodic half-cell reactions in aqueous media involve the
chemical processes require anodes and cathodes in electrical con- reduction of oxygen, protons, and water at the interface between
tact, as well as an ionic conduction path through an electrolyte. the metallic and ionic conducting phases. This process involves
The electron flow between the anodic and cathodic areas quanti- consumption of electrons liberated during oxidation:
fies the rates of the oxidation and reduction reactions. When
anodes are physically separated from cathodes, the current can O2 þ 2H2 O þ 4e ¼ 4OH in aerated neutral or alkaline media,
be readily measured by replacing direct electrical contact with a (5)
zero-resistance ammeter (ZRA). The conversion of the reaction
O2 þ 4Hþ þ 4e ¼ 2H2 O in aerated acid media, (6)
rate per unit area from units of mol/cm2-s to electrical current
density, i (A/cm2) is accomplished with Faraday’s constant, F, 2Hþ þ 2e ¼ H2 in acid media, and (7)
and knowledge of the number of electrons transferred to com-
2H2 O þ 2e ¼ H2 þ 2OH in neutral or alkaline media: (8)
plete the electrochemical reaction a single time, n, as follows:
i ¼ nFJ, (1) The Nernst equation describes the reversible electrode or

equilibrium potential, Eredox, associated with the thermodynamic
tendency for an electrochemical half-cell reaction to occur spon-
1
University of Virginia, 395 McCormick Rd., Charlottesville, VA 22903-2442, USA taneously. At potentials more positive than the equilibrium
J. R. S. http://orcid.org/0000-0001-5353-766X, C. F. G. http://orcid.org/
potential associated with a particular electrochemical half-cell
0000-0002-9220-622X
2
U.S. Naval Academy, 121 Blake Rd., Annapolis, MD 21402, USA http://
reaction, oxidation proceeds spontaneously, whereas at poten-
orcid.org/0000-0002-9676-6312 tials more negative, reduction occurs. The forms of the Nernst
DOI: 10.1520/MNL202NDSUP20190036
equation for the oxidation reactions given in equations (2) and density measured during a polarization experiment, iapp, involving
(7) are, respectively, a single-charge transfer-controlled oxidation and single-charge
transfer-controlled reduction reaction follows:
Eredox ¼ Eo þ ð2:303RT=nFÞlog ðMnþ Þ, and (9)

/a FðE Ecorr Þ /c FðE Ecorr Þ
iapp ¼ icorr exp exp :
Eredox ¼ Eo 2:303RTpH=F, (10) RT RT
(14)
where:
R ¼ the ideal gas constant, cal/mol-K; The corrosion potential, Ecorr, is a kinetically and thermody-
T ¼ temperature, K namically determined “mixed” potential given by the intercep-
n ¼ the number of electrons to complete the half-cell reaction a tion of the lines describing the total anodic and cathodic reaction
single time; and rates. At Ecorr, iox ¼ ired and icorr is described by the magnitude of
E0 ¼ the specific standard half-cell potential for the reaction cited iox at Ecorr as shown in figure 1. Either reaction rate may become
at unity activity for dissolved species and 1 atmosphere mass transport limited under certain circumstances, in which
fugacity for gaseous substances at 25 C. case equations (12)–(14) do not apply.
The standard half-cell potential for the reaction
2Hþ þ 2e ¼ H2 is defined as 0.0 V versus the normal hydrogen Obtaining Corrosion Rates from Electrochemical Kinetic Data
electrode at 25 C. According to mixed-potential theory, any overall electrochemical
Concerning corrosion in aqueous media, metal oxidation reaction can be algebraically divided into half-cell oxidation and
reactions (see equations (2)–(4)) with Nernst or redox potentials reduction reactions, and there can be no net electrical charge
more negative than the Nernst or redox potentials associated accumulation.17 For open-circuit corrosion in the absence of an
with typical cathodic reactions given by equations (5)–(8) will applied potential, the oxidation of the metal and the reduction of
occur spontaneously.4–5 The reaction rate for any single some species in solution occur simultaneously at the metal-
reduction-oxidation process is a function of overpotential E-Eredox, electrolyte interface, as described by equation (14). Under these
where E is the applied potential. For a single charge transfer– circumstances, the net measurable current density, iapp, is zero. A
controlled redox reaction, inet is described as follows: finite rate of corrosion defined by icorr occurs at anodic sites on
the metal surface, as indicated in figure 1. When the corrosion
inet ¼ iex fexp ½aa FðE Eredox Þ=RT exp ½ac FðE Eredox Þ=RTg,
(11)
FIG. 1 Application of mixed potential theory showing the
where the exchange current density, iex, describes the nonzero electrochemical potential-current relationship for a
rate at which the forward (oxidation) and reverse (reduction) corroding system of a single-charge transfer-controlled
reactions occur equally at Eredox. Because Eredox represents an cathodic reaction and single-charge transfer-controlled
equilibrium condition, the forward and reverse rates of the reac- anodic electrochemical reaction. bc and ba are Tafel slopes.
tion must be equal; a is known as the symmetry factor (such that
ac ¼ l aa) in the case of single-step electron transfer processes
representing a reduction oxidation process, and a represents a
transfer coefficient for a multistep reaction process (in this case,
ac þ aa = 1). The factor 2.303 RT/aaF is equal to the anodic Tafel
slope, ba. Similarly, the factor 2.303 RT/acF is equal to the
cathodic Tafel slope, bC. If E-Eredox is a large positive voltage (i.e.,
such that the term [aaF(E-Eredox)/RT] is greater than about 2.303
or (E-Eredox)/ba >1), then the following simplification known as
the Tafel approximation applies for a charge transfer–controlled
process:
iox ¼ iex exp ½aa FðE Eredox Þ=RT: (12)
Similarly, when E-Eredox is a large negative number (i.e.,

such that (E-Eredox)/bc > 1), another analogous simplification is
applied in the case of a single electrode reaction:
ired ¼ iex exp ½ac FðE Eredox Þ=RT: (13)
Typical corrosion processes occurring under freely corroding

conditions involve at least one cathodic and one anodic reaction.
The thermodynamics discussed earlier dictate the circumstances
in which these reactions will proceed spontaneously. The current
ELECTROCHEMICAL TESTS 111
potential, Ecorr, is located at a potential that is distinctly different The constant K1 ¼ 3.27 10-3 when iox is expressed as
from the reversible electrode potentials (Eredox) of either the cor- lA/cm2. K1 has units of mm-g/lA-cm-y when CR is desired
roding metal or the species in solution that is cathodically in mm/yr. ASTM G102, Standard Practice for Calculation of
reduced, the reaction favors reduction and the oxidation of the Corrosion Rates and Related Information from Electrochemical
cathodic reactants or the reduction of any metallic ions in solu- Measurements, gives other values for this constant when CR is
tion becomes extremely small. Because the magnitude of iox at expressed in other units. Expressions are also available to calculate
Ecorr is the quantity of interest in the corroding system, this mass loss rate per unit area from knowledge of electrochemical
parameter must be determined independently of the oxidation corrosion rate. For instance,
reaction rates of other adsorbed or dissolved reactants.
The information obtained in a polarization experiment is MR ¼ K2 iox ðE:W:Þ, (17)
iapp as a function of the potential, E, as shown by the thick solid where:
line in figure 1, where iapp ¼ iox - ired. To obtain iapp as a function
K2 ¼ 8.954 103 g-cm2/ lA m2 d when MR is expressed as
of E, the applied potential between the reference electrode and
g/m2 d.
working electrode is controlled and scanned at constant rate
For alloys, the equivalent weight E.W. should be calculated
(potentiodynamic), instantaneously increased a fixed amount
as outlined in ASTM G102:
(potentiostatic), or stepped at various times (potentiostaircase).18
Iapp is measured and normalized with respect to the surface area, 1
E:W: ¼ X , (18)
A (i.e., iapp ¼ Iapp/A). Conversely, iapp can be supplied between ni fi
the working and counterelectrodes under galvanostatic or galva- A:W:i
nostaircase control, and the resulting potential between the
working and reference electrodes is monitored. Several ASTM where:
standards discuss methods for performing these experiments, fi ¼ the mass fraction of the ith component of the alloy (-);
including ASTM G5, Standard Reference Test Method for Making A.W.i ¼ the atomic weight of the ith component element, g/mol;
Potentiodynamic Anodic Polarization Measurements, and ASTM Ni ¼ the number of electrons transferred or lost when oxidizing
G59, Standard Test Method for Conducting Potentiodynamic the ith component element under the conditions of the cor-
Polarization Resistance Measurements. Several approaches are rosion process (equivalents/mol); and
available to determine icorr from such experimental information. i ¼ the number of component elements in the alloy.
These methods are discussed in the following section. Usually, n is equal to the stable valence of the elements oxi-
dized, or must be determined from either a Pourbaix (potential-
pH) diagram or experimentally from an analysis of the ions in
Conversion of Corrosion Rates to the corrosive solution. This expression assumes that all compo-
Mass Loss and Penetration Rate nent elements oxidize when the alloy corrodes and that they are
all oxidizing at essentially a uniform rate. In some situations,
Determination of Iox at open-circuit potential (OCP) or other these assumptions are not valid and the calculated corrosion rate
potential of interest, where Iox ¼ iox A, over a known period of will be in error. For example, if an alloy is composed of two or
time leads to direct determination of the mass loss: more phases and one phase preferentially oxidizes, the calcula-
tion must take this into consideration.
Iox tðA:W:Þ
M¼ , (15)
nF ELECTROCHEMICAL METHODS FOR THE STUDY OF
where: UNIFORM CORROSION: POLARIZATION METHODS
M ¼ the mass loss, g; One method for examining the corrosion behavior of a metal is
Ioxt ¼ the product of current and time, coulombs; and to determine the E-iapp relationship by conducting a polarization
A.W. ¼ the atomic weight of the electroactive species, g/mol. experiment. The following E-iapp relationship is often experimen-
This relation is known as Faraday’s first law. Rearrangement tally observed between applied current and potential. The
of equation (15) leads to a straightforward determination of the expression is applicable to charge transfer–controlled corrosion
penetration rate (applicable only when iox (lA/cm2) is uniformly processes, regardless of the exact number of charge transfer–con-
distributed over the entire wetted surface area, or where the trolled reactions or reaction steps. It provides the basis for the
localized actively corroding area, A, is known), as follows: electrochemical polarization technique.1,2,17,19

K1 iox ðE:W:Þ 2:303ðE Ecorr Þ
CR ¼ , (16) iapp ¼icorr exp
q ba

2:303ðE Ecorr Þ @E
where: exp þC , ð19Þ
bc @t
CR ¼ the corrosion rate, in mm/year;
E.W. ¼ the equivalent weight (considered dimensionless in this where:
calculation); and C ¼ the interfacial capacitance associated with the electrochemi-
P ¼ the metal or alloy density, g/cm3. cal double layer;
Ba and bc ¼ the anodic and cathodic Tafel slopes (@E/-@log(iapp)) electrode geometry. The error contributes to the measured over-
given by the slopes of the polarization curves in the anodic and potential napp:
cathodic Tafel regimes, respectively; and
g app ¼ g true interfacial þ iapp Rs , (21)
@E/@t ¼ the time rate of change in applied potential, or voltage
scan rate. where:
The second term of the expression (C @E/@t) approaches 0 Rs (X-cm2) ¼ the uncompensated solution resistance between
at low-voltage scan rates dE/dt. Steady state is desirable, because the working electrode and the position at which the reference
the goal is to obtain icorr at Ecorr. Note that iapp becomes approxi- electrode senses the potential in solution (at the tip of the
mately equal to either iox or ired at large g, where g ¼ (E-Ecorr). Luggin-Haber capillary).
At very large anodic or cathodic overpotentials, equation (19) Thus, napp > gtrue at high anodic current densities, high Rs,
can be rearranged in the form of the Tafel expression.1–3,5,7,18,19 or high cathodic applied current density. Eapp > Etrue and the
Tafel slope desired from a fit of equations (19) and (20) to E ver-
iapp
ga ¼ ba log , sus iapp data cannot be obtained from E-logi data. When the
icorr
(20) dominant term in equation (21) is the second term, a linear rela-
iapp
gc ¼ bc log , tionship between g (g ¼ gapp) and iapp is obtained instead of the
icorr
semi-logarithmic relationship discussed earlier. The true scan
where: rate in the potentiodynamic technique also may be altered,
ga and gc ¼ the anodic and cathodic overpotentials, respectively. because the applied potential (that contains the ohmic compo-
Equation (20) is strictly valid only for a single anodic or nent), not the true overpotential, is controlled during the scan.
cathodic reaction, although approximately linear behavior can be Several excellent reviews are available on the subject of the volt-
observed despite several reactions. The linear portion of the solid age error introduced from solution resistance.21–24
line describing E-iapp in figure 1 above Ecorr describes a single
anodic reaction that can be described by equation (20). Similarly, Complications Involving Concentration Polarization Effects
the linear portion of the solid line describing E-iapp in figure 1 The Tafel relationship established through equations (19) and
below Ecorr describes a single cathodic reaction that can be (20) is valid for pure activation control, or charge transfer con-
described by equation (20). trol. An additional consideration involves the concept of concen-
tration polarization. In this case, the reaction rate is fast enough
Tafel Extrapolation to Determine Corrosion Rate
that the reacting species is depleted (reduction reaction) or con-
In cases in which equation (20) is valid, g can be plotted versus
centrated (oxidation) at the reacting surface. Diffusion through
log(iapp) over a sufficient range to obtain a linear relationship
the electrolyte becomes the kinetic limitation which controls the
between the logarithm of current density and potential;1,5,7,20 icorr
reaction rate. The reaction becomes completely diffusion con-
can be determined from extrapolation of iapp from either the
trolled at the limiting current density, iL. The deviation from
anodic or the cathodic Tafel region to the OCP (zero overpoten-
activation control in the case of a cathodic reaction can result in
tial). Figure 1 illustrates this method. The method is potentially
an additional overpotential known as a mass transport over-
damaging to the corroding metal, because a large overpotential
potential, gconc. This overpotential is described as follows:4,5
must be applied. This is true for polarization in either direction

but particularly so in the case of anodic polarization, in which the 2:303RT iapp
g conc ¼ log 1 , (22)
surface is changing because of corrosion and or passivation of the nF iL
metal. No ASTM standard currently exists for this method.
where:
Complications with the Polarization Method Involving iL ¼ the mass transfer limiting current density defined by Fick’s
Solution Resistance first law at steady state.
Tafel extrapolation, as well as other polarization techniques, can As iapp approaches iL, the concentration overpotential, gconc,
be complicated by several factors. One such factor, ohmic resis- becomes very large. The cathodic reaction may be under mixed
tance, arises from the resistivity of the solution, cell geometry, charged transfer-mass transport or mass transport control for
location of the reference electrode, and magnitude of applied many corrosion situations, particularly if the cathodic reaction is
current.2,6 Ohmic resistance can contribute a voltage error to the oxygen reduction.5 The cathodic polarization behavior associated
measured potential. This error is summed algebraically with the with “mixed” charge transfer–mass transfer control can be
true interfacial overpotential across the electrochemical interface described mathematically by the algebraic combination of equa-
(the potential usually sought in electrochemical measurements) tions (20) and (22). Tafel extrapolation of cathodic data becomes
measured with respect to a reference electrode. Placement of the difficult under these conditions because the Tafel region may not
reference electrode near the working electrode with a Luggin- be extensive.
Haber capillary is used to minimize the solution resistance error, For a completely mass transport– limited corrosion process,
which can be estimated from the product of the applied current the concentration of the cathodic reacting species Cb approaches
density, the solution resistivity, and the perpendicular distance zero at the electrode interface and icorr – iL (fig. 2).2 The diffu-
from the Luggin probe to the specimen surface in a planar sional boundary layer thickness, d, is decreased by increasing
Equation (19) can be linearized when g/b < 0.1. This simplified
FIG. 2 Application of mixed potential theory showing the relationship has the following form if the second term describing
electrochemical potential-current relationship for a the capacitive current, C(dE/dt), is negligible:
corroding system consisting of a mass transport–controlled
cathodic reaction and a charge transfer–controlled anodic Diapp ba bc
icorr ¼ , (25)
reaction. As the fluid velocity increases from 1 to 4, the 2:3DE ðba þ bc Þ
corrosion rate increases from A to D.
rearranging

1 ba bc B
icorr ¼ ¼ , (26)
2:3Rp ðba þ bc Þ Rp
where:
Rp ¼ the polarization resistance (X-cm2) given by dE/di at t ¼ 1,
AE ¼ 0, and
B ¼ a constant given by the constant terms shown in equation (26).
As shown for AISI 430 stainless steel in sulfuric acid
(H2SO4), iapp is often approximately linear with potential
within 6 5-10 mV of Ecorr (fig. 3). The slope of this plot, DE/Di,
when determined at Ecorr, as shown in figure 3, defines the polari-
zation resistance, which is inversely proportional to corrosion
rate.27,28 The surface area of the working electrode must be known.
Knowledge of Rp, ba, and bc permits direct determination of the
corrosion rate at any instant in time using equation (26).25–29
ASTM standards G59 and ASTM G96, Standard Guide for
solution stirring or rotation rate, X (rad/s), in the case of a rotat- Online Monitoring of Corrosion in Plant Equipment (Electrical
ing cylinder or disk electrode.1 The limiting current density iL is and Electrochemical Methods) describe standard procedures for
a linear function of concentration gradient.15 The concentration conducting polarization resistance measurements.1
gradient (Cb/d) increases as a function of X0.5 or X0.7 for the
rotating disk and cylinder, respectively.2,15 For a mass transport
controlled cathodic reaction, icorr is increased with flow as shown FIG. 3 ASTM G59 polarization curves used for polarization
in figure 2. The governing equation for the rotating cylinder elec- resistance determinations based on the results from eight
trode is15 independent laboratories for AISI-type 430 stainless steel
in 1N H2SO4. Curve 1 is the mean result, with Curves 2 and
iL ¼ 0:079nFCb D0:64 v0:34 X0:7 r0:4 , (23) 3 showing the 95% confidence limits from the laboratory
and for the rotating disk electrode is 2,15 round robin.
iL ¼ 0:621nFCb D0:67 v0:167 X0:5 , (24)
where:
Cb ¼ the reacting species concentration in the bulk solution,
moles/cm3;
D ¼ the diffusion coefficient for the reacting species, cm2/s;
v ¼ the kinematic viscosity of the solution, cm2/s; and
r ¼ cylinder or disk radius, cm.
Corrosion engineers often favor the rotating cylinder to
simulate flow in turbulent piping systems, because it is readily
obtained.15 In contrast, the rotating disk electrode operates in
the laminar flow regime, even at high rotation rates, and does
not accurately represent many corrosion situations.15 No ASTM
methods currently exist to examine mass transport controlled
corrosion.
Polarization Resistance Methods

Stern and Geary simplified the kinetic expression describing
charge transfer–controlled reaction kinetics, as in equation (19),
for the case of small overpotentials with respect to Ecorr.25,26
Other techniques rely on exploiting nonlinearity at larger extrapolating the results at several slow scan rates to zero scan
overpotentials; however, this invalidates the approximation given rate. Alternatively, one may take two or more current density
by equation (25).30 The Oldham-Mansfeld method calculates icorr measurements from potentiostatic data after long time periods
from nonlinear E versus iapp data obtained usually within 6 30 near Ecorr to minimize fast scan rate effects. These complications
mV of Ecorr, using tangent slopes and intercepts to calculate cor- and others have been reviewed elsewhere.40
rosion rate without high overpotential determination of ba and Many treatments of this subject have used an electrical
bc.31 Computerized curve fitting can exploit nonlinearity to calcu- equivalent circuit model to simulate the corroding metal-
late ba, and bc from low overpotential data, avoiding the destruc- electrolyte interface.*,40,41 The simplest form of such a model is
tive nature of large overpotentials.32 The Mansfeld technique shown in figure 4. The three parameters discussed earlier (i.e., Rp,
substitutes equation (26) into equation (19), eliminating icorr.32 Rs, and C) that approximate a corroding electrochemical inter-
ba and bc are determined from the best fit of the resulting face are shown. The algebraic sum of Rs and Rp is measured
expression containing ba and bc as unknowns to a nonlinear plot when a direct current (DC) measurement is performed. The
of g versus iapp data are obtained within 630 mV of Ecorr. Rp is impedance associated with a capacitor approaches infinity as the
determined from the linear slope of E versus iapp within 65 mV voltage scan rate approaches zero, and parallel circuit elements
of Ecorr, and icorr is subsequently determined from equation (25) are always dominated by the element with the smallest imped-
using Rp, ba, and bc. ance. Therefore, the sum of Rs and Rp is measured and the true
corrosion rate will be underestimated when Rs is appreciable.
Conversely, any experiment conducted at a fast voltage scan rate
Complications with Polarization Resistance Measurements
causes the algebraic sum of the ohmic resistance and the resul-
Complications related to the polarization resistance method and
tant impedance of the parallel resistive-capacitive network to be
possible remedies have been reported in the literature.30–36 Three
measured. This value will be lower than the sum of Rp and Rs
of the most common errors involve (1) invalidation of the results
determined at an infinitely slow scan rate, as current leaks
through oxidation or reduction of some other electroactive spe-
through the parallel capacitive element at a higher scan rate
cies besides the corroding metal in question; (2) a change in the
because of its low impedance at high frequency. This usually will
OCP or corrosion potential during the time taken to perform the
result in an overestimation of the true corrosion rate. These com-
measurement; and (3) use of a large g, invalidating the assump-
plications can be overcome by using the electrochemical imped-
tion of a linear relationship between iapp and E required by equa-
ance method.
tions (25) and (26).
Another source of error involves cases in which both the
anodic and cathodic reactions are not charge transfer–controlled
processes, as required for the derivation of equation (25). Modifi- FIG. 4 Electrical equivalent circuit model simulating a simple
cations to equation (25) exist for cases in which pure activation corroding metal/electrolyte interface. See also figure 5.
control is not maintained, such as in the case of partial diffusion Rs is the solution resistance. Rp is the polarization
control or passivation.37 Other researchers have attempted to cal- resistance. C is the double-layer capacitance.
ibrate the polarization resistance method using gravimetrically
determined mass loss.38 In fact, polarization resistance data for a
number of alloy-electrolyte systems have been compared with
the observed average corrosion currents determined from mass
loss via Faraday’s law.29 A linear correspondence was obtained
over six orders of magnitude in corrosion rates.
Two other frequently encountered complications are the
need to correct polarization data for errors that arise from the
contribution of solution resistance, Rs, and the addition of capac-
itive current, C dE/dt, which occurs with increasing scan rate.16
Capacitive current gives rise to hysteresis in current-potential
plots.39 Solution resistance contributes to a voltage error, as dis-
cussed earlier, as well as a scan rate error. Because the applied
potential is increased by an ohmic voltage component, an appar-
ent value of polarization resistance Rp’ is obtained, which overes-
timates Rp by an amount equal to Rs. Consequently, the *This review focuses on corroding systems with different cathodic and anodic
half-cell reactions. The concept of polarization resistance, however, applies
corrosion rate is underestimated. Hysteresis in the current
equally well to reduction-oxidation systems involving a single half-cell reaction.
density-applied potential plot occurs for combinations of a high Here, the exchange current density, io, may be calculated from the polarization
voltage scan rate and large interfacial capacitances as well as resistance, where R is the ideal gas constant, F is Faraday’s constant, T is the tem-
large polarization resistances. Attempting to determine Rp at too perature, and aa and ac are the anodic and cathodic multistep electron transfer
fast of a scan rate underestimates its true value, leading to an coefficients, respectively, for the reduction-oxidation process, as follows:

overestimation of corrosion rate. This error can be minimized by DE RT
Rn ohm cm2 ¼ ¼ :
Di ðEErev Þ!0 io F ð a a þ a c Þ
determining the polarization resistance at a slow scan rate or by
Electrochemical Impedance Methods Figure 4 illustrates the equivalent electrical circuit model for
One approach for determining the polarization resistance of a an actively corroding metal. The following expression describes
metal involves the electrochemical impedance (sometimes the impedance for that system:
known as alternating current (AC) impedance) method.2,39–43
ASTM G106, Standard Practice for Verification of Algorithm ZðxÞ ¼ Rs þ Rp =ð1 þ x2 R2p C 2 Þ jxCR2p =ð1 þ x2 R2 C 2 Þ, (29)
and Equipment for Electrochemical Impedance Measurements,
contains an appendix reviewing the technique. In this tech- where:
nique, typically a small-amplitude sinusoidal potential pertur- x ¼ the frequency of the applied signal where x ¼ 2pf, rad/s;
bation is applied to the working electrode at a number of f ¼ the frequency of the applied signal, Hz (cycles/sec);
discrete frequencies, x. At each one of these frequencies, the Rs ¼ the solution resistance; and
resulting current waveform will exhibit a sinusoidal response C ¼ the interfacial capacitance, F/cm2.
that is out of phase with the applied potential signal by a certain The Bode magnitude and phase information of figure 5 and
amount (U) and has a current amplitude that is inversely equation (29) show that at very low frequencies,
proportional to the impedance of the interface. The electro-
chemical impedance, Z(x), is the frequency-dependent propor- Zx!0 ðxÞ ¼ RS þ Rp , (30)
tionality factor that acts as a transfer function by establishing a
relationship between the excitation voltage signal and the cur- while at very high frequencies,
rent response of the system:
Zx!1 ðxÞ ¼ RS : (31)
ZðxÞ ¼ VðxÞ=iðxÞ, (27)
Determination of Rp is attainable in media of high resistivity
where: because Rp can be mathematically separated from Rs by taking
V ¼ the time-varying voltage across the circuit, V ¼ V0sin(xt); the difference between Z(x) obtained at low and high x
i ¼ the time-varying current density through the circuit, i ¼ i0 (Rp ¼ Zx!0 - Zx!1). Determination of the corrosion rate using
sin(xt þ U); equation (25) also requires knowledge of ba, bc, and electrode
Z(x) ¼ the impedance, X-cm2; and area, A, which are not obtained in the impedance experiment.44
t ¼ time, s.
Z(x) is a complex-valued vector quantity with real and FIG. 5 Bode-phase angle and magnitude plots demonstrating
imaginary components whose values are frequency-dependent the frequency dependence of the electrochemical
impedance for the circuit model shown in figure 4.
ZðxÞ ¼ Z 0 ðxÞ þ jZ 00 ðxÞ, (28)
where:
Z0 (x) ¼ the real component of impedance, Z0 (x) ¼ jZ(x)jcos(U);
Z00 (x) ¼ the imaginary component of impedance, Z00 (x) ¼ jZ(x)j
sin(U);
j2 ¼ the square of the imaginary number, -1; and
jZ(x)j ¼ the impedance magnitude, where jZ(x)j ¼ (Z0 (x)2 þ
Z00 (x)2)1/2.
The electrochemical impedance is a fundamental character-
istic of the electrochemical system it describes. A knowledge of
the frequency dependence of impedance for a corroding system
enables a determination of an appropriate equivalent electrical
circuit describing that system. Table 1 shows the transfer func-
tions for resistors, capacitors, and inductors.
TABLE 1 Linear Circuit Elements Commonly Used in Electro-

chemical Impedance
Circuit Element Impedance
Resistor Z(x) ¼ R
Capacitor Z(x) ¼ j/xC
Inductor Z(x) ¼ jxL
The minimum applied frequency required to obtain Rs þ Rp can problem in the case of diffusion controlled electrochemical reac-
be approximated by tions is that extremely low frequency (or scan rates) are required
to complete the measurement of Rf. In the case in which Rp is
1
fmin < fbp ¼ : (32) dominated by contributions from mass transport such that equa-
2pCðRs þ Rp Þ tion (33) applies, the Stern approximation of equations (25) and
(26) must be modified to account for a Tafel slope for either the
where:
anodic or cathodic reaction under diffusion controlled condi-
fbp ¼ the lower breakpoint frequency approximated by the point
tions (i.e., ba or bC ¼ 1). In fact, equation (19) becomes invalid.
on the log j Z(x) j versus log f plot where the low-
Similarly, a frequency above fmax must be applied to
frequency plateau dominated by the Rs þ Rp and the slope
obtain Rs.
1 region dominated by the capacitance produce equal
values of Z(x), Hz; and 1
fmin ¼ the minimum required test frequency required according f > fmax ¼ , (35)
2pCRs
to equation (32), Hz.
Because the magnitudes of C, Rs, and Rp are not known where:
explicitly a priori, prudence dictates that fmin be selected as fmax ¼ the frequency required such that Z(x) is dominated
0.1–0.5 of the estimated fbp. Thus, large values of C, Rs, or Rp dic- by Rs.
tate that a low fmin is required to accurately obtain Rp þ Rs at Typically, fapp must be in the kHz range to determine Rs.
Z(x)!0. One mHz is typically chosen as a reasonable initial These issues equally plague time as well as frequency domain
choice of fmin, but it is obvious from equation (32) that either a methods for obtaining Rp, because in the time domain measure-
lower frequency may be required or a higher frequency permit- ment, the triangle waveform is simply the Fourier synthesis of a
ted, depending on the circumstances. series of sinusoidal signal functions.
Either of the anodic or cathodic half-cell reaction can The capacitance is also determined from the impedance
become mass transport limited and restrict the rate of corrosion technique. In many corroding systems, an interfacial capacitance,
at Ecorr. The presence of diffusion-controlled corrosion processes associated with the electrical double layer, scales linearly with the
does not invalidate the EIS method, but this does require extra true electrochemical surface area. An electrochemically based
precaution and a modification to the circuit model shown in estimate of the surface area may be obtained if the area-specific
figure 4. In this case, the finite diffusional impedance is added in capacitance is known or determined from the slope of a plot of C
series with the usual charge transfer parallel resistance shown in versus surface area.44
figure 4. The transfer function for the frequency-dependent finite A common issue in the use of impedance-derived capaci-
diffusional impedance, ZD(x), has been described:45 tance concerns the use of constant phase elements (CPE). The
" pffiffiffiffiffiffiffiffiffiffi# impedance associated with a CPE has been given by the follow-
tanh ðjxsÞ ing expression:46
ZD ðxÞ ¼ RD pffiffiffiffiffiffiffiffiffiffi , (33)
ðjxsÞ
1
ZCPE ðxÞ ¼ n : (36)
where: Yo ðjxÞ
s ¼ 1eff2/D,
Y0 and n are usually assumed to be frequency-independent
1eff ¼ the actual finite diffusion length, and
parameters. The units for Y0 are sn/ohm, and those for capaci-
D ¼ the diffusivity of the diffusing species that limits the interfa-
tance (C) are s/ohm. Hence, in the case of an ideal capacitor or
cial reaction.
resistor, n ¼ 1 or 0, respectively, and either the magnitude of Y0
The value of ZD(x) approaches the real component of diffu-
equals the magnitude of C with the dimensions s/ohms or
sional resistance, RD, as x!0. The frequency required to obtain
1/Y0 ¼ R (ohms). In the case of n ¼ 0.5, an infinite diffusional
RD depends on the value of s. The larger the value of s, such as
impedance best describes the constant phase element. At issue is
when leff is large or D is small, the lower the frequency required.
the task of extracting physically meaningful parameters conveyed
Rp, defined as [@E/@Eiapp] as x!0, is the sum of the charge
by the capacitance in the case of impedance data that is best rep-
transfer–controlled (Rct) and diffusion-controlled (RD) contribu-
resented in an electrical circuit model by a constant phase ele-
tions to the polarization resistance assuming that RD þ Rct >>RS,
ment. Examples of such parameters extracted from ideal
as follows:
interfacial capacitance include electrode areas in the case of a
Rp ¼ Rct þ RD : (34) double-layer capacitance, surface coverage in the case of an
adsorption pseudocapacitance, and dielectric constant or dielec-
A very low frequency or scan rate may be required to obtain tric layer thickness in the case of a coating or oxide with dielec-
Rp defined by equation (34) under circumstances in which reac- tric properties. Other parameters may be extracted from
tions are mass transport limited, as indicated by equation (32). capacitance associated with solid-state impedance experiments,
Here, a 1eff of 0.1 cm and D ¼ 10-5 cm2/sec requires that a fre- but these are beyond the scope of the present paper. In the case
quency below 0.1 mHz be implemented to obtain Rp from jZ(x)j in which n ¼ 0.8–0.99, the CPE is often treated as a nonideal
at the zero frequency limit. Hence, a common experimental capacitance value, and attempts are made to extract physically
meaningful parameters from the CPE data. One equation pro- involves harmonic impedance spectroscopy in which the har-
posed to convert Y0 into C follows:47 monic currents are converted to harmonic impedance values at
various frequencies through knowledge of the magnitude of the
C ¼ Yo ðx00max Þn1 , (37) AC perturbation.
In the EFM method, an AC voltage perturbation is applied
where:
at two frequencies, x1 and x2. As an example, the voltage pertur-
x00 max ¼ the frequency at which the imaginary component of
bation could be given as follows:
impedance, Z00 , is maximized.
This frequency is independent of n. In an earlier approach, g ¼ V0 ½sin ðx1 tÞ þ sin ðx2 tÞ, (38)
the use of C ¼ Y0 (x)n1V sin(np/2) was suggested as a method
for extracting capacitance, C, from Y0, where x was taken as the where:
frequency at which the phase angle was maximized.48 This g ¼ E-Ecorr, and
method has the disadvantage that the exact value of x associated V0 ¼ the magnitude of the voltage amplitude applied.
with the phase angle maximum changes with the value of n. Harmonic current responses occur at x1, 2x1, and 3x1 as
well as at x1, 2x2, and 3x2. Additionally, a current response can
FREQUENCY MODULATION METHODS be seen at various intermodulation frequencies, such as
2x1 6 x2 and 2x2 6 x1. Consider the application of this method
Both harmonic and electrochemical frequency modulation
to a charge transfer–controlled corrosion process with an E-I
(EFM) methods take advantage of nonlinearity in the E-I
response that behaves according to equation (19). Under the
response of electrochemical interfaces to determine corrosion
assumption that x2 > x1 and ba < bC, the corrosion current den-
rate.49–52 A special application of harmonic methods involves
sity, icorr, and Tafel parameters, ba (where ba ¼ ba/ln 10) and bc,
harmonic impedance spectroscopy.53 The EFM method uses one
can be determined from the equations summarized in table 2.
or more AC voltage perturbations to extract the corrosion rate.
The current components at the angular frequency x1 or x2 can
The EFM method has been described in the literature49–52 and
be measured at x1 or x2. The intermodulation components
recently was reviewed.54 In the most often used EFM method, a
x1 6 x2 can be determined from the signal response at x1 þ x2
potential perturbation by two sine waves of different frequencies
or x1 - x2. The method is one of the few that enables extraction
is applied across a corroding metal interface. The E-I behavior of
of corrosion rate and Tafel parameters directly from a single
corroding interfaces is typically nonlinear, so that such a poten-
measurement (see Barnartt30 and Oldham and Mansfeld31). Cur-
tial perturbation in the form of a sine wave at one or more fre-
rently, there are no ASTM standards for this technique.
quencies can result in a current response at the same and at
other frequencies. The result of such a potential perturbation is
various AC current responses at various frequencies such as EN Resistance
zero, harmonic, and intermodulation. The magnitude of these EN analysis can provide a parameter called the EN resistance,
current responses can be used to extract information on the cor- Rn.55–61 It is desirable to utilize this parameter in an analogous
rosion rate of the electrochemical interface, or, conversely, the fashion as the polarization resistance. One electrode configura-
reduction-oxidation rate of an interface dominated by redox tion that enables such a measurement involves connecting a
reactions as well as the Tafel parameters. This is an advantage zero-resistance ammeter (ZRA) between two nominally identical
over linear polarization resistance and EIS methods, which can corroding electrodes immersed in the same solution. A third,
provide the Z(x) and, at x¼ 0, the polarization resistance of the nominally identical electrode can be immersed in solution and
corroding interface, but that do not uniquely determine Tafel connected to the first two using a high-impedance voltmeter.
parameters. As such, separate experiments must be used to This electrode serves as a “noisy” psuedoreference electrode.
define Tafel parameters. A special extension of the method This approach is attractive in field applications because of the
54
TABLE 2 Governing Equations for Extraction of icorr, as well as ba and bc, from Harmonic and Intermodulation Frequency Data
Reaction Type Governing Equation Determination of icorr Determination of Tafel Parameters
Charge transfer control Tafel behavior Equation (19) ix1 ;x2 2 ix1 ;x2 Vo
icorr ¼ p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi ba ¼ pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
2
8ix1 x2 i2x2 6x1 3ix2 6x1 2 8ix1 x2 i2x2 6x1 3ix2 6x1 2
ix26x2
Similar expression for bc

Passive or anodic mass transport control g ix ;x 2 ix1 ;x2
i ¼ icorr 1 exp icorr ¼ 1 2 bc ¼ Vo
bc 2ix2 6x1 2ix2 6x1

Cathodic mass transport control g ix1 ;x2 2 ix1 ;x2
i ¼ icorr exp 1 icorr ¼ bc ¼ Vo
ba 2ix2 6x1 2ix2 6x1
Note: ba¼ ba/ln(10), and bc ¼ bc/ln(10);

i2x1 6x2 can be evaluated at i2x1 þx2 or i2x1 x2 ;
ix1 6x2 can be evaluated at ix1 þx2 or ix1 x2 ; and
ix1 ;x2 can be evaluated at ix1 or ix2 .
more rugged nature of the metallic electrode compared with the change in potential also occurs on the electrode. If the first elec-
laboratory electrodes, but this complicates the analysis because trode is now connected to a second electrode, whose interfacial
two uncorrelated potential sources (i.e., from the couple and the properties and global electrode potential do not change on their
pseudoreference) are measured in the collection of potential own at the same instant in time and by the same degree as on
noise, Vn. Because Vn(meas) ¼ (Vn(couple) þ Vn(pseudo-ref))1/2, the first electrode, then a galvanic cell is momentarily created.
Vn(meas) must be divided by 2 to yield Vn(couple).62 Another alter- This induces a further difference in anodic and cathodic half-cell
native is a four-electrode arrangement in which the first pair is currents on the first electrode. Current now flows between the
coupled through a ZRA to monitor current, and the second pair first and second electrode, such that the sum of anodic and
is connected with a high-impedance voltmeter to sample an cathodic half-cell currents over all patches on both electrodes is
uncorrelated Vn(couple). Alternatively, a less noisy, conventional equal. When the interfacial resistances return to normal values
reference electrode may be utilized in the three-electrode over all patches, the potential difference between the two electro-
arrangement. In this case, Vn(meas) and In(meas) are correlated. des is eliminated and so is the measurable current between the
The reference electrode noise can be separately defined as the two electrodes. Bertocci60 and Bertocci and Huet61 argued that
electrochemical voltage noise between two nominally identical the external current fluctuation measured between two identical
reference electrodes.63 If the reference electrode noise is low, electrodes is identical to the fluctuation in one electrode.
then the correction factor of 2 is not needed. In either case, Theoretical relationships establishing the connection
the third electrode (reference electrode) is connected to the between Rn and Rp have been sought by several researchers,61,65–68
first two through the high-impedance voltmeter. These arrange- but their validity has been questioned. A great concern has been
ments enable simultaneous recording of the galvanic current with that the largest current peaks would occur during the most rapid
time and the galvanic couple potential versus time. The standard voltage fluctuations, because the electrode interface contains a
deviation of the voltage noise divided by the standard deviation capacitance through which current can be shorted.60,61 Thus,
of the current noise has been proposed to yield a statistical when voltage fluctuations are rapid, the measured noise current
parameter called the noise resistance Rn.55–62,64 Analysis of simu- will be shorted through the interfacial capacitance. This is
lated noise data has led to the conclusion that the ratio of the assuming a simple electrical equivalent circuit model consisting
standard deviations of the current and voltage noises, measured of a two parallel resistor-capacitor network describing the inter-
between two identical electrodes, can be normalized by surface face for each electrode connected in series through Rs. This situa-
area by multiplying by the square root of AvAi, as follows:61 tion would lead to the occurrence of the lowest impedance
between the two electrodes during the most rapid voltage fluctu-
rv ðmeasÞ pffiffiffiffiffiffiffiffiffiffiffi ations. This, in turn, would produce the greatest current fluctua-
Rn ðohm cm2 Þ ¼ AV AI , (39)
rI ðmeasÞ tions. The theoretical maximum measured current would be
where: given by the voltage fluctuation divided by Rs. The outcome
rv(meas) ¼ the standard deviation of the voltage noise; would be a statistical noise resistance parameter that is propor-
rI(meas) ¼ the standard deviation of the current noise; and tional to, or heavily influenced by, higher frequency data. Indeed,
Av and A, ¼ the surface areas of the corroding electrodes used Rn was found to equal an absolute impedance at some frequency
for voltage and current measurement, respectively. that depended on the frequency of the voltage fluctuations and
Correlations between this parameter and conventionally the resistor-capacitor (RC) time constant of the electrode inter-
determined polarization resistance, as well as mass loss–based face in one study of simulated noise.60 Unfortunately, an Rn
corrosion rates, have been obtained.56,62 Unfortunately, experi- value obtained at high frequency would be smaller in magnitude
mental confirmation of the area normalization factor has not than the Rp obtained at the zero frequency limit. Hence, it would
been extensively performed. Recall that in the case of a polariza- not represent the desired zero frequency limit interfacial resis-
tion resistance determined from E-iapp data or EIS data at the tance, Rp. Indeed, such underestimations in the true value of Rp
zero frequency limit, measured resistance can be multiplied by have been observed experimentally.62,64
the electrode area and will yield the same area-normalized polar- Recently, a more rigorous theoretical and experimental
ization resistance over a broad range of electrode areas. analysis has been made comparing the spectral noise resistance
Moreover, the correlation has lacked a rigorous fundamen- obtained at each frequency with both the polarization resistance
tal foundation for correlating Rn with corrosion rate, despite the obtained from the zero frequency limit of impedance data
intuitive connection between rv and rI given by the proportion- jZ(x ¼ 0)j, as well as the frequency-dependent impedance of wo
ality factor Rn. The surface of one freely corroding electrode electrodes.69–72 The spectral noise resistance Rsn(x) was deter-
could be divided into areas that experience fluctuations in inter- mined by taking the square root of power spectral density of the
facial resistance that produce changes in anodic and cathodic voltage noise (V2/Hz)1/2 and dividing it by the square root of
half-cell reaction rates in any one patch. The electrode potential power spectral density of the current noise (A2/Hz)1/2 at each
must then change in each patch to drive the half-cell reactions, frequency using the same two-electrode arrangement as dis-
such that the sum of all the anodic half-cell currents from all cussed earlier.72
patches equals the sum of all cathodic half-cell currents, regard- pffiffiffiffiffiffiffiffiffiffiffiffiffi
ðVPSD Þ
less of whether the source of cathodic half-cell current is from Rsn ðxÞ ¼ pffiffiffiffiffiffiffiffiffiffiffiffi , (40)
capacitive discharge or electrochemical reaction.60 Some global ðIPSD Þ
where: impedances that are equally noisy, but this is not always the case.
Rsn(x) ¼ proportional to the magnitude of the cell impedance, For instance, the low-impedance electrode in a two-electrode cell
jZ(x)j in the two electrode arrangement.72 with a third reference electrode can be sensed by Rsn(x) if the
The proportionality factor is unity in the case of identically higher impedance electrode is much noisier than the low-
sized electrodes in a two electrode cell with identical impedances impedance electrode.72 Recent attempts have been made to
and a noiseless reference electrode.72 Therefore, in the theoretical address circumstances in which Rsn(x) lies in between jZ(x)j1
case of identical electrode impedances (i.e., where Rs is negligi- and jZ(x)j2 representing the high- and low-impedance electro-
ble), the spectral noise resistance at the zero frequency limit is des. Methods have been suggested for sensing the current fluctu-
equal to the interfacial impedance at the zero frequency limit ations on both electrodes.73 The reader is referred to these
jZ(x ¼ 0)j. In this case, Rsn(0) ¼ Rp. Figure 6 illustrates data for articles for further information.
identical Fe electrodes in 1 M aqueous sodium sulfate (Na2SO4)
solution with an iron reference electrode. Here Rsn(x) ¼ H3 ELECTROCHEMICAL METHODS FOR THE STUDY OF
jZ(x)j because of the noisy RE. Thus, 2jZ(x)j and Rsn(x) appear
GALVANIC CORROSION
to be similar. For a corroding system, jZ(x ¼ 0)j equals Rp and
Galvanic corrosion is defined and described in Section IV the
Rsn(0) ¼ Rp. Even Rn may equal Rsn(x ¼ 0) ¼ jZ(x ¼ 0)j ¼ Rp if
“Types of Corrosion” section.
jZ(x)j equals Rp in the frequency regime dominating the Rn
value. The frequency range dominating the Rn value is deter- Methods Based on Mixed-Potential Theory
mined by several factors, but this statement is more likely to be The thermodynamic tendency for galvanic corrosion may be
true if jZ(x)j and Rsn(x) both exhibit long low-frequency pla- determined from the electromotive series5 or from the construc-
teaus over a broad frequency range that encompasses the fmin tion of a galvanic series as discussed in ASTM G82, Standard
and fs utilized in the Rn measurement. Here fmin is given by the Guide for Development and Use of a Galvanic Series for Predict-
total sampling time, T, where fmin ¼ 1/T and fs equals the data ing Galvanic Corrosion Performance. Galvanic corrosion rates
sampling rate. Rn typically varies with fs and underestimates can be determined from mixed-potential theory as schematically
jZ(x ¼ 0)j. Unfortunately, Rsn(x!0) does not equal Rp in the illustrated in figure 7. In the case of bimetal or multimetal gal-
zero frequency limit under many other conditions, such as when vanic attack in which two or more metals are electrically in con-
log (Rs/Rp ) > 0 or in the case of very noisy reference electrodes.72 tact with one another, there is in theory a minimum of two
Moreover, Rsn(x) can be dominated by the properties of the cathodic and two anodic reactions. One of each of these reac-
high-impedance electrode in the case of dissimilar electrode tions is occurring on each metal. In this case, the more noble of
the two metals is cathodically polarized, and its anodic reaction
rate will thus be suppressed. Conversely, the less noble or anodic
FIG. 6 Rsn(x) versus frequency for iron in 1 M Na2SO4 at pH 4 material is anodically polarized and the anodic reaction rate is
with a “noisy” iron reference electrode compared with accelerated. The mixed potential (the galvanic couple potential,
two times the impedance jZ(x)j versus frequency using
the EIS method. Impedance measurements were
performed in a two electrode cell with two iron electrodes FIG. 7 Potential-current relationships for the case of a galvanic
to produce 2jZ(x)j. The value of Rsn(x) calculated is equal couple between two corroding metals. Steel is the more
pffiffiffi 5
to 3 jZ(x)j for the case of two iron electrodes coupled noble metal, and zinc is the less noble metal. The
through a ZRA and a third iron electrode as reference corrosion rate of zinc is increased significantly when
72
electrode. coupled, whereas the corrosion rate of steel is decreased.
Ecouple) of the galvanic couple and the resulting galvanic current Potential Probe Methods
can be uniquely determined from the sums of all of the individ-
ual anodic and cathodic currents obtained for each material at Potential probe methods may be used to determine and map the
each potential when the following condition is met: local ionic currents associated with galvanic corrosion cells
X X between dissimilar metals or heterogeneities on complex alloy
ia Aa ¼ ic Ac at Ecouple , (41) surfaces.75–80 In the most straightforward application, the local
potential is mapped over a planar electrode oriented in the x-y
where: plane to give an indication of local current. The basic concept is
ia, ic ¼ the anodic and cathodic current densities, uA/cm2; and that the ionic current density in three dimensions can be mapped
Aa, Ac¼ the anodic and cathodic areas, cm2. by either scanning an array of reference electrodes or by vibrat-
The galvanic couple potential is defined by the potential ing a single electrode. The following equation expresses the
where the sum of the anodic currents equals the sum of the orthogonal ionic current flow in terms of solution conductivity
cathodic currents for all reactions on all of the metals in the cou- and the gradient in potential in the solution above the galvanic
ple. The galvanic couple potential can be determined either by couple,
direct measurement with a reference electrode or from polariza-
tion data if: i ¼ jðrEÞ, (42)
where:
1. polarization data are available for each material in the
j ¼ the solution conductivity; and
galvanic couple,
rE ¼ d1 dE/dx þ d2 dE/dy þ d3 dE/dz, where x, y, and z, define
2. the area of each metal is known, and
axes in a coordinate system and d1 are unity vectors in the x,
3. the current distribution is uniform.
y, and z directions.
The advantage of the vibrating technique is that minor dif-
Once Ecouple is determined, the galvanic corrosion rate may
ferences between the reference potential of separate electrodes is
be estimated for the metal of interest in the couple if a relation-
eliminated by using a single vibrating reference electrode. The
ship such as given in equation (19) is known for that metal. In
component of the ionic current density flowing perpendicular to
simple bimetal cases, direct superposition of polarization data
lines of iso-potential in solution is measured. Such lines are
(corrected for wetted surface area) can yield Ecouple and the gal-
generated because of the galvanic couple and the established
vanic corrosion rate.74 Because applied currents instead of true
potential gradient. Therefore, a map of local current can be con-
anodic or cathodic currents are measured in any polarization
structed by scanning over a planar electrode in the x-y plane,
experiment, the E-log(I) superposition technique will introduce
where z is the vertical distance in the solution above the elec-
the least error when the cathodic reduction reaction rate on the
trode. Locations of high local current imply significant galvanic
anode is negligible and the anodic oxidation reaction rate on the
interactions.
cathode is negligible at the galvanic couple potential. Obviously,
when the OCPs of the anode and cathode are similar, error is
more likely. Fortunately, galvanic corrosion may be less signifi- SCANNING VIBRATING ELECTRODE TECHNIQUE
cant in these cases. In addition, special care must be taken in the The scanning vibrating electrode technique (SVET) has been
procedures used to assess the polarization responses,74 especially used widely for the in situ study of localized corrosion phenom-
if time effects are to be taken into consideration when evaluating ena in full immersion conditions.81–94 A full description of SVET
long-term galvanic corrosion behavior. is given in chapter 16, which focuses on its use for the study of
galvanic corrosion. In brief, SVET records the drop in potential
Direct Measurement of Galvanic-Corrosion Rates generated by ionic currents in solution originating from a corro-
A more straightforward procedure involves immersing the two sion cell. The technique produces a series of current density dis-
dissimilar metals in an electrolyte and electrically connecting tribution maps that provide the size, shape, and location of
the materials together using a ZRA to measure the resulting gal- anodic (positive) current and cathodic (negative) current for a
vanic current.9,75,76 In this method, the galvanic current is specific area. The nondestructive nature of the test enables repeat
directly determined as a function of time. The galvanic corro- scanning of the same corroding surface and a series of time-
sion rate so determined is the additional corrosion created with resolved data is collected, illustrating the evolution of electro-
the couple and will not equal the true corrosion rate. This is chemical processes. Area-averaged integration of all the positive
given by the sum of the galvanic corrosion rate and the corro- values and all of the negative values enables semiquantitative
sion rate under freely corroding conditions, unless the latter is measurement of the respective anodic and cathodic corrosion
negligible. Recall that the corrosion rate of the uncoupled anode activity occurring as a function of time. This technique is partic-
is undetermined by this method, because an equal cathodic ularly useful for studying galvanic corrosion because the current
reaction rate is occurring on the same surface. A reference elec- polarity and current intensity can be mapped across two dissimi-
trode connected to the galvanic couple can be used to deter- lar metals in electrical contact.82,95–97 This is of great interest for
mine the galvanic couple potential. ASTM standards do not the study of sacrificial alloys in which self-corrosion of the anode
exist for direct measurement of galvanic corrosion or scanning can be isolated and quantified.98 The spatial resolution is largely
potential probe methods. controlled by three key factors: the probe-tip diameter, the scan
height, and the number of scanned points per area.99 Typical full immersion conditions. The reaction rate of a redox mediator
probe-tip diameter sizes range from 5 lm to 125 lm depending is used to indirectly sense the local reactivity of the substrate.
on the manufacturer.98,100 Increasing the number of points The mediator typically is used as a supportive reactant added to
increases the scan resolution but also the total scan time and, for a the electrolyte solution and careful selection can enable control
metal with a high corrosion rate, certain information can be over the specific reactions probed in a particular environ-
missed if the scan rate is too slow. The SVET favors the study of ment,109,110,118,119 which will be discussed in more detail. The oper-
localized corrosion occurring because of microgalvanic coupling ation of SECM requires two cells, controlled by a biopotentiostat,
of phases in which anodes and cathodes are separated by a dis- in which the ME or the specimen surface act as the working elec-
tance much greater than the plane of scan, which is typically trodes that share a counter and reference electrode.120 Electro-
100 lm. This is demonstrated in the schematic given in figure 8A, chemical activity in the solution directly above the corroding
which illustrates the movement of the vibrating probe through the substrate is monitored by the oxidation or reduction of dissolved
lines of ionic flux originating from a surface feature, such as an reactants. For example, for the study of galvanic coupling, the
anodic intermetallic-particle coupled to the cathodic matrix phase. typical approach is to monitor the concentration of dissolved
A limitation of this technique is poor efficiency, observed when oxygen on the cathodic areas.109 A comprehensive list of metals
studying uniform corrosion in which the separation distance of and alloys studied with each SECM mode and the most common
highly interspersed anodes and cathodes is much smaller than the redox mediator and ion of interest is given in a recent
plane of scan. The ionic flux lines occur well below the plane of publication.117
scan and, therefore, are undetected by the vibrating probe.87,101 The SECM mode of operation can be adjusted to suit the
particular application. The feedback mode is the most commonly
SCANNING ELECTROCHEMICAL MICROSCOPY used and is particularly useful for studying the corrosion protec-
Scanning electrochemical microscopy (SECM) is another electro- tion of coatings.96,111,121,122 It can be employed over both conduct-
chemical local probe technique that enables time-resolved map- ing and insulating surfaces to enable the distinction between
ping,102–104 in this case, of the heterogeneous reactions across a (1) areas of a coating that are defective, (2) areas where reactions
freely corroding surface. The technique has been used extensively at the exposed substrate are detected, and (3) regions where the
for the study of localized corrosion,105–107 galvanic corrosion of coating is intact. This allows coating deterioration and self-
dissimilar metals/metal alloys,82,108–110 the study of coatings for healing effects to be monitored, as a function of time. In the
corrosion protection,96,111–113 and hydrogen detection.114–116 SECM feedback mode, the ME tip is used as both the current detector
is often used as a complementary technique to the SVET as it and the source.123,124 A redox mediator, in its reduced form, is
enables much higher resolution (i.e., on the micrometer length- added to the electrolyte solution. The SECM measures the cur-
scale). Payne, Stephens, and Mauzeroll provided a summary of rent at the ME tip while simultaneously applying a positive
the capabilities of different techniques compared with SECM in potential (to the ME tip) to oxidize the mediator species in the
a 2017 review article.117 bulk. The rate of this oxidation reaction is governed by the diffu-
SECM operates by scanning a nonvibrating electrochemical sion of the reduced species from the bulk solution to the ME tip.
mapping micro-electrode (ME) tip over a specimen surface in When the tip is positioned above an insulating surface, such as
FIG. 8 Schematic diagrams showing detection efficiency where (A) shows an anode-cathode separation distance greater than the scan
height where a local anode is surrounded by a distributed cathode and (B) shows uniform corrosion with an anode-cathode
separation distance less than the scan height.
an intact polymer coating, replenishment of the reduced species measurements to determine relative susceptibility to localized
at the surface cannot occur and the diffusion of the reduced spe- corrosion. The method is designed for use with iron- or nickel-
cies from the bulk to the tip will be hindered by the presence of based alloys in chloride environments. In this experiment, a
the insulating specimen surface.125 In such cases, the measured cyclic anodic polarization scan is performed at a fixed voltage
current decreases because of the depleted mediator species at the scan rate. Figure 10A shows a schematic of the cyclic potentiody-
surface of the substrate, and the SECM will operate in negative namic method. Particular attention is focused on two features of
feedback mode, as illustrated in the schematic given in figure 9A. cyclic polarization behavior (fig. 10A). The first is the potential at
In the presence of a conducting substrate, the reduced species which the anodic current increases significantly with applied
will be readily replenished at the surface, maintaining a steady- potential (the breakdown potential, Ebd). In general, the more
state measured current, and the SECM will operate in positive noble this potential, obtained at a fixed scan rate in this test, the
feedback mode (fig. 9B). The redox competition mode is another less susceptible the alloy is to the initiation of localized attack.
commonly used mode for corrosion studies and typically is used The second feature of great interest is the potential at which the
for the study of galvanic corrosion because, as described earlier, hysteresis loop is completed during reverse polarization scan
it can be used to monitor the concentration of dissolved oxygen after localized corrosion propagation. This potential is often
on the cathodic areas.109 In brief, a specific redox mediator is taken as the repassivation potential or protection potential, Eprot.
selected that reacts at both the ME and the specimen surface. In general, once initiated, localized corrosion sites can propagate
When the ME is brought close to the surface, from far away, the only at some potential more positive than the potential at which
ME competes with the substrate for the reduction (or oxidation) the hysteresis loop is completed (when determined at a fixed
of the mediator and the current measured by the ME decreases. scan rate). In other words, repassivation will occur at more nega-
tive potentials, even after localized corrosion initiation. There-
ELECTROCHEMICAL METHODS FOR THE STUDY fore, the more positive the potential at which the hysteresis loop
OF PASSIVITY AND LOCALIZED CORROSION is completed, the less likely that localized corrosion will propa-
Pitting and crevice corrosion are associated with the breakdown gate. Additionally, the difference in potential between Ecorr and
of passivity.126 Electrochemical tests for evaluating the suscepti- Eprot (Eprot - Ecorr) is often taken to indicate relative resistance to
bility of a material to pitting and to crevice corrosion include local corrosion. ASTM G61 illustrates cyclic polarization behavior
potentiodynamic, potentiostatic, scratch potentiostatic, poten- for Hastelloy C-276 and 304 stainless steel in 3.5 wt% sodium
tiostaircase, tribo-ellipsometric methods, pit-propagation rate chloride solution. Based on this criterion, it is evident that Has-
curves, galvanostatic, and EN measurements.126–128 telloy C-276 is more resistant to localized corrosion in this envi-
ronment than AISI 304 stainless steel.
Cyclic Potentiodynamic Polarization Methods to Determine
Ebd and Eprot
FIG. 10 Schematic representations of experimental data for
ASTM G61, Standard Test Method for Conducting Cyclic Poten-
(A) a cyclic potentiodynamic polarization curve;
tiodynamic Polarization Measurements for Localized Corrosion
(B) galvanostatic potential-time curve for a material;
Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys, describes a
(C) potentiostatic current-time curve for a previously
procedure for conducting cyclic potentiodynamic polarization
passivated surface, which pits at E1 < EBD < E2; and
(D) potentiostatic current-time curve for active surface.
125
FIG. 9 Schematic diagrams of SECM feedback mode The protection potential is found as E3 < EPROT < E2.
demonstrating (A) the negative feedback mode above an
insulating surface (intact coating), (B) the positive
feedback mode above a conducting surface (damaged
coating), and (C) the redox competition mode used for
galvanic corrosion.
Complications with Cyclic Potentiodynamic Polarization eventually will repassivate and the current subsequently will
Methods decrease with time. The critical potential for pitting is defined as
Although the cyclic method is a reasonable method for screening the most noble potential at which pits repassivate after the stim-
variations in alloy composition and environments, the cyclic ulation step. This approach is covered in ASTM F746, Standard
potentiodynamic polarization method has been found to have a Test Method for Pitting or Crevice Corrosion of Metallic Surgical
number of shortcomings.126–131 One major problem concerns the Implant Materials.
effect of the potential scan rate. The values of both Ebd and Eprot Determination of Eprot by Potential Step-down or Scan-down
are a strong function of the manner in which the tests are per- Methods
formed, particularly the potential scan rate employed. Experi- As stated earlier, Ebd and Eprot often depend strongly on the
mental values of Ebd are linked to the induction time required method by which they are determined and, therefore, do not
for pitting.132 Another complication arises from allowing too uniquely define intrinsic material properties. The Eprot values
much pitting propagation to occur before reversing the scan determined from the scanning method can be complicated by
direction. This either alters the localized chemistry in pits, affects scan rate, pit size or depth, vertex potential/current, polarization
pit depth, or both. Pit depth alters the diffusion length associated curve shape, and specimen geometry.133,134 Investigators have
with the dilution of pit chemistry necessary for repassivation. found more consistent Eprot values after a critical charge has
This factor affects the polarization behavior after the reversal in passed, whereas others report a single critical potential.131 Often
the direction of scanning and influences Eprot. From an engineer- this potential is difficult to choose from E-I data and has been
ing standpoint, metal surfaces held at potentials below the repas- taken at various points on the reverse scan of a cyclic potentiody-
sivation potential of the deepest pits should be safe against stable namic polarization curve.134,135
pit propagation. That is to say, stable pits should not propagate. A method is needed for determination of Eprot that defines a
It has been found that Ebd observed after potentiostatic holds, or conservative value of this potential that likely reflects a true pit
the slowest scan rates, approaches the protection potential found or crevice repassivation potential. Tsujikawa has developed a
after minimal pit growth when pits are small.131 This suggests the method for determination of Eprot from previously grown pits
existence of a single critical potential, Ec, for pit initiation and and crevices.136,137 This method and its variations have been used
growth in the absence of crevices or other occluded sites.131 If the successfully by several research groups and associates the critical
potential can be maintained below Ec, pitting does not occur. potential for repassivation Eprot with the need to grow local cor-
Potentiostatic and Galvanostatic Methods for Localized rosion sites to a critical minimum size.138 The method is an
Corrosion enhancement of the determination of Eprot, from potentiody-
The shortcomings of the cyclic potentiodynamic polarization namic E-I scans that involve scan reversal to the point at which
method have become the basis for several other electrochemical pits are repassivated. In the potential step-down method, the
techniques. Other methods are schematically illustrated in potential is first set at a high enough value to induce and grow
figure 10. In the galvanostatic or galvanostaircase technique stable pits to the specified size. The potential can then be stepped
(fig. 10B), potential is measured versus time at various constant down or scanned downward, while the pit propagation current is
applied currents that are incrementally increased in steps, then recorded. Subsequently, the potential may be held after a pit has
reversed and decreased. In the case of passive materials, a poten- been initiated to determine the time until repassivation.139 More-
tial rise during galvanostatic testing indicates passive film over, long potential holds at selected applied potentials enable
growth, while a decline indicates breakdown and growth of local confirmation of a true repassivation potential, often indicated by
corrosion sites. In the galvanostaircase technique, the current is an abrupt decrease in current density at the time when the chem-
step increased. Potential measurements are made until the time ical conditions favoring pit stability (often expressed as some
rate of change in potential approaches zero. These forward and fraction of the salt saturation concentration) are no longer main-
reverse potential-current density data are extrapolated to the tained. Abrupt transitions in finite repassivation time toward
zero current density to obtain Ebd and Eprot. The technique is infinity with increasing hold potential may indicate that condi-
described by ASTM G100, Standard Test Method of Conducting tions favorable to pit growth are sustained. Another benefit of
Cyclic Galvanostaircase Polarization, as a test method for alumi- determining Eprot from controlled growth of pits and crevices is
num (Al) alloys. Potentiostatic methods can overcome the inher- that the repassivation potential can be determined from pits of
ent problems involving scan rate. A more conservative estimate preselected sizes that can be controlled by the duration of the
of Ebd can be obtained by polarizing individual samples for long potential holds. The method has been applied successfully to
periods of time at potentials above and below the values of Eprot nickel-base alloys, stainless steels, and Al-base alloys, and is
and Ebd previously determined from the potentiodynamic being standardized by the committee for Japanese Industrial
method (fig. 10C). Eventual initiation is indicated by a current Standards. When a one-dimensional pit or pencil electrode is
increase. In another approach (fig. 10D), initiation of pits is inten- tested, the pit propagation kinetics can be recorded from a single
tionally induced by applying a “stimulation” potential well above pit.140 Whether pit growth is ohmic, mass transport, or charge
Ebd and then quickly shifting to a preselected potential below transfer controlled also may be determined. Moreover, the effects
that value. If this second applied potential is above Eprot, propa- of various material and solution parameters (e.g., flow rate, con-
gation of the existing pits will continue and the current will ductivity, and solution composition) on pit propagation rates
increase. At potentials less than Eprot, however, the pits can be determined.
The Scratch-Repassivation Method for Localized Corrosion critical pitting temperature measurement method under the des-
An additional potentiostatic technique to be mentioned in the ignation ASTM G150, Standard Test Method for Electrochemical
area of localized corrosion involves the scratch method.141 In this Critical Pitting Temperature Testing of Stainless Steels and
method, the alloy surface is scratched while being held at a con- Related Alloys.
stant potential and the current is measured as a function of time.
The potential dependencies of the induction time and the repas- STATISTICAL DISTRIBUTIONS IN CRITICAL
sivation time are determined by monitoring the current change POTENTIALS
over a range of different potentials. This is illustrated in figure 11. Ebd is typically observed to be a significantly “statistically distrib-
From this information the critical pitting potential, Ec, thought uted” property compared with the repassivation potential. This
to be more negative than Ebd determined by potentiodynamic often is observed when critical potentials are determined by
scan, can be determined. Other methods of studying localized potentiodynamic scanning, but also can be observed during
corrosion are also available.126 An ASTM standard exists for the potentiostatic tests in which the pit incubation time and subse-
quent survival probabilities also are seen to be distributed. Eprot
distributions are often attributed to distributions in pit size.
FIG. 11 (A) E-log (I) curve showing location of Ebd and Eprot. However, Eprot is not distributed when pits are uniformly large142
(B) Time versus applied potential plot from scratch test
and may not depend on the depth of corrosion damage at all
illustrating a possible location of the critical potential, Ec’
during crevice corrosion when a crevice former controls mass
as it relates to the induction time and the repassivation
125
transport.143 Statistical distributions in pitting potentials have
time. (C) Current versus time plot for a scratched
been observed for AISI 304,144 Fe-Cr-Z (where x ¼ Nb, Mo, or
specimen when scratched above and below Ec’.
Ti) alloys,145 AISI 316,146 Ti,147 high purity Al,148 AA 2024-T3,149
and amorphous Al-base alloys.150 These statistical distributions
imply that significant variations exist when a number of speci-
mens are tested under identical conditions. These distributions
have been attributed to the stochastic nature of pitting,146 distri-
butions in oxide film cation vacancy transport properties,151 the
effects of potential on the nature of the eligible sites for the meta-
stable pit nucleation process,144 and the population of fatal flaws
or pit-initiating defects on an electrode surface.152 The possibility
that oxide defects at densities exceeding millions of sites/cm3
produces specimen-to-specimen variations appears unlikely for
specimens with surface areas of the order of cm2. It appears to be
more reasonable to expect that sample-to-sample variations,
instead, are associated with distributions in the population of
micrometer scale defects, such as sulfide inclusions in stainless
steel153 and constituent particles in Al alloys152 that control the
density of pit nucleation sites and produce micropit to micropit
variations in growth rates and diffusive transport characteristics
(e.g., Deff, pit shape) for a large population of metastable pits
grown at a single potential. A statistical distribution of the prod-
uct ipit * rpit (where ipit is the pit current density and r is pit
radius) was observed for a large population of pits at a fixed
potential in high purity Al.148 This product is linearly related to
the acid pit chemistry. Although not rigorously proven, it is rea-
sonable to argue that a slightly slower rate of pit transport or
slightly larger ipit * rpit product for a given pit might lead to pit
stabilization through achievement of the critical acid pit chemis-
try at different applied potentials on an electrode with a popula-
tion of pits sites. Moreover, such behavior is likely controlled by
micrometer scale defects spaced at tens of micrometer lateral
separation distances across planar electrode surfaces. Investi-
gators seeking information on critical potentials for engineering
use should consider appropriate specimen sizes relative to critical
defect densities and spacings. No ASTM standards address these
issues. However, the sizes of test specimens recommended in
many ASTM standards are conservatively large so as to include
many possible pit sites.
EN Methods arrangement, and environment, including thin-film and full-

EN methods are used increasingly as a nondestructive tool for immersion conditions, with alternating wet-dry cycling,163 as well
evaluating susceptibility to localized corrosion as well as stress- as crevices164 and recesses.165–169 Furthermore, CMEAs can be
corrosion cracking (SCC), particularly in field or process plant built with either nominally identical electrodes that simulate
applications.61,154–158 EN is appealing because it may be conducted large planar electrodes or by combining a mix of electrode mate-
at open circuit without perturbing the corroding system. Cur- rials to simulate complex alloys with nonuniform structure and
rently, however, no consensus exists as to the most appropriate composition.
test procedure or analysis method, or how well results correlate The net current evolved on a freely corroding surface is
with coupon exposures. The origins of EN current and potential always zero, such that the net sum of anodic and cathodic cur-
signals are discussed in more detail in Chapter 1. The transient rent is equal, as per equation (43), but localized dispersions of
development of bare metal at newly formed pit or cracking sites excess anodic or cathodic current density may arise on a finely
as a result of temporary propagation and repassivation can result resolved scale:
in potential noise (open-circuit EN), current noise (potentiostatic X X
EN), or both. In the latter case, the current noise is measured ianodic ¼ icathodic : (43)
with a ZRA used to monitor a galvanic couple consisting of two
identical electrodes, while the potential noise comes from the ref- Localized distribution of current is dependent on such
erence electrode (or third metallic electrode) monitoring the cou- effects as pitting, crevice corrosion, galvanic pairings, water layer
ple potential. The noise signal, hereafter referred to as a potential thickness, and microstructural heterogeneities. For this reason,
or current time record, is caused by the galvanic couple formed CMEAs have been developed for instantaneous assessment of
between the very small anode sites corroding at current densities the spatiotemporal evolution of localized corrosion and current
(c.d.) approaching 10 A/cm2 in pitting corrosion and the much distributions.161,162
larger remaining cathode surface operating at lower cathodic c.d. The CMEA setup incorporates insulated wires of small
(e.g., 10 uA/cm2). Regarding pitting phenomena, a negative shift diameter, typically 0.25 mm, composed of the metal of interest,
in measured potential is observed (OCP and galvanic couple and flush-mounted with a series of exposed discs embedded
EN), an increase in current is observed for potentiostatic EN, within a supporting matrix.170 The wires are individually con-
and current fluctuations of either polarity are observed for gal- nected by a ZRA to individual ports of a multi-electrode ana-
vanic couple EN. lyzer (while remaining insulated from one another) that
Several analysis methods exist, including electrochemi- measures the net current output of each wire, simultaneously
cal,159 statistical,61,158 spectral,154–157 and autocorrelation.156 Some and distinctly. In this way, a spatiotemporal map can be con-
of the approaches for determination of spectral noise resistance structed of the distribution of local current on the surface of the
during uniform corrosion are discussed in the section on polar- sample in an MEA in the desired arrangement for any particu-
ization resistance. Electrochemical analysis may enable the lar experiment.171–175 Two configurations are common: close-
determination of pit sizes from the charge associated with each packed configurations simulate specific conditions and eluci-
pitting event,148 or from attempting to determine pit current date unique corrosion mechanisms as shown in figure 12A. In
densities. Statistical analyses include determining the root contrast, far-spaced configurations that are optimized for high-
mean square (rms), variance, and standard deviations of the throughput experiments are capable of elucidating the statisti-
EN voltage or current time records, as well as a noise resistance, cal distributions of flaws under different variables and their
RN, taken as the ratio of the rms or standard deviation of the effect on corrosion processes.163,170 In this case, the separation
potential and current time records acquired over various peri- distance between wires should be large enough that the electro-
ods of time.158 Spectral analysis consists of Fourier transforma- chemical processes taking place on each electrode has no effect
tion of EN data acquired in the time domain to create a power on neighboring electrodes during anodic or cathodic polariza-
spectral density plot.61,156,157,160 Qualitative assessment of the tion. As such, separation distances greater than characteristic
benefits of inhibitors, or the effects of process stream variations transport lengths are used, as demonstrated in the schematic
are made possible by comparing statistical or spectral results. given in figure 12B.
Quantitative analysis and predictive capability still require fur- Some investigations have demonstrated components that
ther development. have been designed in a crevice configuration to study the cur-
rent profiles along the walls of a crevice. This is shown by the
Coupled Multi-Electrode Arrays dashed line in the schematic given in Figure 12A that represents
Coupled multi-electrode arrays (CMEA) enable the real-time dif- the placement of an artificial crevice.164,174 Figure 12C shows the
ferentiation of local contributions to net anodic and cathodic setup for a simulated rivet that enables measurements to be
currents taking place on an electrode surface on a spatially made throughout the length of the artificial component. Note
resolved scale.161,162 This is of particular interest for engineering that the discs have been turned inward for ease and are shown to
components composed of dissimilar materials and complex demonstrate their location. Simulated engineering components
geometries and service conditions. As such, CMEAs can be can be constructed of dissimilar metals such that the spatial dis-
designed to satisfy specific corrosion problems that replicate tribution of galvanic current can be monitored as a function of
real-life configurations in terms of material, geometry, physical time.170–172 CMEAs also have been used to investigate the
passive film that are electronic or chemical in nature. Such sites

FIG. 12 Schematic diagrams for CMEAs showing (A) close- are not necessarily probed by a mechanical scratch. Scratching
packed, (B) far-spaced, and (C) rivet electrode can simulate SCC where mechanical film rupture processes are
configurations. The dashed line in (A) demonstrates operative and anodic dissolution controls the SCC process. In
where an artificial crevice could be placed. general, once the passive film is mechanically disturbed at some
potential, an electrochemical current can be measured that will
decay back to a low level when repassivation has occurred. A
measure of the crack growth rate, V (cm/s), can be obtained
from these data:

E:W: ect
V¼ Qf , (44)
qF ef
where:
E.W., Ðp, and F have been defined previously, and
t
Qf ¼ 0 iox dt,
Qf ¼ the anodic charge density (coulombs/cm2),
ef ¼ the fracture strain of the film, and
ect ¼ the crack tip strain rate (s1).
Tribo-ellipsometric Methods
The tribo-ellipsometric method is an advancement of the
scratch method and has been used to distinguish between cases
in which an alloy is susceptible to localized corrosion, such as
pitting or SCC, as opposed to general dissolution. The total
spreading of intergranular corrosion by cooperative interactions anodic current transient following film destabilization consists
in which CMEAs were constructed from sensitized 304 stainless of the algebraic sum of the repassivation current and the cur-
steel to understand the origins of persistent interactions in local- rent corresponding to dissolution of the exposed bare metal
ized corrosion sites.161 in lieu of film formation. The electrochemical current measure-
By nature of the technique, a reference electrode is not ment is conducted in conjunction with the optical ellipsometric
needed, as current can be measured in a two-electrode setup. method to measure the rate of film growth and repassivation
Small reference electrodes, however, also can be embedded film thickness. This combination offers a method of separat-
within the array and then connected to individual wires in a ing the two currents (dissolution versus repassivation), assum-
three-electrode setup to monitor the potential of individual wires ing that the valence state and density of the oxide are known so
one-at-a-time or even to conduct potential-dependent measure- that charge can be determined from its volume. Based on the
ments on individual wires of interest, such as potentiodynamic ratio of the charge involved in dissolution and the charge asso-
polarization or EIS. ciated with repassivation, a criterion for stress corrosion is
established by the parameter Rscc:
ENVIRONMENTALLY ASSISTED CRACKING
Rscc ¼ 1 þ Qd IQr , (45)
Several electrochemical techniques can be used to assess suscep-
tibility to environmental cracking. For alloys that are susceptible where:
to SCC by a mechanism of slip-induced passive film rupture and Qd ¼ the charge involved in dissolution, and
anodic dissolution, electrochemical measurement of the dissolu- Qr ¼ the charge associated with repassivation.
tion rate has obvious practical advantages. In this case, the incre- For example, a low-carbon steel was not found to be suscep-
ment of crack growth is defined by the anodic charge associated tible to SCC in a solution in which Rscc was 2.8. In this case,
with each film rupture event. The crack growth rate is defined by repassivation occurred very rapidly. The steel, however, was
this repetitive process. In the case of hydrogen embrittlement found to be susceptible when that ratio was 26, and it was not
(HE) phenomena, determination of the mobile hydrogen con- susceptible again in a solution in which Rscc was 75.172 In the lat-
centration in the metallic lattice is an important consideration. ter case, widespread pitting occurred instead. Hence, a balance
Such a determination is possible using an electrochemical between repassivation and widespread dissolution is required for
approach. Several pertinent methods are discussed in the follow- anodically controlled SCC. Only under intermediate conditions
ing sections. is SCC possible.
Scratch Repassivation Potentiodynamic Methods

The scratch repassivation technique discussed earlier may be Parkins devised a slow and rapid potentiodynamic scanning
more useful for studying SCC than it is for pitting.154 This is method to determine both the relative susceptibility to slip-film
because natural pitting is often initiated at defect sites in the rupture-repassivation SCC susceptibility, as well as possible
ranges of potential where SCC might occur.62,175 The method iox ¼ the current density associated with hydrogen oxidation
applies to metals and alloys whose oxide films can initially be (A/cm2).
cathodically reduced. The validity of the method relies on the The first term solution given in equation (46) is valid if L2/
notion that SCC occurs only when crack walls are readily passiv- Dt 4. The slope of a plot of log(ior) versus log(t) should be -0.5.
ated while the crack tip dissolves at a high rate because of contin- CH is determined from measured values of iox and t if DH is
ual destabilization of the passive film. In this method, the rapid known and the data fit equation (46). If DH is not known, then
scan anodic polarization curve provides a measure of the bare dis- the product CHD1/2 is obtained.
solution kinetics over a range of anodic potentials. A slow anodic
potentiodynamic scan provides a measure of the passive crack The Permeation Method for Determination of Diffusible
flank dissolution kinetics over the same range of potential. Alloy- Hydrogen Concentration
electrolyte combinations that produce potential ranges in which a In this method, an electrochemical technique is used to measure
difference in dissolution rate of 100–1,000 is observed for the two the diffusion coefficient, D, and the solubility, C0, of hydrogen in
scan rates are more SCC susceptible. Caution is warranted, how- iron or other metallic foil, under a variety of experimental condi-
ever, over concern that the differences in current do not merely tions.178,179 The advantages of the electrochemical technique are
reflect capacitive current as indicated in equation (19). All of the twofold. First, as noted earlier, by adjusting the potential one can
techniques mentioned in this section suffer from the need to per- apply a wide range of equivalent hydrogen pressures to the
form testing in solutions that simulate the relevant crack tip chem- charging side of the metal membrane without resorting to high-
istry and at the potentials actually experienced by the crack tip. pressure or high-vacuum techniques. Second, the hydrogen
No ASTM standard exists for these methods. forced through a thin metal foil can be transformed to Hþ ions
(H ! Hþþ e-) when it reaches the solution on the other side of
The Barnacle Electrode Technique for Determination of
the permeation foil, and thus, the permeation rate will be pro-
Diffusible Hydrogen Concentration
portional to the oxidation current required on the exit side of the
The degradation of fracture toughness below levels obtained in
membrane. Highly accurate and sensitive measurements of the
dry air or vacuum is a strong function of the internal diffusible
permeation rate can be made, which can be seen from the fact
hydrogen concentration for alloys prone to HE. Therefore, it is
that a current density of 1 jlA cm-2 corresponds to a permeation
often important to determine this concentration, hereafter
rate of H2 of about 10-7 mL cm-2 sec-1 at standard temperature
referred to as CH. CH can be determined by measuring the anodic
and pressure in palladium.
current density associated with the oxidation of mobile hydro-
The diffusion equation given by Fick’s second law, where
gen, which has diffused to the surface. Of course, precaution
CH(x,t) is the position-dependent diffusible hydrogen concentra-
must be taken to ensure that iox is associated only with the reac-
tion, t is time, D is the diffusion coefficient, and x is distance
tions given by equations (7) or (8) and does not include a contri-
through the foil has been solved for the initial conditions CH(x,
bution from other oxidation processes, such as metal oxidation.
t ¼ 0) ¼ 0 and for the boundary conditions CH(0, t ¼ 1) ¼ Co,
The source of the adsorbed hydrogen is internal hydrogen that
CH(L, t ¼ 1) ¼ 0. In other words, before the experiment is
exists in a precharged specimen that diffuses to the surface across
started, the foil contains no hydrogen and, at any time after the
the concentration gradient created when the surface concentra-
start of the experiment, the hydrogen concentration, CH, on one
tion is lowered to zero as a consequence of hydrogen oxidation
side (where x ¼ 0) is a constant, C0, and on the other side (where
and extraction. In the barnacle electrode method, a hydrogen-
x ¼ L) is equal to zero. The time t ¼ 0, in this case, corresponds
containing steel part, with initial uniform diffusible hydrogen
to the time at which the concentration is switched from 0 to C0.
concentration, CH, is galvanically coupled to a nickel–nickel
The solution of equation (47) with the noted initial and bound-
oxide electrode in an alkaline electrolyte.176,177 This couple polar-
ary conditions yields a series, which, to a good approximation,*
izes the steel to a potential at which the hydrogen is oxidized as
can be given by its first term:
it diffuses out while metal oxidation is minimized; iox is related

to mobile hydrogen concentration in the metal by the first term iðtÞ 2 1 1
¼ exp , (47)
solution to Fick’s second law.176 The appropriate boundary con- ið1Þ 1
p2
1
p2 4s
ditions for this equation are @CH/@x ¼ 0, x ¼ 0, t 0; CH ¼ 0,
x ¼ L, t > 0; C ¼ CH 0 < < L, t < 0. where:
=, 1
i(t) and i(1) ¼ the measured currents (proportional to the per-
iox DH 2
meation rate of hydrogen) at a time t and at steady state,
¼ CH (46)
nF pt respectively; and
s ¼ a dimensionless parameter given by s ¼ Dt/L2, where L is the
where: thickness of the membrane.
CH ¼ the mobile or diffusible hydrogen concentration (1 gram- Figure 13 depicts the relationship between i(t)/i(1) and s.
mole H/cm3 Fe ¼ 1.3 105 wt. ppm); The values of s corresponding to some selected values of c are
DH ¼ the apparent diffusion coefficient for H (cm2/s); given in table 3.
t ¼ time, s;
L ¼ one-half the sample thickness so that x ¼ L at the extraction
surface and x ¼ 0 is the center of the specimen, cm; and *This approximation is valid for i(t)/i(1) < 0.96.
solution given by McBreen for the rise transient is used based on

FIG. 13 Plot of permeation rise transient H oxidation current a rearrangement of equation (47):
density expressed as the ratio of the transient current
pffiffiffiffi
density to the steady-state current density (c ¼ l(t)/l(1) pffiffi 2FCo D L2 LogðeÞ 1
Log iðtÞ t ¼ Log pffiffiffi , (49)
versus s ¼ (D/L2)t. The constants associated from the p 4D t
breakthrough and lag time methods can be obtained
from this plot. Selected values are given in table 3. pffiffi
such that a plot of log iðtÞ t versus 1=t versus 1/t is linear
and has a slope of
L2 LogðeÞ
, (50)
4D
where:
t ¼ time after start of charging in seconds,
i(t) ¼ the time dependent permeation flux in amps/cm2,
L ¼ foil thickness in cm, and
D ¼ the diffusion coefficient in cm2/sec.
This solution assumes that the initial subsurface hydrogen
concentration (Co) is zero. This solution is valid for 0.02 < s < 0.9.
This method has been used to determine the effective diffusion
coefficient in high-strength steels.180
For steady-state conditions we have
nFDCo
ið1Þ ¼ , (51)
L
and knowing the value of D from the transient, the concentration

C0 ¼ C(0, t) at t ¼ 1 can be calculated.
TABLE 3 Selected Values of c and s This is the diffusible hydrogen concentration under the con-
ditions of interest. HE severity is often proportional to this
steady-state diffusible hydrogen concentration when specimens
c ¼ i(t)/i(‘) s ¼ Dt/L2
are charged at the same hydrogen overpotential as used in the
0.10 0.066
permeation experiment. ASTM G148 describes this method.
0.30 0.101
0.50 0.138
Evaluation of Alloy Sensitization
0.63 0.167
0.70 0.192
Measurement of the coulombs generated during the electro-
0.90 0.304
chemical polarization of a material from the passive range to the
active corrosion potential can be used to quantify the susceptibil-
ity to intergranular attack associated with the precipitation of
chromium carbides and chromium nitrides at grain bound-
The diffusion coefficient may be determined from the tran-
aries.181–183 The method is described by ASTM G108, Standard
sient permeation current density at various times and selected
Test Method for Electrochemical Reactivation (EPR) for Detecting
foil thickness,
Sensitization of AISI Type 304 and 304L Stainless Steels. A modi-
D ¼ s c L2 =t c , (48) fication of this procedure, called the double-loop electrokinetic
repassivation test,184,185 involves a potentiodynamic polarization
where: of the metal surface initially from the OCP in the active region to
sc ¼ the time required to reach a current i(t) ¼ ci(1), and a potential in the passive range. This is immediately followed by
sc ¼ the corresponding value of s. reverse polarization in the opposite direction back to the OCP.
This forms the basis of the lag time and breakthrough time The second method is less dependent on surface finish and pre-
methods discussed in ASTM G148, Standard Practice for Evalua- cise knowledge of the grain size. Both variations of the method
tion of Hydrogen Uptake, Permeation, and Transport in Metals are illustrated in figure 14. In the latter method, the degree of sen-
by an Electrochemical Technique. A test of the validity of the sitization is determined by the ratio, (Ir/Ia), of the maximum cur-
assumptions leading to equation (47) is to calculate D from rent generated in the reactivation, lr, or reverse scan compared
equation (48) for different values of c and show that it is inde- with that generated in the initial anodic scan, Ia. The procedure
pendent of c. An alternative approach facilitates determination is contingent on the presence of anodic current during the reacti-
of D from a linear regression of many data points, instead of vation scan that results mainly from incomplete passivation of
relying on a single data point on the rise transient. Here, the the zone adjacent to the grain boundaries that is depleted of
GS ¼ the ASTM grain size in accordance with ASTM E112, Stan-

FIG. 14 Schematics of two procedures for anodic reactivation
dard Test Methods for Determining Average Grain Size.
polarization testing. (A) The Clarke method involves a
180,181
The same procedure can be used to normalize the ratio
downward reactivation scan; and (B) the Akashi
Ir/Ia.185 The current peak, Ir, for the reactivation scan is normal-
method involves an upward scan to the passive state
182,183
ized for the GBA, while the initial anodic current peak remains
followed by a reverse scan.
normalized to As, as follows:

ir Ir
¼ : (54)
ia Ia ½5:09544 103 exp ð0:34696 GSÞ
Ir/Ia ratios approaching 1 imply sensitization. A number of

investigators have correlated this electrochemically derived ratio
with optical metallographic evaluations of the degree of material
sensitization, such as those outlined in ASTM A262, Standard
Practices for Detecting Susceptibility to Intergranular Attack in
Austenitic Stainless Steels. This has been accomplished for several
different iron-nickel-chromium alloys.186–188 The technique is
nondestructive to the underlying metal and can be applied in the
field.
ELECTROCHEMICAL EVALUATION OF PROTECTIVE

COATINGS AND FILMS
Numerous AC and DC electrochemical methods have been used
to study the performance and the quality of protective coatings,
which include passive films on metallic substrates, and to evalu-
ate the effectiveness of various surface pretreatments. Several are
discussed in the following sections.
Anodized Aluminum Corrosion Test

The Ford anodized aluminum corrosion test (FACT)189 involves
the cathodic polarization of the anodized Al surface by using a
small cylindrical glass clamp-on cell and a special 5% sodium
chloride (NaCl) solution containing cupric chloride (CuCl2)
acidified with acetic acid. A large voltage is applied across the
cell by using a platinum auxiliary electrode. The alkaline condi-
tions created by the cathodic polarization promote dissolution at
small defects in the anodized Al. As the coating resistance is
decreased, more current begins to flow, and the voltage
decreases. The cell voltage (auxiliary electrode to test specimen
chromium because of carbide precipitation at grain boundaries.
voltage) is monitored for 3 min and the cell voltage multiplied
For nonsensitized material, the passive film remains essentially
by time is recorded. Former standard ASTM B538-70, Method
intact during the reverse scan and the magnitude of the reactiva-
of FACT (Ford Anodized Aluminum Corrosion Test) (Withdrawn
tion polarization peak remains small. For the same reasons, the
1986), described this method. This standard has been withdrawn
charge, Q, obtained from integration of current versus potential
because some Al alloys failed the test but still performed well
for a known voltage scan rate in the single-loop method is small
in service. A similar test, known as the cathodic breakdown
for nonsensitized material. As a refinement to the method, the
test, involves cathodic polarization to -1.6 V versus saturated cal-
charge is normalized by the grain-boundary area (GBA) because
omel electrode (SCE) for a period of 3 min in acidified NaCl.190
this is the area from which most of the current arises in the sin-
Again, the test was designed for anodized Al alloys because
gle reactivation scan:183
the alkali created at the large applied currents will promote the
P ¼ Q=GBA, (52) formation of corrosion spots at defects in the anodized film.
Today, EIS provides a more informative approach to examining
GBA ¼ As ½5:09544 103 exp ð0:34696 GSÞ, (53) anodized Al.
where: The Electrolytic Corrosion Test

P ¼ the reaction charge density associated with the sensitized The electrolytic corrosion test was designed for electrodeposits of
area, coulombs/cm2, nickel and chromium on less noble metals, such as zinc or
As ¼ the wetted specimen surface area, GBA, and steel.20,191–192 Special solutions are used, and the metal is polarized
to þ0.3 V versus the standard calomel electrode. The metal is interface. It is possible to monitor the polarization resistance of
taken through cycles of 1 min anodically polarized and 2 min the corroding interface under the coating with this technique. In
unpolarized. An indicator solution is then used to detect the pres- this respect, the electrochemical impedance technique offers sev-
ence of pits that penetrate to the substrate. Each exposure cycle eral advantages over DC electrochemical techniques in that resis-
attempts to simulate one year of exposure under atmospheric- tances related to the corrosion rate can be separated from the
corrosion conditions. Former standard ASTM B627, Test Method high DC resistance of the dielectric coating. This is not possible
of Electrolytic Corrosion Testing (EC Test) (Withdrawn 1998), with the DC methods. Because a large frequency bandwidth is
described the method. used for the applied signal (usually from the mHz range to the
kHz range), the electrochemical impedance technique is
The Paint Adhesion on a Scribed Surface Test
“spectroscopic” and surpasses the capabilities of single-frequency
This involves the cathodic polarization of a small portion of
impedance methods. The reason for this lies in the capability of
painted metal. The area exposed contains a scribed line that
the electrochemical impedance technique to discriminate
exposes a line of underlying bare metal. The sample is cathodi-
between the resistive properties of the coating or passive film,
cally polarized for 15 min in 5% NaCl. At the end of this period,
which arise because of its ionic or electronic conductivity and
the amount of delaminated coating is determined from an adhe-
the capacitive nature of the passive film or coating, which result
sive tape pulling procedure.
from its dielectric constant, area, and thickness. Although
impedance circuit models for coatings (fig. 15) contain more ele-
THE SINGLE-FREQUENCY IMPEDANCE TEST FOR
ments than the model shown in figure 4 for bare metals, fre-
ANODIZED ALUMINUM
quency regimes in which impedance information is primarily
The method described by ASTM B457, Standard Test Method for
due to the coating capacitance or coating resistance can be sepa-
Measurement of Impedance of Anodic Coatings on Aluminum, is
rated from one another and analyzed independently by using a
used to study the seal performance of anodized Al.193,194 This
broad frequency bandwidth. If the coating or passive film capaci-
method uses a 1-V rms 1-kHz signal source from an impedance
tance can be determined by impedance analysis and if the dielec-
bridge to determine the sealed anodized Al impedance. The test
tric constant is known, then the film thickness can be estimated
area is again defined with a portable cell, and a platinum or
for a given exposed area, as follows:
stainless steel auxiliary electrode is typically used. The sample is
immersed in 3.5% NaCl (see ASTM B457). ee0 A
C¼ , (55)
d
EIS Methods
The EIS method offers an advanced method of evaluating the where:
performance of metallic-based coatings (passive film forming A ¼ the surface area, cm2;
and/or conversion coatings) and the barrier properties of organic d ¼ the dielectric thickness, cm;
coatings and corrosion rates under paints.195–203 The method e0 ¼ the electric permittivity of a vacuum (8.854 10-12 F/m);
does not accelerate the corrosion reaction and is nondestructive. and
The technique is quite sensitive to changes in the resistive- e ¼ the dielectric constant for the passive film or coating.
capacitive nature of coatings as well as the electrochemical In addition to this relationship between thickness and area
of dielectric and capacitance, the uptake of water in an organic
coating can be monitored because the dielectric constant for
FIG. 15 Electrical equivalent circuit to simulate a coated steel water is more than an order of magnitude greater than the
panel with a defect.
196,197,199
RD is the coating defect dielectric constant for the dry organic coating. The quantity of
resistance, RT is a charge transfer resistance (similar to water absorbed in the organic coating can be estimated as
Rp) at the metal interface where water has penetrated, follows:196,198
and Cc is the coating capacitance. 2 3
100 log CC0t
vol:%H2 O ¼ 4 5, (56)
log ð79Þ
where:
Ct ¼ the coating capacitance after some exposure time, and
C0 ¼ the initial coating capacitance at time zero when the expo-
sure begins.
The coating resistance also can be monitored as a function
of exposure time. Large decreases signify permeation of ionic
species through the coating or the presence of defects in the coat-
ing.202,203 The breakpoint frequency is a useful method for esti-
mating the area fraction of physical defects in an organic
coating.201–204 The following expression describes the dependency
between the high-frequency breakpoint frequency and defect

area: FIG. 16 Theoretical Bode Magnitude and Phase Angle Plots for
various known electrochemically active defect areas for a
1 Ad coating containing a cylindrical defect penetrating to the
fbpt ¼ , (57)
2pee0 q A metal substrate and no delaminated regions: (A) Bode
magnitude, and (B) Bode Phase Angle. ASTM visual
where: ratings with the percent of area damaged as blisters or
Ad ¼ the defect area where electrochemical reactions operate, rust spots according to standards ASTM D610, Standard
A ¼ the total painted surface area, and Practice for Evaluating Degree of Rusting on Painted
q ¼ the resistivity of the coating at defects. Steel Surfaces, and ASTM D714, Standard Test Method for
Thus, fbpt can track with change in defect area provided that Evaluating Degree of Blistering of Paints, are included for
decreases in p over time and increase in e with electrolyte uptake comparison.
202
do not dominate. Under such circumstances, the term preceding

the ratio (Ad/A) remains constant. In this case, increases in fbpt
occur mainly as a function of the increases in the defective area.
Circumstances may exist, however, in which small increases Ad
in e and very large decreases in p occur so that fbpt does not relate
linearly to defect area.
Moreover, bare metal under delaminated coating regions
may not be detected under all circumstances, especially if the
coating resistivity over the delaminated area and dielectric con-
stant are identical to those in regions where the coating is not
delaminated. The hypothetical relationship between fbp, and the
open defect area is shown in figure 16.204 No ASTM standard cur-
rently exists for conducting impedance measurements on coated
metals.
Electrochemical Noise Methods for Organic Coating

Evaluation
Electrochemical noise (EN) methods also have been explored as
a method to analyze the degradation of polymer-coated met-
als.205–209 A variety of methods have been used. A common
method involves the use of a cell with two identical working elec-
trodes connected through a ZRA. The entire galvanic couple is
coupled through a high impedance voltmeter to an ideally noise-
less reference electrode. Two samples often experience drastically
different behavior; for instance, if one electrode has a coating
defect and the other does not, then asymmetrical electrode
behavior results. The spectral noise impedance obtained is equiv-
alent to the geometric mean of the moduli of individual electrode
impedances. Instrument noise should be carefully considered
when this approach is used to analyze high-resistance coatings.
No ASTM standard currently exists for conducting EN tests on
coated metals.
CHARACTERIZATION OF ANODIZED SURFACES

AND CONVERSION COATINGS ON METALS
The impedance technique also provides a useful approach for
characterizing anodization,210–212 conversion coatings, sealing of
anodized layers, and passivity.213 ASTM STP1188, Electrochemi- Apparatus, salt spray test.218 This value must be passed after a
cal Impedance: Analysis and Interpretation, covers some of these 24-h exposure to aerated 0.5 M NaCl solution.219 EIS studies of
applications.214 EIS methods also have been applied to the study synthesized bulk copper-based intermetallic compounds have
of conversion coatings.215–217 In the case of conversion coatings, improved insight on the role of conversion coatings in affecting
an impedance modulus of 1–2 megaohm-cm2 at the DC limit is the electrochemical properties of intermetallic compounds.220
a threshold value required for the conversion coating to pass an Such phases are often responsible for microgalvanic corrosion of
ASTM B117, Standard Practice for Operating Salt Spray (Fog) Al-base alloys.
Scanning Kelvin Probe (SKP) in figure 17 illustrates this. The point at which coating adhesion is
The scanning Kelvin probe (SKP) technique is a local electro- lost is taken as the midpoint of a sharp drop in potential that
chemical technique used for atmospheric-condition investiga- connects the potential in the remaining intact region (Eintact) to
tions of under-film cathodic delamination221–226 and anodic the delaminated region. The latter is polarized by the anodic
filiform corrosion227–233 on polymer-coated surfaces as well as reaction, which typically occurs exclusively in the defect, depend-
hydrogen permeation234–237 and the corrosion underneath a ing on the metallic substrate.224 The build-up of OH- in the
water droplet.238 The technique is completely nonperturbing and underfilm region results in base-catalyzed hydrolysis of the inter-
enables the temporal and spatial resolution of corrosion potential facial bonds, resulting in loss of coating adhesion.229 Cathodic
distributions beneath intact and delaminated organic coatings. A delamination of an uninhibited coating usually will initiate
lateral resolution of 0.1 mm (depending on the probe diameter within several hours depending on the substrate and proceed
and probe-specimen distance239) is typical and a limitation if a with parabolic kinetics where the limiting factor is the migration
study of features on a smaller length scale is required. The of sodium cations from the defect to the delamination front. The
higher-resolution scanning Kelvin probe force microscope mode of inhibition can be determined by analysis of the rate
(SKPFM) is recommended for such requirements.233 The setup kinetics, the Eintact values, and the time for delamination to
and calibration of the SKP is well documented224 and will be occur. A transformation from parabolic to linear kinetics is typi-
described here in brief. A thin (typically between 5 lm and cally a result of, but not limited to, one of the two following
125 lm) gold probe is rastered above a specimen surface at a conditions:
height of approximately 100 lm. An external circuit creates an
electrical connection between the specimen and the probe and 1. The formation of a passive layer during coating deposi-
the potential required to nullify the resultant current flows is tion (typical of an etch primer) such that electron trans-
measured giving the Volta potential difference, or Kelvin probe fer at the substrate/coating interface becomes the rate
potential (EKP). This can be converted to corrosion potential limiting step.
(Ecorr) via the following equation: 2. The addition of pigments to the coating can act as a bar-
rier to oxygen permeation such that the vertical diffu-
Ecorr ¼ Ekp þ constant, (58) sion of oxygen becomes the rate limiting step.
where the constant is obtained from an offset measured by tak-

Retention of parabolic kinetics with a reduced rate is typi-
ing an SKP measurement of a redox couple (typically Cu/Cu2þ)
cally a result of a noncontinuous blocking layer that increases
and comparing it to a known or potentiostat-measured value.
the tortuosity of the pathway of migrating sodium cations. A
The effect of a polymer film must be taken into account in cases
phenomenon has been reported on conducting polymer and
in which a free-standing film is laid over the aqueous media in
graphene-based coatings where parabolic kinetics are accompa-
the redox couple while the SKP measurement is taken. Further-
nied by an elevated Eintact, which has been shown to be the dis-
more, in the case of a delaminated polymer film, where a layer of
placement of the cathodic reaction from the substrate–coating
electrolyte is present through an ingress between the substrate
metal and the polymer layer, a so-called Donnan potential
(DuD) must be taken into consideration. DuD can be described
as the Galvani potential difference established between the poly- FIG. 17 Schematic diagrams showing the cathodic delamination
mer layer and the electrolyte solution (i.e., uEl - uPol240,241). DuD and the progression of SKP-measured corrosion
can be minimized, such that it is considered negligible, by using potentials where the midpoint of the sharp drop in
model coatings that are chemically unlikely to develop a fixed potential represents the point of coating adhesion
charge density (such as polyvinyl-butyral224) and electrolytes failure.
222,240
with high salt content (i.e., 0.86 M NaCl (aq)).224 Experiments

are conducted inside a Faraday cage that also enables control of
the humidity, which must be maintained at a consistently high
level.
The most common use for the SKP in corrosion studies is
to monitor cathodic delamination, which will be discussed
herein. Investigations of this nature were pioneered by Strat-
mann,242,243 who developed a now well-utilized method for
assessing cathodic delamination occurring at coating defects.
The method is particularly useful for assessing the performance
and inhibition mechanism of in-coating corrosion inhibi-
tors.244,245–246 After the introduction of an electrolyte to the
defect, the progression of a cathodic delamination front is moni-
tored periodically using line profiles that extend across the intact
coating from the edge of the defect, the schematic diagram given
interface into the coating, which prevents the increase in local Processes and on the Potential of Mixed Electrodes,”
pH at the interface and, hence, loss of adhesion.222,223 The inhibi- Electrochem 44, (1938): 843–855.
tory effect of inhibitor leaching can be detected by a delay in the 18. W. D. France, Jr., “Controlled Potential Corrosion Tests, Their
onset of delamination and a change in the measured potential Applications and Limitations,” Materials Research
near the defect. This can be demonstrated with an experiment Standardization 9, no. 8 (1969): 21.
with an uninhibited coating and the addition of the inhibitor
19. Z. Tafel, “About the Polarization in Cathodic Hydrogen
into the defect electrolyte.224,230
Evolution,” Physical Chemistry 50 (1904): 641.
20. R. L. Saur and R. P. Basco, “An Accelerated Electrolytic Corrosion

Test and a Corrosion Analysis Procedure for the Nickel-
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Coating Delamination,” Corrosion Science 100 (2015): 607–618.
235. G. Schimo, W. Burgstaller, and A. W. Hassel, “Rolling Direction
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“Evaluation of Multi-Layered Graphene Nano-Platelet Composite SDCM Charging and SKP Probing,” ISIJ International 56 (2016):
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Effects in Polyaniline Inhibition of Corrosion-Driven Organic 3D Printed Microelectrochemical Cell,” Electrochemistry Commu-
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Inhibition of Corrosion-Driven Organic Coating Delamination itors,” Materials and Corrosion 65 (2014): 351–361.
Studied Using a Scanning Kelvin Probe Technique,” Journal of
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by Inhibition of Cation Migration along ZnjPolymer Interface in
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A. J. Coleman, “The Kinetics and Mechanisms of Filiform
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55 (2010): 7843–7852. and K.-H. Grobe-Brinkhaus, “The Scanning Kelvin Probe: A New
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229. G. Williams and H. N. McMurray, “The Mechanism of Group (I) Coatings,” Progress in Organic Coatings (1996): 261–267.
Chloride Initiated Filiform Corrosion on Iron,” Electrochemistry
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Investigations on the Delamination of Polymeric Coatings from
230. G. Williams and H. N. McMurray, “Polyaniline Inhibition of Filiform Metallic Surfaces,” Progress in Organic Coatings 39 (2000): 23–29.
Corrosion on Organic Coated AA2024-T3,” Electrochimica Acta
54 (2009): 4245–4252. 244. C. F. Glover, R. Subramanian, and G. Williams, “In-Coating Phenyl
Phosphonic Acid as an Etch-Primer Corrosion Inhibitor System
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on Polymer Coated AA2024-T3 by Hydrotalcite-Like Pigments Society 162 (2015): C433–C441.
Incorporating Organic Anions,” Electrochemical and Solid-State
Letters 7 (2004): B13–B15. 245. C. F. Glover, C. Richards, J. Baker, G. Williams, and H. N. McMurray,
“In-Coating Graphene Nano-Platelets for Environmentally-Friendly
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“Time-Lapse Potentiometric Imaging of Active Filiform Corrosion 169–172.
Using a Scanning Kelvin Probe Technique,” Physical Chemical
Communications 4 (2001): 1–6. 246. M. Rohwerder, S. Isik-Uppenkamp, and C. A. Amarnath,
“Application of the Kelvin Probe Method for Screening the
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in Shreir’s Corrosion, Vol. 2: Corrosion in Liquids, Corrosion for Corrosion Protection,” Electrochimica Acta 56 (2011):
Evaluation, ed. T. A. J. Richardson (Oxford, UK: Elsevier, [2009] 1889–1893.
2016), 988–1004.
141
Chapter 9 | Immersion Testing
Bradley D. Krantz1
Introduction The following discussion is focused on immersion testing of

metals. Similar procedures can be utilized for nonmetallic mate-
Most chemical plant processes are complex. Materials of con- rials with some modifications to methods of evaluation but are
struction for process equipment and piping must be selected not included in this discussion.
with care to ensure adequate corrosion resistance during opera-
tion of those plants. Sustainable operation is critical to plant
safety and business vitality. In a well-designed plant, materials Basic Principles
selection should be based on as much information as is available.
The information on which materials selection is based can For any given chemical process, it is not always possible to pre-
include the following, in the relative order of usefulness: prior dict which forms of corrosion will occur, or even which chemical
service history, in-plant monitoring and testing, pilot plant eval- or parameter will dominate the corrosion scenario. Process flow
uations, and laboratory corrosion tests. diagrams define certain chemicals and “normal” operating con-
As is usually the case, not all of the desired data are avail- ditions, but they frequently overlook effects of trace elements
able. In many cases, actual service history regarding materials (impurities), transient conditions, or chemical intermediates.
performance is not available or in-plant corrosion studies were Such factors can have a major effect on corrosion and hence
not performed. Plant personnel are rarely trained to evaluate cor- materials performance. Subtle changes in pH can shift electro-
rosion failures thoroughly and detailed failure analysis may not chemical potentials, for example, from a passive range into a pit-
have been performed or sufficiently documented. New processes ting range. Certain ionic species, while having little effect in the
naturally will not have a service history or corrosion studies that bulk environment, can act as accelerating charge carriers when
can be utilized. In such instances, pilot plant studies are critical. concentrated inside a pit or crevice. Such factors must be consid-
For practical and economic reasons, however, such studies usu- ered when designing a laboratory corrosion test.
ally are conducted for short test periods and thus long-term cor- Laboratory corrosion test parameters usually are separated
rosion performance data are unavailable. into two groups: chemical and physical. Chemical parameters
When various factors have eliminated other data sources, include not only the concentration of various compounds but
laboratory corrosion tests are often the only reliable source of also such factors as dissociation, pH, phase equilibrium (espe-
corrosion data for screening candidate materials. If these tests cially vapor phase chemistry), dissolved gases, conductivity, and
are well planned, they can provide the information necessary for degradation reactions caused by the candidate test materials
intelligent plant design and proper selection of materials of con- themselves. Relevant physical parameters include temperature
struction. Laboratory tests also offer unique advantages over in- (including temperature gradients and heat transfer), pressure,
plant tests: for example, many test parameters can be varied and flow velocity, surface area effects (such as ratio of volume-to-
evaluated, and exposure conditions can be controlled or acceler- surface area of corrosion test coupons), and time (i.e., test dura-
ated to simulate worst-case scenarios. In contrast, poorly tion). Also important are cyclical changes in these parameters. It
designed or improperly run and interpreted corrosion tests can is often cost and time prohibitive to conduct a full factorial study
give misleading information that can lead to costly materials to determine the effects of all variables, so educated decisions
selection errors. must be made as to which variables might be important in a par-
ticular process and how many variations of each parameter
should be included in the corrosion test program.
1
Depending on the expected mechanism of corrosion (i.e.,
Corrosion Testing Laboratories, Inc., 60 Blue Hen Dr., Newark, DE 19713, USA
general or localized pitting, crevice, environmentally assisted
The authors acknowledge the previous author of this chapter, Richard A. Corbett, cracking or galvanic attack), different tests are usually required
Corrosion Testing Laboratories, Inc., Newark, DE. to determine the susceptibility to attack. Table 1 summarizes
DOI: 10.1520/MNL202NDSUP20190004
TABLE 1 Common Forms of Corrosion and Laboratory Evaluation Tests
Occurrence in
Mode of Attack Industry (Typical) Evaluation Tests ASTM Std. (Typical)
General 28% Total Immersion Tests (Atmospheric & G31, Standard Guide for Laboratory Immersion Corrosion Testing of Metals
Corrosion Autoclave)
Multiphase (liquid, vapor, condensate, G31
interface) Tests
Hot Wall
Electrochemical Polarization G5, Standard Reference Test Method for Making Potentiodynamic Anodic Polarization
Measurements
Electrochemical Impedance G106, Standard Practice for Verification of Algorithm and Equipment for Electrochemi-
cal Impedance Measurements
Stress Corrosion 24% Boiling Chloride U-Bend Tests G36, Standard Practice for Evaluation Stress-Corrosion-Cracking Resistance of Metals
Cracking and Alloys in a Boiling Magnesium Chloride Solution
G123, Standard Test Method for Evaluating Stress-Corrosion Cracking of Stainless Alloys
with Different Nickel Content in Boiling Acidified Sodium Chloride Solution
Wick Test C692, Standard Test Method for Evaluating the Influence of Thermal Insulations on
External Stress Corrosion Cracking Tendency of Austenitic Stainless Steel
Polythionic Acid Cracking Test G35, Standard Practice for Determining the Susceptibility of Stainless Steels and Related
Nickel-Chromium-Iron Alloys to Stress-Corrosion Cracking in Polythionic Acids
Caustic Solution Cracking Tests
Custom Process Solution Testing
Pitting Corrosion 15% Ferric Chloride Immersion Test G48, Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless
Steels and Related Alloys by Use of Ferric Chloride Solution
Cyclic Potentiodynamic Polarization G61, Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Meas-
(Hysteresis) urements for Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys
Critical Pitting/Crevice Temperature G48
Determination
Seawater/Marine Exposure Testing G78, Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stain-
less Alloys in Seawater and Other Chloride-Containing Aqueous Environments
Surgical Implant Test F2129, Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Meas-
urements to Determine the Corrosion Susceptibility of Small Implant Devices
F3044, Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Meas-
urements to Determine the Corrosion Susceptibility of Small Implant Devices
Green Death Test
Critical Pitting Potential Test G5
(Potentiostatic)
Crevice 2% Critical Pitting/Crevice Temperature G48, G150, Standard Test Method for Electrochemical Critical Pitting Temperature Test-
Corrosion Determination ing of Stainless Steels and Related Alloys
Multi-Crevice Washer/Process Solutions G48, G78
Intergranular 15% Electrolytic Oxalic Acid Screening Test A 262[A], Standard Practices for Detecting Susceptibility to Intergranular Attack in Aus-
tenitic Stainless Steels
Ferric Sulfate-Sulfuric Acid (Stretcher A 262[B]
Test)
Nitric Acid (Huey Test) A 262[C]
Copper Sulfate-Sulfuric Acid Test A 262[D]
EPR Test (Electrochemical Potentioki- G108, Standard Test Method for Electrochemical Reactivation (EPR) for Detecting Sensi-
netic Reactivation) tization of AISI Type 304 and 304L Stainless Steels
Erosion 7% Miller Test G75, Standard Test Method for Electrochemical Reactivation (EPR) for Detecting Sensiti-
Corrosion Rotating Spindle, Cage, or Disk Tests zation of AISI Type 304 and 304L Stainless Steels
De-alloying 2% Total Immersion Testing for De-alloying G31
Galvanic Couple Test G71, Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in
Electrolytes
Electrochemical Tests G5
Exfoliation of Aluminum Tests G34, Standard Test Method for Exfoliation Corrosion Susceptibility in 2XXX and 7XXX
Series Aluminum Alloys (EXCO Test)
(continued)
IMMERSION TESTING 143
TABLE 1 (continued)
Occurrence in
Mode of Attack Industry (Typical) Evaluation Tests ASTM Std. (Typical)
Galvanic 1% Dissimilar Metal Couple Immersion Test G31

Galvanic Couple Test G71
Zero Resistance Ammeter G3, Standard Practice for Conventions Applicable to Electrochemical Measurements in
Electrochemical Tests Corrosion Testing
some of the more common forms of corrosion and the appropri- predict the performance of an alloy to the test solution. In such
ate laboratory tests used to evaluate the susceptibility of a mate- cases, weight loss per unit of surface area and the depth of the
rial to a specific mode of attack.1 Many of these tests are nonuniform attack may be used to avoid implying a uniform
accelerated rather than simulating service conditions and are penetration rate.
performed routinely to provide information for use in Ideally, laboratory tests should use actual solutions from
plant processes. This often can be impractical. In these instances,
• fundamental corrosion evaluation, test solutions are prepared from reagent grade chemicals and
• failure analysis, using reagent water (ASTM D1193, Standard Specification for
• corrosion prevention or control, Reagent Water, Type IV or better) to simulate the environment
as closely as possible. No matter what the source of the test
• acceptance for quality assurance, solution, its composition should be controlled accurately and
• environmental issues involving corrosion, and described in the test report as completely as possible. Minor con-
• new alloy/nonmetallic or product process development. stituents should not be overlooked because they can affect the
corrosion rate. Chemical content may be reported as percentage
Customized and unique test setups to evaluate heat transfer, by weight, molarity, or normality. The composition of the test
thermal shock, velocity, fatigue, or abrasion and wear effects also solution can be checked before and after testing to determine the
are used to determine the susceptibility of a material to a specific extent of change in composition. Evaporation losses should be
environment or process. controlled by a constant level device, by frequent additions of
the evaporating solution, or by use of cooled condensers to
TEST CONDITIONS maintain the original volume within 61%. Sometimes, an envi-
The selection of conditions for a laboratory corrosion test should ronmental sampling plan is necessary to ensure that the solution
be determined by the expected results and the purpose of the test. components of interest remain within the desired range.
If the test is to be a guide for the selection of a material for a par- In some situations, the composition of the test solution may
ticular application, then the limits of the controlling factors under change as a result of the build-up of corrosion products in the
service conditions must be determined. Normally these factors solution, catalytic decomposition, or reaction with the test speci-
include, but are not limited to, service temperature ranges, process mens. If these changes are expected to occur, consideration
fluid flow rates, pH, atmosphere—for example, air, carbon dioxide should be given to periodic solution adjustments or replacement
(CO2), hydrogen sulfide (H2S), ammonia (NH3), nitrogen (N2), with fresh solution. Sometimes it may be of interest to measure
and mixed gases—aqueous or organic phases, and other charac- the metal ion content as a method of measuring corrosion.
teristics of the bulk solution (e.g., impurities or contaminants). Wherever possible, only one type of alloy or family of non-
There should be an effort to ensure duplication of the service metallics should be exposed in a given test apparatus. If several
conditions in the laboratory corrosion test, with conditions alloys or nonmetallics are exposed in the same apparatus the cor-
adequately controlled during the entire test duration to ensure rosion products from one material may affect the corrosion
reproducible results. behavior of other materials. For example, copper corrosion prod-
Experience has shown that, at a minimum, duplicate test ucts can inhibit corrosion of stainless steels but accelerate corro-
specimens should be exposed in each test. Under laboratory tests, sion of aluminum and its alloys.
corrosion rates of duplicate specimens are usually within 6 10% If different alloys are galvanically coupled in a particular
of each other, when the attack is uniform. Occasional exceptions, process, these dissimilar metal couples must be reproduced in
in which a large difference is observed, can occur under conditions the laboratory test. For example, in ASTM D1384, Standard Test
of borderline passivity of alloys that depend on a passive film for Method for Corrosion Test for Engine Coolants in Glassware;
their resistance to corrosion. If the rate difference exceeds 10%, ASTM D2570, Standard Test Method for Simulated Service Cor-
re-testing should be considered, unless it is observed that a rosion Testing of Engine Coolants; or D2758, Standard Test
localized attack is predominant. Corrosion rates are calculated Method for Engine Coolants by Engine Dynamometer, copper,
assuming a uniform loss of metal; therefore, when specimens brass, and solder found in the radiator and heaters in automo-
are attacked nonuniformly, the calculated corrosion rates only biles are electrically connected and tested in the same laboratory
indicate the relative severity of attack and should not be used to apparatus.
PHYSICAL PARAMETERS may affect further corrosion. The preferred minimum solution
Temperature volume-to-specimen surface area ratio is 20 mL/cm2 (130 mL/in2).
The temperature of the test solution should be controlled within When the test objective is to determine the influence of a
61 C and should be stated as such in the report of test results. metal or alloy on the test solution, it may be desirable to repro-
When the test temperature is well above ambient, some form of duce the solution volume-to-surface area ratio that exists in prac-
stirring may be necessary to avoid temperature gradients in the tice. The time of contact also should be replicated in this type of
test solution. If no specific temperature, such as boiling, is application.
required or if a temperature range is selected, this also should be On occasion, a low volume-to-surface area ratio is unavoid-
reported. For processes that are conducted under ambient condi- able. In these instances, periodic replenishment of the corrodent
tions, the laboratory tests should be conducted at the highest or complete replacement of the test solution should be considered.
temperature anticipated, for example, outdoor stagnant storage
Methods of Supporting Test Specimens
during the summer months. This temperature may be as high as
It is important that the supporting device and the test apparatus
55 C (1318F). When testing at or near boiling, the use of reflux
should not be affected by or cause contamination of the test solu-
condensers is highly recommended.
tion. The method of supporting test specimens will vary with the
Laboratory tests conducted at the temperature of a process
apparatus used for conducting the test, but they should be
solution may provide misleading results when compared with
designed to insulate the specimens from each other physically
the heat transfer surfaces within an actual in-service vessel where
and electrically (unless the purpose of the test is to evaluate gal-
heated surfaces can be 10 C (18 F), or more, hotter than the
vanic corrosion) and to insulate the specimens from any metallic
bulk process solution. If this condition is expected, it may be
container or supporting device used with the apparatus. Support
necessary to test at higher temperatures than the bulk solution
systems that hold the test specimens tightly may induce crevice
temperature or, preferably, employ specialized test apparatus to
corrosion, which may be an undesirable result unless crevice cor-
simulate the heat transfer effect.
rosion is part of the study. The shape and form of the specimen
Gas Sparging of Solution support should ensure free contact of the specimen with the test
Most laboratory tests used to replicate process equipment solution, the liquid or vapor interface, or the vapor phase, which-
should be controlled with the natural atmosphere inherent ever is applicable. Common supports include glass or ceramic
under process conditions, such as the vapors of the boiling rods or hooks; glass cradles, fluorocarbon plastic thread, or
solution. Some applications may require aeration or deaeration, string; and various insulated or coated metallic supports.
whereas others may require sparging with a particular gas or
Test Duration
gas mixture. If gas sparging is used, the test specimens should
The duration of any laboratory test should be determined by the
not be located in the direct stream of the gas sparge tube. Unde-
nature and purpose of the experiment. The amount of corrosion
sirable effects can be encountered if the gas stream impinges on
attack under any given test condition will depend directly on the
the test specimens.
duration of the test. Materials that experience severe corrosion
Complete removal of oxygen from a test vessel may require
usually do not require long exposure duration to obtain accurate
special procedures to obtain and prevent subsequent ingress of
corrosion rates, with testing periods typically 24–240 h. Results
oxygen (O2). Certain gasses—for example, hydrogen sulfide
from short duration tests can be used to determine whether a lon-
(H2S), carbon monoxide (CO), chlorine (Cl2)—may have addi-
ger duration exposure is warranted. Experience suggests that labo-
tional safety considerations inherent to them or in combination
ratory tests of longer duration are considerably more realistic. This
with the test solution or test conditions.
is particularly important if localized corrosion such as pitting, crev-
Test Solution Flow ice, or environmentally assisted cracking are being investigated.
The effect of process solution flow is not usually determined in Relying solely on short-term tests can yield misleading
normal laboratory tests, although specific tests have been results. For example, aluminum exposed to solutions of sodium
designed for this purpose. Tests under boiling conditions should hydroxide corrodes at an extremely high rate, often in excess of
be conducted with minimal heat input, and inert boiling chips an inch per year, while it is building up a protective corrosion
should be used to avoid excessive turbulence and bubble product film. Afterward, the rate decreases dramatically so that
impingement. For tests conducted below the boiling point, ther- further corrosion is almost negligible, provided the film is not
mal convection generally is the only source of liquid agitation in damaged. Conversely, the passive films that form on stainless
the laboratory test, which may or may not be adequate. Test sol- steels may be broken down under prolonged exposure leading to
utions with high viscosities or multiple phases may require sup- rapid localized corrosion. Long-term tests, however, should not
plemental controlled stirring with a magnetic stirrer or a gas proceed to the point at which the original specimen size or the
sparge to maintain a uniform environment. exposed area is drastically reduced or the material is perforated
or dissolved.
Test Solution Volume Corrosion rates determined from a single exposure period
The volume of the test solution should be large enough to avoid assumes that metal loss is linear with time. This may not be the
any appreciable change in its corrosiveness, either through deple- case in practice, however, as many factors can affect corrosion
tion of the corrodent or accumulation of corrosion products that reactions over time. A corrosion rate is really an average of the
varied rate measured over a defined period of time. In some materials may require an initiation period before discernible cor-
instances, the variation of the rate is insignificant and the rosion initiates and then proceeds more rapidly once initiated as
assumption of linearity is appropriate. In other cases, this described for stainless steels. Changes in the test solution can
assumption can be misleading. A prime example is in materials cause a similar effect either through depletion of the corrodent
that rely on a passive film for corrosion resistance. These materi- or concentration of a corrosive by-product. The “Planned Inter-
als may experience a very high corrosion rate until a protective val Test”2 is an excellent procedure for evaluating the effect that
layer has developed, significantly decreasing further corrosion as time has on metal corrosion and solution corrosivity. This tech-
described for aluminum in sodium hydroxide. Conversely, some nique and evaluation of the results are presented in table 2.2
TABLE 2 Planned Interval Test
Specimen # 0 1 t tþ1
1 "
2 "
3 "
4 "
5 Calculated Specimen #3 - #2 "
Four test specimens (#1 through #4) are exposed and a fifth (#5) is a calculated value. All test specimens are exposed in the same test vessel. The test conditions are
held constant throughout the test. The parameter being evaluated is the penetration rate,a as defined in the table note.
Interpretation Criteria
Liquid Corrosiveness: Unchanged if 1¼4

Decreases if 1>4
Increases if 1< 4
Metal Corrodibility Unchanged if 4¼5
Decreases if 4>5
Increases if 4<5
Other Combinations of Interpretation
Liquid Corrosiveness Metal Corrodibility Criteria
1. Unchanged Unchanged 1 ¼ 4 ¼5
2. Unchanged Decreases 1¼4>5
3. Unchanged Increases 1¼4<5
4. Decreases Unchanged 1>4¼5
5. Decreases Decreases 1>4>5
6. Decreases Increases 1>4<5
7. Increases Unchanged 1< 4 ¼ 5
8. Increases Decreases 1< 4 > 5
9. Increases Increases 1< 4 < 5
Specimen Duration Mass Loss Penetrationa Apparent Corrosion rateb
# Days mg mm mils mm/y mpy
1 0–1 1495 0.064 2.4 23 880

2 0–4 2240 0.095 3.6 8.7 330
3 0–5 2280 0.097 3.7 7.1 270
4 4–5 95 0.004 0.15 1.5 55
5 calc. 3–2 40 0.002 0.06 0.7 22
a ðmass loss in mgÞðC-factorÞ

Penetration ¼
ðArea in mm2 or in2 Þ density in g/cm2
where:
C ¼ 1 for mm; or
C ¼ 0.061 for mils.
b ðPenetration in mm or milsÞ365
Apparent Corrosion Rate ¼
Time in days
From penetration information: Specimen 1 > 4 > 5

Based on the interpretation criteria, the liquid has decreased its corrosiveness during the test, and suggests the formation of a protective film owing to a decrease in metal
corrodibility.
Types of Tests occur have been designed, they should be repeated a sufficient
number of times to determine whether it meets the desired reli-
The type of laboratory test that should be used is dictated by the ability standard for reproducibility. Changes in test procedures
environmental conditions that are being simulated. For example, may be required if the reliability is not satisfactory.
if the equipment is immersed in service, then the test specimens If the test procedure is to be used by other laboratories,
should be immersed in the laboratory test; if the exposure alter- either to qualify on the basis of a specification or simply to com-
nates between immersion and atmospheric exposure, because of pare results among laboratories, then it is important that repro-
cyclic exposure to wet/dry conditions, an alternate immersion ducibility of results be determined. This is accomplished through
test designed to replicate these cycles should be used. round-robin (interlaboratory) tests conducted by interested labo-
Another factor that dictates test setup is the allowable test ratories to develop standard test procedures, such as those by
duration to obtain the necessary results. This determines the ASTM International, International Organization for Standardi-
degree to which the test method must be accelerated. The princi- zation (ISO), Japanese Standards Association (JSA), Materials
pal reason for accelerated testing is the need to obtain results Technology Institute (MTI) of the Chemical Process Industries,
sooner than can be obtained under field conditions. Acceleration and the Association for Materials Protection and Performance
may be achieved in a number of ways. A common way to accel- (AMPP, formerly NACE International).
erate a corrosion test is to intensify the test conditions by It is not unusual to use a laboratory test procedure for
increasing the solution acidity, corrodent concentration, temper- which there is no direct correlation with service or field results.
ature, or other parameters. The test specimen configuration may Sometimes correlation cannot be obtained immediately because
be altered, for example, by increasing stress intensity (SCC tests), service results are either not available or are not practical to
adjusting crevice geometry or tightness (crevice corrosion tests), obtain in a reasonable time frame. For example, suppose a com-
or increasing cathode-anode area ratio (galvanic tests). In spe- pany wishes to offer a lifetime warranty of a coating exposed to
cific cases, the contact or exposure time may be increased. For an industrial environment but needs data to back up their claim.
example, if a vessel is to be batch processed with a chemical for Humidity chamber tests plus ultraviolet light exposure can give
24 h, then a laboratory corrosion exposure of 240 h should be “best guess” results in a matter of weeks rather than years of
considered. Care should be taken when accelerating the exposure actual exposure to the elements. Long-term behavior in actual
conditions. Overly aggressive conditions may alter corrosion service environments, however, still serves as the gold standard
mechanisms, disqualify materials that otherwise would be for materials performance. For example, many vendors conduct
acceptable for the intended exposure or both. For example, some long-term atmospheric corrosion-performance studies by expos-
materials may exhibit a critical temperature above which they ing large numbers of test specimens (e.g., coated panels, fasten-
will experience rapid corrosion (such as SCC or pitting on stain- ers, hardware, non-metallics) in marine, industrial, and rural
less steels) but little attack below the critical temperature. environments over many years, sometimes decades. This pro-
Electrochemical corrosion tests may be employed to obtain vides information on such effects as climate, salts, pollutants,
rapid results. These tests typically have a short duration, and ultraviolet, and solar radiation on material performance. Test
most can be completed in a matter of hours versus weeks or results from many previous long-term studies have been
months for immersion testing. These tests also can provide addi- reported widely in the published literature, such as ASTM
tional information that may not be readily evident from immer- Selected Technical Papers, ASM Metals Handbooks, and
sion testing. For instance, immersion testing of several stainless government-funded research.
steel alloys in a salt solution may indicate little or no corrosion Laboratory tests are normally designed around a synthe-
on any of the alloys even after several weeks. The results from sized or contrived environment; however, it is important that the
electrochemical potentiodynamic polarization tests, however, results provide reliable information that can be used to screen
can rapidly screen susceptibility to pitting and crevice corrosion candidate materials of construction.
of candidate test alloys.
Both immersion tests and electrochemical tests have their
pros and cons. Immersion tests are time weighted and evaluated SIMPLE IMMERSION TESTS
based on mass loss and visual evidence of corrosion. Electrochem- There are many variations in a laboratory immersion test. NACE
ical tests provide information on metal-environment interactions /ASTM G31, Standard Guide for Laboratory Immersion Corrosion
and corrosion mechanisms based on electrical measurements Testing of Metals, provides general guidelines on how these tests
taken at a given point in time. Immersion test methods may be may be performed (see table 3 for these and other standard cor-
employed in any environment, whereas most electrochemical rosion test procedures). Basically, small pieces (i.e., 2.5 cm by 5
methods are limited to electrically conductive environments. cm by 0.3 cm thick) of the candidate material are exposed to the
Many times it is beneficial to use both testing methods in the test medium, and the loss of weight of the material is measured
materials selection process. A more detailed description of electro- for a given period of time. Immersion testing remains the best
chemical test methods may be found in other chapters of this relatively quick method to screen candidate materials for corro-
book that deal specifically with electrochemical corrosion testing. sion resistance. The most serious disadvantage of this method of
Once the service conditions of the test have been deter- corrosion study is the assumed average-time weight loss. The
mined, and evaluation tests for all forms of corrosion that might corrosion rate could be high initially and then decrease with
TABLE 3 Standard Corrosion Test Procedures
NACE STANDARDS
No. Title
TM-0169 Laboratory Corrosion Testing of Metals at Atmospheric Pressure

TM-0174 Laboratory Methods for the Evaluation of Protective Coatings Used as Lining Materials for Immersion Service
TM-0177 Testing of Metals for Resistance to Sulfide Stress Cracking at Ambient Temperatures
TM-0196 Chemical Resistance of Polymeric Materials by Periodic Evaluation
TM-0284 Test Method for Evaluation of Pipeline Steels for Resistance to Stepwise Cracking
TM-0286 Cooling Water Test Units Incorporating Heat Transfer Surfaces
TM-0416 Test Method for Monitoring Atmospheric Corrosion Rate by Electrochemical Measurements
ASTM STANDARDS
No. Title
A262 Standard Practices for Detecting Susceptibility to Intergranular Attack in Austenitic Stainless Steels
A763 Standard Practices for Detecting Susceptibility to Intergranular Attack in Ferritic Stainless Steels
C692 Standard Test Method for Evaluating the Influence of Thermal Insulations on External Stress Corrosion Cracking Tendency of Austenitic Stainless Steel
D1384 Standard Test Method for Corrosion Test for Engine Coolants in Glassware
D2570 Standard Test Method for Simulated Service Corrosion Testing of Engine Coolants
F2129 Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements to Determine the Corrosion Susceptibility of Small Implant
Devices
F3044 Standard Test Method for Evaluating the Potential for Galvanic Corrosion for Medical Implants
G1 Standard Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens
G3 Standard Practice for Conventions Applicable to Electrochemical Measurements in Corrosion Testing
G4 Standard Guide for Conducting Corrosion Tests in Field Applications
G5 Standard Reference Test Method for Making Potentiostatic and Potentiodynamic Measurements
G28 Standard Test Methods of Detecting Susceptibility to Intergranular Attack in Wrought Nickel-Rich, Chromium-Bearing Alloys
G31 Standard Guide for Laboratory Immersion Corrosion Testing of Metals
G34 Standard Test Method for Exfoliation Corrosion Susceptibility in 2XXX and 7XXX Series Aluminum Alloys (EXCP Test)
G35 Standard Practice for Determining the Susceptibility of Stainless Steels and Related Nickel-Chromium-Iron Alloys to Stress-Corrosion Cracking in
Polythionic Acids
G36 Standard Practice for Evaluating Stress-Corrosion-Cracking Resistance of Metals and Alloys in a Boiling Magnesium Chloride Solution
G44 Standard Practice for Exposure of Metals and Alloys by Alternate Immersion in Neutral 3.5% Sodium Chloride Solution
G46 Standard Guide for Examination and Evaluation of Pitting Corrosion
G48 Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride Solution
G49 Standard Practice for Preparation and Use of Direct Tension Stress-Corrosion Test Specimens
G50 Standard Practice for Conducting Atmospheric Corrosion Tests on Metals
G60 Standard Practice for Conducting Cyclic Humidity Exposures
G61 Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-,
or Cobalt-Based Alloys
G71 Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes
G75 Standard Test Method for Determination of Slurry Abrasivity (Miller Number) and Slurry Abrasion Response of Materials (SAR Number)
G78 Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stainless Alloys in Seawater and Other Chloride-Containing Aqueous
Environments
G106 Standard Practice for Verification of Algorithm and Equipment for Electrochemical Impedance Measurements
G108 Standard Test Method for Electrochemical Reactivation (EPR) for Detecting Sensitization of AISI Type 304 and 304L Stainless Steels
G157 Standard Guide for Evaluating Corrosion Properties of Wrought Iron- and Nickel-Based Corrosion Resistant Alloys for Chemical Process Industries
G162 Standard Practice for Conducting and Evaluating Laboratory Corrosion Tests in Soils
G170 Standard Guide for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors in the Laboratory
G189 Standard Guide for Laboratory Simulation of Corrosion Under Insulation
G205 Standard Guide for Determining Emulsion Properties, Wetting Behavior, and Corrosion-Inhibitory Properties of Crude Oils
G210 Standard Practice for Operating the Severe Wastewater Analysis Testing Apparatus
(continued)
TABLE 3 (continued)
MTI METHODS
No. Title
MTI 1 Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Resistance to Corrosion in Selected Media
MTI 2 Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Resistance to Crevice Corrosion in a Standard Ferric Chloride Solution
MTI 3 Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Resistance to Stress Corrosion Cracking in a Boiling Magnesium Chloride
Solution
MTI 4 Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Resistance to Crevice Corrosion in Sodium Chloride Solutions
MTI 5 Laboratory Testing of Wrought Iron and Nickel Based Alloys for Relative Resistance to Stress Corrosion Cracking in a Sodium Chloride Drop
Evaporation System
time. In other cases, the rate of corrosion might increase gradu- There are many examples where this approach has been
ally with time, could cycle, or could undergo some combination applied. An excellent example is depicted in figure 1 of a circulat-
of these scenarios. No single corrosion test will address every sit- ing brine cooling/heating heat exchanger system. The effect of
uation. The investigator must be aware of the limitations of the brine corrosion, and inhibitors, in the piping system is simulated
selected test methods and test conditions to obtain meaningful by using full-size pipe spool pieces of different alloy composition.
results. The test model further incorporates the use of small test speci-
Besides the full immersion test, several variations could be mens and electrochemical monitoring probes.
used to accentuate certain types of exposure conditions. For
example, the test specimen can be immersed partially in an elec- ACCEPTANCE TESTING
trolyte (liquid or solid) to create an oxygen concentration cell at Acceptance tests expose samples taken from the final products
the vapor-liquid-solid interface (as opposed to an occluded cell). to a corrosive environment to evaluate the materials susceptibil-
ity to a particular type of corrosion or susceptibility in a parti-
ALTERNATE IMMERSION TESTING cular simulated environment or as a quality control test for the
Another variation of the immersion test is the cyclic test proce- material being supplied. Many acceptance tests have been devel-
dure in which a test specimen is immersed for a period of time oped by standards organizations mentioned previously. Typi-
in the test environment, is removed and dried (either air dry or cally, these tests have undergone lengthy studies to affirm their
with heat lamps), and then is re-immersed to continue cyclic applicability to the desired outcome and are continually being
exposure. Normally, hundreds of such cycles are performed dur- reviewed and revised, usually every five years. Acceptance criteria
ing the course of the test program. In ASTM G60, Standard Prac- for some tests are stated in the test procedure, whereas others
tice for Conducting Cyclic Humidity Exposures, test specimens may not provide specific criteria, leaving the details to be speci-
are dipped in a test solution before being exposed to atmospheres fied by the end-user or some other authority. A classic example
varying in relative humidity. The intent of the test is to develop a is the use of acceptance testing for susceptibility of stainless
layered corrosion product similar to that found on sheltered out- steel alloys to intergranular corrosion using the test methods
door exposure test specimens. These tests can be manually per- described in ASTM A262, Standard Practices for Detecting Sus-
formed or conducted in apparatus equipped for automatic ceptibility to Intergranular Attack in Austenitic Stainless Steels.
cycling. Another example is simulation of sour gas or sour oil environ-
ments in NACE International TM0284 and TM0177 procedures
SIMULATED SERVICE TESTING for hydrogen-induced cracking susceptibility and resistance to
Simulated service testing, sometimes called “customized testing,” sulfide stress cracking.
is an attempt by the investigator to replicate actual service condi-
tions in a laboratory setting. This type of test usually requires a
special apparatus to study particular conditions, such as heated Test Specimen Preparation,
vapors, condensate exposure, heat transfer, or flow velocity. Cleaning, and Evaluation
Occasionally, this may be accomplished simply by building a
scaled-down model of a particular operation. If the service oper- PREPARATION
ation is not too large, actual parts of the system can be modified One of the most important aspects of corrosion testing is the
to a laboratory bench-top set-up to permit a better simulation of preparation of test specimens or parts to be tested. It is desirable
the actual process. The simulation also may include exposure to to use the same test specimen surface condition as found in ser-
varying conditions or chemicals that occur in the process envi- vice, although this is not always possible
ronment. The investigator may find it useful to employ a mix of Test specimens should have as many of the characteristics
test methods, such as electrochemical monitoring or stimulation, of the material that will be used for the service application as
cabinet tests, atmospheric exposure, or high temperature expo- possible. This includes composition (elemental chemistry),
sure along with immersion testing. mechanical properties (strength, ductility, hardness), form (sheet,
FIG. 1 Scaled-down model for a circulating brine cooling and heating heat-exchanger system.
plate, bar, cast), size and shape (surface-area-to-corrodent-volume polymeric materials, although ceramic and metal washers may
ratio, flat-stock, end-grain exposure), metallurgical treatment be more appropriate in specific applications. ASTM G48, Stan-
(heat treatment, welding, presence or absence of weld heat-tints, dard Test Methods for Pitting and Crevice Corrosion Resistance of
hot or cold working), and surface finish (die-cut, sheared, saw- Stainless Steel and Related Alloys by Use of Ferric Chloride Solu-
cut, mill scale, ground and polished, electropolished). All of these tion, and G78, Standard Guide for Crevice Corrosion Testing of
factors can influence the corrosion resistance of the material. Iron-Base and Nickel-Base Stainless Alloys in Seawater and Other
Care should be taken in the selection of identification procedures Chloride-Containing Aqueous Environments, provide examples
(stamped, engraved) and cleaning procedures (passivated, on the use and assembly of crevice forming washers. For surfaces
degreased, water washed) because these also can have an impact that cannot be ground flat for seating of the washers, crevices
on the performance of the material. can be simulated using O-rings or by applying an inert (e.g.,
Although the size and shape of the specimen will depend on epoxy) paint coating at the desired local areas.
the purpose of the test, rectangular specimens of the dimensions A reproducible surface finish is desirable for repetitive test-
2.5 cm by 5 cm by 0.3 cm thick are common. A typical variation ing. A common final surface finish for test specimens is No. 120
in test specimen geometry is found when a corrosion test grit abrasive paper or cloth, or their equivalent. Whenever possi-
requires the specimen to be mechanically stressed as part of the ble or known, the same metallurgical treatment should be used
evaluation procedure. Stressed test specimens can be prepared as for the test specimen as for the service part, because heat treat-
U-bends, C-rings, bent beams, tensile specimens, or some other ment or cold work can change the surface composition, grain
form that induces a mechanical tensile stress in the material. size and structure, and residual stresses. Mechanical operations
Standards organizations have developed procedures for prepara- can affect the material’s surface condition. Cutting, shearing,
tion of many types of stressed specimens. Other examples grinding, and polishing operations should be performed in a
include the use of disk-shaped specimens for rotational erosion manner to avoid excessive work-hardening or stresses, overheat-
tests or the use of special (e.g., serrated) washers to evaluate ing, and embedding grinding or blasting-media particles in the
resistance to crevice corrosion. surface—all of which can adversely affect corrosion resistance.
Holes can be drilled in the test specimen for sturdy mount- Similarly, test specimens should be tested with or without heat
ing or to provide crevice formers to simulate crevice conditions tints to simulate post fabrication surface conditions in service.
on tight-fitting parts or under shielding deposits on the metal There are many ways to identify test specimens, such as
surface. The placement of the crevice formers, or washers, should marking with ink or paint, engraving, or stamping numbers or
include contact with the weld, heat-affected zone, and base metal letters on the surface. Precautions should be observed to avoid
on welded test specimens. This typically requires machining or excessive stresses, the creation of sites for pit initiation, or the
grinding the weld bead flat for the crevice washer to seat prop- use of materials that will be reactive with the metal. It is impor-
erly. Crevice forming washers typically are fabricated from tant that the identification endures the duration of the test, so
some of these problems may have to be tolerated. Alternatively, Corrosion rates determined in this manner assume that the mass
small identification tags prepared from a corrosion-resistant loss has been uniform over the entire exposed surface area.
nonmetallic material (e.g., polytetrafluoroethylene), can be When corrosion is nonuniform or localized (i.e., pitting), the cal-
attached to the test specimen using fluoropolymer thread. culated corrosion rate is not representative of the metal penetra-
tion rate and additional means of evaluation should be
CLEANING SPECIMENS BEFORE TESTING considered, such as depth of penetration.
After the test specimens have been prepared for testing, they
must be cleaned to remove oil, soil, and fingerprints. Either EVALUATION OF RESULTS
chemical or electrochemical means can be used for the final Even though each step of the corrosion test procedure is
cleaning, but the effects of cleaning on surface topography must important, proper evaluation of the results is critical to avoid
be considered. A recommended procedure involves scrubbing erroneous data and conclusions. It is important to remember
with a nylon toothbrush and a nonchlorinated scouring powder, that the corrosion rate is often based on the extrapolation of
followed by thorough rinsing with distilled or deionized water results from relatively short-term tests. For example, corrosion
and a suitable solvent (such as acetone or methanol) and warm rates may be reported in terms of mils per year (mpy, where
air-drying. For relatively soft metals (such as aluminum, magne- 1 mil ¼ 0.001 inch ¼ 25.4 lm) or in millimeters per year (mm/y
sium, and copper) scrubbing with abrasive powder may be where 1 mm ¼ 1,000 lm ¼ 39.7 mils) on the basis of results
objectionable as it can mar the surface of the test specimens. obtained from exposure of one month, one week, or one day.
Ultrasonic cleaning techniques may be used, if necessary. Air The degree of extrapolation ranges from a multiple of 12 to 365.
drying is preferred over towel drying, as towels may introduce Because corrosion is rarely linear, with initial rates frequently
contaminates that can influence corrosion behavior. Cleaned test being extremely high and tending to moderate over time, it is
specimens should be handled and stored in a manner that pre- important that the extent of extrapolation be considered in the
vents contamination of the surfaces by foreign matter, including evaluation phase of the test program.
fingerprints. After the specimens have been re-weighed, they should be
If coatings are to be evaluated, it is important that the metal carefully examined visually and under low-power magnification
surface be prepared for coating application in a similar manner for the presence of localized attack. This is very important as
to that used in the service application. This step may involve the localized corrosion can penetrate the material thickness at a
use of commercial production facilities to apply coatings. much higher rate than indicated by the calculated corrosion rate
After cleaning, the test specimens are weighed on an analyt- based on mass loss. If there are pits or creviced areas, the depth
ical balance with a resolution of 0.1 mg, and dimensional meas- of attack can be measured with a pit gauge or a calibrated micro-
urements are made to 60.01 mm to permit accurate calculation scope, which is first focused on the bottom of the pit and then
of the exposed surface area. the specimen surface edge. For localized attack, reported data
can include the depth of the deepest pit, average of the five
deepest pits, and pit distribution (for details, see ASTM G46,
CLEANING SPECIMENS AFTER TESTING
Standard Guide for Examination and Evaluation of Pitting
The effect that corrosion and the resulting corrosion products
Corrosion). Pitting rates should not be reported (e.g., in mpy or
have on the test specimen should be determined to evaluate the
mm/y) based on sparse data because pit growth rates can be
severity of the attack. Locations of deposits or corrosion products
notoriously nonlinear with time. In some cases, pitting rates
are important in evaluating localized attack, such as pitting, crev-
decrease with time, whereas in others they accelerate with time.
ice attack, or cracking. Therefore, before cleaning, the exposed
If the test material is suspected of being subject to dealloy-
specimens should be examined carefully (using a binocular
ing (such as dezincification), intergranular corrosion, or environ-
microscope, if necessary) and the appearance documented pho-
mental cracking, a metallographic cross-section of the specimen
tographically. Although this method is qualitative, it can be help-
should be prepared and microscopically examined. If embrittle-
ful in assessing the nature and extent of corrosion.
ment is suspected, simply bending the specimen may indicate
Corrosion rate calculations are based on weight (mass) loss
this susceptibility. Sometimes it may be desirable to perform
incurred during the test. Therefore, cleaning the specimens to
additional tests to compare mechanical properties of the exposed
remove corrosion products is a vital step in the test protocol.
test specimens versus unexposed specimens.
Generally, the cleaning procedure should remove all corrosion
products from the specimen with minimum metal loss of the
base material. Procedures for specimen cleaning vary depending
on the type of the material being cleaned and on the adherence
Precautions and Validity of Results
of corrosion products. Cleaning methods are divided into three Many metals and alloys are thermodynamically unstable and
general categories: mechanical, chemical, and electrolytic. therefore tend to revert back to their native stable state (e.g., red
Detailed procedures are described in ASTM G1, Standard Practice rust or ferric oxide in the case of iron and steel). The rate at
for Preparing, Cleaning, and Evaluating Corrosion Test Speci- which this reversion (corrosion) occurs varies with the particular
mens, and ISO 8407. After cleaning, the specimens are re- alloy and the environment to which it is exposed. The purpose of
weighed. The weight loss during the test duration is used as the laboratory corrosion tests is to best simulate the service condi-
principal measure of corrosion (i.e., the corrosion rate). tions, determine corrosion rates, and assess the various modes of
attack. Although each data point is important, the results can be International and AMPP (formerly NACE International). Other
misinterpreted and lead to false conclusions if they are not care- organizations that also issue standards for the many types of cor-
fully evaluated. Therefore, a laboratory corrosion test can be rosion tests include, but are not limited to, ISO, British Standards
most useful if the test results can be correlated with actual plant Institution (BSI), JSA, Deutsches Insitut für Normung (DIN, the
or process service experience. German Institute for Standardization), and MTI. These profes-
The precautions mentioned throughout this section focus sional organizations have produced industry-accepted recom-
on the planning and execution of laboratory corrosion tests and mended practices and test procedures that allow for the
particularly the interpretation of test results. These precautions comparison of results with others through direct interaction or
are not intended to suggest that corrosion tests are inherently published data. Numerous corrosion test procedures have been
unreliable. Rather, they are intended to emphasize that when standardized; a partial listing is presented in table 3.
corrosion test procedures are executed carefully and results are
interpreted intelligently, the knowledge of corrosion is enhanced,
which makes for better materials selection decisions. References
1. R. A. Corbett, “Using Corrosion Tests Effectively,” Chemical
Processing 50, no. 12 (1987): 28–32.
Standards
2. A. Wachter and R. S. Treseder, “Corrosion Testing Evaluation of
Reference is made throughout this section to standards and test Metals for Process Equipment,” Chemical Engineering Progress
methods issued regularly by technical societies, such as ASTM 43 (June 1947): 315–326.
153
Chapter 10 | Atmospheric
Sheldon W. Dean, Jr.1
Introduction Basic Principles

Atmospheric corrosion occurs with many metals used in archi- KINETICS OF ATMOSPHERIC CORROSION
tectural, industrial and other services. In outdoor exposures, the In most cases, the kinetics of static atmospheric corrosion fol-
primary cause of the corrosion process is the development of a lows a power law function of the form shown in equation (1):
film of moisture on the surface. This film results from either
direct contact with liquid water, or from condensation (i.e., dew
D ¼ Atb , (1)
deposition). Extensive experience, together with many exposure
programs, has shown that atmospheric corrosion is a phenome-
non that varies greatly from location to location.1 Studies where:
throughout the world have revealed that the rate of atmospheric D ¼ the total damage usually expressed as mass loss per unit area
corrosion is a function of the metal being tested, the location, the or penetration;
climate, the proximity to pollutants, and a variety of other fac- t ¼ the total time the metal has been exposed, usually in years;
tors. Most people understand that atmospheric corrosion can A ¼ the amount or depth of attack experienced in a unit of time
occur in outdoor exposures, but more recent experience has (e.g., one year); and
shown that corrosion can occur from indoor atmospheres under b ¼ the time exponent, usually but not always, less than 1.0.
certain circumstances.2 This power law relationship distinguishes atmospheric cor-
Outdoor atmospheric exposure tests have been carried out rosion from other forms of corrosion where the rate is constant
for a variety of purposes.3 ASTM International has sponsored throughout the exposure.
11 symposia with resulting compilations of technical papers Static exposures have been carried out by several organiza-
on atmospheric corrosion for almost a century. Alloy pro- tions around the world. The ISO CORRAG program was spon-
ducers have used this type of testing to evaluate the perfor- sored by ISO TC156/WG4, at 53 exposure sites located in
mance of new alloys in a variety of atmospheric conditions. 14 countries. This program included both flat panels and wire
Atmospheric corrosion testing also has been used to test both helix specimens of unalloyed steel, rolled zinc, copper, and alumi-
metallic and nonmetallic coatings to demonstrate their perfor- num materials, for exposures of 1, 2, 4, and 8 years. The A values
mance in atmospheric conditions.4 Manufacturers of items represent the initial period mass loss or penetration that occurred
designed to be used in outdoor conditions sometimes expose during the exposure. In most cases, this is a 1-year period, but
components to various atmospheres to demonstrate their per- in the information shown in ASTM G101, Standard Guide for
formance and develop data on the service life that may be Estimating the Atmospheric Corrosion Resistance of Low-Alloy
expected from such components. In some cases, atmospheric Steels, a 1-month period was reported. These results are strongly
exposure programs are run to evaluate the corrosivity of spe- dependent on exposure conditions and the specimen variables,
cific atmospheres. This type of information can be helpful in including surface finish and alloy composition. More detailed
selecting coatings or other corrosion protection systems to be information on numerous exposures has been reported in ISO
used at specific sites. 9223 and is covered later in this chapter.
The results from the ISO CORRAG program were used to
calculate average b values for each of the metals.5 The results of
these calculations are shown in table 1.
In the case of steels, the protectiveness of the rust layer is
largely determined by the alloying elements in the steel, but the
1
Dean Corrosion Technology, Inc., 306 Marshall Landing, Glen Mills, PA 19342, USA microstructure does not appear to affect the corrosion rate.
http://orcid.org/0000-0003-0611-7384 Weathering steels have specific alloying additions that promote
DOI: 10.1520/MNL202NDSUP20190006
where:
TABLE 1 Average Time Exponent Values for Flat Panels in the D ¼ the increase in b value, and
ISO CORRAG Program Cl ¼ the chloride deposition rate in mg Cl/m2.
The data used to develop equation (3) were taken from
Metal b Std. Dev. studies in which 19 different steel materials were exposed at nine
Carbon steel 0.523 0.026 marine sites that had different chloride deposition rates.7–10
Rolled zinc 0.813 0.030 Note that steels hardened to the point at which their tensile
Unalloyed copper 0.667 0.029 strengths exceed 1,000 MPa may suffer environmentally assisted
Unalloyed aluminum 0.728 0.039 cracking if they are subjected to sufficient tensile stress.
Weathering steels are steel alloys that have compositions
Note: The number of sites used for these calculations was 22.
designed to give good long-term performance in non-marine out-
door exposures. There are many applications in which these alloys
the development of a protective rust layer. For these steels, test-
offer significant benefits as they do not need to be painted and
ing has shown that the microstructure (i.e., ferrite-perlite or
maintenance costs are minimal. These include building curtain
tempered martensite) does not affect their corrosion perfor-
walls, lamp poles, and guard rails. These alloys conform to ASTM
mance in atmospheric exposures.6 Other types of carbon steels
A242, Standard Specification for High-Strength Low-Alloy Struc-
and low-alloy steels vary significantly in their performance. The
tural Steel, or ASTM A588 Standard Specification for High-
steel used in the ISO CORRAG program had the following
Strength Low-Alloy Structural Steel, up to 50 ksi [345 MPa]
composition: 0.056% carbon, 0.06% silicon, 0.012% sulfur,
Minimum Yield Point, with Atmospheric Corrosion Resistance.
0.013% phosphorous, 0.02% chromium, 0.01% molybdenum.
Note, however, that designs using these alloys may experience
0.04% nickel, 0.03% copper, 0.01% niobium, 0.01% titanium,
higher corrosion rates in crevices or sheltered areas not exposed to
0.01% vanadium, 0.02% aluminum, 0.005% tin, 0.004% nitro-
direct rain impingement. Crevices may develop deformations
gen, and 0.39% manganese.5
from corrosion product wedging, and significant rust staining may
In cases in which the steel composition is known, the fol-
occur on concrete, stone, masonry, and other porous surfaces
lowing formula can be used to estimate the b value for use in
exposed to rain run-off from steels, including weathering steels.
equation (1).
To evaluate the atmospheric corrosion resistance of weath-
X ering steels, two corrosion indices have been created to provide a
b ¼ 0:569 þ ai xi , (2)
single value that incorporates all of the relevant composition
where: information. The original concept was to use the data generated
ai ¼ the multiplier for the ith element, and in a major study of the effect of composition on the atmospheric
xi ¼ the mass percent of that element. corrosion of steels. The data then were analyzed using a statisti-
This equation is based on data taken from ASTM G101. The cal regression approach to yield a b value for these steels. This
ai values for equation (2) are shown in table 2. analysis was carried out by Lagault and Leckie.11 The equation
The 0.569 value in equation (2) is the average of b values for that they generated was modified to create the corrosion index
pure iron in three non-marine exposures. The standard error of shown in ASTM G101. The second corrosion index was devel-
the regression that produced equation (2) was 0.029. oped to expand the composition range covered and eliminate
In marine atmospheres, chloride deposition reduces the some of the anomalous behavior of the earlier version.12 This ver-
protectiveness of the rust layer that develops on steels. The sion is somewhat more complicated. It is based on calculation
extent of this effect can be estimated if the rate of chloride depo- the times required for pure iron to suffer a 254-lm loss at three
sition is known. Equation (3) shows the magnitude of this effect sites (i.e., Bethlehem, PA, Columbus, OH, and Pittsburgh, PA).
on the b exponent, based on wet candle measurements: These times then are used to determine the material losses
for the alloy composition in question and then these losses are
D ¼ 0:844½Cl0:26 , (3) converted to thousandths of an inch and subtracted from 10.
Then they are averaged to produce the corrosion index for the
alloy. This index is also covered in ASTM G101. In this system, a
TABLE 2 Alloying Element Multipliers for Equation (2) corrosion index of 0 represents pure iron while weathering steels
meeting the ASTM A588 specification exceed 5.5 or 5.0 depend-
Element Multiplier, ai ing on which index is used. For example, the steel used in the
ISO CORRAG program has a corrosion index of 1.3 when calcu-
C 0.084
lated by either method. A calculator program available on the
P 0.490
ASTM Committee G01 website to carry out the calculations.
S þ1.440
The ASTM A588 specification was developed for steels in
Si 0.163
atmospheric exposures. The ASTM A242 specification was devel-
Ni 0.066
oped for steels used in coal-fired power plants in their econo-
Cr 0.124
mizer sections where the flue gases have significant sulfur
Cu 0.069
dioxide contents.
ATMOSPHERIC 155
Stainless steels (i.e., steels with chromium contents greater however, the validity of this relationship is based on the fact that
than 10%) are usually considered resistant to atmospheric corro- the corrosion product layer that develops becomes more protec-
sion. They may, however, experience superficial rust staining in tive as the exposure continues. This may occur because the layer
marine atmospheres. Austenitic stainless steels also may exhibit is thicker or denser, or both. In any event, it seems likely that the
chloride stress corrosion cracking in marine atmospheres if the layer will stabilize at some point, and the rate will become linear
metal temperature exceeds 60 C for extended periods, and the (i.e., the b value becomes 1.0). Unfortunately, no data currently
item is under significant tensile stress. exist that allows a prediction of when this may occur.
Zinc alloys also vary significantly in their atmospheric per-
formance. The b value shown in table 1 was obtained from com- TYPES OF EXPOSURES
mercially available pure rolled zinc, but other zinc alloys have Probably the most common type of atmospheric exposure is con-
shown higher b values in atmospheric exposures. Electroplated ducted in a static location—that is, racks or holding devices are
zinc coatings, mechanically plated zinc coatings, and hot dipped fixed in a location and specimens are exposed for a test period at
zinc coatings all have unique behaviors in atmospheric expo- that site. This type of exposure can be carried out in sheltered
sures. Die cast zinc material are unique in their performance. sites or boldly exposed sites. A wide variety of different types of
Chromate conversion coatings are commonly applied to zinc specimens may be employed in long-term tests.
surfaces to prevent water staining and white rust development, Another type of test is the dynamic or mobile test in which
but such surfaces have shown b values in excess of 1.0.13 Sulfur panels are mounted on vehicles to simulate the service condi-
dioxide pollution in the atmosphere occurs when sulfur- tions of cars or trucks. Vehicles are exposed to significant
containing fuels are burned, and this compound will accelerate amounts of spray and splash from the road surface and, as a con-
the atmospheric corrosion of zinc alloys. In cases in which the sequence, this environment is significantly different from that nor-
life of zinc coatings has to be estimated, it may be reasonable to mally seen in the static exposures. In some cases, panels have been
use a linear relationship (i.e., the b value is 1.0). mounted on the sides of trucks to allow a larger number of panels
Painted steel is commonly used in atmospheric exposures. to be mounted in approximately the same type of environment.15
This material provides all of the benefits of steel construction Panels mounted on automobiles generally are mounted in loca-
along with the aesthetic appeal of a painted surface. A major tions in which they are not visible, although in some cases
drawback of this approach is that holidays in the coating (i.e., bumper-mounted panels have been used.16 Variability in dynamic
areas where the coating has been damaged or is missing) will tests is substantial because no two vehicles see exactly the same
cause both rust staining and loss of paint adhesion. One environment. A similar situation exists for oceangoing vessels.
approach to minimizing these problems has been to apply a zinc The atmospheric corrosion that occurs on aircraft carriers, for
coating between the paint and the steel. This has been shown to example, is distinct because it incorporates both marine spray
be effective in minimizing both problems in automotive applica- from the ocean and flue gases from the engines.
tions.14 In this case the extent of damage was evaluated by mea- Because of the rather substantial variability in dynamic tests,
suring the creep or peel back of the paint from the scribe line coupled with the problem of having limited numbers of panels
after the exposure, and the extent of rust staining was also on each vehicle, some investigators have employed an approach
evaluated. of spraying static panels with simulated road splash solutions,
Copper alloys, such as brasses, bronzes, nickel silvers, and for example, mixtures of sodium and calcium chloride. This is,
cupronickels, have atmospheric corrosion rates similar to pure of course, a much more severe environment than normal static
copper. Brasses with zinc contents above 20% may suffer dezinci- atmospheric exposure. It does have the advantage, however, of
fication in aggressive atmospheres, especially if sulfur dioxide is being more reproducible than a vehicular exposure while allow-
present. Two-phase brass alloys (i.e., those with zinc content ing many panels to be exposed at the same time under the same
greater than 30%) are most susceptible to this form of attack. conditions. Such an approach also allows for the natural wetting
Strain-hardened copper alloys may experience environmentally and drying that is normally seen in atmospheric exposures.
assisted cracking in atmospheric exposures, especially if ammo- These conditions are difficult to simulate in cabinet-type tests.
nia is present in the atmosphere.
Aluminum alloys generally experience pitting in natural MONITORING ATMOSPHERIC VARIABLES
environments. As a result, the damage predicted from equation A conventional weather station approach often has been used to
(1) may seriously underestimate the penetration that corrosion monitor atmospheric variables regarding atmospheric corro-
causes on these alloys. In addition, high-strength, age-hardening sion.17 Temperature and relative humidity may be recorded
aluminum alloys containing significant copper or copper plus continuously, and these data are used to produce average tem-
zinc levels, may show exfoliation in atmospheric exposures, espe- peratures for periods of time such as days, weeks, or months.
cially in marine environments. Alclad materials generally have Electrical monitoring sensors have been developed to measure
better corrosion resistance in these situations. Specific tempers when wetness exists on the surface by means of detecting a
have been developed to minimize the possibility of environmen- potential difference between dissimilar metals.18 A standard
tally assisted cracking of high-strength aluminum alloys. device is shown in ASTM G84, Standard Practice for Measure-
Equation (1) has been observed to be valid for most metals ment of Time-of-Wetness on Surfaces Exposed to Wetting Condi-
up to 20 years. In cases in which the b value is less than 1.0, tions as in Atmospheric Corrosion Testing. The information on
Note that the volumetric measurement of sulfur dioxide by

FIG. 1 Sulfation plate in holder (see ASTM G91). means of infrared absorption and the deposition rate measure-
ment measure different phenomena. The transfer from the gas
phase to the solid surface requires both convective diffusion and
surface adsorption steps.20
Air movement assists the convection process while the
adsorption step is accelerated by the presence of condensed
moisture. As a result, correlations between volumetric concentra-
tion and deposition rate are approximate and may not necessar-
ily apply from site to site. For corrosion correlation purposes, the
deposition rate is a more relevant phenomenon. As a practical
matter, however, the mass transfer rate that occurs on a sulfation
plate or candle probably is not equivalent to what would occur
on a flat surface or a wire. Therefore, the results obtained from
devices such as sulfation plates provide a reasonable measure of
the concentration of sulfur in the atmosphere but not an accu-
rate measure of what deposits are on test samples or structures.
The volumetric concentration monitoring instruments are
clearly the preferred technique because they require less labor to
expose and retrieve samples and can provide much more detailed
information about how the sulfur dioxide concentration varies
with time.
Sulfur dioxide deposition and chloride deposition have been
designated dry depositions in studies concerned with the effects
of acid precipitation in spite of the fact that these processes do
occur when the specimen is physically wet with dew or rain. The
term wet deposition refers to acidity delivered to the specimen
during periods of rain or snow.21 The reason for this distinction
time of wetness is usually reduced to a percentage or fraction of is that the source of acidity in precipitation is probably different
time a surface is wet in a month or in a year. from the source of either atmospheric sulfur dioxide or chloride.
Atmospheric sulfur, usually in the form of sulfur dioxide, is To monitor wet deposition, it is necessary to collect and analyze
measured by means of a volumetric sampling approach in which precipitation samples. In general, the damage to metals from
samples of the air are passed through a detector that directly acid precipitation is relatively small compared with the damage
measures the sulfur dioxide concentration. Another approach is caused by significant levels of sulfur dioxide or chloride on most
to use a sulfation plate or sulfation candle (fig. 1).19 These devices engineering metals.22
rely on lead dioxide to react with the sulfur compounds in the Several techniques have been used to monitor chloride in
atmosphere to form lead sulfate. At the conclusion of a fixed the atmosphere. The wet candle method, ASTM G140, Standard
exposure period, usually 30 days, the sulfation plate or candle is Test Method for Determining Atmospheric Chloride Deposition
removed from exposure and analyzed for the presence of lead Rate by Wet Candle Method, has been used in marine sites and
sulfate. ASTM G91, Standard Practice for Monitoring Atmo- consists of a fabric-wrapped tube in which the fabric is kept wet
spheric SO2 Using the Sulfation Plate Technique, describes the with water (fig. 2).23 The wet fabric acts as a collector for chloride
sulfation plate method. Sulfation plates are exposed in a horizon- particulates or droplets. Exposure periods of 1 week or up to
tal downward-facing position so that the lead dioxide reagent is 1 month have been used. The longer time periods can be a prob-
not exposed to rainwater. ASTM D2010, Standard Test Methods lem because the water source must not be allowed to dry. It is
for Evaluation of Total Sulfation Activity in the Atmosphere by important to protect the wet candle from rain exposure so that
the Lead Dioxide Technique, describes the sulfation candle, wet candle assemblies are usually mounted with a cover over
which is a similar type of collector except that it employs a verti- them.
cal cylinder rather than a flat disk. Again, the sulfation candle With the wet candle method, it is necessary to employ an
must be protected from exposure to rain or snow. Neither the antifreeze solution in cold climates when freezing can occur.
sulfation plate nor the sulfation candle is specific for sulfur diox- Glycerin has been used for this purpose, but if glycerin is used, it
ide. They will respond to reduced sulfur species, such as hydro- is necessary to add an inhibitor to prevent biological growth in
gen sulfide and carbonyl sulfide. The presence of these gases is the solution. Another technique that has been used is the dry
relatively rare, however, and usually a source of such reduced plate method. In this case, a vertical assembly is used with fabric
species would be apparent to investigators at the site. These gases stretched over a frame. Chloride-containing particles adhere to
dramatically enhance the corrosion of some alloys but are not the dry fabric and are extracted from the fabric and analyzed at
equivalent to sulfur dioxide. the end of the exposure period. Figure 3 shows the relationship
ATMOSPHERIC 157
FIG. 2 Wet candle apparatus with holder (see ISO 9225).
dry plate collector give only rough approximations of actual

FIG. 3 Comparison of wet candle and dry plate results for chloride depositions on test samples or structures exposed to the
atmospheric deposition at two sites (see ISO/TC156/ atmosphere. Note that seawater also contains sulfate, so that any
WG4/N236). finding of sulfur compounds in marine locations does not neces-
sarily indicate the presence of sulfur dioxide. The ratio of sulfate
to chloride in most seawater on a mass basis is 0.103.24
In cases in which both chloride and sulfate are found, only
the excess sulfate above this ratio should be designated as sulfur
dioxide. This is important because sulfur dioxide is a much more
aggressive contributor to atmospheric corrosion than is sulfate.
Chlorine and hydrogen chloride are sometimes found in indus-
trial atmospheres. These compounds can cause serious corrosion,
but they are not covered by the ISO standards.
CLASSIFICATION OF THE ATMOSPHERE—ISO

APPROACH
The International Organization for Standardization Technical
Committee on Corrosion of Metals and Alloys, ISO/TCI56, has
developed a systematic approach to classification of atmospheric
corrosivity. This approach is based on two different methods.
between chloride deposition rates measured by both methods at The first method involves exposure of standard coupons of steel,
two sites. zinc, copper, or aluminum to the atmosphere at the site where
Atmospheric chlorides generally originate from marine the classification is to be made. The selection of which metal is to
sources. Surf is a major contributor to atmospheric chlorides. be used will depend on the purpose of the test. Panels are
The spray from surf is entrained in the air and carried inland by exposed for a one-year period, and then they are retrieved, and a
the wind. As a result, spray droplets tend to settle out and dry mass loss per unit area measurement is obtained. This mass loss
out as they move inland, becoming smaller and more concen- value can then be used to determine the corrosivity of the atmo-
trated in an almost exponential decay as they move. Chloride sphere at that location. Table 3 shows the corrosivity classes based
particles are very water soluble so that areas washed by rain tend on mass loss results.
to retain much less chloride than protected areas. Large smooth The second method involves measurement of the tempera-
surfaces are much poorer collectors of salt particles than small ture, time of wetness, amount of sulfur in the atmosphere, and
diameter wires. As a result, devices such as the chloride candle or the amount of chloride in the atmosphere. Temperature and
humidity information can be used to estimate the time of wet-

TABLE 3 ISO Corrosion Classes for Metals Based on 1-Year ness. This estimation is based on the percentage of time that the
Exposure Results temperature is above freezing, 0 C, and the relative humidity is
at the same time above 80%. Once the time of wetness is known,
Mass Losses it is then possible to determine a time of wetness class (table 4).
Sulfur dioxide content of the atmosphere can be estimated either
Corrosion
Steel, g/m Copper, g/m2 Aluminum, g/m Zinc, g/m2 Category by measurement of the concentration in the atmosphere over
<10 <0.9 0 <0.7 Cl some period of time or by means of the sulfation plate or candle.
10–200 0.9–5 <0.6 0.7–5 C2 This information is then used to develop a sulfur dioxide class or
201–400 5.01–12 0.6–2 5.01–15 C3 P class (table 5). The chloride dry plate or wet candle method is
401–650 12.01–25 2.01–5 15.01–30 C4 used to obtain the chloride deposition rate of the atmosphere,
651–1,500 25.01–50 5.01–10 30.01–60 C5 which is then converted to a chloride class or S class (table 5).
The corrosion class or C class can be obtained for the time of
Note: Based on ISO 9223.
wetness, chloride, and sulfur dioxide classes (table 6). Once the
corrosion class is known, it is possible to estimate the corrosion
TABLE 4 ISO Wetness Class Based on Time of Wetness damage that will occur in either short-term or long-term expo-
sures for the five metals, steel, weathering steel, aluminum, cop-
Wetness per, and zinc (table 7). The detailed information on this method
is discussed in tables 4–7. The ISO procedure for estimating long
Class Time Wet, % Examples of Occurrence, hours wet/year
term damage assumes a linear rate after the first year of exposure
Tl <0.1 <10 indoor
shown in table 7 as LT rates.
T2 0.1–3 10–250 indoor—unheated
This system of atmospheric classification is now being
T3 3–30 250–2,500 shed storage—cold climate
revised to create a new approach based on dose-response func-
T4 30–60 2,500–5,500 outdoor temperate climate
tions for steel, copper, and zinc. Because the corrosion of alumi-
T5 60 5,500 tropical outdoor or surf
num occurs by a pitting or localized mechanism, the traditional
Note: Based on ISO 9223. approach of using mass loss to determine severity of attack is
often misleading. Atmospheric corrosion problems with alumi-
TABLE 5 Sulfur Dioxide and Chloride Classes num alloys are most frequently a result of metallurgical condi-
tions rather than environmental conditions, and the behavior of
Sulfur Dioxide Chloride
aluminum may be excluded in the upcoming revision of the ISO
9223-6 documents.
Deposit Rate, Concentration, Deposit Rate,
SO2 Class mg/m2 day mg/m3 Cl Class mg/m2 day
P0 <10 <12 S0 <3 INDOOR ATMOSPHERES

PI 10–35 12–40 S1 3–60 Although the ISO approach to classification of the atmosphere
P2 36–80 41–90 S2 61–300 was envisioned to cover both indoor and outdoor atmospheres,
P3 81–200 91–250 S3 301–1,500 the classification range on indoor atmospheres was too broad to
Note: Based on ISO 9223. be useful for many applications. The corrosion concerns for
TABLE 6 Corrosion Classes for Environmental Classes
T2 T3 T4 T5
S0-S1 S2 S3 S0-S1 S2 S3 S0-S1 S2 S3 S0-S1 S2 S3
Unalloyed Steels
PO-Pl 1 2 3-4 2-3 3 4 3 4 5 3-4 5 5
P2 1-2 2-3 3-4 4 3-4 4-5 4 4 5 4-5 5 5
P3 2 3 4 4-5 5 5 5 5 5 5 5
Zinc and Copper
PO-Pl 1 1-2 3 3 3 3-4 3 4 5 3-4 5 5
P2 1-2 2 3 3 3-4 4 3-4 4 5 4-5 5 5
P3 2 3 3-4 3 3-4 4 4-5 5 5 5 5 5
Aluminum
PO-Pl 1 2-3 4 3 3-4 4 3 3-4 5 4 5 5
P2 1-2 3-4 4 3 4 4-5 3-4 4 5 4-5 5 5
P3 3-4 4 4 3-4 4-5 5 4-5 5 5 5 5 5
Note: T ¼ wetness class, P ¼ SO2 class, S ¼ chloride class. Based on ISO 9223.
ATMOSPHERIC 159
TABLE 7 Atmospheric Corrosion Rates for Corrosion Class
Steel Copper, lm/year Zinc, lm/year Aluminum, lm/year Weathering Steel, lm/year
Class ST LT ST LT ST LT ST LT ST LT
1 <0.5 <0.1 <0.01 <0.01 <0.1 <0.05 <0.01 <0.1 <0.1

2 0.5–5 0.1–1.5 0.01–0.1 0.01–0.1 0.1–0.5 0.05–0.5 0.01–0.025 0.01–0.02 0.1–2 0.1–1
3 5–12 1.5–6 0.1–1.5 0.1–1.0 0.5–2 0.5–2 0.02–0.2 0.02–0.2 2–8 1–5
4 12–30 6–20 1.5–3 1.0–3 2–4 2–4 8–15 5–10
5 30–400 20–90 3–5 3–5 4–10 4–10 15–80 10–80
Note: ST ¼average corrosion rate during the first 10 years of exposure. LT ¼steady state corrosion rate for long-term exposures. Based on ISO 9224.
indoor atmospheres covered three different categories. One major are at substantially lower values than are normally seen in outdoor
area of concern was storage of metallic parts and components in corrosion. In addition, the critical pollutants seem to be reduced
warehouses. The concern is that the storage conditions do not sulfur species such as hydrogen sulfide, and also acid chloride spe-
stain or damage the parts. The second area of concern is the use of cies such as hydrogen chloride. These species are present in indoor
metallic materials in indoor atmospheres where corrosive condi- atmosphere at very low levels, typically 0.1–10 ppb (table 8).
tions can occur, for example, plumbing fixtures in humid environ-
ments such as kitchens and bathrooms. A third area of concern is
for electronic components.25 There have been serious problems Atmospheric Testing
with failures of measuring devices, computers, and related equip-
ment in control rooms, and even in offices, that have been attrib- PROGRAM DEVELOPMENT
uted to corrosion. The ISO system is adequate to deal with the The first step in an atmospheric testing program is to develop a
concerns of warehouse storage but has not been adequate to deal program that will provide answers to the question: What is the
with the concerns of electronic materials degradation. The reason purpose of this program?26 If the purpose of the program is to
for this is that the mechanism of corrosion that causes problems characterize the atmospheric performance of a new material, it
in electronic circuitry is quite different from that encountered by is important to determine what time interval is relevant and
engineering materials in atmospheric outdoor exposure. The prob- what reference materials should be included so that a definite
lems that occur in electronics include the development of resistive comparison can be made. It also is important to determine
films that interfere with switch operation and the migration of what type of exposure will be used and what the specimens
corrosion products causing short circuits or related problems. should look like. Furthermore, it is important to determine at
Two specific problems have been noted. One is the development this time how the results of the program will be evaluated.
of pore corrosion. This phenomenon has been observed on gold Understanding these issues at the beginning of the process is
surfaces in the form of black spots distributed over the gold sur- helpful in determining later how many specimens are needed
face. The second problem is film creep, which refers to a rapid and what types of materials are required and, ultimately, what
diffusion of corrosion products across the gold surface. Other the cost of the exposure program will be. Table 9 lists the key
problems also have been noted. issues that need to be decided at the beginning of any atmo-
In the case of corrosion in storage areas and the protection spheric testing program.
of materials in humid indoor atmospheres, conventional techni-
ques that apply to outdoor corrosion are suitable. The primary EXPOSURE PROGRAM
mechanism seems to be the development of moisture films on The simplest type of exposure program is a fixed material pro-
the metallic surfaces that then promote corrosion. In the case of gram in which a set of specimens is exposed for a fixed time
electronic components corrosion, the critical moisture contents period. At the conclusion of this period, the specimens are
retrieved and evaluated. A variation on this approach is to
TABLE 8 Gaseous and Solid Materials Affecting Indoor

Atmospheric Corrosion TABLE 9 Program Development Issues
Substance Concentration, lg/m3 Comments Purpose of the program?

SO2 1–100 30–50% lower than outdoors Exposure time to achieve purpose?
NO2 2–150 Similar to outdoors Reference materials?
H2S Cl2 1–3 <0.1 Higher in some situations Results evaluation?
HCl NH 0.1–20 20 Usually very low Replication needed?
SootO3 5 2–25 Higher when fires are used Coating for the ground facing surface of panel?
Usually lower than outdoors Edge preparation or masking?
inspect the specimens at the exposure site at intervals during the

exposure period and report results. TABLE 10 Types of Specimens
A somewhat different approach is to expose a group of
specimens initially and then retrieve portions of the group at Type Standards
intervals (e.g., 1 year, 3 years, 5 years, 10 years, and 20 years). Flat Panel ASTM G50
This approach allows the investigator to estimate the kinetics of 100 150 mm
the process if an assumption can be made about the constancy 100 200 mm
of the environment. A variation of this approach is to replace 100 300 mm
each specimen removed with an unexposed specimen to be Helix Wire
retrieved at the conclusion of the test. This approach allows for Stress Corrosion
variations in the environment to be averaged out or at least Bent Beam ASTM G39
acknowledged (fig. 4). C Ring ASTM G38
An important issue in exposure tests is the question of repli- U Bend ASTM G30
cation. It is desirable to use at least duplicate specimens in corro- Direct Tension ASTM G49
sion tests. In atmospheric tests, however, it is good practice to Welded ASTM G58
use a larger degree of replication, preferably five specimens for Galvanic
statistical analysis. Three specimens are generally considered the Plate on Plate ISO 7441
minimum acceptable in most cases to avoid problems from dam- Disk on Disk ASTM G149
age, loss, and unexpected events. Wire on Bolt ASTM G116
In general, indoor exposures usually are made for relatively Coated Specimen ASTM D1654
short periods. In most cases, 30 days and 90 days are typical, Fabricated Items such as fasteners, hardware, beams, etc.
although occasionally a 1-year exposure is used. Because the pur-
pose of these exposures is generally to evaluate the environment,
measurements. It is also used to evaluate coatings and is conve-
it is usually necessary to obtain results rapidly to determine what
nient to handle. For nonferrous metals, investigators have pre-
protective measures are necessary.
ferred to use larger panels, for example, 100 mm by 200 mm.27
Larger sizes do lose some convenience and ability to fit on some
SPECIMEN TYPES balances.
Once the purpose of the program is decided, the next question Wire helix specimens have been used to monitor atmo-
is: What type of specimen should be used? Some typical speci- spheric corrosivity.28 Note that this type of specimen tends to
men types are listed in table 10. Probably the most widely used show higher corrosion rates than flat panels of the same material.
specimen in atmospheric exposure programs is a 100-mm by For this reason, it is likely that helix specimens will be dropped
150-mm panel. This type of panel is suitable for mass loss for the purpose of site monitoring. Wire samples show higher
corrosion rates because of the increased collection efficiency of
small diameter cylinders in gathering other gaseous or solid par-
FIG. 4 Example of exposure program designs.15 Source:
ticles, and these materials tend to stimulate the corrosion
Reprinted from Materials Performance. V
C 1988 by
process.29
NACE International. All rights reserved by NACE;
Atmospheric stress corrosion tests are frequently run with
reprinted with permission.
U-bend specimens or two-point loaded specimens. U-bend
specimens are used when the stress level is not a variable, but it
is desired to determine if an alloy is susceptible to cracking
(fig. 5). Two-point loaded specimens have the advantage of being
held at points of low stress and at locations where a crevice will
do the least damage. It is relatively simple to construct racks to
hold two-point loaded specimens. A two-point loaded specimen
can be designed to cover a wide range of maximum stresses.30
Other types of standard stress specimens also may be used, for
example, direct tension specimens, C-ring specimens, and other
bent beam configurations (fig. 6). Table 10 lists standard stressed
specimens that may be used in atmospheric corrosion.
It is occasionally desirable to evaluate galvanic corrosion
effects from atmospheric exposures (see ASTM G116, Standard
Practice for Conducting Wire-on-Bolt Test for Atmospheric Galvanic
Corrosion, and ASTM G149, Standard Practice for Conducting the
Washer Test for Atmospheric Galvanic Corrosion [Withdrawn
2004]). Several different types of specimens have been used for
this purpose.
ATMOSPHERIC 161
FIG. 5 U-bend specimen designs (see ASTM G30). FIG. 6 Bent beam specimen designs (see ASTM G39).
One approach is to use washers bolted together as shown in

31
figure 7. At the end of the test, it is possible to measure the
depth of corrosive attack associated with the region of galvanic
corrosion by means of mass loss measurements. Other types of
galvanic exposure specimens that have been used have included
plates of different metals bolted together and the helix wire-on-
bolt type of specimen (see ASTM G116).32 In this latter case, the
test specimen is usually a wire that is wrapped around a bolt of a
different material to evaluate the galvanic corrosion that may
occur from this couple. Mass loss measurements are usually used
to evaluate the loss of metal from the wire specimen.
Atmospheric exposure programs are often run to evaluate
coating performance. This is true for both organic coatings and
for inorganic coatings, including metallic coatings such as elec-
troplated coatings,33 flame-sprayed coatings,34 and hot-dipped
FIG. 7 Cross section of washer bimetal assembly (see ASTM
coatings.35 The key issue in the case of organic coatings is the
G149).
adhesion of the coating and particularly the ability of the coating
to maintain adhesion and protection even in the face of mechan-
ical damage. Consequently, it is often desirable to scribe an
x-shaped mark on the surface of the panel after the coating pro-
cess. The scribe should penetrate to the basis metal.
At various times during the exposure, the panel is evaluated
by noting how far the corrosion of the basis metal has proceeded
under the paint or coating. In the case of metallic coatings, visual
examinations usually are conducted during the life of the expo-
sure to look for penetration of rust through the coating, spalling,
or other degradation of the coating itself. It is often desirable to
expose fabricated items, such as roofing panels, automotive trim
parts, wire ropes, wire specimens, and a host of other hardware
items. This type of program allows the performance of a finished
product to be evaluated in a controlled exposure program. It is notches in the side of the panel, so that it will be possible to iden-
especially good for evaluating differences in finishes to determine tify the panel even after extensive corrosion has occurred.28 In
if the difference in the finishing process has caused a change in the case of materials that do not suffer such extensive corrosion
the coating performance. in atmospheric exposures, techniques such as stencil stamping
may be used. It is desirable to use clean, sharp stencils and to
SPECIMEN PREPARATION avoid transferring foreign metals from the stencil stamps to the
The type of preparation that a specimen will require depends metal surface. In the case of coated samples, stencil stamping
very much on purposes of the exposure program.3 In cases in may not be acceptable. Other approaches may be used, such as
which bare metals are to be exposed to the atmosphere, a some- writing the panel identification on the back of the panel with a
what arbitrary decision must be made on what type of surface weather-resistant paint or attaching a tag to the panel with the
finish will be tested. Typical steps in an atmospheric exposure panel identification stamped on it.
program are given in table 11. The panels should be carefully weighed and measured
Characteristically for ferrous metals, it is generally desirable before exposure. This should be the last step before the panel
to employ a mechanical finishing technique that removes the leaves the laboratory. In the case of coated samples, an important
mill scale. Surface grinding with 120-grit abrasive is a typical fin- issue is the edge protection. In some cases, specimens are sheared
ish. Such finishes are rather active, and consequently, panels from larger sheets and, consequently, the edges are left uncoated.
must be wrapped with an inhibiting paper or protected by other In this case, it is essential that measures be applied to edges to
means so that the surface rust does not develop during shipment. prevent edge damage from confusing the results. For short-term
In this case, it is necessary to remove any traces of inhibitor that exposures, vinyl tape is sometimes used to protect the edges. It
might have transferred to the metal surface. A solvent cleaning also may be necessary to carry out preliminary evaluations of the
step immediately before exposure is frequently used. surface of coated samples, including reflectivity measurements,
It is also necessary to place an identifying mark on the pan- color measurements, or related optical measurements before
els before exposure (table 12). In the case of ferrous metals where placing them on exposure.
heavy corrosion occurs, it is necessary to use techniques, such as For indoor exposures, the metals used are usually copper,
drilling holes in the panels in specific locations or milling silver, or steel. Typical exposure panels are 10 mm by 50 mm by
0.5 mm thick. These panels are usually abraded with a fine sili-
con carbide abrasive paper; 1,200 grit for copper and silver and
500 for steel. After polishing, the specimens should be cleaned in
TABLE 11 Specimen Preparation Steps ethanol in an ultrasonic bath before exposure. Occasionally,
nickel or zinc specimens may be used in special circumstances in
• Mechanical preparation which these metals are to be used.
Cut to size
Finish edges
OUTDOOR EXPOSURE
Finish faces
Most outdoor exposures are carried out in static situations with
• Identification and cleaning
the specimens mounted on racks. A standard system has been
• Initial measurement
developed in the United States whereby racks are mounted on
Mass
Size
stands with the panels exposed at an angle of 30 to the horizon-
Optical tal.28 In Europe, the exposure angle is generally 45 to the hori-
Photographic zontal (fig. 8).36 Exposure racks have been designed so that
• Shipment panels can be placed in the rack without disturbing adjacent
• Final cleaning and edge protection, if necessary panels.
• Exposure It is general practice to have the panel racks facing south in
the northern hemisphere. In the case of panels with organic coat-
ings, the top surface will receive the greatest sun exposure if the
panel is mounted at an angle to the horizontal equal to the lati-
TABLE 12 Specimen Identifying Systems tude of the site. When panels are mounted in locations where
sources of atmospheric-borne corrodents are present, generally it
is desirable to have the racks face the source of the corrodent
Type of Panel Appropriate System
species. For example, at seacoast locations, panels should face the
Steel Drilled holes according to matrix
surf. In cases adjacent industrial sites, it may be desirable to ori-
Mill or saw edge notches
ent the panels so that they face the source of the pollutants from
Nonferrous and stainless steel alloys Stencil stamping
the industrial source.3
Metallic coated Stencil stamping
At the time panels are exposed, the weather should be
Plastic or nonferrous tags
recorded. It is also important to record the location of each panel
Paint on back side
on the rack and the rack identification and location at the site.
ATMOSPHERIC 163
FIG. 8 Atmospheric exposure text rack support design (see ASTM G50).
Plans should be made at this time to retrieve the panels or speci- specimen handling. It will detect dust and particulates on the
mens. For short-term exposures, this may not be a problem. For surface that adhere strongly, however, and may overestimate the
programs that go for many years, however, maintenance of the corrosion damage in cases in which this condition occurs.
site can be a problem. Another approach to the microbalance concept is to deposit
In the case of exposure programs where visual examination a thin layer of the metal in question on a quartz crystal and mon-
of the specimens is to be made at intervals during the program at itor the mass change due to oxidation by means of the change in
the exposure site, it is important to set up an evaluation form so resonance frequency of the crystal. Applying an AC potential
that the information desired is recorded along with the specimen across the thickness of the crystal and detecting the resonance
identification (see ASTM G33, Standard Practice for Recording frequency in the shear direction can activate the quartz crystal.
Data from Atmospheric Corrosion Tests of Metallic-Coated Steel By selecting a crystal orientation that has minimal temperature
Specimens). In the case of tests on stress corrosion specimens, it dependence on the resonance frequency, it is possible to obtain a
is desirable to remove specimens at regular intervals during the device that can monitor mass changes on a continuous basis.37
exposure period so that they may be examined for cracking. This This technique can detect mass changes as low as 10-6 g/cm2.
is especially true for specimens that develop thick corrosion The metal chosen for the test is typically deposited by vacuum
product films on their surface because such films often obscure evaporation onto the quartz surface.
the cracks. It is also desirable to retrieve broken specimens in
stress corrosion programs so that the specimen may be evaluated
SITE MONITORING AND EVALUATION OF
for mode of cracking and presence of secondary cracks. For two-
ENVIRONMENT
point loaded specimens, it is desirable to wire both ends to the
One of the distinguishing characteristics of atmospheric expo-
holder in case the specimen fails by total fracture.
sure programs is that the environment is not under the investi-
gator’s control. Sites may be selected to have specific properties
INDOOR EXPOSURE or characteristics; however, unpredictable variations occur in
Indoor exposure sites generally employ vertical panels hung from weather patterns in both short- and long-term exposures. Fur-
hooks or wires through a hole near the top of the specimen. In thermore, the presence of corrosive materials in the environment
some cases, a plastic enclosure is used to protect the specimens is often the function of activities that go on at some distance
from direct exposure to air currents and to shield the specimens from the exposure site and, as such, are entirely outside the con-
from falling dust. In general, it is desirable to avoid locating the trol of the investigator. Consequently, it has long been a desire of
panels near walls and corners where unusual air currents may cir- investigators to develop techniques to evaluate the corrosivity of
culate. It is important that the site location be chosen to be repre- sites where exposure programs are taking place. One approach to
sentative of the conditions in question, but more important, that measuring site corrosivity is to expose a set of standard panels of
they not be damaged or disturbed by the activities in the area. a known material that can be used as a control. Steel panels have
Indoor specimens may be evaluated by several techniques, been widely used for this purpose (see ASTM G92, Standard
including mass gain, mass loss, electrochemical reduction (coulo- Practice for Characterization of Atmospheric Test Sites); however,
metric measurement), and electrical resistance increase. Micro- zinc, copper, and aluminum also have been used.28 The test
balance measurements of mass gain after removal of particulates material performance can be compared to the standard panel
is probably the most popular method because it requires the least material performance and conclusions drawn from that. This
important approach should be practiced as much as possible measured. The deposition method eliminates the stagnant tube
because we may never be able to measure all of the variables that and relies solely on natural convection to transport the species in
affect atmospheric corrosion. question to the reactive surface. The following gases have been
The standard panel approach, however, does not provide monitored using diffusions cells: SO2, NO2, H2S, NH3, and O3.
information as to what caused corrosivity of the environment. Particulates are more difficult to monitor and require different
To understand the factors that contribute to corrosivity, it is methods. Again, active sampling requires a pump to draw a spe-
desirable to obtain data on the temperature, relative humidity, cific volume of air through a filter or onto impingement plates
time of wetness, time during which precipitation occurred, and that is then analyzed. Collection plates also may be used together
wind velocities.27 It is also desirable to obtain samples of precipi- with microscopic methods of analysis and evaluation. Tempera-
tation at various times during the exposure period and have it ture and humidity measurements are also important to measure
evaluated for acidity and the presence of ionic species. Another for evaluation of the environment.
factor is the presence of sulfur species in the air, especially sulfur The corrosivity of indoor atmospheres must be determined
dioxide. The sulfation plate or actual volumetric sampling may by standard panel exposures.
be used. In addition, in marine locations, it is desirable to have
some estimate of the airborne salinity, either through a chloride
candle or the dry plate method.38 Another variable that is impor-
Atmospheric Exposure Standards
tant, but seldom measured, is the temperature during the period ASTM Committee G01 has written a number of atmospheric
which panels are wet. Corrosion occurs mainly during periods exposure standards, which are listed in table 14. ASTM G50,
of wetness, so that the temperature during this period is Standard Practice for Conducting Atmospheric Corrosion Tests on
most important in terms of determining the corrosion kinetics. Metals, provides a recommended practice for atmospheric corro-
Table 13 lists atmospheric variables that are often monitored. sion test programs. ASTM G33 covers visual examination of
In the case of indoor corrosion, several parameters can be panels with metallic coatings. such as galvanized or aluminized
measured to determine the corrosivity of the atmosphere. Unfor- panels.
tunately, there are no standards currently available that relate the
corrosivity of the atmosphere to the concentrations of corrosive
components, but the measurement of such components may be TABLE 14 ASTM Committee G01 Atmospheric Exposure
helpful in determining the cause of problems with an indoor Standards
environment.
For gaseous components, two types of measurements can be Designation Title
used: active sampling and passive sampling. Active sampling G30 Standard Practice for Making and Using U-Bend
requires a pump to draw a specific quantity of air into a mea- Stress—Corrosion Test Specimens
surement chamber. The gaseous components are measured by a G33 Standard Practice for Recording Data from Atmospheric
specific method (e.g., infrared absorption) and are recorded. Pas- Corrosion Tests of Metallic-Coated Steel Specimens
sive samplers use either a diffusion cell or a direct deposition G38 Standard Practice for Making and Using C-Ring
method. The diffusion cell employs a stagnant tube through Stress—Corrosion Test Specimens
which the components must diffuse and then be absorbed and G39 Standard Practice for Preparation and Use of Bent-
Beam Stress—Corrosion Test Specimens
G49 Standard Practice for Preparation and Use of Direct
TABLE 13 Atmospheric Variables for Exposure Programs Tension Stress—Corrosion Test Specimens
G50 Standard Practice for Conducting Atmospheric
Corrosion Tests on Metals
Variable Measurement Frequency Report Typical Units
G58 Standard Practice for Preparation of Stress-

Temperature, hourly 30 day A&R C Corrosion Specimens for Weldments

Temperature when wet, hourly 30 day A C G84 Standard Practice for Measurement of Time-of-Wetness
Relative humidity, hourly 30 day A % on Surfaces Exposed to Wetting Conditions as in Atmospheric
Time of wetness, hourly 30 day T h or % Corrosion Testing

Dew point temperature, hourly 30 day A C G91 Standard Practice for Monitoring Atmospheric SO2
Insolation time, hourly 30 day A h Deposition Rate for Atmospheric Corrosivity Evaluation Using
Insolation, hourly 30 day A J/m2h the Sulfation Plate Technique
Precipitation time, hourly 30 day Th G92 Standard Practice for Characterization of Atmospheric
Precipitation, daily 30 day T mm Test Sites
Precipitation pH, daily 30 day A&R G101 Standard Guide for Estimating the Atmospheric Corrosion
SO2 concentration, hourly 30 day A ppb (vol) Resistance of Low-Alloy Steels
SO2 deposition, 30 day 30 day T mg SO2/m day 2 G116 Standard Practice for Conducting Wire-on-Bolt Test
2 for Atmospheric Galvanic Corrosion
Chloride deposition, 30 day 30 day T mg Cl/ m day
G149 Standard Practice for Conducting the Washer Test for
Note: A ¼ average, R ¼ range (high and low value), T ¼ total, Insolation
Atmospheric Galvanic Corrosion (Withdrawn 2004)
time ¼ time during sun exposure, Insolation ¼ solar heating.
ATMOSPHERIC 165
ASTM Committee G01 has written several standards on

stress corrosion specimens shown in table 14. In addition, several TABLE 16 NACE International Standards Relating to Atmospheric
standards describe galvanic specimen design, sulfation plate, Exposure Tests
time of wetness, and characterization of atmospheric test sites.
ASTM Committee B08 has published a standard on evaluating Designation Title
electroplated samples and atmospheric exposures. This standard, RPO172-72 Surface Preparation of Steel and Other Hard
ASTM B537, Standard Practice for Rating of Electroplated Panels Materials by Water Blasting Prior to Coating or
Subjected to Atmospheric Pressure, includes charts showing pit Recoating—Item #53008-P
densities. RP0176-83 Corrosion Control of Steel, Fixed Offshore Platforms
ISO Technical Committee 156 has written six standards that Associated with Petroleum Production—Item
apply to atmospheric exposures, which are shown in table 15. One #53031-P
standard covers galvanic corrosion specimens, one is a general RP0281-86 Method for Conducting Coating (Paint) Panel
procedure for atmospheric exposures, and four cover the subject Evaluation Testing in Atmospheric Exposure—
of classification of atmospheres for corrosivity. ISO/TCI56 is Item #21026-P
now considering the question of indoor atmospheric corrosivity RP0591-91 Coating for Concrete Surfaces in Non-immersion
classification and will be preparing standards in this area. and Atmospheric Service—Item #21052-P
NACE International has written several standards related to RP0692-92 Application of a Coating System to Exterior Surfaces
atmospheric corrosion, which are shown in table 16. These stand- of Steel Rail Cars—Item #21058-P
ards apply mainly to coating systems to protect from corrosion. TMO170-70 Visual Standard for Surfaces of New Steel Air-blast
The Instrument Society of America (ISA) has established a clas- Cleaned with Sand—Item #21201-P
sification system for indoor corrosivity39 that applies mainly to TM0175-75 Visual Standard for Surfaces of New Steel
electronic devices. Centrifugally Blast Cleaned with Steel Grit and
Shot—Item #21209-P
TABLE 15 ISO Standards Relating to Atmospheric Corrosion.

ACKNOWLEDGMENT
Designation Title The author is grateful to Air Products and Chemicals, Inc. for
ISO 4540 Metallic Coating—Coatings Cathodic to the permission to publish this paper.
Substrate—Rating of Electroplated Test
Specimen Subjected to Corrosion Tests
ISO 4542 Metallic and Other Non-organic Coatings—General References
Rules for Stationary Outdoor Exposure
1. H. Guttman and P. J. Sereda, “Measurement of Atmospheric
Corrosion Tests Factors Affecting the Corrosion of Metals,” in Metal Corrosion
*ISO 7441 Corrosion of Metals and Alloys—Determination of in the Atmosphere, ed. W. Ailor and S. Coburn (West
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the Corrosivity Categories of Atmospheres 195–216.
*ISO 9225 Corrosion of Metals and Alloys—Aggressivity of
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Atmosphere-Methods of Measurement of
Inorganic Coatings,” in Testing of Metallic and Inorganic
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Atmospheres—Methods of Determination of
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Corrosion, ed. W. W. Kirk and H. H. Lawson (West Conshohocken, Chemistry in Canada 10, no. 5 (May 1958): 33–41.
23. S. W. Dean, “Corrosion Testing of Metals under Natural
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and Groundward Exposure of Exposed Surfaces of Zinc and 55%
28. S. W. Dean, “ISO CORRAG Collaborative Atmospheric Exposure
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561–565.
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D. C. McCune, “License Plate Corrosion Test of Automotive
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Atmospheric Corrosion Tests (Part 3),” Materials Performance 27,
32. D. P. Doyle and H. P. Godard, “Rapid Determination of Corrosivity
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in Corrosion in Natural Environments, ed. W. Ailor, S. Dean, and Russia: MIR Publishers, 1969), 429–437.
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19. B. Levadie, “Sampling and Analysis of Sulfur Dioxide with the Coating,” in Atmospheric Corrosion of Metals, ed. S. W. Dean, Jr.
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Evaluation 7, no. 2 (March 1979): 61–67. 1982), 186–213.
ATMOSPHERIC 167
34. K. J. Altorfer, “Service Evaluation of Zinc Thermal Spraying and T. S. Lee (West Conshohocken, PA: ASTM International,
Systems,” in Atmospheric Corrosion, ed. W. H. Ailor (New York: 1988), 264–281.
Wiley, 1982), 645–650.
37. M. Seo, “Application of Quartz Crystal Microbalance to Corrosion
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ments,” in Atmospheric Factors Affecting the Corrosion of Engi-
neering Metals, ed. S. K. Coburn (West Conshohocken, PA: ASTM 38. B. S. Phul and W. W. Kirk, “Monitoring the Corrosivities of
International, 1978), 74–82. Atmospheric Exposure Sites,” Journal of Protective Coatings and
Linings 8, no. 10 (October 1991): 152–162.
36. V. H. Kucera, S. Haagenrud, L. Atteraas, and J. Gullman,
“Corrosion of Steel and Zinc in Scandinavia with Respect 39. Environmental Conditions for Process Measurement and Control
to Classification of the Corrosivity of Atmospheres,” in Systems: Airborne Contaminants, ISA-S 71-04-1985 (Durham, NC:
Degradation of Metals in the Atmosphere, ed. S. W. Dean Instrument Society of America, 1985).
169
Chapter 11 | Standards and Practices on Corrosion under Insulation
John P. Ludman1 and Bert J. Moniz2
Introduction may be used when insulation is needed only for personnel

protection.3
Corrosion under insulation (CUI) occurs on the external surfaces A wealth of industry standards, guidelines, and literature
of hot, thermally insulated carbon steel or austenitic stainless has been developed relating to CUI. The purpose of this chapter
steel process equipment and piping systems within appropriate is to compile them and show how they complement each other.
temperature ranges when moisture penetrates the insulation. Three broad guidelines have been assembled on CUI, representing
Cold thermally insulated carbon steel surfaces may become wet the work of specialists in thermal insulation, risk-based inspection,
and corrode when water condenses from ambient air as the tem- nondestructive testing (NDT), process engineering, maintenance
perature falls below the dew point, as with piping that carries engineering, protective coatings, and materials engineering. The
cold liquids or gases.1 guidelines are American Petroleum Institute Recommended
CUI is a serious problem because it usually is unnoticed Practice (API RP) 583, Corrosion under Insulation and Fireproof-
and, by the time it is noticed, the consequences are potentially ing; National Association of Corrosion Engineers Standard
harmful. Because carbon steel and stainless steel are the most Practice (NACE) SP0198-2016, Standard Practice Control of
common construction materials used on chemical process plants, Corrosion under Thermal Insulation and Fireproofing Materials;
refineries, offshore structures, and power plants, CUI has far- and European Federation for Corrosion (EFC) 55, Corrosion-
reaching implications.2 under-Insulation (CUI) Guidelines. The first two standard practi-
CUI mechanisms (damage mechanisms) are not unique. ces are extensively cited in this chapter. Note that NACE Inter-
They consist of pitting and general corrosion of carbon and alloy national and SSPC, the Society for Protective Coatings have
steels, and external chloride stress corrosion cracking (ECSCC) merged to form AMPP, The Association for Materials Protection
of austenitic stainless steels. Lately, pitting of aluminum and and Performance.
ECSCC of duplex stainless steels have been included as CUI
damage mechanisms, but these problems are less common.
Insulation systems simply do not remain dry in the long API RP583, Corrosion under Insulation and
run. Water enters because the systems are relatively fragile and Fireproofing.4
vulnerable to mechanical damage and deterioration. Insulation API RP583 covers design, maintenance, inspection, and mitiga-
provides an annular space where moisture can be retained on the tion practices for CUI of pressure vessels, piping, storage tanks,
metal surface. Depending on the source of moisture, contami- and spheres. The standard examines factors that affect damage
nants may be present and concentrate, but the principal harmful mechanisms and provides guidelines for prevention, mainte-
species is the chloride ion. nance practices, and inspection practices to detect and assess
It may take several years for CUI to develop and cause damage. It also provides guidelines for conducting risk assess-
equipment or piping rupture or leakage. To combat the problem, ments on equipment or structural steel subject to CUI.
a great deal of effort has gone into the development of managing
systems for CUI to prevent it from becoming a maintenance
AMPP SP0198-2016, Standard Practice Control
headache or the cause of an incident.
of Corrosion under Thermal Insulation and
An important rule to embrace is, “Don’t insulate if it’s not
Fireproofing Materials.5
needed for thermal conservation.” For example, protective cages
SP0198-2016 provides current technology and industry practices
made of steel mesh with standoffs around equipment and piping
for CUI and fireproofing materials. The standard contains sec-
1 tions organized by function on corrosion mechanisms, mechanical
DuPont Company, Dupont Chestnut Run Plaza, 974 Centre Rd., Wilmington, DE
19805, USA design, protective coatings, insulation materials, and inspection
2
Retired, 2201 W 16th St., Wilmington, DE 19806, USA and maintenance.
DOI: 10.1520/MNL202NDSUP20190026
EFC-55, Corrosion-under-Insulation (CUI) high that the system is essentially dry. Cycling through the sus-
Guidelines.6 ceptible temperature range reduces crack incubation time.
These guidelines represent the output of working parties in
Surface versus operating temperature.
major European oil refining, petrochemical, and offshore compa-
It is necessary to consider whether the operating temperature
nies. Appendices amplify topics such as cost analysis, quality
is within the boundaries for CUI, but it is the actual surface
assurance, insulation techniques, coatings and application meth-
temperature of the piece of equipment or piping that is relevant.
ods, cladding, and inspection techniques. The guidelines include
Many factors can influence how closely the exposed metal sur-
a risk-based inspection methodology for CUI and recommended
face temperature approaches the service temperature, including
best practices for various topics.
the type, condition, and thickness of the insulation. Although the
Corrosion under fireproofing is a related problem. It is not
range of susceptibility is relatively wide, there is an optimum
covered in this chapter.7
temperature range for each type of metal affected.
NACE SP0198-2016 and EFC-55 suggest the following tem-
INCIDENTS
perature ranges of susceptibility for CUI:
A symposium was held in 1983 to discuss experience with CUI.
It was sponsored by the American Society for Testing and Mate-
• Carbon steel operating continuously between -4 C and 175 C
rials (ASTM), NACE (now AMPP), and the Materials Technol-
ogy Institute of the Chemical Process Industries (MTI). The • Austenitic stainless steel operating continuously between
proceedings were published as an ASTM Special Technical Pub- 50 C and 175 C
lication, Corrosion of Metals under Insulation, in 1985 and con- • For both types of alloy, intermittent operation within the tem-
tain a number of case histories.8 perature range
Since that symposium, numerous presentations have been
made and several articles has been published describing failures API RP583 encourages consideration of a wider tempera-
that highlight the significance of CUI.9–12 ture ranges to account for variability in insulation and operating
conditions. For example the recommended carbon steel tempera-
MECHANISM ture range for CUI susceptibility is extended to from -12 C to
Insulation systems have the potential to collect and transmit 175 C.17,18
moisture-containing corrosive ions to the metal substrate and
concentrate them as the water evaporates with temperature. The MOISTURE ENTRY SOURCES
chloride ion present in moisture and some insulation is the prin- It is important to identify the most vulnerable areas in a plant
cipal corrosive ion responsible for CUI, although other halides as well as the most vulnerable locations on process equipment
also may assist. and piping systems. For example, areas adjacent to a chlorine-
producing facility or downwind of a cooling tower mist are likely
Carbon steels.
to accelerate CUI. A protected area inside a building is likely
Carbon steels suffer general corrosion and pitting under wet insu- to have no problem. In vulnerable areas, features that exhibit
lation. The corrosion rate increases at elevated temperature.13 warning signs of CUI must be dealt with promptly, such as
CUI continues when insulated carbon steel plant equipment open insulation terminations or mechanically abused insulation
and piping is idled (mothballed) for an extended time. The insu- jacketing.19
lation should be stripped and the equipment and piping painted
if required to prevent atmospheric rusting.14
Susceptible locations on process equipment.
Austenitic stainless steels. The design of vessel attachments can significantly affect CUI
Austenitic stainless steels suffer ECSCC under wet insulation, susceptibility. Improved designs can help prevent moisture pene-
especially in the presence of oxygen.15 Specially formulated insu- trating the insulation boundary. Some methods include provid-
lation materials, however, can inhibit ECSCC in the short term. ing sealing discs on nozzles and other attachments, ensuring that
Although less commonly used, aluminum alloys may suffer nozzle length is adequate to permit effective sealing, and design-
chloride pitting,16 and duplex stainless steels may suffer ECSCC ing insulation rings that can either shed water or drain any water
under wet insulation under applicable conditions.16 Caustic that enters.20,21
attack also has been reported on aluminum components in cold Susceptible locations on equipment are shown in figure 1.
boxes filled with perlite during warm-up periods when moisture
has entered the cold box during operation, has frozen into ice Susceptible locations on piping systems.
balls, and then melted (Sheldon Dean, pers. comm.). Piping systems are the items that usually are most susceptible to
CUI.24 Locations include pipe hangers and other supports, dead
SUSCEPTIBLE TEMPERATURE RANGES FOR CUI legs, valves and fittings, bolt-on pipe shoes, steam and electric
The optimum temperature range for CUI depends on the alloy tracer tubing penetrations, termination of insulation at flanges
and the corrosion mechanism. For example, for ECSCC of aus- and other piping components, damaged or missing insulation
tenitic stainless steels to occur, the temperature must be high jacketing, insulation jacketing seams located on the top of hori-
enough to concentrate chloride ions on the surface, but not so zontal piping or improperly lapped or sealed insulation jacketing,
STANDARDS AND PRACTICES ON CORROSION UNDER INSULATION 171
Standards relating to ECSCC of austenitic stainless steels.

FIG. 1 Vulnerable locations on a vessel.22,23 ASTM standards focused on simulating ESCC of austenitic stain-
less steel and the potential of insulation materials to cause corro-
sion include ASTM C692, Standard Test Method for Evaluating
the Influence of Thermal Insulations on External Stress Corrosion
Cracking Tendency of Austenitic Stainless Steel; ASTM C871,
Standard Test Methods for Chemical Analysis of Thermal Insula-
tion Materials for Leachable Chloride, Fluoride, Silicate, and
Sodium Ions; ASTM C795, Standard Specification for Thermal
Insulation for Use in Contact with Austenitic Stainless Steel; and
ASTM C929, Standard Practice for Handling, Transporting, Ship-
ping, Storage, Receiving, and Application of Thermal Insulation
Materials for Use in Contact with Austenitic Stainless Steel.
ASTM C692, Standard Test Method for Evaluating

the Influence of Thermal Insulations on External
Stress Corrosion Cracking Tendency of Austenitic
Stainless Steel.26
Adopted in 1971, ASTM C692 was originally entitled Evaluating
the Influence of Wicking Type Thermal Insulations on the Stress
Cracking Tendency of Austenitic Stainless Steels,26 and was based
on a test method developed by Dana and DeLong. Wicking
of leachable chlorides to the surface was then considered the
termination of insulation in a vertical pipe, and locations where primary concentration mechanism.27
caulking has deteriorated or is missing. The standard currently covers two types of 28-day labora-
CUI damage on flanged assemblies can be accelerated in serv- tory test procedures to determine which thermal insulations con-
ices such as chlorine, anhydrous hydrochloric acid, and sulfuric tribute to stress corrosion cracking of sensitized austenitic
acid, as well as areas where fugitive emission from bolted assemblies stainless steel caused by soluble chlorides in the insulation.
combine with atmospheric moisture or wet insulation to accelerate The procedures are intended primarily as a preproduction test
corrosion. The insulation can “trap” the fugitive emission at these for qualification of the basic chemical composition of a particular
locations. It is usually advisable to inspect these locations. manufacturer’s lot. They are not intended as routine tests for qual-
The design, installation, and location of piping systems ity assurance or production lot compliance. ASTM C871, however,
have a big impact on susceptibility to CUI. Design details such as is used to confirm acceptable chemical properties of subsequent lots
the piping material, presence of tracing, and type of protective of insulation previously found acceptable by ASTM C692.
coating influence CUI. The quality of the installation, including
the integrity of seals and caulking at penetrations, also will have ASTM C871, Standard Test Methods for Chemical
a significant impact on the level of moisture intrusion and subse- Analysis of Thermal Insulation Materials for
quent CUI. The location of piping relative to moisture sources Leachable Chloride, Fluoride, Silicate, and Sodium
(e.g., deluge systems, cooling towers) also can affect the suscepti- Ions.28
bility to CUI.25 This is the second of a series of standards, first issued in 1977.
It covers procedures for determining water-leachable chloride,
LABORATORY TESTS THAT SIMULATE CUI fluoride, silicate, and sodium ions in thermal insulation materials
All insulation materials support corrosion, although the type of in the parts per million range. Fluoride ions can contribute to
material affects the extent of corrosion. Accelerating factors the chloride stress corrosion cracking of austenitic stainless
include the following: steels. Sodium and silicate ions in insulation have been found to
inhibit ECSCC.29
• Content of damaging water-soluble salts (especially chloride)
ASTM C795, Standard Specification for Thermal
• Presence of inhibiting salts that can delay attack
Insulation for Use in Contact with Austenitic
• Capacity to absorb or retain water and dry again Stainless Steel.30
• Tendency of some organic insulations to produce acid during This is the third of a series of standards, first issued in 1992. It
aging. covers basic material requirements for thermal insulation for use
in contact with austenitic stainless steel piping and equipment. It
Several ASTM standards have been developed to detect and includes physical and chemical requirements and preproduction
measure the extent of corrosion produced by insulation materials corrosion test and chemical analysis, which shall be performed
or the tendency to produce harmful by-products when wet. to conform to the requirements.
The insulation materials also must pass the preproduction INSULATION MATERIALS
test requirements of ASTM C692 for stress corrosion effects on The selected type of insulation affects CUI. For example, some
austenitic stainless steel and the confirming quality control types are more prone to mechanical damage; some are more
chemical requirements of ASTM C871. likely to leach chlorides and other salts; and some contain poten-
tial inhibitors.
ASTM C929, Standard Practice for Handling, Insulation materials are covered by ASTM standards, as
Transporting, Shipping, Storage, Receiving, and given in table 1.
Application of Thermal Insulation Materials for
Use in Contact with Austenitic Stainless Steel.31 PROTECTIVE COATINGS
Insulating materials must be protected from exposure to water- The first line of defense for the metal surface is a protective
soluble, corrosive ion-containing compounds at all stages of coating. Various factors influence coating selection, such as
manufacture, handling, shipping, storage, and application. maximum and minimum surface temperature and single coat
The standard provides guidance and direction on the han- dry film thickness. For example, indoor equipment that is not
dling, transporting, shipping, storage, receiving, and application exposed to external moisture sources may require something
of thermal insulating materials to be used as a surface treatment less conservative than an immersion grade coating. The sub-
or as part of the thermal insulation system in contact with aus- strate must be prepared according to the manufacturer’s guide-
tenitic stainless steel. lines for any type of coating. Inadequate surface preparation
reduces anticipated coating life and increases the likelihood of
Standards relating to general and localized corrosion of
coating failure.
carbon steel.
Relevant standards are ASTM G189, Standard Guide for Labora- Carbon steel.
tory Simulation of Corrosion under Insulation; and ASTM C1617, Commonly used coatings on carbon steel are immersion-grade
Standard Practice for Quantitative Accelerated Laboratory Evalu- organic coatings, fusion bonded coatings, thermal spray aluminum
ation of Extraction Solutions Containing Ions Leached from Ther- (TSA),36 and petrolatum wax tape (for dew point corrosion).37
mal Insulation on Aqueous Corrosion of Metals.
Austenitic stainless steel.
ASTM G189, Standard Guide for Laboratory Commonly used coatings on austenitic stainless steel are
Simulation of Corrosion under Insulation.32 immersion-grade organic coatings, TSA,38 and loose wrapped
Describes a method of simulating CUI on insulated specimens with aluminum foil39 are used.
cut from carbon or low-alloy steel pipe sections exposed to a cor- Austenitic stainless steel coating systems shall not contain
rosive environment, usually at elevated temperature under wet- free, soluble chlorides or other halides after curing to prevent
dry conditions. Temperature simulation may be isothermal or ESCC. Similarly, the coating shall not contain zinc, lead, copper,
cyclic. It is based on a method developed by W. G. Ashbaugh.33 or their compounds because of the risk of liquid metal cracking,
The test apparatus includes (1) an idealized annular geo- for example, from the heat effect of a fire.
metry between piping and surrounding thermal insulation, Inorganic coatings.
(2) internal heating to produce a hot-wall surface on which CUI High-temperature inorganic coatings also are available (see fig. 2).
can be quantified, (3) introduction of ionic solutions into the
annular cavity between the piping and thermal insulation, (4) con- Standards for mastics and coatings and their properties.
trol of the temperature to produce either isothermal or cyclic tem- Relevant standards include ASTM C461, Standard Test Methods
perature conditions, and (5) control of the delivery of the control for Mastics and Coatings Used with Thermal Insulation; and
or solution to produce wet or wet-dry conditions. ASTM C647, Standard Guide to Properties and Tests of Mastics
and Coating Finishes for Thermal Insulation.
ASTM C1617, Standard Practice for Quantitative
Accelerated Laboratory Evaluation of Extraction ASTM C461, Standard Test Methods for Mastics and
Solutions Containing Ions Leached from Thermal Coatings Used with Thermal Insulation.41
Insulation on Aqueous Corrosion of Metals.34 This standard covers test methods and procedures for sampling
Covers procedures for determining the corrosive or inhibiting and testing mastics and coatings for use as weather and vapor
effect of ions extracted from thermal insulation materials. Corro- barrier finishes on thermal insulations and for other accessories.
sion rates are calculated for metals exposed on a hot plate for Properties include uniformity and storage, stability, stability
four days to the leached solutions and the type and depth of under freezing, density and weight per gallon, consistency, solids
localized corrosion recorded. content, coverage, sag resistance drying time, and flash point.
Ions may be added to the extracted solutions to simulate
contamination from an external source. Expected corrosion- ASTM C647, Standard Guide to Properties and
inhibiting ions also can be added to investigate their effect. Other Tests of Mastics and Coating Finishes for Thermal
liquids can be tested for their potential corrosiveness, such as Insulation.42
cooling tower water, boiler feed, and chemical feed stocks. This standard is a key to specific properties of mastics and coat-
Chemical inhibitors also can be evaluated. ing finishes that characterize their performance in application or
TABLE 1 ASTM Insulation Standards35
ASTM Type Kind Form Components
C533, Standard Specification for Calcium Silicate Calcium silicate Homogeneous Block and pipe Hydrous calcium silicate usually with fibrous
Block and Pipe Thermal Insulation inorganic reinforcement
C552, Standard Specification for Cellular Glass Cellular glass Homogeneous Block and shapes Foamed when molten to form a closed cell
Thermal Insulation inorganic structure.
C610, Standard Specification for Molded Expanded Expanded perlite Homogeneous Block and pipe Expanded perlite, inorganic silicate binders,
Perlite Block and Pipe Thermal Insulation inorganic cover fibrous reinforcement, and silicone water-
resistant additions
C553, Standard Specification for Calcium Silicate Mineral fiber Blanket Fiber Rocks, slag, or glass processed from a molten
Block and Pipe Thermal Insulation state into a fibrous form and including organic
binders.
C892, Standard Specification for High-Temperature Ceramic fiber Blanket Fiber Man-made vitreous alumino-silicate fiber
Fiber Blanket Thermal Insulation
C534, Standard Specification for Preformed Flexible Elastomeric Organic foam Sheet and tube Flexible, closed-cell foam formed by extrusion
Elastomeric Cellular Thermal Insulation in Sheet and
Tubular Form
C578, Standard Specification for Rigid, Cellular Polystyrene Organic foam Rigid block and Closed-cell foam formed by either an extrusion
Polystyrene Thermal Insulation extruded or molding
C591, Standard Specification for Unfaced Preformed Polyisocyanurate Organic foam Rigid block and Closed-cell foam formed by a controlled chemi-
Rigid Cellular Polyisocyanurate Thermal Insulation preform cal reaction and may contain leachable chlor-
ides, fluorides, silicate, and sodium ions
C1029, Standard Specification for Spray-Applied Polyurethane Organic foam Rigid spray-applied Closed-cell foam formed by a chemical reaction
Rigid Cellular Polyurethane Thermal Insulation at the time of application
C1126, Standard Specification for Faced or Unfaced Phenolic Organic foam Rigid board or Closed-cell foam formed by a controlled
Rigid Cellular Phenolic Thermal Insulation tubular chemical reaction
C1728, Standard Specification for Flexible Aerogel Silica Aerogel Blanket Air-filled foam
Insulation
FIG. 2 Temperature limitations of protective coatings.40
service. Properties include consistency, coverage, build, wet flam- thaw stability, outdoor durability, temperature limits, chemicals
mability, toxicity, temperature and humidity range, surface wet- and water resistance, mold and mildew resistance, surface flam-
ting and adhesion, gap filling and bridging, sizing and sealing, mability, water-vapor transmission rate, adhesion, impact resis-
drying time and curing time, shrinkage, storage stability, freeze- tance, abrasion resistance, flexure, elongation, color, and odor.
INSPECTION PLANNING documents detail the extent of examination needed and which
Developing an effective strategy for detecting CUI starts with nondestructive examination (NDE) methods should be consid-
planning. During the inspection planning process, essential con- ered. A description of each RAGAGEP is provided in the
siderations such as operating conditions (temperature, cycles), following paragraphs. Table 3 shows which RAGAGEP may be
material systems (insulation, equipment), environmental condi- applicable to a given equipment type.
tions, risk tolerance, and operational requirements are brought
together to establish the type, extent, and frequency of the API 510, Pressure Vessel Inspector Program.44
inspections selected to achieve the appropriate level of confi- This code covers the in-service inspection, repair, alteration,
dence that CUI will not trigger a loss of containment. and rerating activities for pressure vessels and pressure reliev-
The type of inspection technique used for monitoring CUI ing devices protecting them. API 510 provides guidance on
is driven primarily by operation and economic considerations, important considerations when establishing an inspection
while the extent and frequency of CUI inspection will be driven plan for evaluating CUI. In addition to providing susceptible
by likelihood and consequence considerations. For example, temperature ranges for various material systems and defin-
techniques that do not require insulation removal (e.g., profile ing susceptible locations (described earlier), this API Code
radiography, guided wave) may be considered in cases in which gives practical guidance on if and how much insulation to
insulation removal creates operational issues or is expensive. remove. Some of these considerations include insulation type,
Similarly, insulation systems located on equipment that is likely insulation condition, consequence of leakage, and age of the
to have CUI and could result in significant consequences vessel.
require more extensive and frequent inspection than systems
not as likely to have CUI or that result in relatively lower API RP572, Inspection of Pressure Vessels.45
consequences. This recommended practice supplements API 510 with reasons
for inspection, causes of deterioration, frequency and methods of
Inspection methods.
inspection, methods of repair, and preparation of records and
The methods of inspecting for CUI range from visual inspection reports. CUI is discussed.
following insulation removal to various remote examination
techniques that do not need insulation removal. In general,
inspection methods are complementary and more than one may
be required to provide an accurate assessment of condition. See TABLE 3 Inspection RAGAGEPs Covering CUI Requirements/
table 2 for a summary. Guidance
Inspection standards and codes.

Equipment Codes Guidance Documents
API inspection codes and recommended practices provide require-
ments and guidance on important considerations when establish- Pressure Vessels API 510, NB-23 API RP583, API RP572, API RP571,
ing an inspection plan for evaluating CUI. These codes and API RP580/API RP581
recommended practices are often referred to as Recognized and Piping API 570 API RP583, API 574, API RP571,
API RP580/API RP581
Generally Accepted Good Engineering Practices (RAGAGEPs).
Storage Tanks API 653 API RP583, API RP575, API RP571,
In addition to providing susceptible temperature ranges for
API RP580/AP RP581
various material systems and defining susceptible locations, these
43
TABLE 2 Summary of CUI Inspection Methods
Acronym Name Feature Disadvantage
VT Visual examination Qualitative Requires complete or partial insulation removal

PT Penetrant testing Detects ECSCC Requires complete or partial insulation removal
GWT Guided wave For remote inspection of piping Cannot detect pitting
RT Profile radiography For general corrosion Radiation safety hazard
RT Film density radiography Can locate pitting Radiation safety hazard
RT Flash radiography Can detect waterlogged insulation Poorer image contrast and resolution
RT Radiometric profiling Very portable Cannot differentiate between ID and OD corrosion
RTR Real-time radiography Easily viewed digital images Wet insulation hampers testing
CR Computed radiography Image is digitized Plates must be scanned
DR Digital radiography Image electronically stored for distribution Panel detectors prone to damage
PEC Pulsed eddy current Averages corrosion over small areas May not detect pitting
NBS Neutron backscatter Detects wet insulation Does not detect corrosion
IR Infrared thermography Can be done remote from equipment Can only detect wet or damaged insulation
API 570, Piping Inspection Code. Inspection, operators. The initial setup of an RBI program requires extensive
Repair, Alteration and Re-rating of In-Service in-house work, a generous budget, and time to implement. Opera-
Piping Systems.46 tion of a successful RBI program also requires a multiyear commit-
This code provides guidance on the frequency and extent of ment, because scheduled major maintenance programs on
inspection based on several factors including the severity of the insulated equipment and piping can be at 10- to 15-year intervals.
service (toxicity/flammability) and the likelihood of CUI. Some
of the likelihood factors include the pipe material system, operat- API RP580, Risk-Based Inspection.52
ing temperature, insulation type, external environment, and Outlines and explains the basic elements for developing, imple-
insulation condition. menting, and maintaining a credible RBI program. It is a generic
API 570 also includes guidance on determining which pip- document on RBI that can be used as a measuring stick by which
ing systems are most susceptible to CUI, as well as some of the the quality of any and all RBI methods and work processes could
most common locations for CUI on those systems determined to be evaluated to determine if they meet the level of quality pre-
be susceptible to it. scribed in the RP.
API 574, Inspection Practices for Piping System API RP581, Risk-Based Inspection Technology.53
Components.47 Provides a methodology for establishing an inspection program
This recommended practice supplements API 570 by providing for fixed equipment based on risk. The likelihood of various
piping inspectors with information to improve skill and increase damage mechanism occurring is estimated through calculation
basic knowledge of inspection practices. It covers piping, tubing, of a “damage factor.” The magnitude of these damage factors
valves, and fittings used in petroleum refineries and chemical facilitates assignment of a relative likelihood (1–5) that a particu-
plants. It does not cover inspection of specialty items, including lar damage mechanism will occur.
instrumentation, furnace tubulars, and control valves. Part 2 of API RP581 provides specific criteria for calculating
damage factors for insulated carbon steel and stainless steel
API 653, Tank Inspection, Repair, Alteration, and equipment. The assessment requires consideration of many fac-
Reconstruction (5th ed., addendum 1, April 2018).48 tors, including complexity of the installation (number of pene-
This code covers external inspection requirements for storage trations or protrusions, condition, coating quality, inspection
tanks, including computation of frequency based on wall thick- history, and system design (type of insulation, temperature).
ness measurements. CUI aspects are discussed. Producing a risk assessment evaluation requires identi-
fication of potential events and their potential consequences,
API RP575, Inspection Practices for Atmospheric estimating their potential severity and likelihood, and then esti-
and Low Pressure Storage Tanks.49 mating the level of risk based on the combination of severity and
This recommended practice supplements API 653 and covers the likelihood of the event happening. A risk assessment evaluation
inspection of atmospheric and low-pressure storage tanks (fabri- is required for every location. See Annex A, API RP583 for Qual-
cated to API RP620 or API RP650) that have been designed to itative Likelihood Assessment, Tables A3 and A4.
operate at pressures from atmospheric to 15 psig. It includes rea-
sons for inspection, frequency and methods of inspection, meth-
ods of repair, and preparation of records and reports. It also
References
includes CUI guidance. 1. Corrosion under Insulation and Fireproofing, API RP583, Section
5.4.2 (Washington, DC: American Petroleum Institute, 2014).
NB-23, National Board Inspection Code.50
2. R. King, “Does Insulation Cause Corrosion,” in Insulation Outlook,
This code provides limited guidance on inspection for CUI. June 2009, updated May 2019, http://web.archive.org/web/
20220720204408/https://insulation.org/io/articles/does-
API RP571, Damage Mechanisms Affecting Fixed insulation-cause-corrosion/
Equipment in the Refining Industry.51
3. Corrosion under Insulation and Fireproofing, API RP583, Section
This standard provides an in-depth description of more than 60
11.5.6 (Washington, DC: American Petroleum Institute, 2014).
different damage mechanisms (a general term referring to any
cause of problems or failures that can occur to process equip- 4. Corrosion under Insulation and Fireproofing, API RP583
ment in refineries). (Washington, DC: American Petroleum Institute, 2014).
The standardized format includes a general description of the 5. Standard Practice Control of Corrosion under Thermal Insulation
damage mechanism, susceptible materials of construction, critical and Fireproofing Materials, NACE SP0198-2016 (Houston, TX:
factors, inspection methods, selection guidelines, and control fac- AMPP, 2016).
tors. This standard supplements API RP580, Risk-Based Inspection;
6. Corrosion-under-Insulation (CUI) Guidelines, EFC-55, 2nd ed., ed.
and API RP581, Risk-Based Inspection Technology.
S. Winnik (Cambridge, UK: European Federation for Corrosion,
2015).
Risk-based inspection (RBI).
RBI is a complex program that requires support and cooperation of 7. Corrosion under Insulation and Fireproofing, API RP583, Section
the entire organization, from senior management to field-unit 4.4 (Washington, DC: American Petroleum Institute, May 2014).
8. W. I. Pollock and J. M. Barnhart, eds., Corrosion of Metals under http://web.archive.org/web/20220720214326/https://cupdf.com/

Insulation, (West Conshohocken, PA: ASTM International, document/xom-strategy-for-preventing-cui.html?page=1
1985).
25. Corrosion under Insulation and Fireproofing, API RP583,
9. R. Sampaio and A.L. M. V. Leite, “More Lessons ‘Re-Learned’ from Section 5.4 (Washington, DC: American Petroleum Institute,
Corrosion under Insulation” (Dow Chemical Company, Midland, May 2014).
MI, 2009), http://www.penderlo.com/doc/Dow_CUI.pdf
26. Standard Test Method for Evaluating the Influence of Thermal
10. H. Ahluwalia, “The Hidden Enemy: Corrosion under Insulation” Insulations on External Stress Corrosion Cracking Tendency of
(paper presentation, Georgia Tech Renewable Bioproducts Austenitic Stainless Steel, ASTM C692-13(2018) (West
Institute (RBI) 2014 Corrosion Symposium, 2014), https:// Conshohocken, PA: ASTM International, approved November 1,
rbi1.gatech.edu/sites/default/files/documents/Presentations/ 2018), http://doi.org/10.1520/C0692-13R18
2014 Corrosion Symposium - Ahluwalia.pdf
27. A. W. Dana and W. B. DeLong, “Stress Corrosion Cracking Test,”
11. A. A. Al-Beed, “Engineering Approach to Control Corrosion in Corrosion, vol. 12 (Houston, TX: AMPP, 1956), 309t–310t.
under Thermal Insulation (CUTI) in Petrochemical Industries”
28. Standard Test Methods for Chemical Analysis of Thermal
(paper presentation, Petrotech 2001, 12th Industrial Security
Insulation Materials for Leachable Chloride, Fluoride, Silicate, and
Symposium, Saudi Petrochemical Company [SADAF], Jubail,
Sodium Ions, ASTM C871-95(2000) (West Conshohocken, PA:
KSA, 2001), http://www.ndt.net/article/mendt2009/papers/
ASTM International, approved June 15, 1995), http://doi.org/
AlBeed-1.pdf
10.1520/C0871-95R00
12. W. G. Ashbaugh, “Corrosion of Steel and Stainless Steel under
29. K. M. Whorlow, E. Woolridge, and F. Hutto, “Effect of Halogens
Thermal Insulation,” in Process Industries Corrosion—The Theory
and Inhibitors on the External Stress Cracking of Type 304
and Practice, ed. B. J. Moniz and W. I. Pollock (Houston, TX:
Austenitic Stainless Steel,” in Insulation Materials: Testing and
AMPP, 1986), 768–795.
Applications, ed. R. S. Graves and R. R. Zarr (West
13. Standard Practice Control of Corrosion under Thermal Insulation Conshohocken, PA: ASTM International, 1997), 485–497.
and Fireproofing Materials, NACE SP0198-2016, Section 2.1 Cor-
30. Standard Specification for Thermal Insulation for Use in Contact
rosion Mechanisms, Carbon Steel (Houston, TX: AMPP, 2016).
with Austenitic Stainless Steel, ASTM C795-08(2018) (West
14. R. J. Twigg, Guidelines for Mothballing of Process Plants, Conshohocken, PA: ASTM International, approved November 1,
Publication 34 (St. Louis, MO: Materials Technology Institute, 2018), http://doi.org/10.1520/C0795-08R18
2002).
31. Standard Practice for Handling, Transporting, Shipping,
15. Standard Practice Control of Corrosion under Thermal Insulation Storage, Receiving, and Application of Thermal Insulation
and Fireproofing Materials, NACE SP0198-2016, Section 2.2 Aus- Materials for Use in Contact with Austenitic Stainless Steel,
tenitic and Duplex Stainless Steel (Houston, TX: AMPP, 2016). ASTM C929-2014 (West Conshohocken, PA: ASTM
International, approved March 15, 2014), http://doi.org/
16. Corrosion under Insulation and Fireproofing, API RP583, Section 10.1520/C0929-14
4.5 (Washington, DC: American Petroleum Institute, May 2014).
32. Standard Guide for Laboratory Simulation of Corrosion under
17. Corrosion under Insulation and Fireproofing, API RP583, Section Insulation, ASTM G189-07(2013) (West Conshohocken, PA: ASTM
4.2.1 (Washington, DC: American Petroleum Institute, May 2014). International, approved August 1, 2013), http://doi.org/10.1520/
G0189-07R13
18. Corrosion under Insulation and Fireproofing, API RP583, Section
4.2.2 (Washington, DC: American Petroleum Institute, May 2014). 33. D. Abayarathna, W. G. Ashbaugh, R. D. Kane, N. McGowan, and
B. Heimann, “Measurement of Corrosion under Insulation and
19. Corrosion under Insulation and Fireproofing, API RP583, Section Effectiveness of Protective Coatings,” in Corrosion 97, Paper
5.2 (Washington, DC: American Petroleum Institute, May 2014). No. 266 (Houston, TX: AMPP, 1997).
20. Corrosion under Insulation and Fireproofing, API RP583, Section 34. Standard Practice for Quantitative Accelerated Laboratory
9.5.3 (Washington, DC: American Petroleum Institute, May 2014). Evaluation of Extraction Solutions Containing Ions Leached
from Thermal Insulation on Aqueous Corrosion of Metals,
21. Pressure Vessel Inspector Program, API 510, 10th ed.,
(Washington, DC: American Petroleum Institute, March 2018). ASTM C1617-19 (West Conshohocken, PA: ASTM International,
approved May 1, 2019), http://doi.org/10.1520/C1617-19
22. Association for Materials Performance and Protection, “Figure 2.
35. Standard Practice Control of Corrosion under Thermal Insulation
Typical Vessel Attachments Where Water May Bypass
and Fireproofing Materials, Section 5, Insulation, Fireproofing
Insulation,” in Standard Practice Control of Corrosion under
Thermal Insulation and Fireproofing Materials, NACE SP0198- and Accessory Materials, NACE SP0198-2016 (Houston, TX:
2016 (Houston, TX: AMPP, 2016). AMPP, 2016).
36. O. Doble and G. Pryd, “Use of Thermally Sprayed Aluminum

23. American Petroleum Institute, “Figure 20” in Corrosion under
Insulation and Fireproofing, API RP583, Section 9.4.2 in the Norwegian Offshore Industry,” Protective Coatings
(Washington, DC: American Petroleum Institute, May 2014). Europe 2, no. 4 (April 1997), http://www.wermac.org/pdf/
corrosion12.pdf
24. B. J. Fitzgerald and S. Winnik, “A Strategy for Preventing
Corrosion under Insulation on Pipeline in the Petrochemical 37. Thermal Insulation of Pipework, Ductwork, Associated Equipment
Industry,” Exxon Mobil Chemical Company, 2004, and Other Industrial Installations in the Temperature Range of
100 C to þ870 C, BS 5970:2012, Code of Practice, British 44. Pressure Vessel Inspector Program, API 510, 10th ed., Addendum 2
Standards Institution (New York: American National Standards (Washington, DC: American Petroleum Institute, March 2018).
Institute, 2012).
45. Inspection of Pressure Vessels, API RP572, 4th ed. (Washington,
38. P. Bock, “Preventing CUI with Thermal-Spray Metal Coating: DC: American Petroleum Institute, December 2016).
New Use for a Traditional Process,” JPCL (February 2015),
https://www.paintsquare.com/library/articles/(062-70) 46. Piping Inspection Code: In-Service Inspection, Rating, Repair and
Bock.pdf Alteration of Piping Systems, 4th ed. (Washington, DC: American
Petroleum Institute, February 2016).
and Fireproofing Materials NACE SP0198-2016, Section 4.2.3 47. Inspection Practices for Piping System Components, API 574,
Protective Coatings (Houston, TX: AMPP, 2016). 4th ed. (Washington, DC: American Petroleum Institute, 2016).
40. M. O’Donoghue and V. Datta, “From Trauma to Transcendence: 48. Tank Inspection, Repair, Alteration, and Reconstruction, API 653,
CUI and Coatings of Choice,” AkzoNobel, SSPC Webinar, 2016, 5th ed., Addendum 1 (Washington, DC: American Petroleum
http://web.archive.org/web/20220720212645/https:// Institute, 2018).
www.paintsquare.com/webinars/view/?272
49. Inspection Practices for Atmospheric and Low Pressure Storage
41. Standard Test Methods for Mastics and Coatings Used with Tanks, API RP575, 3rd ed., Section 8.2.7 (Washington, DC:
Thermal Insulation, ASTM C461-17 (West Conshohocken, American Petroleum Institute, 2014).
PA: ASTM International, approved September 1, 2017),
50. National Board Inspection Code, NB-23 (Columbus, OH: National
http://doi.org/10.1520/C0461-17
Board of Pressure Vessel Inspectors, 2019).
42. Standard Guide to Properties and Tests of Mastics and Coating
51. Damage Mechanisms Affecting Fixed Equipment in the Refining
Finishes for Thermal Insulation, ASTM C647-19 (West
Industry, API RP571, 2nd ed. (Washington, DC: American
Conshohocken, PA: ASTM International, approved March 1, 2019),
Petroleum Institute, 2011).
http://doi.org/10.1520/C0647-19
52. Risk-Based Inspection, API RP580, 3rd ed. (Washington, DC:
American Petroleum Institute, 2016).
and Fireproofing Materials, NACE SP0198-2016, Section 6.
Nondestructive Moisture and Corrosion Detection Techniques 53. Risk-Based Inspection Technology, API RP581, 3rd ed.
(Houston, TX: AMPP, 2016). (Washington, DC: American Petroleum Institute, 2019).
179
Chapter 12 | Freshwater
Walter T. Young1
Introduction in this chapter. Details on corrosion processes affecting metals in

freshwaters are found in the references provided at the end of
Corrosion testing in freshwater environments is performed to this chapter.1–6
determine the corrosion characteristics of water, evaluate the
behavior of various materials when exposed to water, and evalu-
ate various corrosion mitigation methods. For example, waters in WATER CHEMISTRY
cooling systems often are analyzed to determine how much and Although water has a definite molecular structure, freshwater is
what forms of corrosion might occur on a given metal. Screening not a pure substance and may contain numerous ions, dissolved
tests are used to select the most appropriate metal for use as pip- minerals, and gasses. Examples of dissolved solids include com-
ing material. Various water treatment alternatives can be tested binations of calcium, magnesium, manganese, nitrates, iron, cop-
in the laboratory or in a pilot plant. Tests are used to monitor per, lead, chlorides, sulfates, carbonates, and bicarbonates. Water
the selected treatment scheme. Laboratory screening tests, chemistry is one of the most important factors affecting the cor-
detailed simulations, pilot plant studies, and system monitoring rosion of metals in water. Dissolved salts, such as chlorides and
are typical corrosion testing methods. In any event, the selection sulfates, not only can increase the aggressiveness of the water but
of the appropriate test method will depend on the objectives of also can affect the ability of the water to form protective deposits.
the test, details of the system, and process parameters (e.g., flow, Generally, waters with higher dissolved salt contents are more
temperature, and chemistry). Test design and analysis are cov- corrosive. Dissolved gases also affect the corrosivity of water.
ered elsewhere in this book as well as in the referenced docu- Oxygen and carbon dioxide concentrations can increase corro-
ments. This chapter discusses the causes and types of corrosion sivity, as does hydrogen sulfide. Not all metals are affected the
common in freshwater systems and the standardized tests used same in a given water composition.
for evaluation. Freshwater can be defined as either water with a Acidity and alkalinity affect the corrosion rate. Generally,
salinity between 0.5 and 17 parts per thousand or water having alkaline conditions favor lower corrosion rates; however, some
less salt than seawater but still undrinkable.1,2 Then freshwater metals, such as aluminum and zinc show increased corrosion
can be further defined as water with a salinity less than 0.5 parts rate at pH above 9 because of the adhered aluminum oxide and
per thousand. For the purposes of this chapter, freshwater sys- zinc oxide. For iron alloys, the corrosion rate is relatively steady
tems include potable water, heating/cooling, condensate, rivers, between a pH of 4 and 10 at ambient temperature and where
streams, and lakes. oxygen reduction is the primary cathodic corrosion reaction;
however, the corrosion rate increases rapidly below pH 4.5 Iron
passivates and the corrosion rate decreases rapidly above a pH of
The Freshwater Environment 10 at ambient temperature, except at very high pH levels at
which the corrosion rate again can increase.
In designing an effective laboratory test program, it is important The solubility of elements in freshwater is limited and the
to consider factors that influence corrosion in a freshwater envi- solubility of calcium and magnesium carbonates are of particular
ronment. The following discussion summarizes these factors, but importance in freshwaters. The solubility of carbonates is inversely
the complexity of the topic does not permit a detailed discussion proportional to the temperature of the water. In other words, as
the water temperature increases, calcium and magnesium carbo-
nates become less soluble. If the solubility decreases sufficiently,
1
carbonates will precipitate and form a scale on the surfaces of the
Corrpro Companies, Inc., 470 Lapp Rd., Malvern, PA 19355, USA
system. This scale can provide a protective barrier to prevent cor-
The authors acknowledge the previous authors of this chapter, Walter T. Young rosion of the metallic elements in a system. Excessive scale depos-
and Philippa Fairer, Corrpro Companies, Inc. West Chester, PA. its can interfere with water flow and heat transfer. The quality of
DOI: 10.1520/MNL202NDSUP20190016
the scale depends on the quantity of calcium that can precipitate sections. Bacteria can survive under most conditions found in
as well as water flow and the chloride and sulfate content of the water systems and are either aerobic or anaerobic. Desulfovibrio
water. The tendency of water to precipitate a carbonate scale is desulfricans is an anaerobic sulfate-reducing bacterium that can be
estimated from corrosion indices such as the Langelier Saturation found in cooling towers and potable water piping. Thiobacillus thi-
Index (LSI) and Caldwell-Lawrence calculations,7–9 which use cal- oxidans (an acid producer) is another anaerobic bacterium known
cium, alkalinity, total dissolved solids, temperature, and pH prop- to influence corrosion. An example of aerobic bacteria is iron bac-
erties of the water. Other indices, such as the Ryznar Index, teria (Gallionella), which are found in some water wells. Slimes
purport to indicate corrosivity directly using the same elements as also influence corrosion by promoting concentration cell corro-
the LSI.7 Manganese in excess of 0.50 mg/L can cause pitting of sion.3 Anaerobic metal reducing bacteria cause pitting of stainless
copper in hot water systems.1 Copper in excess of 0.1 mg/L causes steel. Manganese in the presence of anaerobic manganese fixing
pitting of zinc galvanized steel and aluminum if the zinc and alu- bacteria (e.g., Gallionella, Sphaerotilus) and chloride can cause pit-
minum are downstream of the copper.1 The reversal of the poten- ting corrosion of stainless steel in fresh water.
tial between zinc galvanizing and steel can occur in some water,
resulting in the steel becoming the anode in a bimetallic couple. METALLURGY
This normally occurs in hot water with relatively high carbonates, In gray cast iron, the iron can be selectively removed leaving the
bicarbonates, phosphates, and silicates relative to sulfate and graphite matrix, a process called graphitic corrosion, also known
chlorides. as graphitization. High-zinc brasses and aluminum-bronzes are
susceptible to selective leaching of specific elements in the alloy.
PROCESS CONDITIONS In brass, the zinc selectively corrodes, leaving behind a weak,
Water velocity and turbulence can damage protective films and spongy, porous copper-rich matrix. The process, dezincification,
deposits on metal surfaces, causing increased corrosion. Soft met- generally occurs in relatively corrosive, soft, and acidic waters.
als, such as copper, are particularly susceptible to erosion corro- Aluminum bronzes can undergo selective leaching of aluminum
sion, but steel and other metals are also susceptible if the water (dealuminification) under conditions similar to dezincification.
velocity is sufficiently high. The critical velocity for erosion- Stainless steels can undergo intergranular corrosion at welds
corrosion of copper in freshwater is about 5 fps (1.52 m/s), but and elsewhere caused by the effective removal of chromium
this critical velocity can drop sharply as the chemical corrosivity from the metal matrix in combination with carbides under high-
of the water increases. Suspended solids in the water can increase temperature exposure. Denickelification is the selective removal
the erosion characteristics of the water.1 Deposits can result in of nickel from copper-nickel alloys, which has been found in
accelerated corrosion from the formation of oxygen differential fresh waters under conditions of high heat flux and low water
concentration corrosion cells. velocity.10 Brass is also subject to stress corrosion cracking in
Generally, higher temperatures cause an increase in corrosion water where tensile stress and a corrosion species, such as nitrate
activity and a corresponding increase in metal loss, particularly in or ammonia, are present in the water.
a closed (pressurized) system. A closed system does not allow oxy-
gen and other gasses to leave the water. If the system is open, OTHER FACTORS
increasing the temperature beyond 91 C causes a decrease in cor- Poor workmanship and defective materials can increase corro-
rosion because oxygen is removed from the water. Higher temper- sion. Water turbulence effects can be increased by poor work-
atures also can cause the solids in a system (where evaporation manship, such as the failure to ream burrs from the cut ends of
occurs) to concentrate, which can lead to increased corrosion rates. copper pipe. This increases the turbulence at the joints and
Alternately, increased temperature can cause an increase in the results in erosion of the copper. Excessive and corrosive flux
scaling tendency of the water resulting in lower corrosion rates. used in soldered coppers joints results in pitting corrosion along
The use of water treatment can increase or decrease corro- the flux runs. Incomplete longitudinal welds in electric resistance
sion rate. Excessive amounts of chlorine (used as a biocide) can welded (ERW) steel pipe result in concentration cell corrosion
increase corrosion. Water softening is the reduction of hardness, and metal loss.
alkalinity, and other constituents by the use of chemicals or resin Contamination of the water system can increase the corro-
exchange to reduce scaling. Water softening can lead to sion rate. In cooling tower systems, water corrosivity is increased
increased corrosion rates. Conversely, the addition of caustic, by the absorption of sulfur gases from the atmosphere. Airborne
soda ash, or corrosion inhibitors are used to decrease corrosion salts can contaminate open water systems. Process water systems
rates. Aeration can decrease corrosion rates when used to can be contaminated with process debris, such as fibers and
remove carbon dioxide. Deaeration also is used to decrease cor- chemicals that can increase the corrosion rate.
rosion rates in some systems.
BIOLOGICAL FACTORS
Test Methods
Biological activity can increase corrosion rate either by increasing Table 1 shows the most common forms of corrosion that affect
the occurrence of concentration cell corrosion beneath the biomass metals in the freshwater environment. These corrosion forms are
or by producing corrosives from metabolic processes. Corrosion described in ASTM G15, Standard Terminology Relating to Corro-
occurs as one of the common forms discussed in the following sion and Corrosion Testing.
FRESHWATER 181
quantitative corrosion data but will provide insight into the cor-
TABLE 1 Corrosion Forms Affecting Common Engineering Metals rosivity of the water. The chemical constituents of importance in
in Freshwater corrosion are pH, conductivity (or resistivity), total dissolved sol-
ids, chlorides, sulfates, suspended solids, alkalinity, carbonates,
Metal Corrosion Form bicarbonates, hardness, carbon dioxide, oxygen, sulfur dioxide,
Steel Uniform
nitrates, manganese, and heavy metals. Also, the scaling ten-
Pitting dency of the water should be determined by either the LSI or
MIC Caldwell-Lawrence diagrams.8,9 A computer program for calcu-
Erosion lating the scale-forming tendencies is available from the Ameri-
Galvanic can Water Works Association, Denver, CO.
Fretting Applicable test methods are found in the following:
Concentration cell
Galvanized steel Uniform • ASTM Annual Book of Standards11
Pitting
• American Public Health Association’s Standard Methods for
Galvanic
the Examination of Water and Wastewater12
MIC
Concentration cell • NACE TM0374, Laboratory Screening Tests to Determine the
Cast and ductile iron Uniform Ability of Scale Inhibitors to Prevent the Precipitation of Cal-
Pitting cium Sulfate and Calcium Carbonate from Solution 13
MIC
Concentration cell
UNIFORM CORROSION
Copper Uniform
Uniform corrosion is metal that is both evenly distributed over
Pitting
Crevice
the metal surface and uniform in the rate of penetration. Uniform
Erosion corrosion corrosion is readily measured with standard test procedures.
Cavitation Weight loss testing, polarization resistance, Tafel extrapolation,
Galvanic resistance change measurements, and AC impedance all measure
Concentration cell the average corrosion rate of a sample surface. Each test is con-
Bronze Pitting ducted by immersing the sample in the environment and averag-
De-alloying ing the corrosion losses, current flows, or volume changes over the
Cavitation entire surface area. Nonuniform corrosion, however, will provide
Concentration cell
inaccurate corrosion rates because the results are averaged over
Brass Pitting
the surface area. Specimens must be visually examined for signs of
Cavitation
pitting, crevice corrosion, stress-corrosion cracking (SCC), or
De-alloying
Stress corrosion cracking
other localized corrosion. When using electrochemical or resis-
Concentration cell tance tests, parallel immersion testing should be conducted to
Aluminum Pitting determine if localized corrosion will occur.
Galvanic Weight loss is the easiest and least expensive method because
Bacterial that method requires only test specimens, the solution, a con-
Concentration cell tainer, and the appropriate environmental parameters. Weight
Stainless Steel Pitting loss tests can be conducted in low-conductivity solutions, even in
MIC the atmosphere. An analytical balance is required for both before
Stress corrosion cracking
and after weight measurements. Multiple specimens must be used
Crevice
sequentially when evaluating the change in corrosion rate over
Intergranular corrosion
time. Specimens cannot be reused for corrosion rate versus time
Concentration cell
measurements after first exposed and cleaned because high initial
Note: MIC ¼ microbiologically influenced corrosion
corrosion rates will occur each time the specimen is used. This
will lead to artificially high corrosion rate data.
This section, “Test Methods,” provides information about
Weight loss testing is widely used both in the laboratory
the use and applicability of various corrosion tests. Details of
and for in-plant testing. For in-plant tests, racks of corrosion
performing the tests are provided in the cited references and
samples or single coupons are inserted at locations where corro-
in the section “Analysis, Testing, and Environments.” Tables 2
sion rates are desired. Test specimens can be inserted in pipes or
through 10 list the test methods applicable to the various tests.
other structures using “hot-tap” devices and in bypass loops.
Weight loss testing is slow (especially in systems with low corro-
ELECTROLYTE CHEMISTRY sion rates) and does not allow instantaneous measurement.
In designing a test program, it is important to know the chemis- Extreme care must be exercised in designing weight loss tests
try of the system water to accurately simulate the environment of because velocity, crevice, stagnation, and heat transfer conditions
interest. Knowledge of the water chemistry will not provide will influence the results.
DC polarization measurements, both polarization resistance increase in resistance. Resistance probe instruments are commer-
and Tafel extrapolation, provide the ability to measure instanta- cially available on the market. Probes can be made from many
neous corrosion rates and corrosion rate variation over time.14,15 different metals and alloys. The probes are inserted into the envi-
Standard polarization techniques assume a uniform corrosion ronment and the loss of cross-sectional area of the probe element
rate. Special techniques as discussed in the following discussion is detected by its increase in electrical resistance with time. The
and provided in tables 3 to 10 can be used to evaluate localized data obtained by plotting resistance against time of exposure
corrosion. The solution must have sufficient conductivity to per- provide a graphic history of corrosion rate. Resistance probes
form this test. Solutions with low conductivity require correction can be used in low-conductivity solutions. Visual inspection is
factors or special techniques to account for the effect of voltage necessary to differentiate between pitting and general metal loss.
drops on the measured specimen potential caused by current Pitting can result in the appearance of a low corrosion rate fol-
flow through the solution (IR drop). Tafel extrapolation requires lowed by rapid increases in corrosion. The method is not sensi-
relatively large changes to the electrochemical potential that can tive either to very low or to rapid changes in corrosion rate. The
damage the specimen. In addition, relatively long test times are positions of the probe in the environment, the fluid velocity, and
required. Corrosion reactions that are not under activation con- heat transfer have a pronounced effect on the results. ASTM
trol will obscure the Tafel slope. In contrast, significant informa- G96, Standard Guide for Online Monitoring of Corrosion in Plant
tion on the corrosion process can be obtained from full anodic Equipment (Electrical and Electrochemical Methods), provides
and cathodic polarization curves. Polarization resistance requires the details about conducting this test.
only small changes in specimen electrochemical potential; there- Electrochemical impedance spectroscopy (EIS) provides
fore, this method is fast and does less damage to the specimen detailed information on the corrosion reaction by determining
compared with Tafel extrapolation. Polarization can be applied the equivalent electrical circuit of a corroding system. The
to field testing and monitoring. Computerized equipment is method requires low potential changes in the system and can be
available for both types of tests. Instruments based on the used in low-conductivity solutions. Complex equipment is
polarization resistance technique are widely used for process needed to conduct the tests and specialized knowledge needed to
monitoring. interpret the data.16,17
Resistance probes are used for in-plant corrosion testing. As Table 2 provides information on standard test methods for
a metal corrodes, its volume decreases with a corresponding evaluating uniform corrosion.
TABLE 2 Test Methods for Evaluating Uniform Corrosion
Test Method Test Title Application
ASTM D2688 Standard Test Method for Corrosivity of Water in the Absence of Provides weight loss methods to evaluate corrosion directly in
Heat Transfer (Weight Loss Method) piping systems.
ASTM G1 Standard Practice for Preparing, Cleaning, and Evaluating Provides methods for cleaning and evaluating weight loss
Corrosion Test Specimens coupons.
ASTM G3 Standard Practice for Conventions Applicable to Electrochemical Provides information on reporting and displaying polarization
Measurements in Corrosion Testing measuring techniques, including both DC and AC methods.
ASTM G4 Standard Guide for Conducting Corrosion Tests in Field Provides guidelines for in-plant testing: weight loss coupons,
Applications specimen racks, reporting.
ASTM G31 Standard Practice for Laboratory Immersion Corrosion Testing of Describes procedures for conducting laboratory weight loss tests.
Metals Provides information on reporting and factors to be aware of.
ASTM G59 Standard Test Method for Conducting Poteniodynamic Provides details on how to conduct DC polarization resistance
Polarization Resistance Measurements tests.
ASTM G96 Standard Guide for Online Monitoring of Corrosion in Plant Provides details on conducting polarization resistance and
Equipment (Electrical and Electrochemical Methods) electrical resistance tests.
ASTM G102 Standard Practice for Calculation of Corrosion Rates and Related Describes practice for converting corrosion current data from
Information from Electrochemical Measurements electrochemical polarization measurements to corrosion rate.
NACE TM-01-71 (Test Method) Autoclave Testing of Metals in High Temperature Water Methods for testing water at temperatures greater than 100 C but
less than 360 C. Test is weight loss method, but could be
modified for electrochemical techniques.
NACE TM-02-74 Dynamic Corrosion Testing of Metals in High Temperature Water Similar to TM-01-71, but uses circulating loop and heat exchangers;
discusses the weight loss method.
NACE TM-01-69 Laboratory Corrosion Testing of Metals for the Process Industries Discusses factors of concern for laboratory testing. Discusses
planning tests and evaluation. Emphasizes weight loss methods
NACE RP-0775-87 Preparation and Installation of Corrosion Coupons and Discusses the use of weight loss coupons, interpretation of data,
(Recommended Practice) Interpretation of Test Data in Oilfield Operations and analysis. Principals are applicable to freshwater systems.
FRESHWATER 183
PITTING CORROSION evaluate these forms of corrosion. These methods were designed
Pitting corrosion is localized corrosion of a metal surface that is to measure crevice corrosion in severe electrolytes, such as salt
a surface cavity with a depth equal to or greater than the mini- solutions, but can be modified for freshwaters.
mum dimension at the opening. Pitting corrosion is difficult to Electrochemical polarization also can be used by conducting
evaluate because it can initiate at random locations on a metal cyclic anodic polarization scans. This technique, described in
surface. Large areas of a surface can be corrosion-free with pits ASTM G61, Standard Test Method for Conducting Cyclic Poten-
only at a few locations. Small corrosion coupons might not show tiodynamic Polarization Measurements for Localized Corrosion
pitting or might not provide enough pit depth data for a reliable Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys, provides a
analysis. Conversely, the surface can have a large number of pits qualitative approach to evaluate crevice corrosion. Polarization
over a given area. can be used to provide a more quantitative analysis by applying a
Immersion testing using specimens of sufficient size and graphical technique. This approach uses the same general
number should be used to measure corrosion rate accurately. The method as described under galvanic corrosion in ASTM G82,
depth of pitting follows the normal probability distribution. Standard Guide for Development and Use of a Galvanic Series for
Extreme value statistical analysis provides a useful tool to evaluate Predicting Galvanic Corrosion Performance. Its use requires
pitting.18,19 Pit depths can be measured using calipers, micrometer, knowledge of the solution chemistries inside and outside of the
or metallurgical microscope with a calibrated focus. crevice and the ability to simulate these environments for the
Cyclic anodic polarization curves are used to provide rela- anodic and cathodic tests.
tive susceptibility to pitting corrosion. This method does not Table 4 provides information on standard test procedures
provide specific corrosion rate data. Some corrosion rate devices for evaluating crevice corrosion.
that are based on the polarization resistance method use a tech-
nique involving monitoring electrochemical noise to determine a GALVANIC (BIMETALLIC) CORROSION
metal’s resistance to pitting or localized corrosion, sometimes The galvanic series may be used to predict the possibility of gal-
called the pitting index. The pitting index is qualitative and does vanic corrosion, but it cannot be used to predict the quantity of
not provide a corrosion rate. Another factor is the Pitting Resis- corrosion that can occur. Most published galvanic series apply
tance Equivalent Number (PREN) and might be useful for stain- only to the seawater environment and some metals behave differ-
less steel alloys. The PREN, also not quantitative, is calculated ently in different environments. For example, stainless steels can
using a weighted formula typically based on the chromium, behave either in the active state or in the passive state depending
molybdenum, nitrogen, and tungsten content of the alloy, devel- on the environment and the metals to which they are connected.
oped to rank the pitting and crevice corrosion resistance of stain- Sometimes the behavior of a galvanic couple in a particular envi-
less steels and some nickel-based alloys.20 ronment can be the reverse of that shown in most published gal-
Table 3 provides the standard test methods for evaluating vanic series. Metals also polarize (change potentials as a result of
pitting corrosion. current flow) when connected to each other in an electrolyte.
This will affect the corrosion behavior and cannot be predicted
CREVICE AND CONCENTRATION CELL CORROSION from the galvanic series. The area ratio of the two metals has a
Crevice corrosion and concentration cell corrosion susceptibility marked influence on the corrosion rate of the bimetallic couple.
can be measured directly by exposing test specimens to the envi- The solution operating conditions (e.g., aeration, movement)
ronment. ASTM F746, Standard Test Method for Pitting or Crev- also can have significant effects.
ice Corrosion of Metallic Surgical Implant Materials; ASTM G48, Two test methods can be employed to determine the sus-
Standard Test Methods for Pitting and Crevice Corrosion of Stain- ceptibility of two metals to galvanic corrosion in an electrolyte.
less Steels and Related Alloys by Use of Ferric Chloride Solution; In the first method, the two metals are immersed in the electro-
and ASTM G78, Standard Guide for Crevice Corrosion Testing of lyte and the current flow between them is measured using a zero
Iron-Base and Nickle-Base Stainless Alloys in Seawater and Other resistance ammeter. The corrosion current is calculated accord-
Chloride-Containing Aqueous Environments, can be used to ing to the following relationship: Itl ¼ Ig þ Ila, where Itl is the total
TABLE 3 Test Methods for Evaluating Pitting Corrosion
ASTM F746 Standard Test Method for Pitting or Crevice Corrosion of Metallic Surgical Discusses measurement of pitting or crevice tendency by measuring
Implant Materials repassivation tendency after polarization at noble potential. Applicable
only to passive alloys.
ASTM G16 Standard Guide for Applying Statistics to Analysis of Corrosion Data Discusses statistical analysis methods of corrosion data.
ASTM G46 Standard Guide for Examination and Evaluation of Pitting Corrosion Provides information needed for collecting and interpreting pitting data.
ASTM G61 Standard Test Method for Conducting Potentiodynamic Polarization Provides information on conducting cyclic anodic polarization tests. Useful
Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, procedure for evaluating pitting and crevice corrosion susceptibility. Can
or Cobalt-Based Alloys be modified for other alloys that exhibit passive behavior.
TABLE 4 Test Methods for Evaluating Crevice Corrosion
ASTM F746 Standard Test Method for Pitting or Crevice Corrosion of Metallic Surgical Measurement of pitting or crevice tendency by measuring repassivation
Implant Materials tendency after polarization at noble potential. Applicable only to passive
alloys.
ASTM G48 Standard Test Methods for Pitting and Crevice Corrosion Resistance of Method for characterizing crevice and pitting resistance of metals. Specific
Stainless Steels and Related Alloys by the Use of Ferric Chloride Solution to chloride containing environment, but useful for any environment where
ion concentration or oxygen differential corrosion can occur.
Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or procedure for evaluating pitting and crevice corrosion susceptibility. Can
Cobalt-Based Alloys be modified for other alloys that exhibit passive behavior.
ASTM G78 Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Useful for evaluating crevice corrosion susceptibility in any environment
Stainless Alloys in Seawater and Other Chloride-Containing Aqueous where ion or oxygen concentration cells can occur.
Environments
current, Ig is the measured galvanic corrosion current, and Ila is Table 6 provides standard tests for evaluating erosion
the local action corrosion current measured by another tech- corrosion.
nique. The galvanic corrosion rate is calculated using Faraday’s
law. ASTM G71, Standard Guide for Conducting and Evaluating CAVITATION
Galvanic Corrosion Tests in Electrolytes, describes the method. ASTM G32, Standard Test Method for Cavitation Erosion Using
The galvanic corrosion behavior can be predicted using Vibratory Apparatus, provides a standardized method of con-
polarization behavior. Electrochemical potential measurements ducting a cavitation test. Another nonstandard method is to con-
are used to predict which metal is the anode and which is the struct a flow channel and mount the specimens in such a
cathode. Anodic and cathodic polarization curves are produced manner as to produce cavitation on the downstream side of the
for the anticipated environments then superimposed on each specimen. For a detailed discussion about various cavitation
other at the known initial potential difference. The corrosion tests, see the ASM Corrosion Handbook.10
current is graphically determined. ASTM G82 describes the Table 7 provides information on ASTM G32.
method as does Jones.21
Table 5 provides information on standard test methods for STRESS-CORROSION CRACKING
evaluating galvanic corrosion. SCC susceptibility is directly evaluated by immersing stressed
specimens in water, and then evaluating the specimens for cracks
EROSION CORROSION using high-magnification metallographic or low-magnification
Immersion testing and impinging an electrolyte flow onto the macrographic examination. ASTM G30, Standard Practice for
metal of interest measure erosion corrosion resistance. ASTM Making and Using U-Bend Stress-Corrosion Test Specimens;
G73, Standard Test Method for Liquid Impingement Erosion ASTM G38, Standard Practice for Making and Using C-Ring
Using Rotating Apparatus, provides standardized methods for Stress-Corrosion Test Specimens; ASTM G39, Standard Practice
performing these erosion tests. For a detailed discussion about for Preparation and Use of Bent-Beam Stress-Corrosion Test
various erosion tests, see Rowe.22 Specimens; ASTM G47, Standard Test Method for Determining
TABLE 5 Test Methods for Evaluating Galvanic (Bimetallic) Corrosion.
ASTM G71 Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in Evaluation of galvanic corrosion using two dissimilar metals in an
Electrolytes electrolyte connected through a zero resistance ammeter.
ASTM G82 Standard Guide for Development and Use of a Galvanic Series for Procedure for development of a galvanic series in an electrolyte.
Predicting Galvanic Corrosion Performance
TABLE 6 Test Methods for Evaluating Erosion Corrosion.
ASTM G40 Standard Terminology Relating to Wear and Erosion Definition of terms for erosion and wear.
ASTM G73 Standard Practice for Liquid Impingement Erosion Testing Resistance to erosion from impacts of liquid drops or jets.
FRESHWATER 185
TABLE 7 Test Method for Evaluating Cavitation Corrosion
ASTM G32 Standard Test Method for Cavitation Erosion Using Vibratory Apparatus Test for comparing cavitation resistance of different alloys.
Susceptibility to Stress-Corrosion Cracking of 2XXX and 7XXX INTERGRANULAR CORROSION

Aluminum Alloy Products; ASTM G49, Standard Practice for Because intergranular corrosion is limited to corrosion at or
Preparation and Use of Direct Tension Stress-Corrosion Test immediately adjacent to grain boundaries and is detectable at the
Specimens; ASTM G58, Standard Practice for Preparation of microstructural level, simple corrosion rate calculations using
Stress-Corrosion Test Specimens for Weldments; and ASTM G64 weight loss measurements provide no information. Standard
Standard Classification of Resistance to Stress-Corrosion Cracking ASTM tests, such as the oxalic acid etch test (ASTM A262, Stan-
of Heat-Treatable Aluminum Alloys provide methods of prepar- dard Practice for Detecting Susceptibility to Intergranular Attack
ing specimens and conducting immersion tests. ASTM E3, Stan- in Austenitic Stainless Steels) provide relative susceptibility only
dard Guide for Preparation of Metallographic Specimens, and for austenitic stainless steels. These tests have little usefulness in
ASTM E407, Standard Practice for Microetching Metals and freshwater environments. A metallographic analysis performed
Alloys, provide methods of metallurgical examination. after test samples are exposed provides the most useful informa-
SCC susceptibility is more readily detected using slow strain tion about susceptibility to intergranular corrosion (ASTM E3
rate techniques than normal tension testing. This is because the and E80).
slow straining procedure allows the corrosion effects to occur.17 Cyclic polarization measurements provide relative informa-
Table 8 provides information on standard test methods for tion about susceptibility as described in ASTM G61. ASTM G108,
evaluating SCC. Standard Test Method for Electrochemical Reactivation (EPR) for
Detecting Sensitization of AISI Type 304 and 304L Stainless Steels,
DEALLOYING provides a test method applicable to type 304 stainless steel.
Dealloying is a localized phenomenon that can be evaluated Table 9 provides information on standard test methods.
through the use of immersion testing and metallographic techni-
ques (ASTM E3 and ASTM E80, Recommended Practice for Dila- FRETTING CORROSION
tometric Analysis of Metallic Materials [Withdrawn 1986]). Fretting corrosion can occur between two metal parts having an
Energy dispersive X-ray spectroscopy (EDS) and wavelength dis- electrolyte and slight vibratory movement. Although ASTM
persive X-ray spectroscopy (WDS) are used to detect small F897, Standard Test Method for Measuring Fretting Corrosion of
amounts of dealloying. Using EDS and WDS, the surface chemis- Osteosynthesis Plates and Screws, is intended specifically for sur-
try of the sample is examined to detect losses in the active ele- gical implants, it can be modified for use in other environments.
ments and enrichment in the noble alloying elements. Table 10 provides information on ASTM F897.
TABLE 8 Test Method for Evaluating Stress Corrosion Cracking
ASTM E3 Standard Guide for Preparation of Metallographic Specimens Techniques for preparing metal samples for metallographic examination.
ASTM E407 Standard Practice for Microetching Metals and Alloys Techniques for preparing metal samples for metallographic examination.
ASTM G30 Standard Practice for Making and Using U-Bend Stress Corrosion Test Procedures for preparing and testing strip specimens for stress corrosion
Specimens testing.
ASTM G38 Standard Practice for Making and Using C-Ring Stress-Corrosion Test Procedures for preparing and testing tube samples or ring samples from
Specimens thick solid material for stress corrosion cracking immersion testing. For
testing above the elastic limit of the alloy.
ASTM G39 Standard Practice for Preparation and Use of Bent-Beam Stress-Corrosion Testing strip specimens from sheet or plate for stress corrosion cracking
Test Specimens immersion tests. For testing below the elastic limit of the alloy.
ASTM G47 Standard Test Method for Determining Susceptibility to Stress-Corrosion Procedure for using ring or strip samples for testing 2xxx and 7xxx series
Cracking of 2XXX and 7XXX Aluminum Alloy Products aluminum alloys.
ASTM G49 Standard Practice for Preparation and Use of Direct Tension Stress- Procedures for testing axially loaded specimens. Specimens may be
Corrosion Test Specimens straight, or joined (welded, riveted or other means).
ASTM G58 Standard Practice for Preparation of Stress-Corrosion Test Specimens for Procedures for producing welded test specimens for use in other stress
Weldments corrosion tests.
ASTM G64 Standard Classification of Resistance to Stress-Corrosion Cracking of
Heat-Treatable Aluminum Alloys
TABLE 9 Test Method for Evaluating Intergranular Corrosion
Measurements for Localized Corrosion Susceptibility of Iron-, Nickel-, or procedure for evaluating pitting and crevice corrosion susceptibility. Can
Cobalt-Based Alloys be modified for other alloys that exhibit passive behavior.
ASTM G108 Standard Test Method for Electrochemical Reactivation (EPR) for Describes cyclic polarization technique for evaluation of sensitivity to
Detecting Sensitization of AISI Type 304 and 304L Stainless Steels intergranular corrosion. Specific to 300 series stainless steel, but might be
adaptable to other passive alloys with laboratory evaluation.
TABLE 10 Test Method for Evaluating Fretting Corrosion
ASTM F897 Practice for Fretting Corrosion of Osteosynthesis Plates and Screws This test provides a screening test for determining the amount of metal
loss from plates and crews used in medical implants but might also be
useful to evaluate materials and environments where relative motion
between parts could create fretting such as bearings and fasteners.
References 13. Laboratory Screening Tests to Determine the Ability of Scale

Inhibitors to Prevent the Precipitation of Calcium Sulfate and
1. Internal Corrosion of Water Distribution Systems, 2nd ed. Calcium Carbonate from Solution, NACE TM0374, (Houston, TX:
(Denver, CO: AWWA Research Foundation, 1996). NACE International, 2016).
2. J. R. Davis, ed., ASM Materials Engineering Dictionary (Materials 14. M. Stern and A. L. Geary, “Electrochemical Polarization I. A
Park, OH: ASM International, 1992). Theoretical Analysis of the Shape of Polarization Curves,”
3. H. M. Herro and R. D. Port, Cooling Water Systems Failures
(New York: McGraw-Hill, 1993). 15. M. Stern, “A Method for Determining Corrosion Rates from Linear
Polarization Data,” Corrosion 14, no. 9 (1958): 60–64.
4. M. Fontana and N. Greene, Corrosion Engineering (New York:
McGraw-Hill, 1967). 16. F. Mansfeld, “Recording and Analysis of AC Impedance Data for
Corrosion Studies, Part I. Background and Analysis,” Materials
5. H. H. Uhlig, Corrosion and Corrosion Control (New York: Wiley, Performance 37, no. 5 (1981): 301–307.
1967).
17. F. Mansfeld, M. Kendig, and M. W. Tsai, “Recording and Analysis
6. R. W. Lane, Control of Scale and Corrosion in Building Water of AC Impedance Data for Corrosion Studies, Part II.
Systems (New York: McGraw-Hill, 1993). Experimental Approach and Results,” Corrosion 38, no. 11
(November 1982), 301–307.
7. Prevention and Control of Water Caused Problems in Building
Potable Water Systems, 2nd ed., NACE TPC Publication No. 7 18. P. M. Aziz, “Application of Statistical Theory of Extreme Values to
(Houston, TX: NACE International, 1995). the Analysis of Maximum Pit Depth Data for Aluminum,”
Corrosion 12, no. 10 (1956): 35–46.
8. S. T. Powell, Water Conditioning for Industry (New York:
McGraw-Hill, 1954). 19. L. C. Rowe, “Measurement and Evaluation of Pitting Corrosion,”
in Galvanic and Pitting Corrosion—Field and Laboratory Studies
9. Corrosion Control by Deposition of CaCO3 Films (Denver, CO: (West Conshohocken, PA: ASTM International, 1976), 203–216.
AWWA Research Foundation, 1978).
20. Petroleum and Natural Gas Industries—Materials for Use in
10. Corrosion Handbook, vol. 13, Corrosion (Materials Park, OH: ASM H2S-Containing Environments in Oil and Gas Production, NACE
International, 1987). MR0175/ISO 15156 (Houston, TX: NACE International, 2015).
11. Annual Book of ASTM Standards (West Conshohocken, PA: ASTM 21. D. A. Jones, “Polarization Studies of Brass-Steel Galvanic
International, 2022). Couples,” Corrosion 40, no. 4 (1984): 181–185.
12. Standard Methods for the Examination of Water and Wastewater, 22. G. M. Ugiansky and J. H. Payer, eds., Stress Corrosion Cracking—
23rd ed. (Washington, DC: American Public Health Association, The Slow Strain Rate Technique (West Conshohocken, PA: ASTM
2017). International, 1979).
187
Chapter 13 | Seawater
David A. Shifler1
Introduction TABLE 1 Major Seawater Constituents at (35 ppt salinity)

1
Seawater is an aggressive, complex fluid that affects nearly all and 25 C
common structural materials to some extent.1 Two competing
processes operate simultaneously in seawater environments: Concentration
(1) the chloride ion activity, which tends to destroy the passive
Ion or Molecule mmol/kg g/kg
film, and (2) dissolved oxygen, which acts to promote and repair
þ
the passive film on metallic materials of construction.2 Metals Na 468.5 10.77
and alloys that develop protective films by the formation of thin Kþ 10.21 0.399
metal oxides can have the formation of passive films delayed or Mgþ2 53.08 1.290
have films destroyed by chloride ions in seawater.3 Caþ2 10.28 0.4121
The type of corrosion testing required depends on the Srþ2 0.090 0.0079
extent and type of information desired and the environmental Cl 545.9 19.354
conditions expected in service for the alloy component. Seawater Br 0.842 0.0673
corrosion depends on a number of factors, including, but not F 0.068 0.0013
limited to, alloy composition, water chemistry, pH, biofouling, HCO3 2.30 0.140
microbiological organisms, pollution and contamination, alloy SO42 28.23 2.712
surface films, geometry and surface roughness, galvanic interac- B(OH)3 0.416 0.0257
tions, fluid velocity characteristics and mode, ocean depth, oxy-

gen content, salinity, heat transfer rate, temperature, type of
dissolved trace elements and gases, can vary substantially because
exposure, time, and the seawater environmental zone to which
of seasonal changes, storms, or tidal cycles. Biological organisms,
the material is exposed. Understanding how these factors may
combined with the minor constituents, often control the rate of
interact and affect experimental results can help the design of
the corrosion reactions occurring on metals in seawater.1,5,6 In
seawater corrosion testing to best simulate service conditions.
addition, the concentration of seawater can vary from full-
strength ocean water to coastal seawater or brackish conditions.
The type of corrosion and the corrosion rate occurring on metals
Description of the Seawater and alloys in seawater depend on numerous variables in the spe-
Environment cific seawater composition, its salinity, and the environmental
zone to which the material is exposed.
COMPOSITION Seawater is a unique environment that cannot be duplicated
Seawater, the Earth’s most abundant resource, covers 71% of the in the laboratory. Throughout the world, seawater can vary
Earth’s surface. This electrolyte approximates a 3.5 wt% sodium widely in terms of its specific chemical composition, geography,
chloride (NaCl) solution, but it is much more complex, contain- oxygen content, temperature, salinity, pH, and biological activity.
ing almost all naturally occurring elements.4,5 The major chemi- At a given location, seawater is also prone to variations from sea-
cal constituents of seawater, listed in table 1, are consistent sonal influences. All of these variables, combined with the long-
throughout the world.1 The minor constituents, including term time dependence of many metal reactions, affect the corro-
1
sion occurring on metals and alloys in seawater. In addition, the
Office of Naval Research, Naval Materials Division, 875 N. Randolph St., Arlington,
composition of corrosion products and of calcareous deposits
VA 22203-1995, USA http://orcid.org/0000-0002-3709-7825
The author acknowledges the previous authors of this chapter, Denise Aylor and formed under cathodic polarization conditions will influence
David A. Shifler. metal corrosion.
DOI: 10.1520/MNL202NDSUP20190001
Seawater pH ranges from 7.5 to 8.3. This narrow pH range pollutants, solar radiation, composition of the corrosion prod-
is due to reactions that cause the interchange of carbon dioxide ucts, wind velocity, and biological species.10 Deposition velocities
in the air with seawater and photosynthesis. Changes in the pH can vary as much as two orders of magnitude for particles of dif-
of seawater are buffered by the carbonate system and the pres- ferent diameters.11,12 Atmospheric corrosion of a passive alloy
ence of undissociated boric acid.7 The buffering capacity and the tends to be localized. For electrochemical processes related to
constancy of natural waters, such as seawater, are discussed in corrosion to occur, an electrolyte must be present to allow cur-
Stumm and Morgan.8 rent to pass through the diffusion and electrochemical migration
of cations and anions. Seawater is a conductive electrolyte. The
ENVIRONMENTAL ZONES severity of corrosion in an atmospheric environment is related to
Materials are exposed to marine environments in numerous the time of wetness during which electrochemical processes and
applications, such as ships and submarines, offshore platforms, corrosion take place. A direct relationship also exists between
subsea pipelines and telecommunications cables, oceanographic atmospheric salt content and measured corrosion rates.13
instruments, dock bulkheads; heat exchangers, piping, pumps Atmospheric corrosion rates tend to increase with winds
and valves in seawater-cooled power, chemical, and desalination directly from the ocean to the site, at lower elevations, and the
plants; and ferries, yachts, pleasure boats, fishing gear, and closer the ocean is to the specimen, as shown in table 2. The
oceanfront buildings. Marine environments typically are classi- direction and velocity of the wind can affect the accumulation of
fied in terms of “zones” to which materials are exposed in given entrained seawater–related particles on specimen surfaces. Gen-
situations. Environmental zones involving seawater include erally, the closer the site is to the ocean in the face of a prevailing
marine atmosphere, splash-spray, tidal, submerged/shallow wind, the greater the corrosion rate of metals and alloys. Magne-
ocean, deep ocean, and mud. Figure 1 illustrates the relative cor- sium and calcium chlorides are hydroscopic and tend to keep
rosion rates of steel pilings in the different environmental zones.9 surfaces wet or moist. Sulfur dioxide lowers the critical humidity
The marine environment generally is considered to be a highly required to activate corrosion10 and increases the aggressiveness
aggressive environment. of the marine atmospheric environment, such as found in an
industrial marine environment versus a rural marine environ-
Atmospheric ment (table 2). The dew-point temperature and the component
or specimen temperature also will influence the rate of corrosion.
Atmospheric corrosion is responsible for a large fraction of the
Details on the factors affecting the degree of corrosion at atmo-
total corrosion in the world. Factors that affect the atmospheric
spheric locations can be found in Leygraf and Graedel11 and Ley-
corrosion of materials in a marine environment are the time of
graf, Wallinder, Tidblad, and Graedel.12
wetness, temperature, material, atmospheric contaminants and
Solar radiation tends to degrade the performance of organic
coatings and plastics, and stimulates biological formation and
FIG. 1 Corrosion profile of steel piling in seawater. Curve (a)
photosensitive electrochemical-corrosion reactions on copper or
represents behavior of uncoated piling; curve (b)
iron. Ultraviolet (UV) radiation can embrittle polymers unless
represents steel piling corrosion at coating defect coated
UV stabilizers are added.13
18
with organic, insulating substance.
TABLE 2 Corrosion Rates of Uncoupled Steel Panels after Two

Years at Different Atmospheric Test Sites
Steel Corrosion
Rate 2-year test
Distance from
Location Ocean, m mpy mm/y
Cape Canaveral ground level 55 17.37 0.44

Cape Canaveral 9 m elevation 55 6.48 0.165
Cape Canaveral 18 m elevation 55 5.17 0.131
Cape Canaveral 800 3.39 0.086
Point Reyes, CA 400 19.71 0.50
Kure Beach, NC 25 21.00 0.53
Kure Beach, NC 250 5.73 0.145
Dungeness, England Industrial Marine 19.22 0.49
Pilsey Island, England Industrial Marine 4.04 0.013
Durban, Salisbury I., S. Africa 10 2.20 0.056
Esquimalt, B.C. Rural Marine 0.53 0.013
6
Source: Data compiled from Dexter et al., table 13.
SEAWATER 189
Splash-Spray Zone The oxygen concentration also varies with seawater depth,
The splash-spray zone can be characterized as an aerated seawa- as shown in figure 2. This figure compares the concentration level
ter environment where exposed metals are almost continually with depth at sites in both the North Atlantic and North Pacific
wet and biofouling organisms do not attach.13,14 In an excessively Oceans. As the depth is increased to an intermediate level, the
windy seawater environment, the corrosion of metals can be oxygen concentration decreases at both sites; however, the reduc-
increased as a result of seawater impinging on their surfaces. The tion in oxygen is much greater in the Pacific Ocean than in the
aerated condition of the splash-spray environment is detrimental Atlantic. As the depth is then increased even farther, and the
to many metals, such as steel, where its corrosion rate is higher concentration of oxygen increases once again at both ocean
than in any of the other marine environments. This is because sites.6
dissolved oxygen is easily accessible for electrochemical reactions As a general rule, the pH varies with the change in dissolved
and chlorides can concentrate during drying of moist films cre- oxygen content. Both variables decrease with depth and reach a
ated by spray and condensation.15 As illustrated by curve (a) in minimum value before increasing again (as shown in fig. 2 for
figure 1, the most severe corrosion occurs in the splash-spray oxygen content). The dissolved oxygen and carbon dioxide con-
zone for uncoated steel pilings. The splash-spray environment is centrations are related to pH in the ocean according to the fol-
also destructive to protective coatings, such as organic coatings. lowing reaction:16,17
Passive film-forming alloys, such as stainless steels and titanium,
ðphotosynthesisÞ
have good resistance in this well-aerated environment.14
CH2 On þ nO2 () nCO2 þ nH2 O
Tidal Zone ðbiochemical oxidation; respirationÞ !
The tidal zone is an environment where metals are alternately
As organic matter decomposes, the dissolved oxygen content
submerged in seawater and exposed to the splash-spray zone as
decreases and carbon dioxide is produced. The production of
the tide fluctuates. In the submerged condition, metals are
carbon dioxide, a weak acid, results in a pH reduction in seawa-
exposed to well-aerated seawater and biofouling occurs.13,14 A
ter. With photosynthesis, the previous reaction is reversed.1,6
continuous cover of biofouling organisms protects some metal
Beyond a depth of 18–30 m, plant biofouling ceases because
surfaces, such as steel, while the presence of biofouling on stain-
of the lack of solar radiation, and any biofouling present is
less steel surfaces can accelerate localized corrosion. Metals or
entirely due to animal life sources. In general, the degree of foul-
alloys such as steel are influenced by tidal flow, where increased
ing decreases substantially as the depth is increased, an effect
movement resulting from tidal action causes an increased steel
that is independent of the distance from the shoreline.14 In con-
corrosion rate.14 Curve (b) in figure 1 shows that steel corrosion
trast, at a given depth, as one moves away from the shoreline
at exposed coating defect sites is as severe in the tidal zone as it
where breeding of macroorganisms takes place, significantly less
is in the splash-spray zone.
fouling on metal surfaces is observed.
Submerged/Shallow Ocean
The submerged/shallow ocean environmental zone usually is
characterized by well-aerated water combined with marine bio- FIG. 2 Variation in oxygen concentration with depth at sites in
fouling organisms of both the plant and animal variety. As in the the northwest Atlantic (36 440 N, 64 280 W) and northeast
tidal zone, the biofouling can either protect the metal surface 3
Pacific (38 210 N, 133 380 W).
from attack or can accelerate localized corrosion at the site of the
attachment.13,14 The temperature of the seawater in this environ-
mental zone depends on seasonal and specific geographic loca-
tion but, other than in the polar regions, it is substantially
warmer than in the deep ocean environment. The corrosion rate
of metals in the shallow ocean varies. Titanium exhibits excellent
corrosion resistance in this environment, while the corrosion
resistance of steel largely depends on the availability of oxygen to
be transported to cathodic sites on steel surfaces.14
Deep Ocean
The deep ocean environment is very different from the ocean at
the surface. At sites in the North Atlantic and North Pacific
oceans, oxygen, temperature, and salinity vary with depth. At the
ocean surface, the oxygen concentration in the North Pacific is
1.4 times the oxygen content in the North Atlantic. In addition,
both the surface temperature and surface salinity are lower in the
North Pacific than in the North Atlantic. Below about 1,500 m,
however, temperature and salinity levels are approximately the
same at these two ocean sites.1,6
Mud colder.6,14 The effect of temperature as a function of ocean depth

The bottom sediments of the ocean comprise the mud zone. for low-carbon steel alloys is presented in figure 3.
Anaerobic sediments contain bacteria that develop gases such as Metal corrosion rates are similar at different locations
ammonia (NH3), hydrogen sulfide (H2S), and methane (CH4). throughout the world because of a number of controlling factors
Sulfides present in the mud zone can attack metals, such as steels that compensate for one another.20 Increasing seawater tempera-
and copper alloys. The corrosion rate of low-carbon steel (as tures increase diffusion rates but decrease oxygen solubility.
shown in fig. 1) in this environment, however, usually is lower Although increasing temperatures tend to increase corrosion
than that in the other seawater environmental zones just rates, temperature increases also promote the formation of cal-
described, predominantly because of the reduced supply of careous deposits6,14 and microbiological colonization, which
oxygen.14 form barrier layers that often throttle corrosion attack.20 Bacteria
may participate in anaerobic corrosion reactions that replace the
UNIQUENESS cathodic oxygen-reduction reaction.
Seawater is a unique environment that cannot be duplicated in Temperature variations resulting from seasonal changes
the laboratory. A recent worldwide test program recently was also may affect corrosion rates in seawater. For many copper and
completed by ASTM Task Group G1.09.02.03 to evaluate the iron alloys, the corrosion rates increase during the warmer
corrosivity of seawater at a number of sites.18 Although these months of the year. The start of the corrosion test, therefore,
results indicated the uniqueness of natural seawater, corrosivity may be affected by the time that a corrosion test is initiated, and
was site specific and influenced by numerous factors. Seawater the tendency is for corrosion rates to slow down with increased
can vary widely in terms of chemical composition, dissolved oxy- times of exposure to the natural seawater environment, depend-
gen content, temperature, salinity, pH, carbonate levels, flow, ing on the actual environmental zone.
degree of fouling, biological activity, and pollution.19 Some of the highest corrosion rates in the world, however,
are found in cold-weather climates. Corrosion rates in Alaska are
reported to be twice as high as those in the North Sea and six
Environmental Variables Affecting times greater than the rates reported in the Gulf of Mexico. The
Corrosion Rates in Seawater high corrosion rates are caused by the high dissolved oxygen lev-
els, abrasion from glacial silts, tidal changes of more than 30 feet
TEMPERATURE (9.1 m) and the action of ice floes in winter.21 Corrosion rates on
As a general rule, the corrosion reaction rate in seawater steel in the splash zones on docks are estimated to be as high as
increases as the temperature is increased. This applies only when 30–35 mpy (761–889 lm/y) in the Aleutians.22
the effect of temperature alone is a factor. Other variables such
as oxygen concentration, diffusion rates, salinity, calcareous DISSOLVED OXYGEN
deposit formation, and biological activity vary as a function of Dissolved oxygen in seawater has a major influence on corrosiv-
temperature and also must be considered as to how it affects the ity because oxygen is the principal reactant involved in the
corrosion rate of a material, component, or system. cathodic reaction and is involved in the passivation reactions
Surface water temperatures vary mainly by latitude, with that occur for most metals and alloys in seawater. The solubility
the temperature ranging from approximately –2 C in the arctic of oxygen decreases as the temperature is increased. The oxygen
to about 35 C in the tropics.19 Table 3 shows the variation of sur- content in surface seawater can be as high as 11–12 ppm in the
face temperatures in selected oceans as a function of latitude in arctic as compared with 6 ppm in the tropics. Oxygen solubility
the northern and southern hemispheres.6 The data suggest that in surface seawater can become supersaturated by as much as
for a given latitude, corrosion tests results may vary slightly 200% of its equilibrium concentration because of photosynthesis
depending on the ocean location chosen. Also, metal corrosion by marine plants19 and by wave action.19,23,24 The change in the
rates are usually higher at the surface where temperatures are degree of saturation of the surface waters, with respect to the
warmer than in the deep ocean where the temperatures are major atmospheric gases, depends on the aerosol productivity of
TABLE 3 Average Surface Temperature ( C) of the Oceans as a Function of Latitude
North Latitude Atlantic Ocean Indian Ocean Pacific Ocean South Latitude Atlantic Ocean Indian Ocean Pacific Ocean
70 –60 5.60 – – 70 –60 1.30 1.50 1.30

60 –50 8.66 – 5.74 60 –50 1.76 1.63 5.00
50 –40 13.16 – 9.99 50 –40 8.68 8.67 11.16
40 –30 20.40 – 1 8.62 40 –30 16.90 17.00 16.98

30 –20 24.16 26.12 23.38 30 –20 21.20 22.53 21.53
20 –10 25.81 27.23 26.42 20 –10 23.16 25.85 25.11
10 –0 26.66 27.88 27.20 10 –0 25.18 27.41 26.01
Source: Data courtesy Prentice Hall.

SEAWATER 191
FIG. 3 Corrosion rate of low carbon steels at varying ocean TABLE 4 Equilibrium Concentration of Oxygen in Seawater as a
14
depths. Function of Temperature and Salinity
Salinity (ppt)
0 8 16 24 31 36
Temperature, 8C Oxygen Solubility (ppm) at Specific Salinity Levels
0 14.6 13.9 13.1 12.4 11.8 11.4

5 12.5 11.9 11.3 10.7 10.2 9.9
10 10.9 10.4 9.8 9.4 8.9 8.7
15 9.5 9.1 8.7 8.2 7.9 7.7
20 8.5 8.1 77.7 7.3 7.0 6.8
25 7.6 7.2 6.9 6.6 6.3 6.2
30 6.8 6.5 6.2 6.0 5.7 5.6
6
Source: Calculated based on data from Dexter et al.
dissolved oxygen depends on the seawater flow velocity. The

oxygen concentration has a negligible effect on copper alloy cor-
rosion rates in quiescent seawater, while at a seawater flow rate
of 1.8 m/sec, an increasing oxygen content accelerates the copper
corrosion rate. For metals such as iron and steel, the corrosion
rate increases linearly with an increasing oxygen concentration
at a constant temperature.14,25
Oxygen concentration cells can be created from deposits on a
an individual whitecap.23 As the level of dissolved oxygen
metal’s surface or may be due to improper component design,
increases from 100% saturation to 130% supersaturation, the
which introduces crevices. Differences in oxygen content due to
production of aerosol droplets by the whitecap waves generated
discrete films or deposits randomly scattered along a metal surface
by a standard laboratory breaking wave was found to increase by
can cause pitting or crevice corrosion at these localized sites. In
a factor of 2.4 in the case of submicron radius droplets, whereas
contrast, complete coverage of a surface by a film or a deposit can
the generation of larger droplets (r > 2.5 lm) was observed to
provide an effective barrier and reduce corrosion of the metal.6,26
increase by at least a factor of 4.0. Conversely, the dissolved oxy-
gen concentration can decrease and become undersaturated
SALINITY
because of oxygen consumption created by the decomposition of
Salinity in marine atmospheres accelerates metallic corrosion
organic matter.
and varies within broad limits, ranging from extremely high val-
The combined influence of these natural cycles on the dis-
ues close to surf to low values near calm waters. The concentra-
solved oxygen content can vary as a function of seasonal changes
tion of marine aerosol in the atmosphere depends on several
and the ocean depth at any given location.14 Oxygen solubility in
factors, such as altitude, distance from the sea, land geography,
seawater goes through a minimum at intermediate ocean depths:
land topography, direction, and velocity of prevailing winds.27
the depth of minimum oxygen solubility ranges from 400 m in
Salinity is defined as the total weight of solids dissolved in
the equatorial eastern Pacific to 2400 m in the Central Pacific
1,000 g of water. For example, 35 parts per thousand (o/oo) salin-
Ocean. The minimum oxygen concentration at these ocean
ity is equivalent to 35 g of solids dissolved in 1,000 g of water or
depths ranges from 0.16 to 6.4 ppm.6
a dissolved matter content of 35,000 ppm.14 Salinity usually is
Seawater temperature and salinity also affect the dissolved
determined by measuring chlorinity and then deriving the salin-
oxygen content, with temperature having a larger influence on
ity from the following relation:
the oxygen solubility. The general rule is that as either the tem-
perature or the salinity is decreased, the dissolved oxygen con- S ¼ 1:80655 Cl, (1)
tent increases.1,6 The equilibrium concentration of dissolved
oxygen in seawater as a function of salinity and temperature is where S (salinity) and Cl (chlorinity) are measured in parts per
shown in table 4.6 thousand.1,6
The effect of the dissolved oxygen level on corrosion The salinity of open ocean water at the surface typically
depends on the metal or alloy. For metals or alloys that form varies from 32 to 37.5o/oo. Generally, this degree of variation
passive films like stainless steel and aluminum, a high oxygen does not alter metal corrosion rates. Some of the more isolated
content is favorable in that it helps to delay the initiation of pit- seas, such as those shown in table 5, can have large variations in
ting on the metal surface. Once pitting is initiated, however, the salinity, which may influence metal corrosion rates. Salinity var-
propagation rate is increased with high oxygen content in the iations can affect a metal’s uniform corrosion rate. For example,
seawater. For common steels and copper alloys, the effect of in areas with high evaporation rates, the salinity can be very
where:
TABLE 5 Total Solids in Different Seawater Locations [Caþ2], [CO32] ¼ calcium, carbonate measure concentrations,
respectively;
Body of Water Total Dissolved Solids, ppm K0 sp ¼ apparent solubility product; and
Baltic Sea 8,000 X ¼ CaCO3 saturation value.
Caspian Sea 13,000
The calcareous deposits formed by cathodic protection will be
Black Sea 22,000
stable when the degree of saturation is X > 0.6 as in most ocean
Irish Sea 32,500
areas down to depths of 3,000 m.31 At depths greater than 3,000
Atlantic Ocean 37,000
m, however, the CaCO3 formation may be unstable. At X ¼ 0.6,
Mediterranean Sea 41,000
the dissolution rate of CaCO3 may be at around 1 lm/y.
Arabian Sea(Doha, Kuwait) 39,000–47,000
Dead Sea 260,000 BIOLOGICAL ORGANISMS
Source: Compiled from various sources. Seawater is a living medium sustaining a wide variety of organ-
isms.32 Marine biological organisms consist of either micro (bac-
high. Conversely, at the mouth of a river, seawater salinity is terial) and macro (algae, barnacles) speciation. These organisms
more dilute than in open ocean water. can affect the corrosion behavior of metals and alloys in a num-
Variations in salinity also alter the localized corrosion resis- ber of ways, including the following: (1) influencing one or both
tance of metals in seawater. As the salinity is increased, the chlo- of the anodic and cathodic reactions occurring, (2) influencing
ride ion activity increases and can result in increased pit and the formation or maintenance of protective films, (3) producing
crevice corrosion initiation and propagation.6 deposits on metal surfaces, and (4) creating a corrosive environ-
ment. The previous factors can act singly or can be combined to
pH AND CARBONATES alter a metal’s corrosion behavior.26
The pH of open ocean water varies from approximately 7.5 to One of the keys to the alteration of the condition at the
8.3 and is buffered by a complex carbonate system. This varia- metallic surface, and the subsequent delay or acceleration of corro-
tion in pH does not affect the corrosion of most metals, except sion, is the formation of a biofilm. The exact sequence of events
for aluminum. As the pH decreases from 8.3 at the surface to leading to biofilm formation depends on the environment and the
7.5–7.7 in deep water, the initiation of pitting and crevice corro- organisms present.32 Biological organisms can attach and multiply
sion in aluminum alloys is accelerated.1,6 on any solid surface in seawater. Within 2 h of immersion, a non-
Depending on various conditions, calcareous deposits form living organic conditioning film develops on a solid surface.
when the solubility of calcium and magnesium ions is exceeded. Within the first 1–2 days, a bacterial slime film develops over the
Calcareous deposits form at pH levels between 8 and 10 and con- conditioning film. The slime film creates a partial barrier to diffu-
sist mainly of calcium carbonate (CaCO3), magnesium carbonate sion between the liquid–metal interface and the bulk seawater
(MgCO3), and magnesium hydroxide (Mg(OH)2).14 Although environment. Slime films usually are not continuous and can cre-
changes in pH do not directly alter the corrosion behavior of ate oxygen or chemical concentration cells on the metal surface,
most metals, pH variations can influence the formation of pro- which can result in accelerated localized corrosion.
tective calcareous scales that subsequently can affect the corro- Biofilms are structured, but complex assemblages of microor-
sion rate of the substrate alloy. Spontaneous calcareous deposits ganisms embedded in exopolymers (extracellular material pro-
are more likely to occur at higher pH values, but the function of duced by microorganisms that define their shape, their ability to
these deposits is limited because of the presence of organic mat- adhere to solid surfaces, and their ability to trap particulate
ter and seawater salinity.16 nutrients).32 Biofilms include communities of colonies, consortia,
At the surface, the ocean waters throughout most of the newly created cells, dying cells, extracellular products, polymers,
world are 200 to 500% supersaturated in CaCO3 and precipita- and trapped inorganic material. Biofilms and individual organisms
tion of these carbonate scales will influence the corrosion reac- that are contained within the biofilm interact with external influ-
tion occurring at the metal surface.6 The buildup of protective ences originating from the substratum and the bulk medium to
calcareous deposits by cathodic protection can lower the subse- cause oxygen or chemical concentration gradients and other local-
quent current demand in natural seawater.28–30 ized effects related to mitigating or accelerating corrosion.32,33
Dilute seawater is undersaturated in carbonates, which Ammonia and sulfides also can be produced from the decay
reduces the likelihood of forming protective calcareous films on of organic matter within the slime film, resulting in increased
a metal surface. In deep ocean waters, the calcareous deposits are corrosion of some alloys.34 Sulfur-oxidizing organisms produce
not spontaneously formed in an ambient environment and often sulfuric acid from sulfur or other reduced sulfur species.34 The
are not precipitated under cathodic protection conditions.6 In presence of ammonia is known to cause stress corrosion cracking
the cold waters of the deep ocean environmental zones, the pre- (SCC) of copper alloys, whereas sulfides may lead to an acceler-
cipitation and dissolution of the calcareous deposits is controlled ated attack on copper alloys and steel. The presence of the slime
mainly by the CaCO3 saturation level, X:31 film on the metal surface can locally change the local environ-
ment at the liquid–metal interface such that the corrosion behav-
X ¼ ½Caþ2 ½CO2 0
3 =K sp ; (2) ior of a metal can be considerably altered from one that
SEAWATER 193
normally displays low corrosion rates in seawater to conditions however, can decrease corrosion rates by eliminating aggressive
in which corrosion is accelerated.6 ion concentration or enhancing passivation or inhibition by
The reduction or complete elimination of marine organisms transporting the protective species to the fluid–metal interface.26
in dilute seawater reduces the probability of forming protective Under high flow conditions, corrosion may take the form of
biofilms and could result in increased metal corrosion caused by impingement, erosion corrosion, or cavitation.14 In any given
a different mechanistic pathway.14 velocity domain, different local velocities may exist over diverse
Macrofouling films begin to develop over the conditioning areas of the component because of factors such as geometry or
and slime films within 2–3 days after immersion in seawater.6 If mode of fabrication.2 The effect of seawater velocity on a metal’s
the macrofouling is continuous along the solid surface, the film corrosion rate varies with the particular alloy. Alloys such as 304
can decrease the amount of dissolved oxygen present at the sur- and 316 stainless steel or nickel-chromium-molybdenum alloys
face and thus decrease the overall metal corrosion rate. If, how- exhibit deep pitting in static and low-flow conditions, yet at high
ever, the macrofouling is discontinuous, the film acts in the same seawater velocities, their corrosion rate decreases to less than
manner as discontinuous slime films in which case oxygen or 25 lm per year. Contrary to this, iron and copper show signifi-
chemical concentration cells can be formed and result in local- cantly lower corrosion rates at low flow velocities than under
ized corrosion of the metal.6 high seawater flow conditions.37 The corrosion rates for various
The macrofouling organisms attach in embryonic form to metals as a function of seawater velocity are included in figure 4.
the slimed solid surfaces. Once attached, they metamorphose Seawater velocity for immersed samples may decrease to a
and mature. The most common sessile fouling organisms in sea- lower value as the seawater depth is increased; this decrease typi-
water include the following: (1) organisms with hard shells, cally begins at depths of 18–30 m. Lack of flow can exacerbate
annelids, barnacles, encrusting bryzoa, mollusks, and corals; and crevice corrosion, which takes place with passive oxide film for-
(2) organisms without hard shells, such as marine algae, filamen- mers, such as stainless steels. When occluded, stagnant areas
tous bryzoa, coelenterates or hydroids, tunicates, and calcareous become oxygen-deficient anodic sites as compared with outer
and siliceous sponges.14 The accumulation of these biological cathodic, oxygenated regions.26,38
organisms depends on specific environmental conditions. Condi- Removal of the corrosion product or oxide layer by exces-
tions that are most conducive to their development are (1) rela- sive flow velocities leads to increased corrosion rates of the
tively shallow water such as in a harbor, (2) warm temperatures, metallic material, particularly when bounded in a piping or tub-
(3) low seawater flow, and (4) smooth hard surfaces.26 ing system. Although corrosion rates often depend on fluid flow
Both macro- and microfouling can have a major impact on and the availability of appropriate species required to drive elec-
the performance of marine components.6,14,26 Macro- and micro- trochemical reactions, surface shear stress is a measure of the
fouling organisms can break down protective paint films on a force applied by fluid flow to the corrosion product film. For sea-
component surface. On ship hulls, these organisms increase drag water, this takes into account changes in seawater density and
and power requirements. In heat exchangers, fouling limits the kinematic viscosity with temperature and salinity.39 Accelerated
heat transfer and seawater flow, and severe fouling can cause corrosion of copper-based alloys under velocity conditions
complete blockage.26 Fouling also shields the component surface occurs when the shear surface stress exceeds the binding force of
from any oxygen supply, thereby creating the possibilities that the corrosion product film. Alloying elements, such as chro-
differential aeration cells can develop. Fouling can cause catalytic mium, improve the adherence of the corrosion product film on
effects.7 Fouling, in addition to causing drag or blockage, can
cause localized turbulence. Plant decay or secretion products
from animal life can accelerate corrosion processes.7 FIG. 4 Corrosion rate of metals and alloys in seawater as a
137
function of flow velocity. denotes critical range.
FLOW VELOCITY OF SEAWATER

Fluid velocity can significantly affect metal corrosion rates in sea-
water by increasing anodic or cathodic species to the metal sur-
face. Flow-assisted corrosion depends on variables such as water
chemistry, pH, component geometry, surface roughness, biofoul-
ing, microbiologically influenced corrosion, pitting and crevice
corrosion, water pollution and contamination, alloy composition
and surface films, galvanic interaction, fluid velocity and mode,
oxygen content, heat transfer rate, and temperature.35
Corrosion rates and the type of corrosion often depend on
environmental factors such as fluid flow and the availability of
appropriate species required to drive electrochemical reactions.36
A change in the motion of a corroding metal or alloy relative to
its environment by fluid flow can increase corrosion rates by
removing protective films or by increasing the diffusion or
migration of deleterious species. An increase in fluid flow,
copper alloys in seawater based on measurements of the surface A number of variables, including duration of sulfide expo-
shear stress. The critical shear stress for C72200 (297 N/m2, sure, system operating velocity, and degree of turbulence, must
6.2 lbf/ft2) far exceeds the critical shear stresses of both C70600 be assessed in conjunction with the sulfide concentration to
(43 N/m2, 0.9 lbf/ft2) and C71500 (48 N/m2, 1.0 lbf/ft2) copper- accurately predict the sulfide susceptibility of copper-nickel alloys.
nickel alloys.39 Other research14 on copper-base alloys has found that 3-ppm
Seawater turbulence can substantially alter the flow rates hydrogen sulfide significantly increases the corrosion rates of
and subsequent corrosion rate of metals. Consider, for example, several copper alloys as indicated in table 6.
a seawater piping system that operates at a 1.8 m/sec velocity.
Increases of pipe diameter will increase the thickness of the HEAVY METALS
velocity boundary layer and the diffusion boundary layer. The Concentrations of copper in seawater can cause accelerated cor-
thicker velocity boundary layer leads to a decreased velocity gra- rosion of metallic components. In unpolluted seawater, the cop-
dient and reduced shear stresses at the piping wall. For design per concentration is 0.2 ppb, which typically is not high enough
purposes, a single-velocity value marking the initiation of erosion to influence a metal’s corrosion behavior. If, however, the copper
corrosion can provide misleading service life prediction.35 Fac- concentration is increased above approximately 30 ppb, corro-
tors that affect erosion in pipe bends include the degree of inter- sion of aluminum alloys can occur. The copper concentration
nal ellipticity and asymmetry, sudden changes in cross-section, may be increased because of a number of factors, including cop-
and a reduction in cross-sectional area.40 As the radii of direc- per leaching from antifouling paints, pollutants containing cop-
tional change are reduced, the erosion corrosion rates are per, or nearby copper alloy corrosion. If the copper deposits
expected to increase. Ledges, crevices, deposits, and other onto aluminum alloy surfaces, a galvanic couple is formed,
obstructions disturb laminar flow and result in turbulence at resulting in localized pitting of the aluminum.6
sometimes significant velocities.26 In a turbulent area, such as The corrosion products generated from iron and steel also
downstream of a valve, velocities far exceeding the 1.8 m/sec have been known to cause corrosion of aluminum alloys in desa-
nominal velocity may occur and cause accelerated corrosion of lination plants. The iron contamination effects, however, are less
the metal. In testing piping systems, turbulent areas should be and are not as consistent as they are for copper.6
accounted for and mitigated by choosing appropriate erosion
and cavitation-resistant materials37 and by implementing a
proper design.41 Corrosion Mechanisms
Seawater is an aggressive, complex aqueous medium that has
SULFIDES unique properties that affects most common structural materials
Sulfides, sulfur, and other sulfur compounds can produce pitting, somewhat differently than in most other natural media. As stated
crevice corrosion, dealloying, SCC, and stress-assisted hydrogen- earlier, two competing processes operate simultaneously in sea-
induced cracking of susceptible metals and alloys.34 Polluted water environments: (1) the chlorinity in seawater tends to
waters, like those found in coastal harbors and estuaries, contain destroy alloy passive films, while (2) dissolved oxygen acts to
hydrogen sulfide and sulfur-containing compounds. Sulfides can promote and repair passive films on metallic materials.2
be generated in several ways: (1) bacterial reduction of naturally Although oxygen is the reactant involved in the major cathodic
occurring sulfates in seawater; (2) rotting vegetation; and (oxygen reduction) reaction that occurs in seawater, species such
(3) industrial waste discharge.35 Hydrogen sulfides are known to as hydrogen (involved with cathodic protection applications),
adversely affect the corrosion rate of various metals and alloys. sulfates, nitrates, or ammonium compounds (related to reactions
Sulfates themselves are not usually harmful; however, sulfates via bacteria or other microorganisms in polluted waters) can be
can be reduced to harmful sulfides by sulfate-reducing bacteria. involved in other cathodic reactions in seawater. Seawater is also
These sulfide pollutants can contribute to the corrosion of steels,
stainless steels, copper, and aluminum alloys.6
TABLE 6 Corrosion of Copper-Base Alloys in Clean and Polluted
Sulfide corrosion has been found to occur on a number of 14
Seawater
different copper-base alloys. Wrought 90/10 copper-nickel can
exhibit sulfide-induced attack in the form of accelerated pitting
with as little as 0.01 ppm sulfide concentration, whereas 70/30 Seawater Velocity, 7.5 fps (2.3 m/sec), Test Duration, 64 Days
copper-nickel is susceptible at sulfide concentrations of 0.05 Corrosion Rate, mpy (mm/yr)
ppm or greater.42 The presence of sulfide-modified films inter-
Alloy CDA No. Clean Seawater Seawater (3 ppm H2S)
fered with the formation of normal passivating films of copper
90/10 Cu-Ni 706 3 (0.08) 34 (0.86)
nickel alloys found in unpolluted waters.43,44 Sulfide-modified
70/30 Cu-Ni 715 5 (0.13) 26 (0.66)
films generally are more loosely adherent than the normal
2% Al Brass 687 3 (0.08) 22 (0.56)
cuprous oxide films; turbulence tends to selectively remove the
6% Al Brass 608 5 (0.13) 21 (0.53)
sulfide-modified films. The accelerated corrosion rates of
As-inhibited admiralty 443 13 (0.33) 35 (0.89)
copper-nickel alloys in aerated sulfide-containing seawater
brass
remain high because the sulfides prevent protective corrosion
Phosphor copper 122 14 (0.36) 105 (2.67)
product layers from forming.45
SEAWATER 195
a conductive medium because of its inherent electrolyte content, when the bulk of the system is dry due to retention of moisture
leading to reactions detrimental to alloy performance. in the poultice. The corrosion mechanism is similar to crevice
Corrosion can occur by numerous pathways. Fontana and corrosion in that the deposits act to limit the migration of oxy-
Greene.46 list eight forms of corrosion: (1) uniform corrosion, gen to the covered area. This leads to acidic shifts in pH, concen-
(2) pitting, (3) crevice corrosion, (4) galvanic corrosion, (5) inter- tration of Cl ions in the shielded area, and a shift to a more
granular corrosion, (6) selective leaching or dealloying, (7) erosion active corrosion potential under the deposit. Local corrosion
corrosion, and (8) stress corrosion. Some of these “classic” forms rates can be extremely high because of the large cathode-to-
of corrosion are somewhat simplistic and are discussed in more anode area ratio.
detail.47 Some additional background information on these cor- The coupling of dissimilar alloys in conductive, corrosive
rosion mechanisms is discussed in “Corrosion Testing.” solutions, such as seawater, is called galvanic corrosion and can
Uniform corrosion is characterized by an electrochemical– lead to accelerated corrosion of the more anodic, electronegative
corrosion reaction that proceeds over an entire surface area. This alloy and protection of the more cathodic, electropositive alloy.
form of corrosion can be measured easily and is conducive to The extent of galvanic corrosion depends on the following fac-
prediction of component failure. tors: (1) the effective area ratio between the anodic and cathodic
Pitting is a mode of localized dissolution leading to the for- members of the couple; (2) solution conductivity; (3) flow char-
mation of cavities within a passivated surface that is boldly acteristics of the solution; (4) temperature; (5) system geometry;
exposed.47 Pitting is a probabilistic or stochastic corrosion mech- (6) the potential difference of the dissimilar alloys; (7) solution
anism that depends on electrochemical potential, alloy chemical composition and environment; and (8) the cathodic efficiency of
composition and microstructure, electrolyte composition, and the more noble metal or alloy.52–54 Galvanic corrosion and ero-
temperature.47 Natural seawater, with a relatively high concen- sion corrosion can synergistically attack the passive films of sus-
tration of chlorides, contributes to the development of pitting of ceptible alloys. Galvanic action between dissimilar metals can
passive alloys, such as stainless steels. destroy the passive film of the more anodic member exposing
Pitting corrosion usually initiates at surface inhomogenei- the bared substrate to possible erosion corrosion. The removal of
ties, such as intermetallic phases, nonmetallic inclusions, grain the protective films on copper-nickel alloys by flow may promote
boundaries, dislocations, defects, or mechanically damaged dissolution of the bare, exposed areas by galvanic interaction
sites.47 At low potentials, pitting is followed by repassivation; this with the surrounding surfaces covered by corrosion product
is termed metastable pitting. Above a certain potential or poten- scales.
tial range, a transition from metastable pitting to stable pitting Under certain conditions, grain boundary interfaces are
formation occurs. If the environmental conditions do not change quite reactive, causing intergranular corrosion. Intergranular
in the anodic pit site(s), the pit continues to grow, in part, corrosion can be caused by impurities at the grain boundaries, or
because of the large cathode (where oxygen reduction occurs)- enrichment or depletion of one of the alloying elements in the
to-anode ratio over the specimen or component surface. grain boundary region.43 Iron segregation at the grain boundaries
Crevice corrosion is localized corrosion that occurs within of aluminum alloys can initiate intergranular corrosion. Deple-
crevices or at shielded surfaces where a stagnant solution exists. tion of chromium makes sensitized, unstabilized, austenitic
To develop as a corrosion site, a crevice must be wide enough to stainless steels susceptible to intergranular corrosion.46 A form of
permit entry of a corrodent but sufficiently narrow to cause and intergranular corrosion called knife-line attack may occur on
maintain a stagnation environment. Crevices can be formed at welded, stabilized austenitic stainless steels if proper post-weld
metal-metal or nonmetal-metal junctions or at holidays that heat treatment is not implemented.46
form in coatings on metals or alloys. The parameters leading to Dealloying is the selective removal of one element from an
geometries that will cause crevice corrosion of an alloy are diffi- alloy by corrosion processes. Dealloying, also called selective
cult to quantify.46 Like pitting, crevice corrosion involves both leaching, parting, and selective corrosion, is a type of corrosion
initiation and propagation processes. During the initiation stage, found in some solid solution alloys. When in suitable conditions,
discrete areas develop within the crevice.48,49 In a creviced site a component of the alloys is preferentially leached from the
exposed to a seawater environment, the crevice becomes oxygen material leaving a modified residual microstructure.55,56 The
deficient. The increasing concentration of metal cations causes most common example is the selective removal (dezincification)
an associated migration and buildup of chloride ions within the of zinc in brass alloys. Dezincification may either be plug-type or
crevice to maintain electroneutrality. Metal chlorides then are uniform. In other alloy systems, aluminum, iron, cobalt, nickel,
hydrolyzed by water to form an insoluble metal hydroxide and chromium, and other elements may be selectively removed.57
free acid (in the case of chloride environments, HCl) thus creat- The less noble metal is removed from the alloy by a microscopic-
ing overall acidification of the crevice site. The loss of oxygen, scale galvanic corrosion mechanism. Little work has been done
chloride ion buildup, and acidification, and a large IR drop in differentiating susceptibility of selective leaching of alloys in
between the boldly exposed cathodic sites outside of the crevice synthetic seawater (this usually refers to ASTM D1141, Standard
and the anodic crevice propagate crevice corrosion.50 Practice for the Preparation of Substitute Ocean Water) and natu-
Under-deposit attack or “poultice” corrosion may occur ral seawater.6
when a metal is locally covered by foreign, absorbent (organic or A change in the motion of a corroding metal or alloy rela-
inorganic) materials.46,51 In this case, attack can proceed even tive to its environment by fluid flow can increase corrosion rates
by removing protective films or by increasing the diffusion or Copper-based alloys are susceptible to a critical surface
migration of deleterious species. An increase in fluid flow also shear stress in seawater where the corrosion product film begins
can decrease corrosion rates by eliminating aggressive ion con- to break down and is removed from the alloy surface, subse-
centration or enhancing passivation or inhibition by transporting quently causing accelerated attack.62 The generally accepted criti-
the protective species to the fluid–metal interface. Accelerated cal velocity for 70/30 copper-nickel in unpolluted seawater is
corrosion resulting from flow has been termed flow-assisted, about 15 fps (4.5 m/s).62 Copper-based alloys are susceptible to a
flow-influenced, flow-induced, or flow-accelerated corrosion. critical surface shear stress in seawater where the corrosion prod-
Several mechanisms are described by the conjoint action of flow uct film begins to break down and is removed from the alloy sur-
and corrosion that result in flow-influenced corrosion: (1) mass face, thereby initiating accelerated attack.62 The generally
transport–controlled corrosion; (2) phase transport–controlled accepted critical velocity for 90/10 copper-nickel (C 70600) is
corrosion; (3) erosion corrosion; and (4) cavitation.58–59 about 12 fps (3.6 m/s)63 for large piping sizes before erosion cor-
Mass transport–controlled corrosion implies that the rate of rosion becomes a problem. This corresponds to a critical shear
corrosion depends on the convective mass transfer processes at stress of 43 N/m2 (0.9 lbf/ft2). Erosion corrosion rates also
the metal–fluid interface. Mass transfer can have a significant depend on parameters such as pH, dissolved oxygen content or
effect on corrosion rates of metals and alloys depending on fac- other entrained gases, and temperature.
tors, such as bulk solution chemistry, temperature, flow condi- Cavitation sometimes is considered a special case of erosion
tions, surface roughness, and geometry. corrosion and is caused by the formation64 and collapse of vapor
Phase transport–controlled corrosion suggests that the wet- bubbles in a liquid near a metal surface. Cavitation is a process
ting of the metal surface by a corrosive phase is flow dependent. by which a liquid is ruptured by decreasing the pressure at
This may occur because one liquid phase separates from another roughly constant liquid temperature. Cavitation removes protec-
or because a second phase forms from a liquid. The distribution tive surface scales by the implosion of gas bubbles in a fluid; cal-
and morphology of the corrosive attack will be related to the dis- culations have shown that the implosions produce shock waves
tribution of the corrosive phase; the corroded sites will frequently with pressures approaching 60 ksi.46 Cavitation damage often
display rough, irregular surfaces and be coated with or contain appears as a collection of closely spaced, sharp-edged pits or cra-
thick, porous corrosion deposits.35 ters on the surface. It has been suggested64 that the corrosion
Erosion corrosion is associated with a flow-induced rate by cavitation can be influenced by surface roughness that
mechanical removal of the protective surface film that results in permits a large number of nuclei for bubble formation. Under
subsequent corrosion rate increases through either electrochemi- this condition, the concentration of deleterious ions in solution
cal or chemical processes. It is often accepted that a critical fluid next to the metal surface will be greater, and the observed corro-
velocity must be exceeded for a given material. The mechanical sion damage indicates that the steam bubbles may provide crevi-
damage by the impacting fluid imposes disruptive shear stresses ces or enhanced possibilities for dissolution at the solution-
or pressure variations on the material surface or the protective metal-steam interface.
surface film. Erosion corrosion may be enhanced by particles Environmental cracking can take several forms: (1) SCC,
(solids or gas bubbles) and affected by multi-phase flows.35 (2) corrosion fatigue, and (3) hydrogen embrittlement. SCC is
Increased flow stream velocities and increases of particle size, caused by the presence of a tensile stress and a specific corrosion
sharpness, density, and concentration increase the erosion corro- medium to a susceptible alloy. Failures from corrosion fatigue of
sion rate. Increases in fluid viscosity, density, target material alloys occur with time after the application of repeated cyclic
hardness, or pipe diameter tend to decrease the corrosion rate. stresses below the yield stress in a corrosive environment. It is
The morphology of surfaces affected by erosion corrosion may generally considered that steels stressed below a fatigue limiting
be in the form of shallow pits or horseshoes or other local phe- stress will endure an infinite number of cycles without fracture
nomena related to the flow direction. in noncorrosive environments.46 Corrosion fatigue is influenced
Factors that affect erosion in pipe bends include the degree by the corrosive medium, pH, temperature, oxygen content, and
of internal ellipticity and asymmetry, sudden changes in cross- the presence of any contaminants. In seawater, aluminum
section, and reduction in cross-sectional area.40 As the radii of bronzes and austenitic stainless steels retain about 70% and 80%
directional change are reduced, the erosion corrosion rate is of the normal fatigue resistance, whereas high-chromium alloys
expected to increase. Ledges, crevices, deposits, and other retain only 30% to 40% of normal fatigue resistance.46
obstructions disturb laminar flow and result in turbulence at sig- Hydrogen embrittlement lowers the yield stress and the
nificant velocities.46 Short distances less than 10 diameters after ultimate tensile stress of a metal or alloy from the penetration
directional changes or obstructions do not allow turbulence to of atomic hydrogen into susceptible alloys. This may occur in
dissipate.60 Above a critical Reynolds (Re) number, a given sur- seawater for high-strength steels subjected to overprotection
face roughness increases mass transfer and the critical Re num- from cathodic protection systems. The term hydrogen embrit-
ber decreases with increasing roughness.61 During testing, tlement is used to characterize the near-room-temperature
Poulson61 observed that failures that occurred on the bend intra- effects of hydrogen on materials. Hydrogen can have a consid-
dos about 45 into an 180 copper pipe bend were associated erable effect on susceptible alloys when it enters into the atomic
with possible flow separation, whereas surface roughening structure and causes embrittlement. Embrittlement phenom-
occurred only at high Re numbers. ena, including the acceleration of crack formation and growth,
SEAWATER 197
are well known, and hydrogen, generated from cathodic protec-

tion can be a considerable problem in areas of stress corrosion FIG. 5 Alloy 625/70:30 copper-nickel piping couple. Potential
or corrosion fatigue. The effects increase as the strength of the profile shown as a function of time and location along
steel increases and absorbed hydrogen has been a major cause the pipe (junction between the dissimilar alloys is
of failure of components, structures, pipelines, and pressure located 10 feet [3 m] from inlet). Source: Courtesy of
76
vessels.65 The amount of hydrogen available to enter the steel, U.S. Navy.
and the ease with which it moves into the steel, is influenced by
the nature of the environment in which the steel is placed. In 250
seawater, where structures are protected from corrosion by 200
Potential (mV vs. Ag/AgCl)

150
cathodic protection, hydrogen is available at the metal surface, 0 days
100
particularly in anaerobic (oxygen free) environments, because 37 days
50
of the cathodic electrochemical reactions The main bacteria 0
51 days
100 days
responsible for the enhancement of hydrogen entry are the -50
220 days
sulphate-reducing bacteria (SRB).66 -100
379 days
More recently, attention has been directed to the “ninth” -150
form of corrosion, biologically influenced corrosion, which -200
-250
include studies on an area referred to as “ennoblement.” The
-300
presence of biofilms on metals and alloys immersed in natural
0 5 10 15 20
seawater produces a complex, heterogeneous chemistry along the
Distance from Inlet (feet)
metallic surface. It usually has been observed that passive alloys,
such as aluminum, stainless steels, nickel-base alloys, or tita- applications must consider the presence of seawater salts con-
nium, show an increase to more noble (electropositive) poten- tained in the air intake of the turbines or waste incinerators
tials or ennoblement of several hundred millivolts with exposure because such electrolytes enhance the high-temperature corro-
time in natural seawater, thus magnifying the potential differ- sion processes of hot corrosion, sulfidation, and carburization.
ences that may exist between dissimilar alloys.32,67–76 Ennoble- Testing should be properly planned. Tests should be relevant
ment is likely caused by the formation of microbiological films, and correlate with actual field use. Accelerated tests often provide
which increase the kinetics of the cathodic reaction.67–75 useful information, but degradation processes in such tests may
The ennoblement of these passive alloys by biofilms has not reflect the actual corrosion mechanisms by which the materi-
been attributed to increasing the kinetics of the oxygen reduction als naturally deteriorate. Testing may require laboratory, field,
reaction, or by the introduction of alternative redox reactions, simulated service evaluations, or a combination of the tests. Spe-
such as peroxide production or heavy metal (Mn or Fe) reduc- cific test methods are discussed in the following sections.
tion.71 The ennoblement caused by the influence of cathodic Before testing components in most practical applications,
reactions occurring on these passive alloys results in increasing one should be knowledgeable of the corrosion properties of pos-
the initiation and propagation of crevice corrosion,29,73 pitting,73 sible candidate materials, an idea of the type and complexity of
and galvanic corrosion.75,76 However, if natural seawater is testing desired, and have a sufficient level of experience to com-
heated above 50 C to 60 C, the biofilm ceases to form and enno- prehend possible materials interactions that a component may
blement does not occur.77 have with other material components and be able to interpret
Figure 5 illustrates that the ennoblement of Alloy 625
and translate the test results into the requirements of the service
occurred between 37 and 51 days of exposure to flowing natural application.6
seawater.75,76 This ennoblement of Alloy 625 increased the driv- The objective for performing a corrosion test should be
ing force for increased galvanic corrosion of the 70/30 copper- identified during the initial phase of designing the testing proce-
nickel pipe.76 Continued buildup of the microbiological film dure. The test conditions, including specimen size, test environ-
thickness gradually decreased the potential difference between ment versus service environment, geometry, sample preparation,
the Alloy 625 and the copper-nickel alloy.76 temperature, flow velocity, potential, and type of corrosion test
(e.g., general, crevice, pitting resistance, galvanic, stress-related,
dealloying) should be considered.
Corrosion Testing
Corrosion testing is important in evaluating materials in seawa- LABORATORY EVALUATION
ter and related marine environments. Such tests can ascertain The corrosion behavior of metals or coatings is often evaluated
the performance of different materials, measure the degradation in the laboratory rather than in an actual service environment
processes, and evaluate alternative materials and designs that because of time or budget limitations. Laboratory evaluation is
optimize service life for given marine environments. Marine generally of relatively short duration and is often used to study
environments may include high-temperature oxidizing or reduc- environmental effects on a metal’s corrosion behavior because
ing conditions found in marine gas turbines or waste incinera- the specific environmental conditions can be controlled. The
tors; testing also may be done in the marine environmental major disadvantage of testing in the laboratory is that the actual
zones discussed earlier. High-temperature testing for marine service environment and conditions may not be fully duplicated.
Service conditions are being simulated, which involves accepting the nature and extent of corrosion after one-year exposure from
certain assumptions. It is important when testing in the labora- 800 feet from the shore at Kure Beach, NC, was equivalent to 24
tory to correlate field data with laboratory data so that the valid- days’ salt spray exposure.80 Care must be taken in the interpreta-
ity of the laboratory information can be assessed.78 tion and use of this data, however. The acceleration factor
Natural seawater is the preferred environment for labora- (approximately a factor of 15) applies only to the specific set of
tory testing, but synthetic seawater solutions are often utilized. environmental conditions that were evaluated. When materials
The term natural seawater refers to fresh seawater that is are exposed closer to the shore or at higher elevations from the
pumped directly into the laboratory, rather than seawater that shore, it was clearly demonstrated that the acceleration factor
has been stored and possibly shipped to an onshore location for would be different.
the testing. Once seawater is removed from its natural environ-
ment, its composition changes, and this can have a large impact IMMERSION TESTING
on the resultant metal corrosion rate. Synthetic seawater solu- Immersion testing usually is performed on panel specimens or
tions that typically are used include 3.5-wt% NaCl and substitute small component parts, such as fasteners. Specimens are exposed
ocean water per ASTM D1141.79 The substitute ocean water can to the seawater environment in fully immersed, partially
be used either with or without heavy metals added according to immersed, or alternately wetted and dried in a cyclic pattern. Sam-
ASTM D1141.79 Both 3.5% NaCl and substitute ocean water solu- ple weight loss, physical surface changes, visually assessed modifi-
tions do not contain the same organic and biological compo- cations, and surface compositional changes can be documented.
nents as natural seawater. Substitute ocean water with heavy For example, long-term uniform corrosion testing usually is per-
metals most nearly approximates the actual composition of natu- formed in test racks or in test loops. Immersion testing is useful to
ral seawater. The disadvantage in using any of the synthetic solu- examine different variables, such as environmental compositions,
tions is that, like the stored natural seawater, the composition alloying elements, coating type, surface condition, and controlled
varies from that of fresh, natural seawater and thus the corrosion defects. Immersion testing may be done in either natural or syn-
behavior of the metals evaluated can be considerably affected. thetic seawater. Natural seawater for laboratory immersion testing
One advantage of using 3.5% NaCl is that calcareous deposits is often filtered to prevent macrofouling on the specimen surfaces.
will not form under cathodic polarization conditions in this solu- The filtering can be accomplished by passing seawater through a
tion. This is extremely useful in fracture surface evaluation of sequence of coarse to fine filters, with final filtering through 5- to
metal specimens, where the presence of calcareous deposits often 10-lm pore-size filter cartridges. Stagnant natural seawater solu-
prohibits examination of the surfaces unless the deposits are dis- tions are not recommended for testing because of decay of the
solved or mechanically removed, which could alter the original marine biological organisms, which will alter the seawater compo-
fracture surface. sition and can affect the resultant corrosion behavior.71
A primary goal of accelerated testing is to be able to per- NACE/ASTM G31, Standard Guide for Laboratory Immersion
form tests over a short time period that can then be used to pre- Corrosion Testing of Metals,82 describes accepted procedures for
dict long-term performance (e.g., service life). To do this, two and factors that influence laboratory immersion corrosion tests.
things must be determined. For example, in atmospheric corro- Factors that may influence test results may include sample prepa-
sion testing, the rate of atmospheric corrosion must be quantified ration, apparatus, test conditions, methods of cleaning samples,
in both the field conditions being simulated and the accelerated evaluation of results, and calculation and reporting of corrosion
test conditions. Direct measurements of the atmospheric corro- rates. Natural seawater for laboratory immersion testing is often
sion rate typically are not available, making it necessary to derive filtered to prevent macrofouling on the specimen surfaces. The fil-
the atmospheric corrosion rate from an indirect measurement, tering can be accomplished by passing seawater through a
such as weight loss, corrosion product thickness, or, for labora- sequence of coarse to fine filters, with final filtering through 5- to
tory tests, contaminant consumption rate. Second, the corrosion 10-lm pore-size filter cartridges. Stagnant natural seawater solu-
mechanisms (and resulting corrosion products) must be deter- tions are not recommended for testing because of the decay of the
mined to be nominally identical for the two conditions—in other marine biological organisms, which will alter the seawater compo-
words, it must be established that the more aggressive conditions sition and can affect the resultant corrosion behavior.13
are accelerating the same mechanisms that exist under field During the alternative immersion corrosion test, ASTM
exposure in such a manner that the final result is comparable to G44, Standard Practice for Exposure of Metals and Alloys by
what is observed in the field. As such, it must be determined that Alternate Immersion in Neutral 3.5% Sodium Chloride Solution,83
new corrosion processes are not activated, or that the correct the specimen is immersed for a specified time period in a test
mechanisms are not altered in a manner such that the final result environment then removed and dried before being re-immersed
is different than field exposure. There are examples throughout to continue the cycle. Normally, hundreds of these immersion-
the literature in which acceleration factors have been properly drying cycles are completed during the course of a test program.
determined. Consider, as an example, the work of Pednekar80 in This standard is intended for alloy development for applied pro-
evaluating the marine corrosion of AISI 1020 steel at Kure tective coatings on alloys and for applications where the alternate
Beach, NC, and comparing those results with ASTM B117, Stan- immersion test is to serve as a control test on the quality of suc-
dard Practice for Operating Salt Spray (Fog) Apparatus, neutral cessive lots of the same material. Alternative immersion would
salt spray exposure.81 In their evaluation, researchers found that help distinguish performance of alloys or coated alloys exposed
SEAWATER 199
to the marine tidal zone. Artificial seawater can replace the 3.5% large body of data available for different materials acquired under
NaCl solution, and although ASTM G44 often has been used to nominally identical conditions, salt fog testing often is used as a
evaluate resistance to stress corrosion, it also has been used for generic metric for coating and material performance, irrespective
uniform, pitting, crevice, and galvanic corrosion evaluations. In of its applicability to any specific set of environmental conditions.
field testing, specimen racks may be placed between low-tide and In this test, as the name implies, the materials under test are
high-tide levels with the objectives to observe performance of exposed to a mist or fog of a salt solution for a period of time, and
materials in the tidal zone. the degree of attack is used as a metric to gauge performance.
Assessment of performance is typically qualitative in nature,
SALT SPRAY/SALT FOG TESTING assessing the total extent of corrosion, rather than making specific
Salt spray (fog) testing is an accelerated laboratory method for measurements as to the depth of attack.
assessing the corrosion behavior of coated and uncoated metals. A typical salt spray system consists of two basic components:
The generally accepted methods in the United States for salt the exposure chamber, and the salt spray/fog delivery system, both
spray testing are discussed in ASTM B117;81 ASTM G85, Standard of which have a number of key features. The salt fog delivery sys-
Practice for Modified Salt Spray (Fog) Testing (superseded);84 and tem consists of a reservoir for the salt solution, a source of a com-
GM9540P.85 These tests have been used successfully used to pressed carrier gas, typically air, and one or more spray nozzles.
screen both coated and uncoated metals as well as to evaluate The salt fog is created by feeding the compressed gas alongside the
coating performance as shown in figure 6, particularly in terms salt solution into the spray nozzles, where the solution is atomized
of thickness uniformity and porosity. Cyclically acidified salt and driven into the system. The chemistry of the salt solution (i.e.,
spray tests also have been used to determine the exfoliation cor- concentration, pH) varies depending on the specific environmen-
rosion resistance of aluminum alloys.86 tal conditions being evaluated, but generally consists either of a
A common atmospheric corrosion laboratory test, particu- simple sodium chloride solution or artificial seawater.
larly when exploring the behavior of a material or an applied coat- The second component of a salt spray system is the test
ing on alloys in marine environments, is the salt spray, or salt fog chamber itself. The chamber is relatively simple in design, its key
test. The environmental safety and health concerns associated requirements being that it allow for the maintenance of the
with the salt spray technique are readily mitigated in most labora- desired target temperature, that it deliver the salt fog, and that it
tory environments, and as such, this technique is appealing in an provide an appropriate means to secure the specimens and ensure
industrial setting. This procedure is of most use when evaluating they are exposed only to the salt fog, and not condensate or corro-
materials for exposure to high-chloride environments, such as sion product from other samples. Achieving proper exposure
marine exposure. Because of its widespread use, and hence, the requires that the roof of the chamber, as well as all of the internal
components, must be designed such that no liquid or condensa-
tion may fall on the specimens under test. Furthermore, the speci-
FIG. 6 Example of salt fog cabinet capable of ASTM B117 and G85 men racks are positioned such that condensation from one sample
of coated and uncoated alloys. Source: U. S. Navy. cannot fall onto another sample. Finally, a collection and removal
system must be present to collect and remove condensed salt solu-
tion from the chamber such that it does not build up and allow
the samples to be exposed to a bulk liquid phase.
Types of Salt Spray Environments

The solution used to generate the salt spray or fog generally is
selected based on the material being investigated, and the environ-
mental conditions in which the material or the applied organic
coating on an alloy will be used. Although virtually any salt solu-
tion can be used, some standard solutions are described in a series
of ASTM and ISO specifications, as well as in the literature.
5 wt% NaCl solution (ASTM B117;81 ISO 9227, Section

3.2.2).87 The standard solution for salt fog testing does not
correspond to any particular set of environmental
conditions. The test temperature is typically 35 C, and the
solution pH is approximately neutral. This environment
generally selected as a standard solution for comparing
materials and generally is not used to ascertain specific
performance characteristics in other environments.
Acetic acid-salt spray test (continuous or variable)
(ASTM G85, Annex 112;84 ISO 9227, Section 3.2.3).87
This test solution consists of 5 wt% NaCl that has been pH
adjusted to approximately 3 using acetic acid. Exposure is
performed at a temperature of 35 C. This test has been individually tailored to achieve any desired level of
applied successfully to evaluate the impact that process corrosion exposure. Synergistic effects resulting from
parameters have on deposit quality for decorative temperature, mechanical, and electrical cycling can be
chromium plating on steel or die-cast zinc, as well as for the comprehended by this test. The test method is composed of
evaluation of the overall quality of the plated deposit. 1.25% g (0.9% sodium chloride, 0.1 o/o calcium chloride
Seawater acidified test, cyclic (SWAAT) (ASTM G85, and 0.25% sodium bicarbonate) salt mist applications
Annex 3).84 The test solution in this exposure is ASTM coupled with high temperature and high humidity and
artificial ocean water that has been pH adjusted to 2.8 to 3 moderately high temperature dry-off.
with acetic acid. The test temperature is selected based on the
material or property being assessed. This variant of the salt Limitations of Salt Spray Testing
fog test has been applied to assess the performance of 2000, Although salt spray testing is simple to use, is readily accessible,
5000, and 7000 series aluminum alloys, as well as to evaluate and enables the ready differentiation between materials in terms
the performance of organic coatings on a variety of substrates. of their relative corrosion performance in high chloride condi-
SO2 salt spray test, cyclic (ASTM G85, Annex 4).84 The tions, care must be taken to avoid over-interpretation of the
test solution consists of either a 5 wt% NaCl solution or results. There are only a few environmental conditions for which a
ASTM artificial ocean water, and testing is performed at salt fog experiment accurately reproduces the relevant corrosion
a temperature of 35 C. SO2 is added periodically at a mechanisms. Furthermore, there can be considerable variability in
flow rate of 1 cm3/min per cubic foot of cabinet volume the test results as demonstrated in the work of Sterling,89 in which
(35 cm3/min per m3 of cabinet volume). The test is cyclic in a wide variety of copper alloys were exposed to several variations
nature, with specimens exposed to a series of cycles, the of the salt spray technique, resulting in considerable variability in
nature of which is dictated by the environmental conditions weight change observations and no discernable trends in corrosion
the test is attempting to probe. The test will consist of behavior. As such, careful consideration must be given to the
periods when the samples are exposed to salt fog, periods nature and extent of corrosion that results from salt spray expo-
when they are exposed to SO2, and a drying period. An sure. Because of the severe nature of the test, it is possible that the
example cycle might consist of 30-min exposure to salt observed response does not probe degradation mechanisms rele-
spray, followed by 30-min exposure to the SO2, and then vant to field exposure. Therefore, before interpreting and assigning
finally a 2-h thermal soaking and drying period. meaning to the results of a salt spray exposure, it must be deter-
Dilute electrolyte cyclic fog dry test (ASTM G85, Annex mined whether the nature of the resulting corrosion damage is rel-
5).84 In this test, the exposure solution is an 0.05 wt% evant to the intended application for which corrosion testing is
sodium chloride and 0.35 wt% ammonium sulfate solution. being performed.
Each cycle consists of 1-h salt fog exposure followed by 1-h Another limitation of the salt spray test is that the coupons
dry-off period. During the fog portion of the cycle, the tem- are not instrumented and not typically monitored throughout
perature is ambient/unheated. During the dry-off period, the test. It generally is not possible to measure electrochemical
the chamber is heated to 35 C and specimens must be dry variables such as the open circuit potential or the polarization
within 45 min. The cycling from wet to dry subjects the behavior of the surface during salt spray testing. Information
specimens to a range of solution concentrations varying is acquired by interrogating materials after the test has been
from very dilute during the fog period to very concentrated completed, rather than continuously throughout the experiment.
just before the water dries off completely. Interrupted testing is possible; however, removing and cleaning a
Copper-accelerated acetic acid-salt spray (CASS) ASTM material under evaluation can have a significant impact on the
B368, Standard Test Method for Copper-Accelerated Acetic observed corrosion behavior and, as such, is not recommended.
Acid-Salt Spray (Fog) Testing (CASS Test);88 ISO 9227 Outdoor corrosion is influenced by a number of variables,
section 3.2.4).87 In this test, the test solution is made from 5 including corrosive atmospheres, UV light, wet/dry cycling, and
wt% NaCl to which 0.25 g of copper chloride (CuCl22H2O) temperature cycling that can occur to varying degrees in environ-
is added to each liter of the salt solution. The solution pH is mental zones discussed earlier. ASTM D5894, Standard Practice
then adjusted to between 3.1 and 3.3 using acetic acid. This for Cyclic Salt Fog/UV Exposure of Painted Metal, (Alternating
test method is applicable to evaluating the corrosive Exposures in a Fog/Dry Cabinet and A UV/Condensation Cabi-
performance of decorative copper/nickel/chromium or net),90 alternatively exposes samples to UV light with ASTM G85
nickel/chromium coatings on steel, zinc alloys, aluminum salt fog exposures. Although salt spray testing is commonly used
alloys, and plastics designed for severe service. It is also as a screening test, this method is not reliable for accurately pre-
applicable to the testing of anodized aluminum. dicting the corrosion rate of a metal in its service environment.6
Accelerated Corrosion Tests GM9540P.85 Test procedure
provides combination of cyclic conditions (salt solution, ELECTROCHEMICAL TESTING
various temperatures, humidity, and ambient environment) Electrochemical techniques utilize mixed-potential theory.91 The
to accelerate metallic corrosion. The procedure is effective corrosion potential, Ecorr, or the open-circuit potential is the
for evaluating several corrosion mechanisms, such as mixed potential in which the anodic and cathodic reactions are
uniform, galvanic, and crevice. The test duration can be exactly equal. Applying a potential or a current to a sample in a
SEAWATER 201
conducting electrolyte alters the relative balance of the anodic spectroscopy, electrochemical noise resistance, rotating disk, or
and cathodic reactions. Raising the potential in an electropositive cylinder electrodes to characterize corrosion affected by flow,
direction relative to a reference electrode like a saturated calomel polarization (either current- or potential-driven) methods for
electrode (SCE) or a Ag/AgCl electrode will increase the anodic assessing susceptibility to localized corrosion (polarization,
reaction on the sample relative to the cathodic reaction (electro- potential-step repassivation or scratch repassivation, electrochemi-
chemical conditions become more oxidizing in place of prepar- cal noise applied to pitting, and potentiodynamic repassivation for
ing a more oxidizing solution chemically). Likewise, lowering the assessing sensitization.102 ASTM G61, Standard Test Method for
potential in an electronegative direction, lowers the anodic reac- Conducting Cyclic Potentiodynamic Polarization Measurements for
tion leading to reducing conditions. The idealized potential ver- Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based
sus log current density plots tend to show a linear relationship of Alloys, presents a standard for conducting cyclic potentiodynamic
potential versus current density termed the cathodic and anodic polarization measurements to determine relative susceptibility to
Tafel slopes, respectively. Raising or lowering the applied poten- localized corrosion (pitting and crevice corrosion) for iron-,
tial or applied current and then keeping it fixed as a function of nickel-, or cobalt-based alloys in a chloride environment.103 An
time is a potentiostatic or galvanostatic polarization that com- indication of the susceptibility to initiation of localized corrosion
monly is used in electrochemical testing. in this test method is given by the potential at which the anodic
The electrochemical test setup generally consists of the current increases rapidly, generally termed Ebd (Ebd depends on
usual three-electrode test cell, a potentiostat, and a computer the scan rate of the potentiodynamic test, a higher scan rate will
loaded with the software to run various types of electrochemical tend to have a higher Ebd).104 The more noble Ebd, observed at a
tests. Specific methods include potentiodynamic polarization, fixed scan rate during this test, the less susceptible the alloy is
potentiostatic polarization, galvanostatic polarization, Tafel to the initiation of localized corrosion. When the scan is reversed,
extrapolation, and polarization resistance determinations that the localized corrosive stops when repassivation occurs at Eprot.
reproduce data and investigator check techniques.92 In seawater, The hysteresis loop forms from the resulting electrochemical
passive film-forming alloys like aluminum alloys or stainless steel behavior of the alloy of the corresponding forward and reverse
require an induction time for pitting to occur, and thus the scan potentiodynamic scans. The cyclic potentiodynamic test results
rate in a potentiodynamic test can significantly influence the are not intended to correlate in a quantitative manner with the
results obtained. Also, the dynamic nature of these test methods rate of propagation that one might observe in service when local-
may preclude the natural formation of films on a metal or alloy ized corrosion occurs, but the size of the hysteresis is a qualitative
surface, which can cause the distorted results. Potentiostatic and measure of the localized corrosion susceptibility of the alloy; the
galvanostatic polarization methods often are applied in studying larger the hysteresis, generally the more susceptible the alloy is
localized corrosion. Electrochemical methods to measure the sus- to localized corrosion as shown in figure 7 for 304 stainless steel
ceptibility of alloys to pitting corrosion are reviewed else- vice C-276.102
where.93,94 The disadvantages associated with selecting the
proper scan rate in the potentiodynamic method do not apply to
the potentiostatic and galvanostatic methods.86 FIG. 7 Cyclic potentiodynamic polarization scans for 304
The Tafel extrapolation test is capable of determining very stainless steel and Alloy C-276 in 3.5% NaCl. The area of
low metal corrosion rates in a short period of time. When condi- the hysteresis of the 304 SS cyclic is much larger than that
tions are ideal, its accuracy is equivalent to or better than weight generated from the cyxlic scan of C-276, indicating that
loss measurements.95–98 To maintain accuracy, however, the 304 stainless steel is more susceptible to localized
Tafel regions must encompass at least one order of magnitude of corrosion than C-276.
104
current. Also, this method can be applied only to systems that

have one reduction process or the Tafel region may be distorted
and corrosion rate determinations will be inaccurate. Finally, the
Tafel method yields only an average, uniform corrosion rate and
is not sensitive to localized corrosion. Therefore, use of this tech-
nique in seawater is considered to be limited primarily to obtain-
ing an indication of the corrosion rate within an order of
magnitude.99,100 Tafel slope extrapolations are complicated by
ohmic resistance from low conductivity solutions, cell geometry,
and the magnitude of the applied current as well as from mass-
transport, concentration polarization rather than activation con-
trol, charge-transfer processes.101
Laboratory tests involving electrochemical testing may pro-
vide instantaneous corrosion rates and ways to characterize corro-
sion thresholds before the onset of high corrosion rates or cabinet
tests that provide a mean mass loss. Techniques may include Tafel
extrapolation, polarization resistance, electrochemical impedance
ASTM G150, Standard Test Method for Electrochemical Crit- used to monitor corrosion of a system or coating resistance as a
ical Pitting Temperature Testing of Stainless Steels and Related function of time. EIS has demonstrated its usefulness for corro-
Alloys,104 determines the potential independent critical pitting sion measurements involving: (1) rapid estimation of corrosion
temperature (CPT) by way of a potentiostatic technique using a rates (within 30 min to 24 h); (2) estimation of extremely low
temperature scan and a specimen holder that is designed to elim- corrosion rates and metal contamination rates (<104 mm/yr,
inate the occurrence of crevice corrosion in 1 M NaCl solution 0.01 mpy); (3) estimation of corrosion rates in low-conductivity
After an initial temperature stabilization period, a potential is media; (4) rapid evaluation of corrosion inhibitor performance
applied to the test specimen that is above the pitting potential in aqueous and nonaqueous media; and (5) rapid evaluation of
range and the solution is heated at a rate of 1 C/min. The cur- coatings.119 Decreases in the measured coating resistance suggest
rent is monitored during the temperature scan, and the CPT is that an electrolyte has permeated through the coating, that there
defined as the temperature at which the current increases rap- are defects in the coating, or that corrosion has initiated.86
idly, which for practical reasons is defined as the temperature at Reducing the distance between the working and counter electro-
which the current density exceeds 100 lA/cm2 for 1 min. des to approximately 50 lm allows local EIS measurements to be
ASTM G192, Standard Test Method for Determining the Crev- done over uncoated and coated metal and alloy surfaces to dis-
ice Repassivation Potential of Corrosion-Resistant Alloys Using a cern surface inhomogeneities that may lead to corrosion initia-
Potentiodynamic-Galvanostatic-Potentiostatic Technique (super- tion before corrosion is visually observed.117,118
seded),105 is a laboratory anodic polarization test method that Electrochemical noise (ECN) involves the nondestructive
measures the crevice repassivation potential by combining poten- measurement of electrochemical transients or noise generated
tiodynamic, galvanostatic, and anodic polaotentiostatic polariza- during corrosion processes without disturbing the system. Meas-
tion techniques. ASTM G192 is more time-consuming than the urements are made by (1) monitoring potential noise through
already well-established cyclic potentiodynamic polarization measurement of potential difference between two identical elec-
(CPP) described under ASTM G61. The crevice repassivation trodes, (2) monitoring the current noise by assessing the current
potential is the highest potential during potentiostatic control for fluctuations between two short identical electrodes through a
which current density does not increase as a function of time. It is zero resistance ammeter, or (3) monitoring both potential and
understood that at a potential below the crevice repassivation current perturbations. No external potential or current signal is
potential, an alloy will not develop crevice corrosion under the applied during ECN measurements. The current noise is associ-
tested conditions. This test method may be used to rank several ated with discrete dissolution events. Electrochemical noise has
alloys by using the same testing electrolyte and temperature. been used to evaluate localized corrosion, SCC, or uniform cor-
Many of the disadvantages discussed for the Tafel extrapola- rosion in laboratory or field applications.120–125 Electrochemical
tion method can be eliminated by using the polarization resis- voltage or current noise can determine the onset of pitting or
tance technique. This nondestructive method can be used on crevice attack.126,127 ASTM G199, Standard Guide for Electrochem-
systems that have either activation or diffusion controlled reac- ical Noise Measurement (superseded),128 covers the procedure for
tions. A comprehensive review of the polarization resistance conducting online corrosion testing and monitoring of metals
method was compiled by Mansfeld.106 Very low corrosion rates using the ECN technique. ECN can be used to detect localized
can be determined accurately and quickly and can be monitored corrosion activity and to estimate corrosion rate on a continuous
as a function of time. Polarization resistance also can be used to basis without removal of the monitoring probes from the plant
measure the corrosion rate of a component, such as a seawater or an experimental cell.128 This guide covers zero-resistance
tank or piping system, where inspections and weight loss tests ammeter-based current and potential measurements, potentio-
are difficult if not prohibitive. The major disadvantage with this static current measurement with standard reference electrode,
technique is that, like the Tafel extrapolation method, the calcu- and galvanostatic potential measurements.
lated corrosion rate represents a uniform value and does not
indicate localized corrosion. Corrosion rates can be underesti-
Direct Current Methods
mated in low-conductivity solutions or when very high corrosion
Laboratory test methods include a number of direct current mea-
rates are experienced.102
surement techniques that are commonly used in electrochemical
testing. Specific methods include potentiodynamic polarization,
Nondestructive Electrochemical Methods potentiostatic polarization, galvanostatic polarization, Tafel
Electrochemical impedance spectroscopy (EIS) has become a extrapolation, and polarization resistance determinations. In sea-
tool for practical corrosion prediction. EIS uses an applied small- water, passive film-forming alloys like aluminum or stainless
amplitude, sinusoidal potential perturbation to the material in steel require an induction time for pitting to occur, and thus the
question and is useful for examining the corrosion behavior of scan rate in a potentiodynamic test can significantly influence
both coated and uncoated metals and alloys.100,107–118 EIS techni- the results obtained. Also, the dynamic nature of these test meth-
ques record impedance data as a function of the frequency of the ods may preclude the natural formation of films on a metal or
applied perturbation at a fixed potential. A large frequency range alloy surface, which can cause the distorted results. Potentiostatic
(1 mHz to 65 kHz) is needed to obtain a complete impedance and galvanostatic polarization methods often are applied when
spectra. This method is nondestructive and does not cause any studying localized corrosion. Electrochemical methods to mea-
acceleration of the corrosion reaction. The EIS technique can be sure the susceptibility of alloys to pitting corrosion are reviewed
SEAWATER 203
elsewhere.118,119 The disadvantages associated with selecting the Fluid flow interactions with material surfaces should be defined in
proper scan rate in the potentiodynamic method do not apply to terms of wall shear stress or mass transfer coefficient.134 LaQue
the potentiostatic and galvanostatic methods.117 developed several in-house apparati to evaluate mass transfer phe-
The Tafel extrapolation test is capable of determining very nomena and wall shear stresses from relatively low velocity
low metal corrosion rates in a short period of time. When condi- regimes to very high fluid flows over 100 fps.135
tions are ideal, its accuracy is equivalent to or better than weight High velocity flow laboratory testing has a number of disad-
loss measurements. To maintain accuracy, however the Tafel vantages. First, the results from these tests can vary widely
regions must encompass at least one order of magnitude of cur- because of differences in test technique, specimen size and shape,
rent. Also, this method can be applied only to systems that have and environmental conditions like salinity, pH, temperature, and
one reduction process or the Tafel region may be distorted and oxygen content. Second, these tests are designed to expose small
corrosion rate determinations will be inaccurate. Finally, the specimens to high intensity flow conditions; however, the edges
Tafel method yields only an average, uniform corrosion rate and of the small specimens utilized can alter turbulent flow condi-
is not sensitive to localized corrosion. Therefore, use of this tech- tions in such a manner that the results do not simulate the actual
nique in seawater is considered to be limited primarily to obtain- service environment. The flow dynamics and conditions pro-
ing an indication of the corrosion rate within an order of duced by the different high velocity techniques vary significantly.
magnitude.21,95 Although these high velocity laboratory tests may not accurately
simulate the desired service condition, they are still useful in
HIGH VELOCITY FLOW TESTING ranking different metals according to their resistance to velocity
A variety of high velocity tests have been designed to simulate effects. For reproducibility among test laboratories, it is impor-
and evaluate cavitation and erosion properties in seawater envi- tant to run a standard control material along with the candidate
ronments. Specific tests are as follows: (1) high velocity flow test materials so that the data can be normalized with respect to
tests, which include venturi tubes, rotating disks, and ducts with the control standard.86,131
specimens positioned in the throat sections; (2) high-frequency
vibration tests that utilize magnetostriction or piezoelectric devi- ENVIRONMENTAL CRACKING TEST METHODS
ces (described in ASTM G32, Standard Test Method for Cavita- A wide variety of SCC, corrosion fatigue, and hydrogen embrittle-
tion Erosion Using Vibratory Apparatus);129 and (3) impinging jet ment tests to study environmental cracking phenomena have been
tests where rotating or stationary specimens are exposed to a developed. These tests, which employ either a static or a dynamic
high-velocity jet or droplet impact described in ASTM G73, Stan- load, can vary widely in terms of specimen configuration, cost,
dard Test Method for Liquid Impingement Erosion Using Rotating and test duration. These tests may include the effects of cathodic
Apparatus).130,131 A test loop using flowing artificial seawater and protection on the susceptibility of materials to environmental
1 wt% sand was able to evaluate the relative erosion resistance of cracking. In general, they fall into three major categories:
materials under consideration for valves in a piping system.132
ASTM G134, Standard Test Method for Erosion of Solid Materials 1. Constant displacement techniques include bent-beam,
by Cavitating Liquid Jet,133 which can compare the cavitation ero- U-bend, wedge-open loading, and proving ring tests. In
sion resistance of solid materials provides an alternative to these tests, specimens are loaded to some fixed displace-
ASTM G32. In ASTM, cavitation is induced by vibrating a sub- ment and are exposed to the corrosive environment. Ini-
merged specimen at high frequency (20 kHz) at a specified tiation of cracking causes the stress to be relieved, thus
amplitude. In ASTM G134, cavitation is generated in a flowing causing crack arrest. These tests tend to be plagued by a
system so that both the jet velocity and the downstream pressure high degree of data scatter and, in many cases, do not
(which causes the bubble collapse) can be varied independently. result in providing useful design parameters. ASTM G30,
This test method covers a test that can be used to compare the Standard Practice for Making and Using U-Bend Stress-
cavitation erosion resistance of solid materials. A submerged cav- Corrosion Test Specimens,136 describes the procedures for
itating jet, delivering from a nozzle, impinges on a test specimen making and using U-bend specimens in metals and alloys
placed in its path so that cavities collapse on it, thereby causing for the evaluation of stress-corrosion cracking.92 ASTM
erosion. ASTM G134 is carried out under specified conditions in G38, Standard Practice for Making and Using C-Ring
a specified liquid, usually water.133 Stress-Corrosion Test Specimens, describes the essential
The test may deviate from actual service conditions. For features of the design and machining, and procedures for
example, do single or multi-phase (liquid-gas, liquid-solid particle, stressing, exposing, and inspecting C-ring type of stress-
or liquid-gas-solid) conditions exist in marine environments that corrosion test specimens.137 The C-ring, as generally used,
could affect the life of a material or corrosion control application? is a constant-strain specimen with tensile stress produced
Is the flow laminar or turbulent? How is the fluid dynamics char- on the exterior of the ring by tightening a bolt centered
acterized? Are there contaminants or corrodents in the fluid that on the diameter of the ring. Preparation and use of bent-
alone could cause degradation of passive films? Erosion-type tests beam stress-corrosion test specimens are covered under
should attempt to simulate disturbed turbulent flow conditions ASTM G39, Standard Practice for Preparation and Use of
with sudden changes in flow geometry, such as bends, tube inlets, Bent-Beam Stress-Corrosion Test Specimens.138 ASTM
orifice plates, valves, fittings, pumps, compressors, or propellers. G49, Standard Practice for Preparation and Use of Direct
Tension Stress-Corrosion Test Specimens (superseded), evaluation. The slow constant extension produces a gauge
describes procedures for designing and preparing stan- section strain rate, which is usually in the range from
dard tension test specimens for investigating susceptibil- 104 to 107/s1. The SSR test is used for relatively rapid
ity to stress-corrosion cracking. Axially loaded specimens screening or comparative evaluation, or both, of environ-
may be stressed quantitatively with equipment for appli- mental, processing or metallurgical variables, or both,
cation of either a constant load, constant strain, or with a which can affect the resistance of a material to EAC.142
continuously increasing strain.139 SSR tests tend to produce conservative results (i.e., mate-
ASTM G36, Standard Practice for Evaluating Stress- rials that show susceptibility in these tests may not
Corrosion-Cracking Resistance of Metals and Alloys in a show susceptibility in service) in a relatively short
Boiling Magnesium Chloride Solution,140 is an accelerated period of time. This conservatism may result from the
test method, using boiling magnesium chloride, to evalu- fact that engineering structures are rarely loaded in this
ate the relative ranking of stress corrosion susceptibility fashion. As such, these tests typically are used only to
for stainless steels and related alloys in aqueous chloride- relatively rank susceptibility of materials to different
containing environments. ASTM G4483 and ASTM G47, environments.143
Standard Test Method for Determining Susceptibility to 2. Load-controlled techniques include methods such as the
Stress-Corrosion Cracking of 2xxx and 7xxx Aluminum cantilever beam test. In these tests, specimens are dead-
Alloy Products (superseded),141 evaluate the stress corro- weight loaded to produce the desired stress. Any cracks
sion susceptibility of stressed 2xxx and 7xxx aluminum that initiate then grow into an increasing stress field,
alloy test specimens under alternative immersion in 3.5% resulting in failure of the specimen. Unfortunately, these
NaCl solution. This test provides an environment for tests are time-consuming and costly. A critical linear
assessing the SCC resistance of materials similar to natu- elastic stress intensity factor can be obtained from these
ral outdoor marine environments. Uniaxial direct tension tests, however, and this parameter subsequently can be
SCC tests by alternate immersion in 3.5% NaCl (ASTM used in design or to determine the flaw tolerance of an
G44 and ASTM G49) show that during uniaxial loading, engineering structure. ASTM G139, Standard Test
5xxx alloys, when sensitized, are particularly susceptible Method for Determining Stress-Corrosion Cracking
to SCC when tested in the short-transverse orientation Resistance of Heat-Treatable Aluminum Alloy Products
but are not susceptible to SCC when tested in the Using Breaking Load Method,145 evaluates SCC resis-
long-transverse orientations unless the alloy is fully tance using residual strength as the gauge of damage
recrystallized.83,139 evolution through EAC by the breaking load test
Rising load techniques include the slow strain rate method. In this test, tensile bars or direct tension sheet
(SSR) test.142 In this technique, axially loaded tension test specimens are exposed to 3.5 wt% aqueous sodium
specimens or fatigue precracked (fracture mechanics) chloride solution, are removed before they fail, and are
specimens are subjected to a rising stress, typically applied tension tested to determine the amount of corrosion
by a screw-driven testing machine. SSR tests deliver a damage that has occurred. This test method145 was
result in a reasonably short time, usually within 1–2 days. developed for use with high-strength, heat-treatable alu-
The dynamic straining reduces incubation time to the minum alloys (2xxx and copper-containing 7xxx).
onset of cracking in susceptible materials and sustains the ASTM G168, Standard Practice for Making and
cracking process. The SSR method allows for evaluation Using Precracked Double Beam Stress Corrosion Speci-
of the effects of metallurgical variables, such as alloy com- mens,146 is a standard practice covers procedures for fab-
position, heat treatment, and processing and or environ- ricating, preparing, and using precracked double-beam
mental parameters in shorter times than is usually stress corrosion test specimens. This specimen configura-
possible with constant load or stress specimens.143 SSR tion as formerly designated the double cantilever beam
evaluation of materials through environmentally assisted specimen. Guidelines are given for methods of exposure
cracking (EAC) is generally obtained through the com- and inspection. The precracked double-beam specimen is
parison of test results conducted in a corrosive environ- conducive for evaluating a wide variety of metals exposed
ment versus corresponding SSR results obtained in an to corrosive environments. It is particularly suited to
inert environment.143 ASTM G129, Standard Practice for evaluation of products having a highly directional grain
Slow Strain Rate Testing to Evaluate the Susceptibility of structure, such as rolled plate, forgings, and extrusions,
Metallic Materials to Environmentally Assisted Crack- when stressed in the ST direction. The precracked
ing,144 describes steps for the design, preparation, and use double-beam specimen may be stressed in constant dis-
of axially loaded, tension test specimens and fatigue pre- placement by bolt or wedge loading or in constant load
cracked (fracture mechanics) specimens for use in SSR by use of proof rings or dead weight loading. The pre-
tests to investigate the resistance of metallic materials to cracked double beam specimen is amenable to exposure
EAC. Strain is imposed by an external means on the to aqueous or other liquid solutions by specimen immer-
gauge section or notch tip of a uniaxial tension specimen sion, by periodic drop-wise addition of solution to the
or crack tip of a fatigue precracked specimen for materials crack tip, or exposure to the atmosphere.146
SEAWATER 205
ASTM E1681, Standard Test Method for Determining Thresh- fatigue crack growth rate (da/dN) from near-threshold to Kmax
old Stress Intensity Factor for Environment-Assisted Cracking of (maximum stress intensity controlled instability).158 Results are
Metallic Materials (superseded),147 provides a standard method expressed in terms of the crack-tip stress-intensity factor range
for determining a threshold stress intensity factor for EAC of (DK), defined by the theory of linear elasticity. ASTM E647159 is
metallic materials under constant load using a cantilever beam. divided into two main parts. The first part gives general informa-
The cantilever-beam technique utilizes long-term static load test- tion concerning the recommendations and requirements for
ing of fatigue precracked, single-edge notched beam specimens fatigue crack growth rate testing. The second part is composed of
manufactured according to guidelines designed to produce annexes that describe the special requirements for various speci-
plane-strain SCC data.148 Test durations range from several hours men configurations, special requirements for testing in aqueous
to more than 10,000 h. The 10,000-h runout time is preferred to environments, and procedures for nonvisual crack size determi-
ensure sufficient time for crack incubation (hydrogen entry and nation. In addition, appendices cover techniques for calculating
transport to the crack tip region in the case of hydrogen embrit- da/dN, determining fatigue crack opening force, and measuring
tlement) without being excessively long. The threshold stress the growth of small fatigue cracks. This method is applicable in
intensity (KIscc) obtained from these tests subsequently can be marine atmosphere and seawater.157,168
used in design or to determine the flaw tolerance of an engineer- ASTM F1624, Standard Test Method for Measurement of
ing structure. Hydrogen Embrittlement Threshold in Steel by the Incremental
Two concepts are central to understanding the effects of Step Loading Technique,159 establishes a procedure to measure the
mechanical, metallurgical, and chemical variables to corrosion susceptibility of steel to a time-delayed failure caused by hydrogen.
fatigue. First, many variables, such as electrolyte composition and It does so by measuring the threshold for the onset of subcritical
pH, are governed by mass transport and electrochemical reaction crack growth using standard fracture mechanics specimens,
conditions within the crack. Second, corrosion fatigue can be time irregular-shaped specimens such as notched round bars, or actual
dependent.149,150 The most common apparatus for conducting cor- product such as fasteners (threaded or unthreaded), springs, or
rosion fatigue tests in seawater is the rotating beam type using a components.159 It also can be used to test the effect of hydrogen
specimen machined to distribute stress uniformly along the gauge introduced into the steel caused by external environmental sources
section when loaded. High-cycle fatigue specimens are loaded in of hydrogen, such as excessive cathodic protection or galvanic
uniaxial tension or bending (three-point, four-point, or cantilev- coupling, in a marine aqueous environment.
ered).151,152 ASTM E466, Standard Test Method for Conducting
Force Controlled Constant Amplitude Axial Fatigue Tests of Metal-
lic Materials,151 covers a standard procedure for the performance Field Evaluation
of axial force controlled fatigue tests to obtain the fatigue strength
of metallic materials in the fatigue regime where the strains are IN-SERVICE TESTING
predominately elastic, both upon initial loading and throughout In-service testing provides the advantage of examining the corro-
the test. This practice is limited to the fatigue testing of axial sion behavior of a metal in the actual service environment. The
unnotched and notched specimens subjected to a constant ampli- advantages and disadvantages of some of these tests are briefly
tude, periodic forcing function in air at room temperature. This described below. More detail can be found in NACE/ASTM
82
standard was intended to evaluate steels and aluminum alloys in G31. Guides for conducting corrosion testing under field condi-
aqueous chloride solutions.153,154 tions can be found under ASTM G4, Standard Guide for Con-
For low-cycle fatigue (<104 cycles), tests are conducted ducting Corrosion Tests in Field Applications,160 and ASTM G50,
with controlled cycles of elastic plus plastic total strain range Standard Practice for Conducting Atmospheric Corrosion Tests on
rather than controlled load or stress cycles. ASTM E606, Stan- Metals (superseded).161
dard Test Method for Strain-Controlled Fatigue Testing (super-
seded),155 determines the fatigue properties of nominally Small-Specimen Testing
homogeneous materials by the use of test specimens subjected to Small-specimen testing allows a large number of variables to be
uniaxial forces. It is intended as a guide for fatigue testing per- evaluated at minimal cost. Small specimens can be designed to
formed in support of such activities as materials research and determine specific types of corrosion; for example, creviced
development, mechanical design, process and quality control, specimens can be exposed to assess localized corrosion.86 ASTM
product performance, and failure analysis. Although this practice G16, Standard Guide for Applying Statistics to Analysis of Corro-
is intended primarily for strain-controlled fatigue testing, some sion Data (superseded),162 provides guidance for establishing the
parts of the standard test method may provide useful informa- number of replicate samples required for the desired reliability of
tion for force-controlled or stress-controlled testing. the test results.
For a given material, the fatigue strength, or fatigue life at a Although small-specimen testing allows for examination in
given value of maximum stress, generally decreases in the pres- the actual service environment, the corrosion rate determined on
ence of an environment that is aggressive to the material. The a small specimen usually is not consistent with the corrosion rate
environment affects the fatigue crack initiation, the fatigue crack of a large-scale piece of equipment primarily because it is diffi-
growth rate, or both.156 ASTM E647, Standard Test Method for cult to duplicate all of the metallurgical conditions of the large
Measurement of Fatigue Crack Growth Rates,157 determines equipment on a small specimen. In addition, it is difficult to
simulate erosion-corrosion by small-specimen testing, because removal of the macrofouling after testing could cause partial
small specimens can shield each other from turbulence, thus pro- removal of the coating as well, making an accurate corrosion
viding inaccurate results.86 The use of spool pieces for piping and assessment impossible. For this reason, simulated service testing
tubing may provide useful test information related to in-service in the full immersion testing is often conducted using filtered nat-
performance for similar components. ural seawater to eliminate microorganisms.
Electrical Resistance Probes

Electrical resistance probes are small in size and can be installed Standards for Seawater Testing
easily in the service environment; however, the walls of the test
equipment must be penetrated for the probes to be installed and, The following standards are specific to testing in seawater:
consequently, care must be taken to avert leakage in the system.
The usefulness of the probes is limited in that they provide a • ASTM G52, Standard Practice for Exposing and Evaluating
measurement of uniform corrosion and can be continuously Metals and Alloys in Surface Seawater
monitored, but they provide no information on localized corro- • ISO/CD 23226, Corrosion of Metals and Alloys: Guidelines for
sion, such as pitting or crevice corrosion. In addition, errors can Corrosion Testing of Metals and Alloys Exposed in Deep Sea
result in the probe data if the temperature is varied during the Water
time of the measurement.86 ASTM B826, Standard Test Method
for Monitoring Atmospheric Corrosion Tests by Electrical Resis- The following standards apply only to artificial seawater
tance Probes (superseded),163 describes a test method that environments:
employs a resistance monitor probe fabricated from a chosen • ASTM D1141, Standard Practice for the Preparation of Substi-
metal conductor, with one conductor segment uncovered to per- tute Ocean Water
mit exposure of the chosen metal conductor to the corrosive gas
• ASTM D5894, Standard Practice for Cyclic Fog/UV Exposure
mixture and the second conductor segment covered to insulate
of Painted Metal, (Alternating Exposures in a Fog/Dry Cabinet
the metal conductor of this segment from exposure to the corro-
and a UV/Condensation Cabinet)
sive gas mixture. The covered conductor segment provides a ref-
erence for evaluating changes in the uncovered segment. ECN • ASTM E1524, Standard Test Method for Saltwater Immersion
can be utilized to conduct online corrosion monitoring of metals and Corrosion Testing of Photovoltaic Modules for Marine
within the limitations of the ASTM G199 guidance.128 Environments
Ultrasonic Measurements • ASTM G44, Standard Practice for Exposure of Metals and
The ultrasonic thickness measurement method is quite popular Alloys by Alternate Immersion in Neutral 3.5% Sodium Chlo-
for in-service corrosion testing. The major advantage of this ride Solution
method is that the equipment is portable and easy to use. The • ISO 4623, Paints and Varnishes—Filiform Corrosion Test on
major disadvantage is that a bare metal surface is required for Steel
accurate measurements. The presence of coatings or corrosion • ISO 7384, Corrosion tests in Artificial Atmosphere—General
products can introduce errors into the thickness measure- Requirements
ments.86 Curved surfaces such as piping bends and small tubing
• ISO 16539, Corrosion of metals and alloys—Accelerated cyclic
diameters require special attention.
corrosion tests with exposure to synthetic ocean water salt-
deposition process—”Dry” and “wet” conditions at constant
SIMULATED SERVICE TESTING
absolute humidity
Like in-service testing, simulated service testing provides the
advantage of exposure to the actual environment. Fluctuations in The standards listed below describe corrosion testing and data
the weather, the influence of geographical location, and bacterio- evaluation in natural seawater or artificial seawater environments:
logical influences are part of the simulated service test environ-
ment and are factors that cannot be simulated in the laboratory.86 • ASTM E606, Standard Test Method for Strain-Controlled
Simulated service testing in seawater typically consists of panel Fatigue Testing
specimens exposed on test racks suspended from a pier or a float.13 • ASTM E647, Standard Test Method for Measurement of
Testing in this environment is discussed in ASTM G52, Standard Fatigue Crack Growth Rates
Practice for Exposing and Evaluating Metals and Alloys in Surface
• ASTM E1681, Standard Test Method for Determining a Thresh-
Seawater (superseded).164 Specimens may be exposed in full
old Stress Intensity Factor for Environment-Assisted Cracking
immersion, splash-spray, or tidal conditions. The disadvantage of
of Metallic Materials
exposing panel specimens in the full seawater immersion environ-
ment is the occurrence of extensive macrofouling on the panel • ASTM E739, Standard Practice for Statistical Analysis of
surfaces. The presence of these organisms prohibits inspection of Linear or Linearized Stress-Life (S-N) and Strain-Life (e-N)
the test panels during the exposure period and can result in the Fatigue Data
difficult task of removing the macrofouling after testing to obtain • ASTM E1049, Standard Practices for Cycle Counting in Fatigue
accurate weight loss measurements. For coated specimens, Analysis
SEAWATER 207
• ASTM G1, Standard Practice for Preparing, Cleaning, and • ASTM G107, Standard Guide for Formats for Collection and
Evaluating Corrosion Test Specimens Compilation of Corrosion Data for Metals for Computerized
• ASTM G3, Standard Practice for Conventions Applicable to Database Input
Electrochemical Measurements in Corrosion Testing • ASTM G129, Standard Practice for Slow Strain Rate Testing to
• ASTM G4, Standard Guide for Conducting Corrosion Tests in Evaluate the Susceptibility of Metallic Materials to Environ-
Field Applications mentally Assisted Cracking
• ASTM G5, Standard Reference Test Method for Making • ASTM G139, Standard Test Method for Determining Stress-
Potentiostatic and Potentiodynamic Anodic Polarization Corrosion Cracking Resistance of Heat-Treatable Aluminum
Measurements Alloy Products Using Breaking Load Method
• ASTM G16, Standard Practice for Applying Statistics to Analy- • ASTM G150, Standard Test Method for Electrochemical Criti-
sis of Corrosion Data cal Pitting Temperature Testing of Stainless Steels and Related
Alloys
• ASTM G30, Standard Practice for Making and Using U-Bend
Stress-Corrosion Test Specimens • ASTM NACE/ASTM G193, Standard Terminology and Acro-
nym Relating to Corrosion
• NACE/ASTM G31, Standard Guide for Laboratory Immersion
Corrosion Testing of Metals • ASTM G199, Standard Guide for Electrochemical Noise
Measurement
• ASTM G32, Standard Test Method for Cavitation Erosion
Using Vibratory Apparatus • GM9540P, Accelerated Corrosion Test
• ASTM G38, Standard Practice for Making and Using C-Ring • ISO 1462, Metallic Coatings—Coatings Other Than Those
Stress-Corrosion Test Specimens Anodic to the Basis Metal—Accelerated Corrosion Tests—
Method for the Evaluation of the Results
• ASTM G39, Standard Practice for Preparation and Use of
Bent-Beam Stress-Corrosion Test Specimens • ISO 4540, Metallic Coatings—Coatings Cathodic to the Sub-
strate—Rating of Electroplated Test Specimens Subjected to
• ASTM G46, Standard Practice for Examination and Evalua-
Corrosion Tests
tion of Pitting Corrosion
• ISO 7539, Corrosion of Metals and Alloys—Stress Corrosion
• ASTM G47, Standard Test Method for Determining Suscepti-
Testing, Parts 1–7
bility to Stress-Corrosion Cracking of 2xxx and 7xxx Alumi-
num Alloy Products • ISO 8993, Anodized Aluminum and Aluminum Alloys—Rating
System for the Evaluation of Pitting Corrosion—Chart Method
Direct Tension Stress-Corrosion Test Specimens • ISO 8994, Anodized Aluminum and Aluminum Alloys—Rating
System for the Evaluation of Pitting Corrosion—Grid Method
• ASTM G59, Standard Practice for Conducting Potentiody-
namic Polarization Resistance Measurements • ISO 9591, Corrosion of Aluminum Alloys—Determination of
Resistance to Stress Corrosion Cracking
• ASTM G61, Standard Test Method for Conducting Cyclic Poten-
tiodynamic Polarization Measurements for Localized Corrosion • ISO 11306, Corrosion of Metals and Alloys—Guidelines for
Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys Exposing and Evaluating Metals and Alloys in Surface Sea
Water
• ASTM G69, Standard Test Method for Measurement of Corro-
sion Potentials of Aluminum Alloys • ISO 11463, Corrosion of Metals and Alloys—Evaluation of Pit-
ting Corrosion
• ASTM G71, Standard Guide for Conducting and Evaluating
Galvanic Corrosion Tests in Electrolytes • ISO 11782-1, Corrosion of Metals and Alloys—Corrosion
Fatigue Testing, Part 1: Cycles to Failure Testing
• ASTM G73, Standard Test Method for Liquid Impingement
Erosion Using Rotating Apparatus • ISO 11782-2, Corrosion of Metals and Alloys—Corrosion
Fatigue Testing, Part 2: Crack Propagation Testing Using Pre-
• ASTM G78, Standard Guide for Crevice Corrosion Testing of
cracked Specimens
Iron-Base and Nickel-Base Stainless Alloys in Seawater and
Other Chloride-Containing Aqueous Environments • ISO 11845, Corrosion of Metals and Alloys—General Principles
for Corrosion Testing
• ASTM G82, Standard Guide for Development and Use of a
Galvanic Series for Predicting Galvanic Corrosion Performance • NACE RP0173-73, Collection and Identification of Corrosion
Products
• ASTM G100, Standard Test Method for Conducting Cyclic Gal-
vanostaircase Polarization
The following standards apply to atmospheric environments:
• ASTM G102, Standard Practice for Calculation of Corrosion
Rates and Related Information from Electrochemical • ASTM B117, Standard Practice for Operating Salt Spray (Fog)
Measurements Apparatus
• ASTM G33, Standard Practice for Recording Data from Atmo- the number of sites for crevice or poultice attack.81 Type 304 and
spheric Corrosion Tests of Metallic-Coated Steel Specimens 316 stainless steels are not recommended in flow conditions less
than approximately 1.5 m/sec because of the deep pitting of these
• ASTM G50, Standard Practice for Conducting Atmospheric
alloys from crevices created by biofouling.25 Surface roughness
had a pronounced effect on the pitting corrosion of stainless
• ASTM G84, Standard Practice for Measurement of Time-of- steels in chloride solutions. A smoother surface finish reduced
Wetness on Surfaces Exposed to Wetting Conditions as in the incidence of metastable pitting substantially by reducing the
Atmospheric Corrosion Testing number of sites capable of being activated into metastable pit
• ASTM G91, Standard Practice for Monitoring Atmospheric growth. Once growing, however, a metastable pit on a smoother
SO2 Deposition Rate for Atmospheric Corrosivity Evaluation surface had a greater probability of achieving stable pit growth.
• ASTM G140, Standard Test Method for Determining Atmo- The origin of the observations was in the geometry of the sites,
spheric Chloride Deposition Rate by Wet Candle Method particularly in the openness. A more deeply recessed pit site
(expected on a rougher surface) had a greater probability of
being activated into diffusion-controlled dissolution, but because
it was more deeply recessed, it grew at a smaller current
Corrosion Performance of Specific density.166
Materials Nickel and Ni alloys owe their corrosion resistance partly to
the inherent lower reactivity of nickel relative to iron as mea-
Metals and alloys commonly used in the seawater environment
sured by its more noble oxidation potential in the EMF series.
include carbon steels, stainless steels, nickel (Ni) alloys, copper
Similar to stainless steels, chromium-containing Ni alloys have
(Cu) alloys, titanium (Ti) alloys, and aluminum (Al) alloys. All
the capability to passivate (i.e., to spontaneously form an ultra-
of these alloys exhibit differing degrees of corrosion resistance in
thin but tenacious surface oxide that functions as an effective
seawater, and in general, coatings and cathodic protection often
corrosion barrier). Types of corrosion-resistant nickel and Ni
are applied to decrease the corrosion of these metals. The corro-
alloys: (1) commercial nickel; (2) Ni-Cu alloys; (3) Ni-Fe-Cr-Mo
sion resistance within a class of alloys also may depend on metal-
alloys, such Incoloy alloy 825; (4) Ni-Cr-Mo alloys, such as Has-
lurgical differences caused by fabrication and processing or heat
telloy C-276; and (5) Fe-Ni-Cr alloys, such Incoloy alloy 800. Ni-
treatments. Joining processes, such as welding, brazing, and sol-
Cu and Ni-Cr-Mo alloys are the nickel-base alloys that typically
dering, use of adhesives or coatings, surface roughness, and prox-
are used in seawater. The Ni-Cu alloys have good corrosion
imity to dissimilar metals or alloys, also will cause changes in the
resistance in high-velocity seawater, but they do exhibit localized
corrosion resistance of materials.
corrosion in quiescent seawater.25
Carbon steels corrode in aerated seawater conditions. Their
Ni-Cr-Mo alloys generally have high resistance to localized
corrosion rate decreases with time as protective barrier films are
corrosion. Alloy 625 was developed for high-temperature service,
formed on the carbon steel surfaces. These protective films may
but it was observed that it also had high resistance to localized
be a rust layer, calcareous deposits, or biofouling. The corrosion
corrosion in aqueous chloride. Alloy 625, a Ni-Cr-Mo alloy, is
rate of carbon steels increases in high-velocity seawater because
susceptible to crevice corrosion in both quiescent and flow con-
the protective barrier layer is either not allowed to form or is
ditions.167–169 Further alloy development to maximize the levels
stripped away under the flow conditions. Also, the available oxy-
of Cr, Mo, and W has led to Ni-Cr-Mo alloys (UNS N06059,
gen at the metal surface is increased in flowing seawater, which
N06022, N06686, N06200) with vastly increased resistance to
promotes a higher carbon steel corrosion rate. A 2.5-year study
pitting and crevice corrosion as suggested by their respective pit-
showed that immersion corrosion mass loss as a function of time
ting resistance equivalence number (PRENW; see equation (3)),
for mild steel exhibits a characteristic monotonic bi-modal
ranging from 67 to 76. Equation (3) includes nitrogen, but the
behavior, both for natural and for sterile seawater. The bimodal
solubility of nitrogen is very low and is not included by some
behavior can be explained as arising from a change from local-
researchers.170 The higher the PRENW, the greater resistance of
ized cathodic oxygen reduction to localized cathodic hydrogen
an alloy to pitting and crevice corrosion, though it is not absolute
reduction. This change is the direct result of the decreasing abil-
predictor of resistance in all seawater applications.
ity of oxygen to diffuse through the increasing thickness and
reducing the permeability of rust layers as corrosion proceeds. PRENW ¼ %Cr þ 3:3ð%Mo þ %WÞ þ 16ð%NÞ: (3)
The cathodic hydrogen reduction reaction is rate controlled by
the outward diffusion of hydrogen through the rust layers.165 These Ni-Cr-Mo alloys are strong, weldable, and highly resistant
Stainless steels are used in a variety of applications in to localized corrosion and also can be used for weld overlays.162
marine service. Stainless steels may be chosen for corrosion resis- Cu alloys exposed to seawater depend on the alloy and
tance, strength, resistance to flow velocity, weight savings, and water composition. In unpolluted seawater, a loosely adherent
fabricability. Stainless steels are susceptible to localized corrosion porous cupric hydroxy-chloride (Cu2(OH)3Cl) corrosion prod-
in quiet seawater but maintain good corrosion resistance in sea- uct scale forms over a thin, tightly adherent layer of cuprous
water flow conditions because of the increased oxygen supply, oxide (Cu2O) that increases corrosion resistance with increased
which promotes passivity of these alloys. Biofouling is also mini- exposure times.171,172 The iron and nickel from the Cu-Ni alloy
mized in high-velocity conditions, and this in turn minimizes are concentrated in the inner portion of the porous layer.173 Iron,
SEAWATER 209
if present in solid solution, also increases the corrosion resistance and near-alpha alloys, do exhibit a susceptibility to stress corro-
of Cu-Ni alloys by assisting in the formation of the protective sion cracking.12
film.174 The initial corrosion rate of Cu-Ni alloys is relatively high Titanium and Ti alloys continue to see increased usage in
but quickly decreases as the oxide film and the corrosion product naval and commercial and marine applications for many rea-
layers are formed. sons. It is unsurpassed in its corrosion immunity in marine ser-
A variety of Cu alloys are used in seawater applications. vice, its low density provides for significant weight reductions, it
Their generally good resistance is due to the formation of a protec- has a high strength–to–weight ratio, has high erosion resistance,
tive film of cuprous oxide on the metal surface. Additional depos- and is highly shock resistant. All these factors allow design engi-
its such as Cu-containing compounds and calcareous materials neers the opportunity to provide systems that significantly
often form on top of this film, which can further increase their reduce (or eliminate) maintenance time and costs while provid-
corrosion resistance.12 Cu-30Ni (C71500) and Cu-10Ni (C70600) ing unexcelled performance and a practically unlimited service
generally have excellent uniform and pitting corrosion resistance life. It is available as fittings, flanges, pipe, tube, plate, sheet, and
in seawater.14,25 Copper and some Cu alloys do exhibit erosion fasteners and is formable into most all required forms. It has a
corrosion under high-velocity conditions. Their corrosion resis- long history in heat exchanger service (shell and tube and plate
tance depends on the growth and maintenance of the protective and frame), in piping systems, and in components.
layers formed on the metal surface. The maximum velocity rec- Titanium’s exceptional corrosion resistance is derived from
ommended for Cu in seawater is 0.9 m/sec. Alloying with nickel, its protective oxide film, TiO2, which has motivated extensive
aluminum, or chromium increases the resistance of Cu alloys to applications in seawater, marine, brine, and aggressive industrial
impingement attack.14,25 Cu-Zn alloys (brasses) with more than and chemical service over the past 50 years. Today, titanium and
15% zinc are susceptible to a type of dealloying called dezincifi- its alloys are extensively used for the following applications: desali-
cation. Some aluminum bronze (Cu-Al) alloys, especially those nation; offshore, marine deep sea applications; and Navy ship
containing more than 8% aluminum, are also susceptible to deal- components, such as seawater piping. Ti alloy forms form a pro-
loying. The dealloying in Cu-Al alloys can be prevented by add- tective oxide scale under different environmental conditions stud-
ing more than 3.5% nickel or by heat treating to obtain an a þ b ied at both low and higher temperatures. The corrosion rate
microstructure.25 evaluated in different environments and at different temperatures
Hack and Gudas175 showed that 90/10 Cu-Ni was suscepti- was correlated. Pitting corrosion studies in different environments
ble to sulfide-induced pitting in natural, flowing seawater con- revealed that the alloy is resistant to pitting and crevice corrosion
taining 0.01 ppm or more sulfides. Similarly, 70/30 Cu-Ni was in marine environments at 25–50 C.178 Titanium and its alloys are
susceptible to sulfide-induced pitting but required higher sulfide extremely resistant to pitting attack in seawater and other
concentrations. Sulfide-modified films generally were more chloride-containing solutions at ambient and moderately elevated
loosely adherent than the normal cuprous oxide films; turbulence temperatures. The pitting potential is well above that associated
tended to selectively remove the sulfide-modified films. The with naturally occurring environments. Ti alloys typically have
exposed surfaces are anodic to the surfaces covered by the films poorer resistance to pitting than commercially pure titanium.179
and localized corrosion at the exposed sites is promoted. When iron, low-alloy steel, or carbon steel are gouged, smeared,
Depending on water quality, additional sulfide-modified films or embedded on the surface, penetrating the Ti oxide film, pitting
may form and the process becomes cyclic. of unalloyed titanium occurs in hot brines. This pitting may also
Al alloys are susceptible to localized corrosion in seawater be viewed as a special case of crevice corrosion.180
under both low- and high-velocity conditions. However, these Mg alloys are starting to see limited applications in marine
alloys, particularly 5000 series and 6061 Al alloy, are commonly applications. A new alloy system, high entropy alloys (also called
used in marine applications.14,25 In most freshwater applications, multiple principal element alloys) are compositionally complex
crevice corrosion of aluminum is negligible. In seawater, how- alloys that were first developed in 2004, but their complexity has
ever, crevice corrosion can be quite active and takes the form of kept them largely in the experimental stage at this writing. In addi-
pitting. Unlike steel, localized corrosion of aluminum is primar- tion to metals and alloys, organic composites, such as graphite-
ily determined by the properties, size, and distribution of inter- reinforced epoxy, are gaining increasing use in the marine environ-
metallic precipitates and less so by the properties of the solid- ment. The advantage of these composites over conventional mate-
solution matrix. Resistance to crevice corrosion in Al alloys par- rials is in their high strength-to-weight and stiffness-to-weight
allels its resistance to pitting. The pitting–crevice corrosion resis- ratios. These composites also offer excellent marine corrosion
tance of Al-Mg alloys (5xxx) is higher than observed in Al-Mg-Si resistance.181,182 but may be susceptible to attack from the alkaline
(6xxx) alloys.176 The corrosion potential of Al 1100 in natural environment produced by cathodic protection techniques.
and synthetic seawater is more positive than its repassivation
potential and consequently aluminum would be expected to suf-
fer localized corrosion.177
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85. Accelerated Corrosion Test, General Motors Engineering
Standards: Materials and Processes-Procedures, GM9540P 103. B. J. Little, R. I. Ray, and J. S. Lee, “Diagnosing, Measuring, and
(Detroit, MI: General Motors Corporation, December 1997). Monitoring Microbiological Influenced Corrosion,” in Uhlig’s
Corrosion Handbook, 3rd ed., ed. R. W. Revie (New York: Wiley,
86. J. R. Davis, ed., “Corrosion Testing and Evaluation,” in Metals 2011), 1202–1212.
Handbook: Corrosion, vol. 13 (Metals Park, OH: ASM International,
1987). 104. Standard Test Method for Electrochemical Critical Pitting
Temperature Testing of Stainless Steels and Related Alloys, ASTM
87. Corrosion Tests in Artificial Atmospheres—Salt Spray Tests, ISO G150-18 (West Conshohocken, PA: ASTM International, approved
9227:2012 (Geneva, Switzerland: International Organization for May 1, 2018), https://doi.org/10.1520/G0150-18
Standardization, 2012).
105. Standard Test Method for Determining the Crevice Repassivation
88. Standard Test Method for Copper-Accelerated Acetic Acid-Salt Potential of Corrosion-Resistant Alloys Using a Potentiodynamic-
Spray (Fog) Testing (CASS Test), ASTM B368-09(2014) (West Galvanostatic-Potentiostatic Technique, ASTM G192-08(2014)
Conshohocken, PA: ASTM International, approved May 1, 2014), (West Conshohocken, PA: ASTM International, approved
https://doi.org/10.1520/B0368-09R14 November 1, 2014), https://doi.org/10.1520/G0192-08R14
89. A. Sterling, A. Atrens, and I. O. Smith, “Accelerated Atmospheric 106. F. Mansfeld, M. W. Kendig, and S. Tsai, “Evaluation of Corrosion
Corrosion of Copper and Copper Alloys,” British Corrosion Behavior of Coated Metals with AC Impedance Measurements,”
Journal 25, no. 4 (1991): 271–278. Corrosion 38, no. 9 (1982): 478–485.
SEAWATER 213
107. J. D. Scantlebury, K. Ho., and D. Eden, “Impedance Measurements Cracking” (paper presentation, Corrosion/91, paper 444, NACE
on Organic Coatings on Mild Steel in Sodium Chloride Solutions,” International, Cincinnati, OH, March 11–15, 1991).
in Electrochemical Corrosion Testing, ed. F. Mansfeld and U.
Bertocci (Philadelphia, PA: ASTM International, 1981), 187–197. 122. B. C. Syrett and W. M. Cox, “Electrochemical Noise Measurement
for Corrosion Applications,” in Proceedings of the First
108. J. N. Murray and H. P. Hack, “Testing Organic Architectural International Symposium on Electrochemical Noise
Coatings in ASTM Synthetic Seawater Immersion Conditions Measurements for Corrosion Applications, ed. J. R. Kearns, J. R.
Using EIS,” Corrosion 48, no. 8 (1992): 671–685. Scully, P. R. Roberge, D. L. Reichert, and J. L. Dawson (West
109. J. R. Scully, Electrochemical Impedance of Organic Coated Steel:
Correlation of Impedance Parameters with Long Term Coating 123. F. Mansfeld, Z. Sun, E. Speckert, and C. H. Hsu, “Electrochemical
Deterioration, DTRC/SME-86/108 (Annapolis, MD: David Taylor Noise Analysis (ENA) for Active and Passive Systems” (paper
Research Center, April 1988). presentation, Corrosion/2000, paper 418, NACE International,
Orlando, FL, March 26–31, 2000).
110. D. D. MacDonald and M. C. H. McKubre, “Electrochemical
Impedance Techniques in Corrosion Science,” in Electrochemical 124. G. L. Edgemon and E. E. Barr, “Applications of Electrochemical
Corrosion Testing, ed. F. Mansfeld and U. Bertocci (Philadelphia, Noise: Real Time Plant and Field Challenges” (paper
PA: ASTM International, 1981), 110–149. presentation, Corrosion/2001, paper 283, NACE International,
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111. J. R. Scully, D. C. Silverman, and M. W. Kendig, eds.
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112. F. Mansfeld, L. T. Han, and C. C. Lee, “Analysis of Electrochemical
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129. Standard Test Method for Cavitation Erosion Using Vibratory
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Apparatus, ASTM G32-16 (West Conshohocken, PA: ASTM
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Rotating Apparatus, ASTM G73-10 (2017) (West Conshohocken,
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Candidate Seawater Valve Materials” (paper presentation,
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148. S. R. Novak and S. T. Rolfe, “Comparison of Fracture Mechanics
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136. Standard Practice for Making and Using U-Bend Stress-Corrosion 149. R. P. Gangloff, in Environment Induced Cracking in Metals, ed. R.
Test Specimens, ASTM G30-97(2016) (West Conshohocken, PA: P. Gangloff and M. B. Ives (Houston, TX: NACE International,
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10.1520/G0030-97R16
150. R. P. Wei and R. P. Gangloff, “Environmentally Assisted Crack
137. Standard Practice for Making and Using C-Ring Stress-Corrosion Growth in Structural Alloys: Perspectives and New Directions,”
Test Specimens, ASTM G38-01(2013) (West Conshohocken, PA:
in Fracture Mechanics: Perspectives and Directions (20th
ASTM International, approved May 1, 2013), https://doi.org/
Symposium), ed. R. P. Wei and R. P. Gangloff (West
10.1520/G0038-01R13
138. Standard Practice for Preparation and Use of Bent-Beam Stress-
151. Standard Practice for Conducting Force Controlled Constant
Corrosion Test Specimens, ASTM G39-99(2016) (West
Amplitude Axial Fatigue Tests of Metallic Materials, ASTM E466-
Conshohocken, PA: ASTM International, approved May 1, 2016),
15 (West Conshohocken, PA: ASTM International, approved May
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1, 2015), https://doi.org/10.1520/E0466-15
139. Standard Practice for Preparation and Use of Direct Tension
Stress-Corrosion Test Specimens, ASTM G49-85(2011) (West 152. E. J. Czyryca, in Metals Handbook: Mechanical Testing, 9th ed.
Conshohocken, PA: ASTM International, approved March 1, 2011), (Materials Park, OH: ASM International, 1985), 366–375.
https://doi.org/10.1520/G0049-85R11
153. R. A. Cottis, A. Markfield, A. Boukerrou, and P. Haritopoulos,
140. Standard Practice for Evaluating Stress-Corrosion-Cracking “Crack Initiation and Short Crack Growth during the Corrosion
Resistance of Metals and Alloys in a Boiling Magnesium Chloride Fatigue Steels in Saline Solutions,” in Environment Induced
Solution, ASTM G36-94(2018) (West Conshohocken, PA: ASTM Cracking in Metals, ed. R. P. Gangloff and M. B. Ives (Houston, TX:
International, approved October 1, 2018), https://doi.org/ NACE International, 1990), 223–227.
10.1520/G0036-94R18
154. W. J. Derrick Jones and A. P. Blackie, “Cyclic Tension Corrosion
141. Standard Test Method for Determining Susceptibility to Stress- Fatigue of High Strength Steels in Seawater,” in Environmentally
Corrosion Cracking of 2xxx and 7xxx Aluminum Alloy Products, Assisted Cracking: Science and Engineering, ed. B. Lisagor, T. W.
ASTM G47-98(2011) (West Conshohocken, PA: ASTM Crooker, and B. N. Leis (West Conshohocken, PA: ASTM
International, approved September 1, 2011), https://doi.org/ International, 1990), 447–462.
10.1520/G0047-98R11
155. Standard Test Method for Strain-Controlled Fatigue Testing,
142. R. N. Parkins, “Slow Strain Rate Testing—25 Years’ Experience,” ASTM E606/E606M-12 (West Conshohocken, PA: ASTM
in Slow Strain Rate Testing for the Evaluation of Environmentally International, approved June 1, 2012), https://doi.org/10.1520/
Induced Cracking, Research and Engineering Applications, ed. R. E0606-04E01
D. Kane (Philadelphia, PA: ASTM International, 1993), 7–21.
156. B. Phull, “Evaluating Corrosion Fatigue,” in ASM Handbook vol.
143. R. D. Kane, “Testing for Environmentally Assisted Cracking,” in 13A, Corrosion: Fundamentals, Testing, and Protection (Materials
Uhlig’s Corrosion Handbook, 2nd ed., ed. R. W. Revie (New York: Park, OH: ASM International, 2003), 625–638.
Wiley, 2000), 1117–1128.
157. Standard Test Method for Measurement of Fatigue Crack Growth
144. Standard Practice for Slow Strain Rate Testing to Evaluate the
Rates, ASTM E647-15e1 (West Conshohocken, PA: ASTM
Susceptibility of Metallic Materials to Environmentally Assisted
International, approved May 1, 2015), https://doi.org/10.1520/
Cracking, ASTM G129-00(2013) (West Conshohocken, PA: ASTM
E0647-15E01
International, approved May 1, 2013), https://doi.org/10.1520/
G0129-00R13 158. T. W. Crooker, F. D. Bogar, and G. R. Yoder, “Standard Method of
Test for Constant-Load-Amplitude Fatigue Crack Growth Rates
145. Standard Test Method for Determining Stress-Corrosion Cracking
in Marine Environments” (Naval Research Laboratory Report
Resistance of Heat-Treatable Aluminum Alloy Products Using
Breaking Load Method, ASTM G139-05(2015) (West 4594, Washington, DC, 1981).
Conshohocken, PA: ASTM International, approved November 1,
159. Standard Test Method for Measurement of Hydrogen
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Embrittlement Threshold in Steel by the Incremental Step
146. Standard Practice for Making and Using Precracked Double Beam Loading Technique, ASTM F1624-12(2018) (West Conshohocken,
Stress Corrosion Specimens, ASTM G168-17 (West PA: ASTM International, approved November 1, 2018), https://
Conshohocken, PA: ASTM International, approved November 1, doi.org/10.1520/F1624-12R18
2017), https://doi.org/10.1520/G0168-17
160. Standard Guide for Conducting Corrosion Tests in Field
147. Standard Test Method for Determining Threshold Stress Intensity Applications, ASTM G4-01(2014) (West Conshohocken, PA:
Factor for Environment-Assisted Cracking of Metallic Materials, ASTM International, approved November 1, 2014), https://
ASTM E1681-03(2013)e1 (West Conshohocken, PA: ASTM doi.org/10.1520/G0004-01R14
SEAWATER 215
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10.1520/G0050-10R15 171. H. P. Hack, H. Shih, and H. W. Pickering, “Role of the Corrosion
Product Film in the Corrosion Protection of Cu-Ni Alloys in Salt-
162. Standard Guide for Applying Statistics to Analysis of Corrosion water,” in Surfaces, Inhibition, and Passivation, PV86-7, ed. E.
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10.1520/G0016-13
172. H. P. Hack, “Role of the Corrosion Product Film in the Corrosion
163. Standard Test Method for Monitoring Atmospheric Corrosion Protection of Cu-Ni Alloys in Saltwater,” DTNSRDC SME-87-22
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217
Chapter 14 | Soils
Mike Horton,1 Lucien Veleva,2 and Edward Escalante3
Description of Soils FIG. 1 Buried pipe with detected corrosion failure. Source: Photo
courtesy of Corrpro, an Aegion Company.
DEFINITION AND CLASSIFICATION
Soil as a corrosive environment is probably of greater complexity
than any other environment.1–6 The corrosion process of buried
metal structures is extremely variable and can range from rapid
to negligible. In fact, some pipes in corrosive soils can be perfo-
rated within a few years, presenting very localized or uniform
corrosion attack (fig. 1). Other pipe in nonaggressive soils may
serve for decades or even centuries, such as sections of a more-
than-350-year-old cast iron pipeline installed in 1664 providing
water to the fountains at the Palace of Versailles (fig. 2). With
background knowledge of the principal soil specifics and their
influence on metal corrosion, the most serious corrosion prob-
lems can be prevented. In discussion of the soil as an environ-
ment for corrosion, no strict definitions exist. The origin of soil
is in the earth’s crust and the following four main classes of soil FIG. 2 350-plus-year-old cast iron pipeline furnishing water to
have been proposed: the fountains at the Palace of Versailles. Source: Photo
courtesy of the Ductile Iron Pipe Research Association.
1. soils formed in situ from soft rocks, such as chalk and
volcanic ash;
2. soils formed in situ from hard rocks, such as granite,
limestone, and marble;
3. soils transported from their place of origin before weath-
ering to form soils, including those moved by water,
such as marine and beach sediments, and also those
moved by wind, such as sands, and those moved by gla-
cial drift; and
4. soils formed in situ from organic material, such as peat.
Soils are commonly named and classified according to the
size range of their particulate matter. For example, sand, silt, and
clay derive their name from the predominant size range of their
inorganic constituents. Particles between 0.02 and about 2 mm sands. Silt particle sizes range from 0.002 to 0.02 mm and clay
are classed as fine (0.02–0.2 mm) and coarse (0.20–2.00 mm) particles have a mean diameter of <0.002 mm down to colloidal
matter. Table 1 presents the terminology for different soils
1
U.S. Pipe and Foundry, 2023 St. Louis Ave., Bessemer, AL 35020, USA according to ASTM D2488, Standard Practice for Description and
2
Applied Physics Department, CINVESTAV-IPN, Unidad Merida, Yucatan, C.P.
Identification of Soils (Visual-Manual Procedures). The United
97310, Mexico
3
National Institute of Standards and technology, Gaithersburg, MD, USA
States and more than 50 other countries now use a more detailed
The authors acknowledge the previous author of this chapter, Edward Escalante, classification of their soils, which includes 11 major orders and
NIST, 100 Bureau Dr., Gaithersburg, MD 20899. 47 suborders.
DOI: 10.1520/MNL202NDSUP20190009
the various layers). Complex physical, chemical, and biological

TABLE 1 ASTM D2488, Terminology for Soils nature; corrosion aggressiveness; and dynamic interactions with
the environment distinguish the soil.
Term Description Climatic changes of sun irradiation; air temperature and rel-
Clay <0.75 :m (passes No. 200 sieve) ative humidity; rainfall, winds, and mechanical action of natural
Gravel <75 mm and >4.75 mm (No. 4 sieve) forces; various physical, chemical, and biological factors; and
Organic clay Clay, except that its liquid limit values after oven human manipulation can alter soil properties, which directly
drying are <75% of its liquid limit value before oven affect the corrosion rate of metals buried in the soil. The
drying. amounts of moisture and rainfall are considered to be of primary
Organic silt Silt, except that its liquid limit values after oven importance in soil evolution. They affect the type of soil that
drying are 75% of its liquid limit value before oven forms, the weathering process, and all changes taking place
drying. within the soil. Plant and animal life with their soil-building
Peat Soil, primarily vegetable tissue, in various stages of action, acid or base reactions in the parent material, dissolution
decomposition, usually with organic odor, dark brown of soluble components, the leaching out of alkaline minerals of
or black, spongy consistency, with fibrous to the weathering rock, and other phenomena are strictly influ-
amorphous texture.
enced by changes in these factors.
Sand Rock particles passing No. 4 sieve (4.75 mm) and
The conditions in soils can range from atmospheric to
retained on a No. 200 (75 :m).
completely immersed metal, depending on the soil compactness
Silt Soil passing No. 200 sieve; nonplastic or very slightly
(existence of capillaries and pores) and moisture content. The
plastic, and exhibiting little or no strength when air-
corrosiveness of a soil depends on an interaction between climate
dried.
and soil reactions. The variation in soil composition and struc-
Variation of the proportion of soil size groups determines ture can create distinct corrosive environments, which results in
many of the properties of the soil. Terms commonly used for soil different metal activities and oxygen concentrations (differential
classification include sandy clay, clay loam, silt loam, loamy aeration) at the metal–soil interface.
sand, silty clay loam, sandy loam, and gravel. The clays are plas-
tic mixtures with high moisture content and are considered to be
the most important inorganic constituents of the soil. Often the Characteristics and Testing of Soils
clays are grouped depending on the weathering conditions (e.g.,
Related to Corrosion
montmorillonite, illite, kaolinite). Soils of fine texture, because of
their high clay content, present more packed particles and have The metal corrosion in soils is determined primarily by such fac-
less pore capacity for moisture and gas (oxygen) diffusion than tors as moisture content and its level of electrical (ionic) conduc-
an open-type soil such as sand. The clay mineralogy and proper- tivity, aeration and oxygen content, relative acidity or alkalinity,
ties are closely related to the corrosion aggressiveness of soil, and bacterial activity, and amount of dissolved salts.1–6,8–13,23,29 The
this fact needs attention. two primary conditions necessary to initiate metal corrosion in
Soil has a specific gravity from 1.1 to 1.7, which is measured soil are water (moisture) and oxygen. After these factors, a num-
as described in ASTM D2937, Standard Test Method for Density ber of variables can affect the corrosion process.
of Soil in Place by the Drive-Cylinder Method. The main chemical
constituent of soils, such as loam, clay, and silt is silicon dioxide SOIL MOISTURE
(SiO2), usually along with aluminum oxide (Al2O3). Commonly Principally, three types of water provide the soil moisture: free
dissolved species in wet soils are Hþ, Cl, sulfate (SO42), bicar- ground water, gravitational water, and capillary water. They have
bonate (HCO3) ions. The soil mineralogy and chemistry deter- a significant influence on the metal and environmental charac-
mine the corrosion aggressiveness of soil. Soils with the poorest teristics and on the determination of the corrosion rate. The
drainage, like clay, silt, and loam, are generally the most corro- amount of moisture in a soil can be determined by the method
sive, whereas soils with excellent and good drainage (gravel and described in ASTM D2216, Standard Test Methods for Laboratory
sand, respectively) are generally the least corrosive. Determination of Water (Moisture) Content of Soil and Rock by
Because of the complex content of the soil (including Mass.
organic matter and organisms, gases, mineral particles, mois- The free ground water is present in the soil at some depth (a
ture), the relative size range does not represent the whole nature few meters to hundreds of meters) below the surface, and usually
of the soil. In fact, most soils consist of aggregates of particles, only river-crossing pipelines are surrounded by ground water. In
which give the possibility for moisture penetration, less erosion such a situation, metal corrosion occurs in an aqueous environ-
by water and wind, and generally great aeration and biological ment (e.g., on a fully immersed metal structure). The principal
activity. The destruction of this structure by mechanical action sources of the gravitational water are rainfall, snow, flood, and
or chemical alteration (such as excess alkali or salt accumulation) irrigation. This water enters and flows through the soil, governed
can alter the physical nature of the soil. To understand the corro- by its physical structure, including pore and capillary spaces at
sion behavior of buried metal, it is also important to have infor- various zones in the soil profile, and usually percolates to the
mation about the soil profile (section through the soil showing level of permanent ground water. A measure of the compactness
SOILS 219
of mineral soils is the apparent specific gravity index. The amount

of organic matter influences this value markedly. Some impervi- FIG. 3 Low-resistivity layer over high-resistivity layer.
ous soils, such as clay and water-resistant materials, act as effec-
tive barriers to the passage of gravitational water and cause zones
of water accumulation and saturation. The tendency of the soil
to crack on drying and swell when wetted is defined by the term
volume shrinkage, and it is an indicator of the colloidal nature of
the clay and loam particles in a soil. In drying, the soil forms
cracks that allow oxygen to flow freely to buried metals.
The capillary water represents an important reservoir of
water in soil. A considerable amount is held in the capillary
spaces of silt and clay particles. The term moisture equivalent
of soil is a measure of the retentiveness or water holding capac-
ity of the soil. The water retained by a soil is a consequence of
equilibrium between capillary and gravitational forces. The FIG. 4 High-resistivity layer over low-resistivity layer.
permeability and moisture retention of granular soils can be
measured by the method described in ASTM D2434, Standard
Test Method for Permeability of Granular Soils (Constant
Head). For the water-holding capacity of peat, one can use
ASTM D2980, Standard Test Method for Saturated Density,
Moisture-Holding Capacity, and Porosity of Saturated Peat
Materials. The existence of moisture in good conductivity soil
indicates high ion content and the possibility for very strong
corrosion attack.
SOIL RESISTIVITY
The soil resistance (R) to passage of electrical current is the most
The resistivity of sand and gravel deposits is generally high
used parameter as an indicator of corrosion aggressivity of soils.
and uniform, whereas many bedrock formations have high but
It is related to three terms in the following equation:
erratic resistivity. Table 2 gives typical resistivity values of various
R ¼ qI=A; (1) minerals and soils.
Along the length of the pipe, variations in soil resistivity
where: may stimulate localized metal corrosion and can cause long line
q ¼ specific resistivity of the particular soil, currents; in the area of lower resistivity soil, the buried metal sur-
I ¼ a length of the electrical path, and face is usually anodic, with a more negative potential, compared
A ¼ the cross-sectional area of the electrodes. with that in the soil of higher resistivity. Table 3 relates soil resis-
Soil resistivity is normally reported in the units ohm-cm tivity values with corrosion.11
(i.e., Xcm). Field soil resistivity measurements are normally carried out
The resistivity indicates the probable corrosivity of the soil. by the Wenner technique, four-pin method, with or without the
Its value depends on the soil water content on the layers and on Barnes method, according to ASTM G57, Standard Test Method
types of soils underneath (e.g., sand, rock, gravel, clay, mud). for Measurement of Soil Resistivity Using the Wenner Four-
Vertically homogeneous soils are virtually nonexistent. Thus, it Electrode Method. (The Barnes method is a mathematical proce-
is convenient to consider a nonuniform soil to consist of differ- dure for calculating the resistivity of the soil in each incremental
ent layers or strata.13 Electron flow will deflect downward in the layer.) Four steel electrodes, each spaced an equal distance from
case of a high-resistivity strata over a low-resistivity one, and the next, are driven into the ground. The depth of soil being eval-
vice versa, as shown in figure 3 and figure 4. The electrical resis- uated depends on the pin spacing. An alternating current (ac) or
tivity of the surface strata has a greater influence on test results direct current (dc) is passed between the outer two pins, and the
than does that of deeper strata. Also, the soil resistivity decreases corresponding potential drop (voltage AV) is measured between
with increasing water content and with increasing water salinity the inner pins, as shown in figure 5. The resistance R ¼ AV/I,
because of high contents of ions. Thus, nonporous soils exhibit where I is the applied current.
relatively high values of resistance, because the water content is The average resistivity value depends on how many meas-
small. These include nearly all of the igneous and metamorphic urements are taken in the area and when they were taken. Meas-
rocks, such as granite, plus many sedimentary rocks, such as urements should be made at various times and under various
dense limestone or sandstone. The resistivity of bedrock can vary weather conditions (e.g., dry or rainy seasons, summer or win-
considerably depending on the type of bedrock and the extent of ter). It is impossible, therefore, to give any precise assessment as
weathering and fracturing. to the rate at which corrosion will occur under any particular
TABLE 2 Electrical Resistivity of Various Minerals and Soils FIG. 5 Four-electrode method for the electrical soil resistance
measurement.
Minerals and Soils Resistivity, ohm-cm
Minerals
Pyrite magnetite 0.1 0.6–1.0
Graphite 0.03
Rock salt (impure) 3,000–500,000
Serpentine 20,000
Sederite 7,000
Igneous Rock
Granite 500,000–100,000
Diorite 1,000,000
Gabbro 10,000,000–1,400,000,000
Diabase 310,000
Metamorphic Rocks
Garnet gneiss 20,000,000
Mica chist 130,000 Several commercial meters allow measurement of soil resis-
Biotite gneiss 100,000,000–600,000,000 tivity. A commonly used resistance meter is shown in figure 6.
Slate 64,000–6,500,000 One reliable and widely used instrument uses an alternating cur-
Sedimentary Rock rent 97-Hz square wave. It offers several advantages, such as
Chattanooga shale 2,000–130,000 eliminating the effect of polarization that can affect the measure-
Michigan shale 200,000 ments when using dc, and eliminating interference by 60-Hz
Calumet and hecla conglomerates 200,000–1,300,000 sinusoidal currents.
Muschelkalk sandstone 7,000 Soil resistivity can be measured under either field or labora-
Ferruginous sandstone 18,000 tory conditions. In the laboratory, the soil sample is placed and
Muschelkalk limestone 18,000 compacted to the same amount as the soil at the site in a soil
Marl 7,000 box. The resistivity is measured by applying low voltage dc or ac.
Glacial till 50,000 Errors could result from polarization when using a dc or ac cur-
Type of Soil rent of too low a frequency. The soil box measurement (repre-
Sand 10,000–500,000 senting a specific soil sample) is a point measurement, not an
Oil sand 400–22,000 average soil resistivity as is the Wenner method.
Gravel 20,000–400,000 Soil resistivity testing using a soil box may be conducted
Loam 3,000–20,000 with a four-electrode soil box as described in ASTM G57 (fig. 6)
Clay 500–2,000 or a two-electrode soil box method (fig. 7 and fig. 8) as described
Silt 1,000–2,000 in ASTM G187, Standard Test Method for Measurement of Soil
Resistivity Using the Two-Electrode Soil Box Method. ASTM G57
TABLE 3 Soil Resistivity versus Degree of Corrosivity

FIG. 6 General view of four-pin soil resistance meter and four-
pin soil box. Source: Photo courtesy of U.S. Pipe and
Soil Resistivity (ohm-cm) Degree of Corrosivity
Foundry.
0–500 Very corrosive
500–1,000 Corrosive
1,000–2,000 Moderately corrosive
2,000–10,000 Mildly corrosive
Above 10,000 Negligible
condition, and the results of any survey must be taken as giving

only a general indication of the probability of corrosion. Chemi-
cal and other forms of industrial contamination of the soil can
significantly influence soil resistivity and corrosivity. In real life,
the soil is not homogeneous and layers are not always horizontal.
In fact, as the spacing between Wenner pins changes, soil resis-
tivity readings also may change.
SOILS 221
AERATION AND OXYGEN CONTENT

FIG. 7 ASTM G187, two-electrode soil box. The percentage of the volume of the soil occupied by air at a cer-
tain moisture content is determined by air-pore space and is used
for permeability characterization of the soil. High values of air-
pore space could provide a dry soil environment, which may not
permit the electrochemical development of corrosion. The aera-
tion and oxygen content in soil moisture are important for the
corrosion process, because the oxygen is the principal oxidizing
agent in the cathodic (electron consumption) corrosion reaction.
It is generally assumed that the gases of the upper layers of soil
are similar in composition to the atmosphere above the soil,
except for a higher carbon dioxide content. By the fact that the
plant roots require oxygen to penetrate a soil, it may be assumed
that gases in some soils at depths of 6 m or more contain a sig-
nificant amount of oxygen. For soils with coarse texture, such as
sand and gravel, the circulation of air is relatively free and the
corrosion rate may reach that in the atmosphere.
From a corrosion perspective, the solubility of oxygen in
soil moisture (electrolyte) is one of the most significant effects.
The dissolved oxygen concentration increases until the saturation
limit is reached. The solubility of oxygen in water is a function of
temperature and the oxygen solubility decreases as soil tempera-
FIG. 8 Typical connections for use of two-electrode soil box with ture increases. The temperature, however, also increases the corro-
soil resistance meter. sion kinetics, even at lower levels of oxygen concentration. Some
specific climates, such as warm and tropical humid (and their
daily temperature variations), may cause expansion and contrac-
tion of the surface-soil gases. The oxygen content also depends
on the biological activity within the soil and the consumed oxy-
gen can be replaced with gases from metabolic activity, such as
carbon dioxide.
Differences in oxygen concentration in layers of soils can
result in the development of oxygen concentration corrosion
cells. When the concentration of dissolved oxygen at two points
on a metal surface is different, the surfaces in contact with the
solution or soil containing the higher concentration of dissolved
oxygen will become cathodic to the surfaces in contact with the
solution or soil containing the lower concentration of dissolved
oxygen. These surfaces exposed to the lowest O2 concentration
will suffer accelerated corrosion as anodes in an oxygen concen-
tration cell. For example, on a buried pipe, an oxygen concentra-
tion corrosion cell may be set up between the pipe in contact
emphasizes an in situ measurement commonly utilized in the
with nonaerated undisturbed soil (i.e., bottom of a pipeline
design of a buried structures’ corrosion control system (e.g.,
trench), and areas of the pipe in contact with aerated disturbed
cathodic protection systems, ground bed design) and also
soil (i.e., backfill around a pipe). Corrosion will occur preferen-
includes information and procedures on a four-pin soil box
tially on the bottom of the pipe in contact with the low-oxygen-
method. The two-electrode soil box method is an accurate and
content nondisturbed soil.
more expeditious method than the four-pin soil box and often
complements the four-pin in situ soil resistivity method.
In laboratory tests, the soil resistivity also can be measured OXIDATION-REDUCTION POTENTIAL
at 100% water saturation using distilled water, which gives a Oxidation-reduction potential (also called redox potential or
value that could correspond to that of rainy climatic periods, ORP) for soil is defined by ASTM G200, Standard Test Method
when a lot of salts may be dissolved and cause a decrease of the for Measurement of Oxidation-Reduction Potential (ORP) of Soil,
soil resistivity. The temperature changes have only a slight effect as an “electrical potential measurement to determine the ten-
on the soil resistivity value until total freezing of soil moisture dency of a soil to transfer electrons between its chemical species.
occurs. The ice resistance, however, increases sharply as temper- It is the measured potential of an inert metal electrode (generally
ature drops. ASTM G57 includes a correction chart for resistivity platinum) with respect to a reference electrode such as silver/
based on temperature. silver chloride.” In soils, redox potential can be used as an
indication of aeration, corrosivity, and the potential for microbi- pH for use in corrosion testing are covered in ASTM G51, Stan-
ologically influenced corrosion (MIC) by sulfate-reducing bacte- dard Test Method for Measuring pH of Soil for Use in Corrosion
ria (SRB). The use of redox potentials as one of the methods to Testing. Two electrodes, glass and calomel (or other reference
predict soil corrosivity is presented in table 4. electrode), of a standard pH meter are pressed into the soil and
Soil test procedures described in Appendix X1 of ASTM the value of their potential difference is linearly related to pH.
A674, Standard Practice for Polyethylene Encasement for Ductile A combination electrode consisting of a reference electrode and
Iron Pipe for Water or Other Liquids, states the following: “The a glass electrode combined as a single electrode also is used com-
oxidation- reduction (redox) potential of a soil is significant monly. By the nature of the measurement, pH is determined for
because the most common SRB can live only under anaerobic a small volume of soil at each reading, and it is important that
conditions. A redox potential greater than þ100 mV shows the three measurements at different locations be made and that a
soil to be sufficiently aerated so that it will not support sulfate simple average is calculated.
reducers. Potentials of 0 to þ100 mV may or may not indicate The pH of soil may be sampled in situ, from disturbed sam-
anaerobic conditions; however, a negative redox potential defi- ples in the field brought to the surface, or in the laboratory. Of
nitely indicates the anaerobic conditions in which sulfate reduc- these three methods, the least desirable is that which is based on
ers thrive.” Conditions under which SRB could grow do not a soil sample transported to a laboratory for evaluation. If this
prove that SRB are present. must be done, it is recommended to make the pH measurement
as quickly as possible after the soil is taken from the field.
RELATIVE ACIDITY (pH) OF SOIL In the case of soils rich in sulfide, the pH value could be more
The soil moisture (electrolyte) can be described as acidic acidic because of the oxidation of sulfides to sulfates as the soil dries
(pH < 7), neutral (pH ¼ 7), or alkaline (pH > 7), based on the out. The treatment of the soil before pH measurement remains an
relative ratio of hydrogen ions (Hþ) to hydroxyl ions (OH-). open issue. Drying of soil samples and addition of distilled water
When Hþ ions predominate over OH- ions, the soil is acidic and are two of the treatments used. The soil pH value, however, is not
vice versa. In a neutral solution, both ions are in balance. (The sufficient to unambiguously indicate soil corrosivity. For example, a
value of pH indicates only the hydrogen ion concentration.) neutral soil (pH 6.6–7.3) could be corrosive because of the presence
Fresh water and seawater typically have a near-neutral pH. Con- of chloride ions or the presence of SRB bacteria.
crete environments are strongly alkaline (pH 13). The corro- In some cases, a determination of the total acidity may be
sion effect of soil moisture acidity or alkalinity depends very desirable. Additional measurement requires a soil treatment by
much on the specific metal of interest. mixing the soil with a solution of neutral salts like potassium
Acidity in soils is the result of processes of weathering chloride (KCl) or calcium dichloride (CaCl2) to determine the
under humid conditions, such as mineral leaching, decomposi- exchange or total acidity of the soil, which includes the hydrogen
tion of acidic plants, industrial wastes, acid rain, and certain ions loosely bonded to soil minerals. This extraction method is
forms of microbiological activity. Most soils range from pH 4.5 practically unaffected by fertilizers or other salts that may be pre-
to pH 8. In this range, pH generally is not considered to be a sent in the soil.
problem for buried iron, steel, or concrete pipelines and steel
tanks. Corrosion causing SRB, which are anaerobic and live in
DISSOLVED SALTS AND CORROSION AGENTS
poorly drained soils, require a near-neutral pH environment
The soil water is a good solvent for salts of the soil, which disso-
from 6 to 8. More acidic soils (pH lower than 4.5) can cause
ciate to form cations and anions and render the soil conductive.
rapid metal corrosion and serious risk to common construction
In moderate rainfall areas, the soil solution is relatively dilute (80
materials, including some stainless steel (SS) grades. In areas
to 1,500 ppm total dissolved salts). Lower salt concentrations
with moderate rainfall, soluble salts accumulate only where the
characterize regions with extensive rainfall as a result of leaching
water concentrates in depressions. In areas with considerable
action. Soils in arid regions usually are quite high in salts,
rainfall, soluble salts and bases may be removed, potentially
because of surface evaporation.
resulting in increased acidity.
The most common cations in the soil electrolyte are potas-
Soil acidity, or its pH, is an important measured parameter.
sium and sodium in alkaline soils, magnesium and calcium in
Details for conducting field and laboratory measurements of soil
basic (calcareous) soils. Salts containing the four cations, Kþ,
Naþ, Mgþ, and Ca2þ, can accelerate metal corrosion. In nonacid
TABLE 4 Soil Redox Potentials as an Indicator for Soil Corrosivity
soils, however, calcium and magnesium tend to form insoluble
metal oxides or carbonates, which act as an effective barrier
against corrosion. The corrosion rate in these soils may diminish
Redox Potential versus SHEa Aeration Soil Corrosivity Indicator
significantly. From a corrosion point of view, the important
Negative Not aerated Extremely severe anions found in soil and moisture are chloride (Cl-), sulfate
0–100 mV None to weak Severe (SO4-2), nitrate (NGy), phosphate (PO4-3), carbonate (CO3-2),
100–200 mV Weakly aerated Moderate and bicarbonate (HCOy). These anions play an important role in
200–400 mV Aerated Slight the corrosion process because if they react with metal ions, pro-
Above 400 mV Strongly aerated Noncorrosive duced during the anodic corrosion reaction, and form an insolu-
a
SHE, standard hydrogen electrode, conventionally accepted to be 0.00. ble salt precipitate on the metal surface, this layer could act as an
SOILS 223
effective barrier against corrosion. This is the case of corrosion production, and many others. Another important relationship
of lead sheathing for power and communications cables in a soil between the salt in the soil and corrosion has to do with biologi-
solution that contains SO4-2. This protective effect also has been cal activity. Because the growth of plants and microorganisms
reported for metallized zinc coatings on ductile iron pipe in depend on the proper inorganic mineral nutrients, the action of
which a protective layer was formed consisting of zinc carbonate, these forms of life varies with the salt content of the soil.
oxy-chloride of zinc, and other complex combinations.14
The most corrosive anion for metals is the chloride ion
MICROBIOLOGICAL ACTIVITY
(Cl-), which usually is naturally present in soils and sands of the
The role of microbes or bacteria in the corrosion of metals is due
marine-coastal regions, or it may be present as a result of exter-
to the chemical activities associated with their metabolism,
nal sources, such as de-icing salts applied to roadways. Its attack
growth, and reproduction. For example, the MIC of metals by
is localized and more dangerous than the uniform corrosion,
SRB is a recognized problem in pipelines. These bacteria are
because the formed pits could perforate the metal surface. The
anaerobic and live in poorly drained wet soils, with a pH from
chloride ion concentration in corrosive soil electrolytes (mois-
6 to 8, that contain sulfate ions, organic compounds, and miner-
ture) varies as soil conditions alternate between wet and dry, and
als in the absence of oxygen and temperature from 20 C to
can significantly affect the soil resistivity. ASTM D512, Standard
30 C. In well-aerated soils, the anaerobic bacteria cause no prob-
Test Methods for Chloride Ion in Water, may be used to analyze
lem. During metabolism of the bacteria, oxygen is extracted from
for chloride ions in water.
the sulfate ions, and this reaction converts the soluble sulfates to
Sufficient chloride ion concentration can destroy the passiv-
sulfides, which attack the metal surface, forming, for example,
ation of steel embedded in concrete and initiate corrosion if oxy-
iron sulfide (FeS). Numerous studies have established the rela-
gen is also present at the steel surface. Where concrete cylinder
tionship of sulfides and sulfates to bacterial activity in microbio-
pipe are to be buried in soils with resistivity readings below 1,500
logically induced metal corrosion.16–22
ohm-cm and the water soluble chloride contents exceed 400
The corrosive microbial effect on metals can be attributed
ppm at those same locations, corrosion protection in the form of
to removal of electrons from the metal and formation of corro-
a moisture barrier, silica fume addition, or cathodic protection
sion products principally by the following:
(CP) is recommended.15
Compared with the corrosion aggressivity of chloride ions,
• Direct chemical action of metabolic products, such as sulfuric
sulfate ions generally are considered to be less aggressive for iron
acid, inorganic or organic sulfides, and chelating agents, such
and steel. They can be converted, however, into highly corrosive
as organic acids; and
sulfide ions by anaerobic SRB. Soil test procedures in Appendix
IX of ASTM A674 includes a quantitative sodium azide-iodine • Changes in oxygen content, salt concentration, and pH that
test for sulfides as an indicator of the presence of SRB. increase the possibilities for differential diffusion and concen-
According to American Water Works Association (AWWA) tration gradients, which establish local electrochemical corro-
Manual M9, Concrete Pressure Pipe, sion cells.
Instances of sulfate attack on concrete or mortar are Anaerobic bacteria have been reported to accelerate the
generally limited to partially buried structures in soils normal corrosion process and convert noncorrosive soil to an
containing high concentrations of sodium, magnesium, or aggressive environment (fig. 9). The environmental conditions
calcium sulfate. For buried concrete pipe installations in under which the microorganisms normally operate are as fol-
soils with more than 2,000 ppm sulfate, cement with a lows: temperature from 20 C to 30 C, pH from 6 to 8, and soil
tricalcium aluminate (C3A) content not exceeding 5 percent
should be specified. For installations of mortar-coated pipe
in soils with more than 5,000 ppm water-soluble sulfates, FIG. 9 Localized corrosion attack on a buried pipe accelerated
use of both low C3A cement and a barrier material should by the presence of SRB.
be considered.15
In some cases, the presence of sulfides such as hydrogen sul-

fide (H2S) also should be determined. The ion concentration is
measured in a water soil extract using various analytical techni-
ques. Slightly alkaline ground water usually contains Naþ, Ca2þ,
Mg2þ, SO42, and HCO3 ions, as part of the dissolved salts
(<1,000 mg/L or in a higher range of 1,000–10,000 mg/L). In
slightly acidic water, the principal ions are Naþ, Ca2þ, Mg2þ,
and HCCV, with a lower concentration of total dissolved solids
of <100 mg/L.
The salt content of soil may be altered by several human
activities, such as fertilizer use in heavy doses, industrial wastes,
deicing salts on road and walkways, salt brines from petroleum
resistivity from 500 to 20,000 ohm-cm. Rate and extent of corro- previous factors may create conditions for accelerated localized
sion are related directly to bacterial growth in contact with the corrosion attack.
metallic surface. Bacteria have been found that are capable of
growing on many kinds of coating materials, including hydrocar-
bons. One survey reported that MIC was responsible for 27% of Corrosion in Soils
the corrosion deposits on the exterior of line pipe.12 The metal corrosion in soils is aqueous (in an electrolyte) and its
National Association of Corrosion Engineers (NACE) mechanism is electrochemical.1–6,8,9,11,23 It is generally accepted
TM0106-2016, Detection, Testing, and Evaluation of Microbio- that four elements are necessary for the formation and operation
logically Influenced Corrosion (MIC) on External Surfaces of of an electrochemical corrosion cell: an anode, a cathode, an
Buried Pipelines, states the following: electrolyte, and a metallic path. The terms are defined by NACE/
ASTM G193, Standard Terminology and Acronyms Relating to
Microbiologically influenced corrosion (MIC) is corrosion Corrosion, as follows:
caused by the presence or activity (or both) of microorgan-
isms in biofilms on the surface of the corroding material. Electrochemical cell: an electrochemical system consisting of an
Many materials, including most metals and some nonme- anode and a cathode in metallic contact and immersed in an
tals, can be degraded in this manner. Microbiologically electrolyte.
mediated reactions can alter both rates and types of elec- Anode: the electrode of an electrochemical cell at which oxida-
trochemical reactions in a corrosion cell. These reactions tion occurs. (Electrons flow away from the anode in the exter-
influence pitting, crevice corrosion, differential aeration nal circuit. It is usually the electrode where corrosion occurs
cells, concentration cells, de-alloying, and galvanic corro- and metal ions enter solution.)
sion. Therefore, MIC investigations require microbiological, Cathode: the electrode of an electrochemical cell at which reduc-
chemical, and metallurgical testing for proper diagnosis. tion is the principal reaction. (Electrons flow toward the cath-
The conclusion that MIC has taken place should be based ode in the external circuit.)
on the preponderance of circumstantial evidence. Electrolyte: a chemical substance containing ions that migrate in
MIC typically takes place in the presence of microbial an electric field.
consortia that are comprised of more than one physiological
type of microorganism. Depending on the environment, The electrochemical corrosion of metals buried in wet soils is
these microbes may include metal-oxidizing bacteria, based on the creation of multiple corrosion cells, formed by cou-
sulfate-reducing prokaryotes (SRP), acid-producing bacteria pled anodes and cathodes. The cathodes are characterized by metal
(APB), metal-reducing bacteria (MRB), and methanogens areas with a higher level of potential energy (Gibbs free energy)
that interact in complex ways within the structure of the and the anodes have a lower potential energy. This energy differ-
biofilm. MIC does not produce a unique form or morphol- ence between anodes and cathodes sites usually is due to the het-
ogy of corrosion. Instead, MIC can result in pitting, crevice erogeneity of composition of the metal structure. The soil in which
corrosion, underdeposit corrosion (UDC), and de-alloying, the metal resides also could contribute to corrosion cell formation.
in addition to galvanic corrosion.12 The metal corrosion is an oxidation process and it occurs at
the anode areas where the metal goes into soil moisture as metal
Test methods and procedures for evaluating external MIC cation (ion), leaving electrons. The principal anodic reaction is
include but are not limited to the following: microbiological cul- as follows:
ture testing, general microscopy, epifluorescent microscopy,
adenosine triphosphate photometry (ATP), hydrogenase meas- M ! Mnþ þ ne
urements, adenosine phosphosulfate reductase (APS), molecular ði:e:; Festeel ! Fe2þ þ 2e Þ
microbiological methods (MMM; also referred to as genetic
methods), organic acid analysis, and chemical analysis. See also The generated free electrons flow through the metal to the
chapter 35, “Microbiological Effects,” of this manual for addi- cathode areas, where they are accepted by oxidizing agents, such
tional information. as air oxygen dissolved in the moisture. The oxidizing agents
undergo a reduction process in the cathodic reaction:
DISTURBANCE OF NATURAL SOILS O2 þ 2H2 O þ 4e ! 4OH

Experience shows that the pipeline ditch markedly disturbs natu-
In weak acid soils, the cathodic reaction involves the partici-
ral soil. The operation of ditching and backfilling create several
pation of oxygen molecules and hydrogen ions (Hþ):
zones around the metal structure. The soil in the ditch is less
compact and sometimes the disturbed soil is a mixture of surface O2 þ 4Hþ þ 4e ! 2H2 O
and subsurface soils. This new heterogeneous soil environment
may have higher moisture content, increased aeration, and In strong acid soil the principal oxidizing agent is the
microbial population, which may result in differential aeration hydrogen cation:
or concentration corrosion cells developing. Contact with
organic matter in coatings applied over the pipeline and the 2Hþ þ 2e ! H2 "
SOILS 225
Sometimes pipes are buried with mill scale (FeO and Fe3O4
FIG. 10 A metallic pipe is anodic in wet soil with a lower oxygen gray oxide layer) that is formed on their surface as a product of
content and cathodic in better oxygenated soil. high-temperature chemical corrosion during hot-rolling produc-
tion and thermal treatments. This layer is an efficient protective
coating for the metal, because it is resistant to corrosion and it is
quite adherent. It is brittle, however, and its structure presents a
lot of heterogeneity and cracks that contribute to creation of local
corrosion cells at the interface metal or scale. The scale oxides are
electronic semiconductors, and they can serve as cathodes. Areas
covered with scale are more cathodic than those in which the
metal is not covered and open to the environment. Such bare area
can be a perfect anode for a corrosion cell (fig. 13).
If the buried metal structure involves contact between dif-
ferent metals (e.g., mild steel, copper, bronze, brass, aluminum,
Different oxygen contents in the soil moisture at the metal
zinc, lead, SS, cast iron), it is possible that local galvanic cells can
surface can create local oxygen concentration cells. Wet soil with
form in the contact areas (fig. 14 and fig. 15). Each metal has its
lower oxygen usually gives rise to anodic areas, whereas well-
own tendency to corrode. An alternative way to express the
aerated soils form cathodic areas on the metal surface (fig. 10). In
metal reactivity is to look at the excess of its free energy (stan-
most cases, when the metal structure is exposed to different tem-
dard electrochemical metal potential) and predict the electromo-
peratures, the areas at higher temperatures become anodes and
tive force (emf) between metals in contact, as a general
those at lower temperatures become cathodes. Because soils usu-
indication for the corrosion process (table 5). The metal that has
ally are a mixture of different kinds of soils, they often provide
a more positive potential is nobler in the galvanic cell, and it is a
no uniform environment for the metal structure. This heteroge-
cathode. The metal with a more negative potential is more active
neous environment creates different and local aeration zones on
and acts as an anode in the corrosion cell (e.g., it suffers
the metal surface, and as a consequence, can cause serious local-
corrosion).
ized corrosion attack (fig. 11 and fig. 12).
As corrosion proceeds, the steel changes its surface
physical-chemical properties because of the formed corrosion
layer. Insoluble corrosion products partially act as a physical bar-
FIG. 11 Oxygen concentration corrosion cells caused by a rier against the corrosion process. In this case, when a new
mixture of different soils.
FIG. 13 Corrosion cell created on metal surface due to the

presence of heterogeneity in the formed corrosion layer.
FIG. 12 General view of corrosion attack in soil at local aeration

zones.
FIG. 14 Galvanic corrosion caused by contact of dissimilar metals.

Steel is the anode, which suffers corrosion, and brass is
the cathode. Electrons leave the steel and flow to brass.
FIG. 15 Galvanic corrosion attack produced on the surface of TABLE 5 Electromotive Series of Metals (continued)
buried pipe.
Metal Metal / Formed Ion Potential, Va
Palladium Pd/Pd þþþþ þ 0.86

Gold (auric) Au / Au þþþ þ 1.36
Gold (auras) Au / Au þ þ 1.50
a
The metal that has a more positive potential is more noble in a galvanic cell
between two metals, and it is the cathode. A more negative potential corre-
sponds to the more active anodic metal. The state of oxidation of the metal ion
(cation) is equal to the number of electrons liberated by the metal during the
anodic corrosion process, for example: Ni ¼> Ni2þ þ 2e.
repaired part of steel is connected to old steel, which has been in

the soil for a relatively long time, the new section suffers corro-
sion because it is anodic with respect to old steel, even when the
steel composition is identical.
STRAY CURRENT CORROSION

Stray currents, picked up by a buried structure, also can cause
TABLE 5 Electromotive Series of Metals metal corrosion. They are usually direct electric currents (dc)
deflected from their principal service. Sources of stray currents
could be direct current equipment and systems, such as electric
Metal Metal / Formed Ion Potential, Va
railway systems, grounded dc power supplies, electric welders,
Lithium Li / Li þ 2.96
CP systems for underground natural gas pipelines, and electro-
Rubidium RbRb þ 2.93
plating plants that are not well insulated from the earth. The
Potassium K/K þ 2.92
metal structure suffers severe stray current corrosion at the area
Strontium Sr/Sr þþ 2.92
where the stray current discharges and leaves the metal, as it
Barium Ba/Ba þþ 2.90
seeks for a new low resistance path. As shown in figure 16, when
Calcium Ca/Ca þþ 2.87
tracks are laid at ground level and not insulated well from the
Sodium Na / Na þ 2.71
earth, some part of the load current enters the ground where the
Aluminum Al / Al þþþ 1.70
tracks are most positive (at the load) and follows an earth path
Beryllium Be/Be þþ 1.69
back to the substation. The stray current corrosion looks like pit-
Manganese Mn/Mnþþ 1.10
ting on an otherwise-smooth surface where the stray current is
Zinc Zn / Zn þþ 0.76
discharged. Figure 17 is a photo of stray current corrosion on a
Chromium Cr/Cr þþ 0.56
ductile iron pipe joint. Corrosion occurred at the rubber gasketed
Iron (Ferrous) Fe/Fe þþ 0.44
joint, which increased resistivity of the pipeline and caused
Cadmium Cd / Cd þþ 0.40
the current to seek an alternate lower resistivity return path.
Indium In / In þþþ 0.34
Stray current prevention measures include corrective design
Thallium Tl m þ 0.33
Cobalt Co / Co þþ 0.28
Nickel Ni/Ni þþ 0.23
Tin Sn / Sn þþ 0.14 FIG. 16 Stray current in street railways. The area near the
Lead Pb/Pb þþ 0.12 substation, where a current flowing in a pipeline leaves
Iron (ferric) Fe / Fe þþþ 0.04 its surface to return to the negative bus, can suffer severe
Hydrogen H2/H þ 0.00 corrosion attack.
Antimony Sb/Sb þþþ þ 0.10
Bismuth Bi / Bi þþþ þ 0.23
Arsenic As /As þþþ þ 0.30
Copper (cupric) Cu / Cu þþ þ 0.34
Copper (cuprous) Cu/Cu þ þ 0.47
Tellurium Te / Te þþþþ þ 0.56
Silver Ag/Ag þ þ 0.80
Mercury Hg/Hgþþ þ 0.80
Platinum Pt/ Pt þþþþ þ 0.82
(continued)
SOILS 227
often mask the pits. Soils in marine-coastal environments con-

FIG. 17 Stray current corrosion failure on ductile iron pipe joint. taining relatively high concentrations of chloride ions (active
Corrosion occurred where dc currents left the pipe and anions) cause chloride-induced pitting corrosion on the metal
entered the soil. Source: Photo courtesy of U.S. Pipe and structure. Once a pit initiates, an active corrosion cell is set
Foundry. up as shown in figure 19. The rapid dissolution of metal in
the pit produces an excess of positive metal ions, which hydro-
lyze in the water solution, causing a high concentration of
hydrogen ions. The cause of pitting could be associated with
local inhomogeneity on the metal surface, mechanical or chem-
ical defects (holidays) in a protective organic or oxide coating
(Fig. 20), galvanic corrosion, or the presence of biological
organisms. Pitting corrosion occurs most commonly in buried
metals and alloys.
Some specific corrosion environments, in the presence of
applied tensile stress on the metal surface (above some threshold
value), can cause stress-corrosion cracking (SCC). The source of
stresses can be external, but residual stresses can also cause SCC
failures. Specific corrosive pollutants, which may contribute to
the SCC of carbon steels, are for example, the carbonates in
water. Sulfide stress cracking (SSC) commonly occurs on the
FIG. 19 Pit action and active pitting cell.

modifications, repair of electrical systems, corrective drainage,
and good insulation. Lead pipelines and lead cable sheathing also
can suffer severe stray current corrosion caused by minor earth
currents.
PITTING CORROSION
In certain specific soil chemistries, the metal corrosion may be
nonuniform, concentrated in relatively small areas that form
sharply defined local holes called pits (fig. 18) that grow deep into
the metal and can cause failure by perforation. The pits are usually
small in diameter, isolated from each other, and occur in more
anodic metal areas with respect to the rest of the surface. The pit-
ting corrosion is a dangerous form of localized metal attack and
FIG. 20 Localized corrosion on buried metal structure,
sometimes cannot be detected by simple visual examination.
concentrated at holidays (defects) of the coated surface.
For example, when pitting corrosion occurs along with
Source: Photo courtesy of Corrpro, an Aegion Company.
slight or moderate general corrosion, the corrosion products
FIG. 18 General view of localized pitting corrosion on an

underground pipe surface. Source: Photo courtesy of
Corrpro, an Aegion Company.
outside of a pipe where SRB are present at a soil pH of 3–7. Coatings of coal tar, coal tar/epoxy, extruded polyethylene, tape
Because of the produced FeS, which adsorbs readily on the steel wraps, polyurethane, or fusion-bonded epoxy powders are used
surface, hydrogen atoms generated during the cathodic corrosion to ensure a passive metal protection, isolating the metal from the
reaction cannot combine to form molecular hydrogen, and soil environment, and also to decrease the current required for
therefore, enter into the iron crystal, causing hydrogen embrittle- CP. Several references provide a more detailed discussion of CP
ment and initiating microcracks. and coatings for carbon steel.9,11,25,26
SS also is used as a material for buried metal structures. In
GENERAL METHODS FOR CORROSION principle, the SS should be in the passive state in soils, because of
PROTECTION the naturally formed resistive oxide layer on its surface, com-
The electrochemical corrosion of metals occurs at the metal– posed of oxides of different alloying elements (nickel, chromium,
corrosive electrolyte (metal–soil moisture) interface. Conse- molybdenum, copper) and iron. The presence of chloride in the
quently, the first group of methods for corrosion protection aims soil, however, can cause SS to pit or corrode in crevices, so this
to create an efficient separation of the metal from the aggressive material should be avoided in chloride-containing soils. It is also
environment, using metallic, organic, and inorganic coatings. known that SS can be attacked by certain species of microbes,
Organic and inorganic coatings often are used in conjunc- contributing to MIC. An increase in chromium content of steel
tion with CP. From the thermodynamic point of view, some met- decreases the observed weight loss in a variety of soils, but above
als can be polarized in a range of potentials where the metal 6% chromium, the depth of pitting increases.
enters into an immune (no corrosion) or passive state (creation
of resistant oxides). These states could be achieved, respectively, DUCTILE IRON PIPE IN SOILS
by cathodic and anodic electrochemical methods of protection, Ductile iron piping is used primarily in water and wastewater
applying external polarization (potential) using dc. Pourbaix dia- service. The primary method of external corrosion control is
grams provide useful thermodynamic information on the possi- polyethylene encasement installed in accordance with ASTM
ble metal states using metal potential-pH of water solution A674. In Europe, the primary method for corrosion protec-
coordinates. tion for ductile iron pipe has been metallic zinc coatings for
When it is economically and technically feasible, a third typical soils supplemented with polyethylene encasement for
method includes modification or chemical treatment of the cor- aggressive soils. Recently in the United States, an enhanced
rosive environment, to decrease its aggressiveness, by changing polyethylene encasement infused with corrosion inhibitor and
its pH, salt, and moisture content; oxygen content; existing antimicrobial additives has become commercially available. CP,
microbes; and existing bacteria. An example of environment with and without coatings and polyethylene encasement, also
modification which is described in ASTM G218, Standard Guide has been used. Several references provide a more detailed dis-
for External Corrosion Protection of Ductile Iron Pipe Utilizing cussion of corrosion protection methods for ductile iron pipe in
Polyethylene Encasement Supplemented by Cathodic Protection is soils.7,9,10,14,26,27
the use of a corrosion inhibitor and antimicrobial enhanced
polyethylene encasement film to wrap ductile iron pipe in corro- CONCRETE PRESSURE PIPE IN SOILS
sive soils.7 Concrete pressure piping is used primarily in water and waste-
A fourth method is decreasing the metal activity, by alloying water service. Types include pre-stressed concrete cylinder pipe
with metals, like chromium, nickel, molybdenum, cobalt, tita- (AWWA C301), reinforced concrete cylinder pipe (AWWA
nium, and copper, that usually form passive oxide layers and C300), reinforced concrete noncylinder pipe (AWWA C302),
that are resistant in a given environment. and concrete bar-wrapped cylinder pipe (AWWA C303). Vari-
ous corrosion control recommendations are given based on pH,
STEELS IN SOILS carbon dioxide content, chloride content, and sulfate content of
One of the most frequently used materials for buried metal struc- the soils. Corrosion control recommendations include moisture
tures is carbon steels. For prevention of their corrosion the most barrier, bonded joints, a system to monitor corrosion activity,
recommended method is CP, which normally is used in conjunc- CP, silica fume addition equal to 8–10% of concrete, membrane,
tion with coatings. The use of CP is now standard procedure for sealer, barrier coating, consolidated limestone, and consolidated
long-term corrosion protection of underground regulated pipe- clay. Several references provide a more detailed discussion of
lines, oil and gasoline tanks, and other structures. With a shift of corrosion protection methods for concrete pressure pipe.9,15,24,26
the metal potential to more of a negative value of -0.85 V versus
a copper/copper sulfate (Cu/CuSO4) reference electrode, it is LEAD IN SOILS
possible to make the metal surface a cathode, which ensures an Another metal with a successful service record in soils is lead.
immune state of the carbon steel. Cathodic polarization is Thousands of kilometers of lead-sheathed power and communi-
achieved by dc, which can be supplied either by sacrificial anodes cation cables and lead pipes have shown good performance
in galvanic contact with the steel structure, or by impressed cur- underground. They are directly buried in the ground or installed
rent from a rectifier. in ducts or conduits. Lead corrodes less on the average than does
Some organic coatings like polymers, plastics, and rubbers, steel. Most of the initially formed corrosion products of lead are
other than paint, are used to advantage along with CP of steels. relatively insoluble salts, such as carbonates, silicates, or sulfates.
SOILS 229
They are deposited on the lead surface and ensure compact and
dense protective layers for the metal. The formation of such a FIG. 21 Apparatus for conducting ASTM G162.
layer is responsible for the high resistance of lead to corrosion.
Because of its less negative potential (table 5), the lead is cathodic
when connected to steel (except for strongly alkaline environ-
ments), aluminum, zinc, or cadmium, and thus will accelerate
the corrosion process of these metals. Only in galvanic contact
with copper, SS, and titanium, will lead be an anode in the
formed corrosion cell and suffer corrosion attack. In poorly aer-
ated soils or soils high in organic acids, the corrosion rate may
be four to six times higher than the average. Other factors that
may accelerate the corrosion of lead are stray currents, microor- or to determine the soil corrosivity.32–36 These tests can be car-
ganisms (like SRB), a high concentration of hydroxides (e.g., up ried out in water extract of soil or in water-saturated soil, when
to 1,000 ppm in a wet concrete tunnel), and contact with acetic all dissolved salts (ions) are present.
acid (in a wooden duct). CP criteria and test methods are given Electrochemical test methods and practices are described in
in NACE RP0194, Criteria and Test Methods for Cathodic Protec- several of the following ASTM Tests Methods and Practices:
tion of Lead Sheath Cable.28
• ASTM G3, Standard Practice for Conventions Applicable to
COPPER IN SOILS Electrochemical Measurements in Corrosion Testing
Copper is another metal used for underground cables and it
• ASTM G5, Standard Reference Test Method for Making Poten-
usually has very good corrosion resistance. Copper, on average,
tiostatic and Potentiodynamic Anodic Polarization
corrodes at about one-sixth the rate of iron, but in tidal marsh,
Measurements
the rate is higher than in most other soils (i.e., about half that
of iron). When connected to buried steel or iron, the copper • ASTM G59, Standard Test Method for Conducting Potentiody-
will be a cathode of the galvanic cell and will not suffer any namic Polarization Resistance Measurements
corrosion. • ASTM G61, Standard Test Method for Conducting Cyclic
Potentiodynamic Polarization Measurements for Localized
Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based
Laboratory Corrosion Testing Alloys
in Soils • ASTM G71, Standard Guide for Conducting and Evaluating
Galvanic Corrosion Tests in Electrolytes
LABORATORY SOIL BOX CORROSION TESTING
• ASTM G102, Standard Practice for Calculation of Corrosion
ASTM G162, Standard Practice for Conducting and Evaluating
Rates and Related Information from Electrochemical
Laboratory Corrosion Tests in Soils, covers procedures for con-
Measurements
ducting laboratory corrosion tests in soils to evaluate the corro-
sive attack on engineering materials.29–31 The test is conducted • ASTM G106, Standard Practice for Verification of Algorithm
under laboratory ambient temperature unless the effect of tem- and Equipment for Electrochemical Impedance Measurements
perature is being evaluated. It does not include provisions for • ASTM G148, Standard Practice for Evaluation of Hydrogen
MIC testing, nor its influence on results. Structures and compo- Uptake, Permeation, and Transport in Metals by an Electro-
nents may be made of several different metals; therefore, the chemical Technique
practice may be used in conjunction with ASTM G71, Standard
Guide for Conducting and Evaluating Galvanic Corrosion Tests These standard methods and practices provide the necessary
in Electrolytes, to evaluate galvanic corrosion effects. This prac- information for electrochemical potentiostatic and potentio-
tice also may be used in conjunction with ASTM G46, Standard dynamic anodic measurements, calculation of corrosion rate
Guide for Examination and Evaluation of Pitting Corrosion, to from electrochemical measurements, and conducting potentio-
evaluate pitting corrosion. A minimum of 40 cm3 soil is specified dynamic polarization resistance measurements. Recently, electro-
to be used for each 1 cm2 of exposed metal surface area (fig. 21). chemical impedance spectroscopy (EIS) has been introduced for
This practice is used to determine corrosion rates based on corrosion measurements of steel structures corroding in soils.
weight loss, pitting corrosion, galvanic corrosion effects, effect of These tests can be performed using a commercial potentiostat,
defective metallic coatings, effect of defective or incompletely appropriate computer software for analysis of the results, a stan-
covering coatings and jackets, and the effect of multiple types of dard electrochemical cell, a platinum or carbon counter electrode
soils on specific materials. (CE), a reference electrode, and a sample of the metal as a work-
ing electrode (WE). Figure 22 presents a general view of equip-
ELECTROCHEMICAL LABORATORY TESTS ment in use for electrochemical measurements, figure 23 shows a
Several electrochemical tests have been used successfully over the standard electrochemical test cell as described in ASTM G5, and
years to estimate the corrosion behavior of a given metal in soil figure 24 shows a test cell specially constructed to conduct
FIG. 22 General view of equipment for electrochemical FIG. 24 Special electrochemical test cell constructed to conduct
36
measurements. Source: Photo courtesy of U.S. testing in soil and drilling fluids. Source: Photo courtesy
Pipe and Foundry. of U.S. Pipe and Foundry.
FIG. 23 Standard electrochemical test cell as described in

ASTM G5.
controlled site testing. At a controlled exposure site, metal sam-

ples are intentionally exposed so that control of variables such
as specimen surface area and size, depth of burial, minimum
electrical and mechanical interference, and site accessibility are
maximized. The design of this type of site allows for retrieval of
specimens from the ground without interrupting services, as
may be the case with a real structure. In an uncontrolled expo-
sure site, these variables may be in question, and this situation
usually applies to any real underground structure. For example,
the surface area of an underground pipeline is difficult to deter-
mine, because from the standpoint of electrochemical polariza-
tion measurements, the pipeline is of infinite length. In
addition, electrical isolation from other structures or services
may not be possible with an underground system in use. In
general, techniques for measuring corrosion are the same for
electrochemical corrosion testing in soils and horizontal direc-
controlled and uncontrolled sites, but some precautions and
tional drilling fluids.36
limitations must be kept in mind when these techniques are
applied to real structures, and these will be discussed where
appropriate. Assessing the corrosion of buried steel tanks is
Field Burial Corrosion Testing complicated by the presence of internal corrosion as well as
external wall deterioration. This special case is addressed in
Underground corrosion is particularly insidious in that, gener-
ASTM G158, Standard Guide for Three Methods of Assessing
ally, we are not aware of its progress until a failure occurs. Physi-
Buried Steel Tanks.
cal and electrochemical techniques are available, however, that
will provide information on corrosion processes.29–31,37–54 Physi-
cal measurements furnish cumulative corrosion information MAINTAINING RECORDS
obtained at the final removal stage, while monitoring and elec- Determining corrosion performance of metals in underground
trochemical measurements supply data during the period of environments generally requires long-term testing, sometimes
exposure to soil. exposures of several years or even decades. Such long-term stud-
This section on field testing will concentrate on the types ies make it imperative that information be maintained in a read-
of underground corrosion measurements that can be made in able, accessible, permanent system. Experience has shown that a
controlled and uncontrolled conditions, with an emphasis on bound notebook with numbered pages is one format that has
SOILS 231
proven successful for keeping these records. These data must CONSIDERATIONS FOR PHYSICAL MEASUREMENTS
include the exact location of the test site and its configuration. Weight loss, pit depth, or wall thickness determinations are
Identifying the location of the site with reference to survey physical measurements used as a reference to correlate nonde-
markers or other reliable long-term features may be warranted, structive electrochemical techniques. Physical measurements are
and this becomes more important as the length of exposure is considered destructive because, generally, the specimen must be
increased. Computer files are invaluable for organizing and removed from the site and cleaned. The process of extraction
examining data, but they are a poor format for long-term storage and preparation for examination changes the surface condition
of data. Changes in computer equipment, software, or damage of the specimen, effectively destroying the possibility of continu-
may make it difficult or impossible to access old data files. For ing the exposure test with that particular specimen. Nevertheless,
this reason, hard paper copies of burial plots and records are rec- to rely solely on electrochemical measurements can result in mis-
ommended to supplement electronic records. The importance of leading information, and it is strongly recommended that the
maintaining good records cannot be overemphasized. test design include some form of physical verification of nonde-
Using global positioning satellite (GPS) technology, a structive measurements. To obtain corrosion data from physical
point on the surface of the earth can be identified with an error measurements during long-term exposures, it is common prac-
of less than 61 m, making it an attractive means of identifying tice to place enough samples in the ground to allow for removals
the location of buried specimens. One test site out of the direct at intervals of time. The most meaningful data are obtained
control of this author was paved over for parking motorized when duplicate samples are used for each removal, allowing for
equipment, and survey information allowed for successful data averaging and providing a better representation of material
retrieval of the specimens. Specimen surface treatment, heat performance.
treatment, and identification marks must be carefully described
in these records. Photographic records during all phases of BURIAL SITE
preparation and burial are useful for future site and specimen Choosing the correct burial site is important, because the envi-
evaluation. ronment will have a direct effect on the performance of buried
materials. This choice must take into account more than just
SPECIMEN DESIGN characteristics of a soil and long-term availability; it also must
The design of specimens is determined by several factors, such as include consideration of local conditions of temperature, rainfall,
the form of corrosion expected (e.g., uniform corrosion, pitting), and location. For example, a soil located in a valley near a stream
the type of structure in question (e.g., pipe, tank), and the meas- provides a different environment to the same soil on a nearby
urements necessary for obtaining the data. Measurement hill. In general, the best test site is near the structure in question.
requirements for determining the loss in a cross section of a Such a site has the added advantage that measurements can be
structural H-pile are different from measurements designed to made on the real structure, which then can be compared to data
examine pitting of a pipeline material. In general, the larger the obtained from controlled specimens nearby. Where a variety of
sample exposed, the better the data, but a size limitation may be soils are encountered, several soil sites may be needed. If only
imposed by the measurements. Weight loss data requires weigh- one site is chosen, then the site with the worst-case conditions
ing a specimen before and after exposure, and for this type of will provide the most conservative data. Where anaerobic bacte-
data, the size and weight of a sample is limited by the capabilities rial corrosion is of concern, redox potential measurements of the
of the weighing equipment. Surface preparation of a sample soil can identify the sites where these bacteria are most likely to
must be considered. If the sample is a simulation of a real struc- be present.44 Soil characterization and testing methods are dis-
ture, then care should be taken to ensure that the specimen sur- cussed in other sections of this chapter.
face is representative of that structure. Thus, chemical cleaning,
abrading, and polishing of the specimen surface may be undesir- SPECIMEN EMPLACEMENT
able if the real structure is not subjected to the same surface The manner in which a sample is buried is influenced by the
treatment. For evaluation of pipeline materials, a segment of the configuration of the specimens. For example, steel piling speci-
pipe with endcaps to protect the interior may be the most suit- mens are driven into the ground with pile drivers, whereas small
able design for a test specimen. It is also common practice to use specimens will most likely be buried in trenches dug with a back
sheet material for specimens, where sheet metal is used to pro- hoe. A typical steel pile test site involves the placement of five
duce containers such as holding tanks. Where welds are encoun- pilings in a 2-m radius circle around a sixth centrally located
tered, it is valuable to include specimens with welded sections in pile, as illustrated in figure 25.45 The central pile was used as a CE
the burial test. Coated panels and coated panels with intentional during electrochemical polarization measurements of the other
breaks in the coating may be desirable. Galvanic coupling of piles, as will be explained later. The top of each pile was 0.6 m
specimens is also a consideration, where two unlike metals are below ground level, and a steel rod that extended to just below
expected to be in contact. Stressed U-bend or C-ring type speci- the surface of the ground was welded to the top of each pile. A
mens are used for studies of stress corrosion failures. Specimen removable concrete marker, extending above ground, was placed
identification marks stamped or scribed must be easy to read. over the rod to help locate the steel rod. Because the study
Thus, the design of the specimen is tailored to meet the needs of included an examination of the effect of disturbed soil, a seventh
the study. pile was buried horizontally in a nearby trench.
FIG. 25 Typical view of steel pile placement at an underground FIG. 27 Specimens for a given removal can be grouped together
test site. in one section of the trench, so that when a group is
retrieved, those remaining are not disturbed during
digging. Source: Photo courtesy of U.S. Pipe and
Foundry.
Small specimens can be buried in a long, narrow excavation

made by a backhoe, as shown in figure 26. Such a trench is typi-
cally 1–2 m deep and is as wide and long as necessary to accom-
modate the specimens placed along the length of the trench. In
cases in which several retrievals are to be made over a period of
time, specimens for a given removal can be grouped together in FIG. 28 Commercially available test stations used for
one section of the trench, so that when a group is retrieved, those aboveground monitoring wire attachment. Source:
remaining are not disturbed during digging (fig. 27). In cases in Photo courtesy of U.S. Pipe and Foundry.
which electrical wires from specimens extend above ground,
commercially available test stations, as shown in figure 28, are
commonly used. Wood posts also may be used to serve as
markers and hold the wires. Untreated wood is recommended,
because leaching of chemicals from treated wood will modify the
surrounding soil and possibly affect the results of the corrosion
test. It is especially important to avoid placing wood treated with
copper salts near aluminum specimens, because it is known that
copper ions accelerate the corrosion of aluminum. Retrieval of
specimens without wires may be simplified by tying specimens
together with a small-diameter plastic cord and attaching the
cord to wood posts. In this way, finding the cord or one
FIG. 26 Long narrow trench used for burial of corrosion test specimen allows retrieval of all other specimens in a group.
specimens. Source: Photo courtesy of U.S. Pipe and Wooden posts can be used as trench markers to delineate groups
Foundry. of specimens, or metal markers can be located just below the
ground surface and later can be found using a metal detector.
More than one system of specimen identification should be
incorporated in the test. For example, stamping identification
characters on the specimen and on an attached plastic label
reduces problems of identification in the future. In addition,
specimens can be buried in a known sequence for further verifi-
cation of identity.
SPECIMEN RETRIEVAL
Immediately after excavation, a rapid superficial cleaning of
specimens with a scrubbing brush and water allows for easy
removal of oxides and soil–oxide conglomerates that harden as
they dry, making later cleaning difficult. An immediate cursory
examination of specimens on initial removal, coupled with pho-
tographic documentation, has several advantages. This examina-
tion can become important in those unfortunate cases in which
SOILS 233
specimens are lost or damaged in transit. Furthermore, although of data is most meaningful when corrosion is uniform over the
identification of a specimen may be obvious on removal, it may be surface of the specimen, because normally the entire exposed
difficult later if tags are separated or lost, and thus documentation surface area of the specimen is used for calculating corrosion
with photographs or notes becomes crucial for identification. In rate. If corrosion attack is localized and the total exposed sur-
cases in which specimens have corroded to the point of separation, face area is used for the corrosion rate calculation, then the
it is important to tag the parts for later identification, and this result will underestimate penetration. One possible way around
may include placing specimens in envelopes or bags. In some this problem is to measure the area where the localized attack
cases, metal specimens undergo surface changes after retrieval, has occurred and use this corrected area in the calculation of
especially if there is a long period of time between removal and corrosion rate. Possible sources of error in weight loss determi-
final examination, and photographs help identify those instances nations are (1) excessive removal of metal during cleaning,
in which this happens, allowing the examiner to differentiate (2) inadequate cleaning of specimen, and (3) using the total
between burial damage and damage from subsequent handling. surface area for calculating corrosion rate when the attack is
This can be especially important in cases in which coatings are localized.
involved in the test. Thus, the employment of some precautions A typical approach that has been used to determine weight
and documentation on initial removal of specimens will save time loss of specimens through physical measurements is as follows.
and effort in subsequent examination procedures. Small steel coupons, weighing approximately 200 g, were
Some information can be obtained from the soil at the time exposed to a soil environment. The samples were weighed
of sample extraction. For example, soil conditions may vary before and after exposure. Prior to the “after exposure” weigh-
along the length of a trench, resulting in a variation in the corro- ing, the samples were cleaned using the ASTM solution desig-
sion performance of similar samples, and these soil differences nation C.3.1, which is an inhibited hydrochloric acid solution
should be noted. In some cases, where warranted, local measure- described in detail in ASTM G1. To determine the immersion
ments of soil pH, resistivity, and redox at the depth of the speci- time necessary for the removal of the oxide, the specimens were
mens can provide insight to material performance. When in situ cleaned and weighed repeatedly, until weight loss stabilized,
pH measurements as described in ASTM G51 cannot be per- indicating that the cleaning reaction had gone to completion.
formed, the use of pH paper is an excellent method of obtaining Figure 29 shows an example of these data. Note that specimen 9
a rapid reading on a soil. Unusual conditions of pH found with required immersion of only 30 s to remove the oxide, whereas
pH paper can be verified with more traditional pH electrodes. specimen 7 took approximately 2.5 min to clean. This cleaning
The resistivity of small samples of soil can be measured using a and weighing procedure allows for monitoring of the chemical
soil cup or soil box. The use of these techniques is an excellent process and reduces the likelihood of error from removing too
way of getting information on localized soil conditions in the much base metal. ASTM G1 also provides information on the
vicinity of the specimens. Always be aware that local, small soil mathematical procedure for calculating corrosion rate from
sample readings can change dramatically from place to place in weight loss in terms of a variety of units, both English and
the same trench, and these readings must not be assumed to be metric.
representative of the soil as a whole.
CLEANING AND EXAMINATION OF SPECIMENS FIG. 29 A plot of weight loss versus time for three steel coupons
Examination of specimens at the time of excavation is a critical in inhibited hydrochloric acid, showing the initial rapid
step in the process of obtaining information from underground oxide removal and the slower dissolution of metal as a
exposure studies. As has already been suggested, it is instructive to function of time.
examine and characterize the condition of specimens before the
final cleaning process. The presence or absence of an oxide on a
corroded surface, the color of an oxide, and its location on the
metal surface provide clues to the mechanism of attack. This ini-
tial examination is followed by removal of all corrosion products
from the specimen. Fortunately, information on this difficult pro-
cess, including the removal of oxide layers with minimum sub-
strate attack, has been published by ASTM Committee G01 on
Corrosion of Metals, in ASTM G1, Standard Practice for Preparing,
Cleaning, and Evaluating Corrosion Test Specimens. This publica-
tion describes reagents and detailed chemical and electrochemical
methods for cleaning ferrous and nonferrous metallic specimens.
PHYSICAL MEASUREMENTS
Weight Loss
Determining weight loss resulting from exposure to soil is a
common technique used to measure corrosion rate. This type
Pit Depth the coating for damage. Direct assessment also gives a possibility
Obtaining information of the degree of pitting involves some for direct mechanical or ultrasonic measurement of pit depth
form of visual inspection, so that the shape, depth, and density and wall thickness change due to the corrosion. X-ray radiogra-
of pitting can be determined. Large shallow pits are relatively phy can be used to inspect welds. This technique also can show
easy to evaluate, compared with small, narrow, deep pits. The SCC and corrosion pits in the weld area where the coating has
degree of pit penetration of wide pits can be measured with a pit failed to seal the metal structure. The following NACE Standard
depth micrometer or by the use of a microscope that allows for Practices (SPs), Recommended Practices (RPs), Test Methods
measuring the change in movement of the stage when focusing (TMs), and other publications discuss direct and indirect meas-
between the bottom of the pit and the surface of the metal. urements and techniques for corrosion monitoring in soils:
Determining the shape and depth of a narrow, deep pit is more
challenging and may involve a metallographic cross-sectional • SP0104, The Use of Coupons for Cathodic Protection Monitor-
examination of the pitted area. This same metallographic tech- ing Applications
nique may be the most effective way of examining pits that get • SP0169, Control of External Corrosion on Underground or
wider with depth. A crude but effective way of measuring the Submerged Metallic Piping Systems
depth of relatively straight-line pits is to insert a small diameter
• SP0207, Performing Close-Interval Potential Surveys and DC
wire into the pit and measuring the length of penetration by the
surface Potential Gradient Surveys on Buried or Submerged
wire. In some cases, the rate of wall penetration is critical, as for
Metallic Pipelines
pipeline material, and identifying and measuring the deepest pit
is important, along with information on the average penetration • TM0497, Measurement Techniques Related to Criteria for
of the 10 deepest pits. Density of pitting can be obtained by Cathodic Protection on Underground or Submerged Metallic
counting pits in a known area or by comparing the pitted surface Piping Systems
to standard charts as described in the ASTM G46. • RP0174, Corrosion Control of Underground Residential Distri-
bution Systems
STRESS INDUCED FAILURE • RP0177, Mitigation of Alternating Current and Lightning
Determining susceptibility of a material to SCC or hydrogen Effects on Metallic Structures and Corrosion Control Systems
embrittlement in a soil environment has been studied using bur-
• RP0194, Criteria and Test Methods for Cathodic Protection of
ied U-bend specimens.46 This approach provides information on
Lead Sheath Cable
whether or not a specimen failed, but it will not reveal when,
during the exposure period, the failure occurred. One novel • RP0274, High-Voltage Electrical Inspection of Pipeline
method for the application of stress allows for monitoring the Coatings
condition of the specimen from the surface, using a steel ring • RP0285, Corrosion Control of Underground Storage Tank Sys-
located above ground level to apply the stress to a tubular tensile tems by Cathodic Protection
specimen in the soil via a steel rod.47 By monitoring the load on • RP0286, Electrical Isolation of Cathodically Protected Pipelines
the steel ring, the failure of the tensile specimen is detected.
• RP0375, Wax Coating Systems for Underground Piping
Another technique that provides a remote indication of failure is
Systems
the aboveground monitoring of gas pressure used to apply a
hoop stress to small containers buried in the ground. The ASTM • RP0502, Pipeline External Corrosion Direct Assessment
committee on the corrosion of metals has developed and pub- Methodology
lished standard methods for the use of U-bend (ASTM G30, • Pub. 05107, Report on Corrosion Probes in Soil or Concrete
Standard Practice for Making and Using U-Bend Stress-Corrosion
• Pub. 07037, Use of CP Coupons and Soil corrosion Probes in
Test Specimens) and C-ring specimens (ASTM G38, Standard
Application of Pipeline Cathodic Protection Criteria
Practice for Making and Using C-Ring Stress-Corrosion Test
Specimens) for the application of stress.
POTENTIAL MEASUREMENT IN SITU
This measurement establishes the corrosion potential of buried
Corrosion Monitoring in Soils metal in a given soil. Its value is an indication of the degree and
extent of corrosion attack and the efficiency of applied CP. The
DIRECT AND INDIRECT CORROSION metal potential usually shifts with time to less negative values if
MEASUREMENTS AND TECHNIQUES FOR USE the corrosion products form an inert and compact layer on the
The corrosion behavior of a buried metal structure needs to be metal surface. As a result, it is possible to observe more positive
indirectly controlled or monitored to determine the time for potential values on an old structure than those measured on a
direct examination when repairs may be necessary.29–35,37–43,55–58 new metal surface. A new, coated steel pipe may have a potential
Looking at the corroded surface is usually expensive and is of -0.7 V versus a Cu/CuSO4 reference electrode, whereas an old
acceptable only for a special corrosion situation. Direct external pipe surface is generally more positive (-0.1 to -0.3 V). The sur-
surface assessment, however, may be imperative, for example, to face areas where the potential is less negative will be more
verify some indirect measurements or for visual examination of cathodic, and as a consequence, they will suffer less corrosion.
SOILS 235
Stray currents or interference from foreign CP systems may POTENTIAL MAPPING

cause potential fluctuations and have to be taken into account. Measured potentials at the soil surface above a utility, such as a
The in situ CP test criteria for full protection of steel is that pipeline, are often used to evaluate the effectiveness of CP sys-
all measured points are more negative than -0.85 V versus a tems and coatings. One technique that has been applied for
Cu/CuSO4 reference electrode. For long pipelines, passing many years uses two sets of measurements where one of the elec-
through different types of soil, the potential is usually measured trodes is positioned over the pipeline and the second electrode is
every 30 m or less (often at 1.5 m). placed several meters to the side. The data from this approach
Experience indicates that the corrosion potential value of provide a comparison of the local potential to the more distant
buried copper cable correlates with its corrosion behavior potential made to the side of the pipeline, as illustrated in
(table 6). A potential value of -0.50 V or more negative, versus a figure 30. Regions where the “over pipe” potential are more posi-
Cu/CuSO4 reference electrode, indicates full CP of this metal, tive than the “25 ft from pipe” potential are cathodic to other
typically provided by a connection to a steel structure. sections of the pipe line. Potential effects of stray currents, gal-
Potential measurements of metal in soil require the use of vanic currents, and CP interference are identified from this
some assistance tools, such as insulated wire, reels, alligator clips, information.52
terminal connectors, hand tools, a reference electrode (RE), and Another technique relies on a set of potential measurements
specialized equipment like voltmeters and ammeters. The satu- between the pipeline and an RE, where the electrode is posi-
rated Cu/CuSO4 RE is the most used in soils (þ 0.316 V versus tioned directly over the pipeline, and measurements are made
SHE standard potential). This RE has poor reproducibility and along its length at intervals. Computerized data logging permits
needs to be frequently checked and renewed. In high chloride a detailed analysis of discontinuities in potentials that reveal
environments, the most appropriate electrode is a silver/silver areas of active corrosion.54 Improvements in programming and
chloride RE (Ag/AgCl/KCl (0.1N) þ0.288 V versus SHE stan- equipment permit elimination of IR error from CP potential
dard potential). Usually it provides reproducible and reliable val- measurements and also incorporate use of “over the pipe” and
ues. The lead sulfate RE (Pb/Pb02/PbS04/ H2S04 (0.1M), þ 1.565 “beside the pipe” potential data.
V versus SHE standard potential) is connected to lead-sheathed
cables for measurement of their potential. Very dry soils may be POLARIZATION
wetted or a shallow hole may be dug to establish good electrical The technique of electrochemical polarization is a useful tool for
contact between the electrode and the soil moisture. The RE obtaining corrosion rate data nondestructively during exposure,
should be placed near the metal structure, auguring a hole down with a minimum of disruption to the test. The polarization resis-
to near the pipeline surface, to minimize ohmic potential drop tance measurement is especially attractive because its use is well
(IR) resulting from the soil and coating resistance. The tester documented, and it requires a minimal amount of equipment,
must avoid any damage to the coating or protective scale on the some of which is commercially available. The measurement
metal. The potentials over well-coated pipelines do not vary involves applying current to a specimen from a second electrode,
much over distance.
Factors affecting the potential measurements are broken
test leads, corroded contact points, inaccurate RE, and defective FIG. 30 A plot of potential over a pipeline and to the side of the
insulation of test leads. The existence of vegetation or of other pipeline versus distance, illustrating the presence of
metals may introduce errors of more than 100 mV. An improp- cathodic regions where “over the pipe” potentials are
erly calibrated RE can also be an important source of errors. more positive than “beside the pipe” potentials.
ASTM G215, Standard Guide for Electrode Potential Measure-

ment, and Appendix A of NACE TM0497 contain information
regarding calibration, care, and maintenance of reference
electrodes.
The metal potential can be measured using voltmeters with
more than 10 MX input impedance. Ammeters are used to mea-
sure electric current passing through the structure protected by
CP and are relatively low-resistance instruments.
TABLE 6 Copper Potential and Corrosion Behavior
Potential vs. Cu/CuSO Corrosion Behavior
Positive to -0.1 V Probably corroding

0.1 to -0.25 V Possibly corroding
0.25 to -0.50 V Probably not corroding
0.50 V or more negative Full protection
changing the potential of the specimen by approximately 10 mV extends from the 4 m mark to the 18 m mark. From this infor-
versus an RE, and noting the amount of current needed to make mation, the approximate polarized area can be calculated.
that change. The slope of the change in potential versus the
applied current is inversely related to the corrosion current of CORROSION COUPONS AND PROBES
the specimen.48 With information on the Tafel slope of the mate- Direct measurement of metal corrosion rate can be achieved
rial in that environment, the corrosion current can be deter- using pre-weighed metal coupons. They are buried in the pipe-
mined. This approach uses (1) a specimen as the WE, (2) a line trench and are unconnected or connected to the structure at
reference potential electrode (REF), and (3) a CE to apply the a controlled test post. Periodically, they can be removed and
polarizing current. Additional information on polarization is processed for weight loss resulting from corrosion. A simple cal-
available in ASTM G59, the previous section in this chapter culation can give the corrosion rate value, expressed, for exam-
on electrochemical testing, and chapter 8 of this manual, ple, in g/m2 year. This method is time consuming, especially
“Electrochemical Tests.” when a large number of samples are needed for removal at con-
Corrosion current density, and corrosion rate, can be calcu- sistent intervals.
lated when the entire specimen is polarized and its surface area The buried coupons can be made in a wide variety of sizes
is known. This is the case for finite area specimens, as illustrated and shapes and are made of the same metal as the structure. Com-
in figure 25 for steel piling. The reference electrode is located at paring the mass loss of connected and unconnected coupons may
the soil surface approximately 30 m from the WE. For these provide information about the effectiveness of CP. Electrical resis-
measurements, each of the seven piles was polarized using the tance (ER) probes and linear polarization resistance (LPR) probes
centrally located pile as the CE with the REF at a fixed location. are designed to measure corrosion in soil, without the necessity to
In this way, measurements could be duplicated from year to year be dug up for examination. This is an advantage over the coupons.
and the results compared.45 From this corrosion current mea- These probes also give indirect information about the soil corro-
sured over a period of time, in this case 14 years, an estimate of sivity and its changes with time.49
weight loss can be calculated. Special probes with associated measuring equipment that
In some situations, the polarized area of the specimen is not provide a means of determining the corrosion rate of a material
known, as is the case where the WE is a long structure such as a in soil are commercially available. An attractive feature of this
pipeline or electric power utility. In this situation, the WE is equipment is that the data read out directly in terms of corro-
essentially infinitely long, and the CE can only supply current to sion rate or can be readily converted to corrosion rate. The big-
a portion of the structure. An estimate of how much of the struc- gest concern is that the specimen in the probe may not be
ture is polarized when current is applied can be made by measur- representative of the structure of interest because of the small
ing the potential of the structure in the vicinity of the CE, as size of the probe specimen or its isolation from the structure.
illustrated in figure 31.24 In this example, the polarization region Corrosion probes and coupons are discussed in the following
NACE Publications: Publication 05107, Report on Corrosion
Probes in Soil or Concrete; NACE SP0104 (formerly RP0104),
FIG. 31 A plot of over-potential versus distance, illustrating the The Use of Coupons for Cathodic Protection Monitoring Appli-
distribution of current on an underground cable when cations; and NACE Publication 07037, Use of CP Coupons and
1.5 mA is applied from a rod placed 1 m to the side of Soil Corrosion Probes in Application of Pipeline Cathodic Pro-
the cable. tection Criteria.
ER Probe
ER probes, also known as soil corrosion probes, measure a
change in the resistance of a metallic sensing element, made of
the material of interest or a representative alloy. The resistance
changes as a function of metal loss in the cross section of the
sensing element. This reading is then converted to corrosion
rate. Several types of ER probes are shown in figure 32.
LPR Probe
An LPR probe determines the corrosion rate on its metal elec-
trode or electrodes by measuring the polarization resistance
under the application of a small applied potential, typically 10 to
20 mV, above the free corroding potential of the electrode or
electrodes.
Cathodic Protection Coupons

CP coupons have been shown to be a simple tool for determining
the level of polarization of a cathodically protected pipeline and
to confirm the IR drop in a potential measurement. CP coupons
SOILS 237
FIELD SOIL TESTS

FIG. 32 Several types of commercially available ER corrosion A number of soil tests are used to correlate soil corrosion aggres-
probes. Source: Photo complements of U.S. Pipe and sivity to its physical and chemical properties. These tests are dis-
Foundry. cussed in previous sections of this chapter. Sampling errors are
the most common errors encountered in soil analysis, because of
the extreme heterogeneity of the material. In the laboratory,
grinding and mixing can minimize such errors, but the largest
sampling error occurs in field measurements. In field measure-
ments of soils, each of the different types of soil in contact with
the structure (i.e., organics, sand, clays) should be tested individ-
ually. For resistivity, this can be performed with either a four-pin
or a two-pin resistivity soil box as described in ASTM G57 and
G187. The most desirable measurements of redox potential, pH,
and resistivity are those conducted in the field adjacent to the
structure of interest. If it is not possible to conduct redox and pH
measurements in the field, soil samples should be collected in
are installed in the soil or electrolyte near the pipeline and then air-tight containers and tested as soon as possible when received
are connected to it through a test station. The CP coupon can be at the laboratory.
easily disconnected from the pipeline for periodic monitoring of
“instant off” and depolarization potential measurements. FIELD BIOLOGICAL ACTIVITY TEST
Other types of probes use electrochemical polarization tech- Testing for MIC has been discussed in a previous section of this
niques and two or three electrodes to measure the corrosion rate chapter. As specified in NACE TM0106-2016, Detection, Test-
of the WE in the probe.50,51 Details on calculating corrosion rate ing, and Evaluation of Microbiologically Influenced Corrosion
from electrochemical data are discussed in ASTM G102. (MIC) on External Surfaces of Buried Pipelines, “MIC investiga-
In the laboratory, the technique of ac impedance is supple- tions require microbiological, chemical, and metallurgical test-
menting polarization resistance because it provides additional ing for proper diagnosis. The conclusion that MIC has taken
information on mechanisms of the processes involved. Guidance place should be based on the preponderance of circumstantial
on performing corrosion tests in the laboratory in liquids or in evidence.”12
soils is provided in ASTM G31, Standard Guide for Laboratory Chemical analysis of the water source and the soil is helpful
Immersion Corrosion Testing of Metals. Although ac impedance in determining the critical nutrients necessary to support micro-
systems are now commercially available, these units generally are biological activity. These tests should be conducted under the
limited to low polarization currents of 1 A or less, making them direction of a microbiologist who has experience in microbiolog-
unsuitable for most field applications in which larger current ically influenced corrosion. Field test kits are currently available
capabilities (>1 A) are needed. that employ an antibody tagging technique to identify and that
facilitate the determination of the population of microbes.56,57
MIC can be studied using field survey and other techniques,
GALVANIC CORROSION
such as electrochemical polarization curves, polarization resis-
The galvanic coupling of unlike metals in soil is an all too com-
tance, EIS, thin-film ER probe, galvanic current measurement,
mon occurrence, and the need to obtain information on the con-
scanning electron microscopy, and energy-dispersive X-ray spec-
sequences of this condition is recognized. Copper ground rods
troscopy surface analysis.22
and copper mesh ground beds are typically connected to steel
piling supported structures and underground telephone, water,
EXTERNAL CORROSION DIRECT ASSESSMENT
and fuel utilities to the detriment of the less noble steel. Burial of
(ECDA) OF BURIED PIPELINES
galvanically coupled metals in soil provides information on the
degree of corrosion and the possibility of hydrogen embrittle- As a result of regulatory changes in the United States, the pipe-
ment. The effect of relative surface area of the coupled metals line industry needed an alternative method to pressure testing on
and the spacing between them are important.52 in-line tool inspection to assess buried pipelines.55,58 External
Measuring the galvanic current of the coupled metals dur- corrosion direct assessment (ECDA) is a four-step process con-
ing the exposure period allows for monitoring of changes in the sisting of the following:
magnitude of the current and direction of current flow. This can
be accomplished by attaching insulated wire conductors that • Pre-assessment: assesses pipe data, construction data, soil/
extend above the surface of the soil where they are connected environmental conditions, corrosion protection data, and
together. Periodically, an ammeter is inserted in the circuit and operating parameters/history
the current is measured. To reduce the possibility of affecting the • Indirect inspection: identifies the locations of coating faults,
current during the measurement, which may involve currents in insufficient CP, and electrical shorts (close-interval, on/off
the milliamp range or less, the use of a zero-resistance ammeter potential surveys, electromagnetic current attenuation surveys,
is recommended.46 alternating current voltage gradient surveys), interference,
geological current surveys, and other anomalies along the 6. E. E. Stansbury and R. A. Buchanan, Fundamentals of
pipeline. Electrochemical Corrosion (Materials Park, OH: ASM
• Direct examination: excavates the pipe and performs physical
inspections and tests on the pipe surface and the surrounding 7. DIPRA/CORRPRO, Advancements in Pipe Longevity–The Design
soil/water electrolytes, to assess the degree of corrosion Decision Model (Birmingham, AL: Ductile Iron Pipe Research
Association, 2018).
• Post-assessment: assesses the overall effectiveness of direct
assessment and to define reassessment intervals based on 8. J. H. Fitzgerald, III, “The Future as a Reflection of the Past,” in
Effect of Soil Characteristics on Corrosion, ed. V. Chaker and
remaining-life calculations
J. D. Palmer (West Conshohocken, PA: ASTM International, 1989),
1–4.
The ECDA process incorporates standard techniques for
compiling historical information, pipeline and soil surveys, exter- 9. External Corrosion Control for Infrastructure Sustainability, 3rd.
ed., AWWA Manual M27 (Denver, CO: American Water Works
nal pipeline inspections, and data analysis. The procedure
Association, 2014).
includes no new measurement techniques, but it does allow for
the future addition of such techniques. New advances in satellite 10. Ductile Iron Pipe and Fittings, 3rd. ed., AWWA Manual M41
technology may soon help pipeline operators and utilities (Denver, CO: American Water Works Association, 2009).
observe encroachments and ground movements near their assets 11. A. W. Peabody and R. L. Bianchetti, Control of Pipeline Corrosion,
with unprecedented details.55 Some rules and information about 2nd ed. (Houston, TX: National Association of Corrosion
ECDA are present in NACE RP0502, Pipeline External Corrosion Engineers, 2001).
Direct Assessment Methodology. 12. Detection, Testing, and Evaluation of Microbiologically Influenced
Corrosion (MIC) on External Surfaces of Buried Pipelines, NACE
TM0106-2016 (Houston, TX: National Association of Corrosion
Summary Engineers, 2016).
As discussed in the beginning of this chapter, soil as a corrosive 13. Earth Resistivity Manual (Evanston, IL: Soiltest Inc., 1968).
environment is probably of greater complexity than any other 14. A. M. Horton, “Zinc Metallizing for External Corrosion Control of
environment. The corrosion process of buried metal structures is Ductile Iron Pipe” (paper presentation, ASCE Pipelines Conference,
extremely variable and can range from rapid to negligible. With American Society of Civil Engineers, Reston, VA, 2014).
background knowledge of the principal soil characteristics and
15. Concrete Pressure Pipe, 3rd. ed., AWWA Manual M9 (Denver, CO:
their influence on metal corrosion, the most serious corrosion American Water Works Association, 2008).
problems can be prevented. ASTM Committee G01 on Corro-
16. E. G. Pont, “Association of Sulfate Reduction in the Soil with
sion of Metals and other ASTM committees have prepared test
Anaerobic Iron Corrosion,” Journal of Australian Institute of
methods, recommended practices, guides, and other documents Agricultural Science 5, no. 5 (1939): 170–171.
to aid in the testing and identification of corrosive soils. Many of
these are listed in Appendix A. The NACE, AWWA, Societies of 17. G. Seelmeyer, “Biological Corrosion of Iron and Steel,”
Werkstoffe und Korrosion 4 (1953): 241–247.
Protective Coatings (SSPC), and other organizations have pre-
pared documents to aid in the protection and monitoring of bur- 18. J. C. Senez, “Investigation in Biological Corrosion in Anaerobic
ied structures. The information presented in this chapter, and in Soils by Sulfate-Reducing Bacteria,” Corrosion and Anti-Corrosion
this manual, will assist the reader not only in identifying corro- 1 (1953): 131–132.
sive environments but also aid in preventing corrosion of our 19. J. O. Harris, “Bacterial Activity at the Bottom of Back-Filled Pipe-
valuable infrastructure. Line Ditches,” Corrosion 16 (1960): 149–154.
20. W. P. Iverson, “Biological Corrosion,” Advanced Corrosion Science

and Technology 2 (1972): 1–42.
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(February 1988): 310–313.
51. G. A. Marsh, “The Measurement of Instantaneous Corrosion
36. A. M. Horton, Corrosion Rates of Ductile Iron Pipe in Drilling Rates,” in 2nd International Congress on Metallic Corrosion
Fluids: A Comparison of ASTM Electrochemical Test Standards (Houston, TX: NACE International, 1963), 936–941.
G59, G102, AND G106 to ASTM Weight Loss Standard G162,
(West Conshohocken, PA: ASTM International, 2018). 52. M. G. Fontana and N. D. Greene, Corrosion Engineering (New
York: McGraw-Hill, 1978).
37. J. B. Bushman and T. E. Mehalick, “Statistical Analysis of Soil
Characterization to Predict Mean Time to Corrosion Failure of 53. B. Husock, “Use of Pipe-to-Soil Potential in Analyzing
Underground Metallic Structures,” in Effects of Soil Underground Corrosion Problems,” Corrosion 17, no. 8 (1961):
Characteristics on Corrosion, ed. V. Chaker and J. D. Palmer 97–101.
54. D. Kroon and K. W. Nicholas, “Computerized Potential Logging:
38. C. P. Dillon, Corrosion Control in the Process Industries (New Results on Transmission Pipelines” (paper presentation,
York: McGraw-Hill, 1986). Corrosion/82, NACE International, Houston, TX, 1982).
39. V. Chaker, “Simplified Method for Electrical Soil Resistivity 55. M. V. Veazey and S. Writer, “The Next Big Thing in Pipeline
Measurement,” in Underground Corrosion, ed. E. Escalante (West Monitoring,” Materials Performance 42 (June 2003): 16–21.
56. D. H. Pope, “Discussion of Methods for the Detection of
40. E. Escalante, “The Effect of Soil Resistivity and Soil Temperature Microorganisms Involved in Microbiologically Influenced
on the Corrosion of Galvanically Coupled Metals in Soil,” Galvanic Corrosion,” in Biologically Induced Corrosion—Proceedings of the
Corrosion, ed. H. P. Hack (West Conshohocken, PA: ASTM International Conference (Houston, TX: NACE International,
International, 1988), 193–202. 1986), 275.
57. J. G. Stoecker, “Guide for the Investigation of Microbiological ASTM G5, Standard Test Method for Making Potentiostatic
Induced Corrosion,” Materials Performance 23, no. 8 (1984): 48–55. and Potentiodynamic Anodic Polarization Measurements
58. D. H. Kroon, “External Corrosion Direct Assessment of Buried ASTM G16, Standard Guide for Applying Statistics to Analy-
Pipelines: The Process,” Materials Performance 42 (June 2003): sis of Corrosion Data
28–32. ASTM G30, Standard Practice for Making and Using U-Bend
Stress-Corrosion Test Specimens
Appendix A. ASTM Standards ASTM G31, Standard Guide for Laboratory Immersion Cor-
rosion Testing of Metals
Related to Soil Corrosion and Soil
ASTM G38, Standard Practice for Making and Using C-Ring
Testing Stress-Corrosion Test Specimens
ASTM A674, Standard Practice for Polyethylene Encasement for ASTM G46, Standard Guide for Examination and Evaluation
Ductile Iron Pipe for Water or Other Liquids, Appendix XI (Soil of Pitting Corrosion
Tests) ASTM G51, Standard Test Method for Measuring pH of Soil
ASTM D512, Standard Test Methods for Chloride Ion in for Use in Corrosion Testing
Water ASTM G57, Standard Test Method for Measurement of Soil
ASTM D516, Standard Test Method for Sulfate Ion in Water Resistivity Using the Wenner Four-Electrode Method
ASTM D653, Standard Terminology Relating to Soil, Rock, ASTM G59, Standard Test Method for Conducting Potentio-
and Contained Fluids dynamic Polarization Resistance Measurements
ASTM D1452, Standard Practice for Soil Exploration and ASTM G61, Standard Test Method for Conducting Cyclic
Sampling by Auger Borings Potentiodynamic Polarization Measurements for Localized Corro-
ASTM D1586, Standard Test Method for Standard Penetra- sion Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys
tion Test (SPT) and Split-Barrel Sampling of Soils ASTM G71, Standard Guide for Conducting and Evaluating
ASTM D2216, Standard Test Method for Laboratory Determi- Galvanic Corrosion Tests in Electrolytes
nation of Water (Moisture) Content of Soil and Rock by Mass ASTM G102, Standard Practice for Calculation of Corrosion
ASTM D2434, Standard Test Method for Permeability of Rates and Related Information from Electrochemical Measurements
Granular Soils (Constant Head) ASTM G106, Standard Practice for Verification of Algorithm
ASTM D2487, Standard Practice for Classification of Soils for and Equipment for Electrochemical Impedance Measurements
Engineering Purposes (Unified Soil Classification System) ASTM G158, Standard Guide for Three Methods of Assessing
ASTM D2488, Standard Practice for Description and Identifi- Buried Steel Tanks
cation of Soils (Visual-Manual Procedures) ASTM G148, Standard Practice for Evaluation of Hydrogen
ASTM D2937, Standard Test Method for Density of Soil in Uptake, Permeation, and Transport in Metals by an Electrochemi-
Place by the Drive-Cylinder Method cal Technique
ASTM D2980, Standard Test Method for Saturated Density, ASTM G162, Standard Practice for Conducting and Evaluat-
Moisture-Holding Capacity, and Porosity of Saturated Peat ing Laboratory Corrosion Tests in Soils
Materials ASTM G187, Standard Test Method for Measurement of Soil
ASTM D4083, Standard Practice for Description of Frozen Resistivity Using the Two-Electrode Soil Box Method
Soils (Visual-Manual Procedure) NACE/ASTM G193, Standard Terminology and Acronyms
ASTM D4427, Standard Classification of Peat Samples by Relating to Corrosion
Laboratory Testing ASTM G200, Standard Test Method for Measurement of
ASTM E11, Standard Specification for Woven Wire Test Sieve Oxidation-Reduction Potential (ORP) of Soil
Cloth and Test Sieves ASTM G215, Standard Guide for Electrode Potential
ASTM G1, Standard Practice for Preparing, Cleaning, and Measurement
Evaluating Corrosion Test Specimens ASTM G218, Standard Guide for External Corrosion Protec-
ASTM G3, Standard Practice for Conventions Applicable to tion of Ductile Iron Pipe Utlizing Polyethylene Encasement Sup-
Electrochemical Measurements in Corrosion Testing plemented by Cathodic Protection
241
Chapter 15 | Petroleum Chemistry
K. Daniel Efird1
Introduction Chemical and Physical

The petroleum production environment provides a unique Characterization of Petroleum
challenge for corrosion testing in that it is not a controlled Environments
chemistry, as a chemical process environment, but is an envi-
ronment provided by nature, with all the potential variability in Petroleum production is generally classified on the basis of exist-
phase distribution and chemical composition this implies. ing phases in the production stream, the relative proportions of
Petroleum environments are always complex, and often change these phases, and the presence or absence of hydrogen sulfide
during production from a formation, or they may change (H2S). Carbon dioxide (CO2), H2S, hydrocarbons and organic
because of production from formations that were not included compounds (gas and liquid), water, and dissolved salts are the
or anticipated in the original planning for field exploitation. primary constituents of the petroleum environment, and provide
The corrosion test program for petroleum environments, the basis for additional characterization. The acid gases, CO2,
therefore, must account for the environment nature has created and H2S, have the primary effect on corrosion, and hence,
with little ability to alter or control it. In a very real sense provide a primary basis of classification.
the petroleum chemistry environment is a case of, “what you The term “sweet” is commonly applied to petroleum pro-
see is what you get.” The primary concern with corrosion duction environments containing CO2 and no H2S. These envi-
testing in petroleum environments is to ensure that what you ronments generally are defined for corrosion purposes on the
test is, in fact, what really exists in the actual production basis of the partial pressure of CO2 in the gas phase. This grossly
environment. defines the level of dissolved CO2 in the water phase and, accord-
The effect of petroleum chemistry on corrosion lies pri- ing to many sources, roughly defines the relative aggressiveness
marily in its influence on the formation, chemical composition, of the water phase.
and characteristics of a liquid water phase, because liquid water The term “sour” is applied to petroleum production envi-
in contact with the containing material is a necessary condition ronments containing H2S. Sour environments generally contain
for corrosion to occur for the operating temperatures and pres- CO2 as well as H2S. The concentration of H2S required to con-
sures encountered in petroleum production. This fact dictates sider an environment “sour” is not well defined. The currently
the direction of the discussion on the influence of petroleum accepted definition is found in Specification ANSI/NACE
chemistry in corrosion testing. This chapter deals solely with MR0175/ISO 15156,1 which in Part 1 defines “sour service” as
the effects of naturally occurring petroleum chemistry on cor- exposure to oilfield environments that contain sufficient H2S to
rosion testing and methods to deal with the effects of petroleum cause cracking of materials by the mechanisms addressed in the
chemistry in corrosion testing. It does not elaborate on the standard. This definition is based on safety considerations and
actual test techniques except as they are affected by the petro- the susceptibility of materials to sulfide stress corrosion cracking
leum chemistry considerations, and it does not consider refin- and is not related to general or localized corrosion. The term
ery operations or alterations to the petroleum chemistry used “sour” also can be defined as an environment containing suffi-
to control corrosion. cient H2S to produce a primarily iron sulfide corrosion product
on steel. The H2S concentration in the water phase required for
this to occur is not well defined; however, a concentration of
more than 50 ppm H2S in the water phase is sometimes used as
a criteria for a sour environment.
The physical phases in a petroleum environment—including
gas, liquid hydrocarbon (gas condensate or crude oil), and liquid
1
Stress Engineering Services, Inc., Houston, TX 77041, USA water phases—may occur singly or in combination in a wide range
DOI: 10.1520/MNL202NDSUP20190029
of phase ratios, and these phase ratios and compositions may GAS PHASE AND GAS CONDENSATE PHASE
change during production. Producing fields and individual wells The gas phase is composed of various combinations and ratios of
are broadly classified as gas or oil fields or as wells depending on methane (CH4), heavier hydrocarbons (e.g., ethane, propane),
the primary phase produced. Other types of wells or systems for acid gases (e.g., CO2 and H2S), water (H2O), dinitrogen (N2),
which corrosion testing may be considered are used for subsur- and helium (He). The primary gas is usually CH4. A typical gas
face injection (e.g., CO2, water or gas injection wells, and pro- analysis for a producing well is given in table 1. The gases of
duced water disposal wells). A gas well is defined as one whose greatest importance to corrosion are the acid gases CO2 and H2S.
production consists primarily in a a gas phase with possibly The other gases in the well stream are important to corrosion
some gas condensate, condensed water, or produced water, but primarily because of their influence on the concentration of the
no crude oil. An oil well is defined as one whose production con- acid gases dissolved in a liquid water phase.
sists of crude oil with varying amounts of gas and produced The gas condensate phase is composed of C3 and heavier
water. The relative proportion of gas and crude oil in the well alkanes and alkenes, present in the gas phase at reservoir condi-
production is expressed as the gas-to-oil ratio in units of volume tions, that condense as a result of the temperature and pressure
of gas at standard conditions per volume of crude oil at 20 C drop in the well string during production or in flowlines and
(68 F). production facilities. The gas condensate phase can occur in gas
wells, flowlines, and in crude oil well gas processing facilities
after the separation of gas from the crude oil. The primary effect
TEMPERATURES AND PRESSURES ENCOUNTERED
of gas condensate on corrosion is the result of the displacement
The temperatures and pressures encountered in oil and gas pro-
of liquid water from the metal surface by the gas condensate,
duction can vary widely. In general, high pressures and high
thus inhibiting corrosion of the metal by the water phase. This
temperatures go together for gas wells, but this is not necessarily
relative condensation of liquid hydrocarbon and liquid water is
the case for crude oil wells. The total bottom hole pressure in gas
difficult to simulate in laboratory tests, but the effect on corro-
wells can range from a low of 40 to 60 bar to a high of more than
sion must be accounted for in assessing the corrosivity of pro-
1,500 bar. Bottom hole temperatures can range from 50 C to
duction from a well. At this time, there is no simple answer to
well over 150 C. The temperatures and pressures normally
the problem. Calculations of relative condensation from well
encountered in surface production facilities are generally signifi-
data are about the only recourse.
cantly lower.
Changes in temperature and pressure occur along the length
of a tubing string during well production. The temperature and LIQUID WATER PHASE
pressure variations for a typical well are shown in figure 1.2 The The liquid water phase in petroleum production can consist of
significance of the change in temperature and pressure is that the either produced water, injected water, or condensed water, and
phases present in the formation can change in the tubing string combinations of these in varying proportions. Produced water is
during production and in surface facilities. This can result in the present in the reservoir as a liquid water phase and is produced
formation of liquid water and gas condensate that were not pre- along with the gas, gas condensate, or crude oil. Condensed
sent in the original produced fluid, which can dramatically affect water is liquid water condensed directly from gaseous H2O in
corrosion. A valid corrosion test procedure must account for this the gas phase.
effect. Condensed water is condensed from H2O in the gas phase
as a result of changes in temperature and pressure along the
length of a tubing string during production and in flowlines and
surface facilities. The condensed water contains dissolved acid
FIG. 1 Subsurface variation in temperature and pressure in a well
2
gases (CO2 and H2S) and low levels of dissolved corrosion
as a function of depth from downhole surveys.
120 10000
TABLE 1 Typical Gas Analysis for a Producing Well
100
8000
Compound Mole, %
TEMPERATURE, C
PRESSURE, KPa
80
Methane (CH4) 81.5%
6000
Ethane (C2H6) 3.6%
60 TEMPERATURE
Propane (C3H8) 2.0%
4000 Butane (C4H10) 0.4%
40 PRESSURE
Pentane (C5H12) 0.2%
2000 > C5 1.0%

20
CO2 4.6%
H2S 1.4%
0 0
0 500 1,000 1,500 2,000 2,500 N2 5.2%
DEPTH, m He 0.04%
PETROLEUM CHEMISTRY 243
product from the well tubing. It can be corrosive. Condensed aromatic hydrocarbons, heterocyclic and metal organic com-
water is the fluid studied by de Waard and Milliams in their pounds, high-molecular-weight organic compounds, and a broad
landmark work on the effects of CO2 on steel corrosion in gas assortment of nitrogen-, sulfur-, and oxygen-containing organic
transmission lines, and the equations developed apply to con- compounds.
densed water.3 The equation has since been modified to account
for additional variables.4
A special case of corrosion by condensed water occurs in Chemical and Physical
the vapor phase of pipelines and vessels. This condensed water Characterization of Crude Oil
can be corrosive and must be accounted for in designing a corro-
sion test program, if the phenomenon is anticipated in the spe- Crude oils are generally classified according to API gravity
cific production system being studied. Extensive discussion of (inversely proportional to the crude oil density), sweet or sour,
vapor phase corrosion by water condensation and possible reme- and asphaltenic or parafinic (hydrocarbon characteristics). A so-
dies are given by Dugstad, Lunde, and Olsen,5 Olsen and Dug- called heavy crude oil has a low API gravity (<20), a medium
stad,6 and Nyborg, Dugstad, and Lunde.7 crude oil has an intermediate density (20 to 34), and a light crude
Produced water is an extremely complex chemical solution, oil has a high API gravity (>34). These ranges are not absolutely
composed of liquid water, minerals dissolved from formation defined, but they serve as a general reference. All crude oils are
rocks, and water-soluble organics from the hydrocarbon phase, composed of some or all of eight basic classes of organic com-
because it originates within the formation source rocks. The pounds as given in table 3. Another way to classify crude oils is
most important inorganic compounds with corrosion implica- based on the nature of the organic compounds that make up the
tions are chlorides and buffering compounds (e.g., bicarbonate, crude oil, specifically the proportions of paraffins, aromatic com-
borate, silicate). The presence of buffering compounds reduces pounds and naphthenic compounds, as shown in figure 2.13
corrosion by raising the solution pH, countering the effect of dis- The recommended physical and chemical analyses for
solved acid gases. An accurate, detailed analysis of the produced determination of the general characteristics of a crude oil are
water is essential so it can be accurately reproduced for corrosion given in table 4 and table 5. Results of these analyses provide a
testing, and accurate simulation of the produced water is essen- solid basis for comparison of crude oils from different forma-
tial for realistic laboratory corrosion test results. The basic ana- tions and fields. The crude oil components that have the greatest
lytical detail needed for produced water is given in table 2. This
degree of detail is necessary to allow the required simulation of
the produced water for the laboratory corrosion experiments. TABLE 3 Basic Organic Compound Groups for Crude Oils
Research into the effects of produced water chemistry have
been reported by Crolet and Bonis,8,9 Schmitt,10 Murata,11 and 1. n-alkanes
Videm.12 2. iso-alkanes
The original produced water chemistry can be altered dur- 3. mono- and poly-nuclear naphthenes
ing production by dilution with condensed water in the tubing 4. mono- and poly-nuclear aromatics
string and in production facilities. The effect of this dilution is to 5. mono- and poly-nuclear naphthenoaromatics
reduce the concentration of buffering compounds in the pro- 6. hetero-compounds
duced water, resulting in potentially lower pH and increased 7. asphaltenes
corrosion. 8. carbenes
CRUDE OIL PHASE

The crude oil phase is the most chemically complex phase in the 8
FIG. 2 Classification of crude oils based on petroleum fractions.
petroleum environment. Crude oil contains alaphatic and
AROMATICS
AROMATIC
TABLE 2 Recommended Analysis for Produced Waters ASPHALTIC
CRUDE OIL
Anions Cations Additional

AROMATIC
AROMATIC NAPHTHENIC
Na Cl pHa
PARAFFINIC INTERMEDIATE CRUDE OIL
K SO4 TDS NAPHTHENIC CRUDE OIL
Ca HCO3 CO2a CRUDE OIL
Mg CO3 H2Sa,b
Ba F O2a,b
Sr NO3 PARAFFINIC NAPHTHENIC
CRUDE OIL CRUDE OIL
Fe CH3COO
a
Analysis at the time of taking the sample is preferred.
b
Sampling technique must prevent iron contamination. PARAFFINS NAPHTHENES
CHEMICAL CONSTITUENTS OF CRUDE OIL THAT

TABLE 4 Recommended Analysis for Crude Oils AFFECT CORROSION
As stated earlier, the effect of petroleum chemistry on corrosion
1. Gravity, API @ 15 C 2. Pour point, C ( F) lies primarily in its influence on the formation, composition, and
3. Flash point, Pensky-Martens 4. Base sediment and water, vol% characteristics of a liquid water phase. This discussion deals with
5. Carbon residue, Conradson 6. Salt content, ptb the chemical constituents in crude oil that affect the chemical
7. Ash content, wt% 8. Wax content, wt% composition of the liquid water phase. The water soluble constit-
9. Neutralization number, mg/g 10. N-heptane insoluble, wt% uents in crude oil are primarily the heterocyclic and metal
11. Toluene insoluble, wt% 12. Colloid content organic compounds, and the nitrogen-, sulfur-, and oxygen-
(ethyl acetate pptn), wt% containing organic compounds. These include pyridines, indoles,
13. Bubble point pressure benzofurans, phenols, amines, organic acids, thiols, ketones, and
14. Element analysis: Sulfur, wt% Nitrogen (total), wt% .aldehydes. All are organic compounds that are water soluble
Copper, ppm Iron, ppm and surface active to varying degrees.14–16
Nickel, ppm Vanadium, ppm The effect of these organic compounds on the corrosivity of
Calcium, ppm Magnesium, ppm the water phase is not well understood, but it probably results
Sodium, ppm from either direct chemical interaction with the metal surface in
the manner of a chemical corrosion inhibitor, or their effect on
wetability. An example of the effect of the crude oil acid number
TABLE 5 True Boiling Point Crude Oil Distillation on crude oil wetability is shown in figure 4.14 The relative wetabil-
ity of the crude oil and water phases determines whether the
Crude Oil True Boiling Point
metal surface will be oil wet or water wet, with significant effects
on corrosion.17 Data also correlate with the corrosion rate of steel
Light ends to 32 C (90 F), vol%
in crude oil–brine mixtures with the total nitrogen and acid con-
Light naphtha 32 C to 171 C (90 F to 340 F), vol%
tent of the crude oil as shown in figure 5.18
Kerosene 171 C to 260 C (340 F to 500 F), vol%
Diesel 260 C to 353 C (500 F to 700 F), vol%
Light distillate 353 C to 409 C (700 F to 800 F), vol% VARIABILITY OF CRUDE OIL
Medium distillate 409 C to 464 C (800 F to 900 F), vol% The problem with corrosion testing for crude oil environments is
Heavy distillate 464 C to 520 C (900 F to 1,000 F), vol% the wide variability in the composition of the crude oils and the
Residue >520 C (>1,000 F), vol% resulting variability in their effect on corrosion. Examples of the
variability in composition are shown for 10 crude oils in figure 6
and figure 7.14 Differences in aromatic and polar organic content
potential effect on corrosion are the polar organic compounds,
for the 10 crude oils are shown in figure 6, and differences in the
because the polar organic compounds are the most water soluble
acid numbers for these crude oil fractions are shown in Figure 7.
components in the crude oil and are surface active. A procedure
These differences in composition result in wide variability
for the extraction of the polar components of a crude oil pub-
in corrosion for various crude oils. The effect of specific crude
lished by Donaldson is diagrammed in figure 3.14
oils on the corrosion rate of carbon steel as a function of the
FIG. 3 Schematic diagram of chromatographic separation

procedures for extraction of polar compounds from FIG. 4 Effect of acid number and interfacial tension of the crude
9
crude oil. oil water interface on crude oil wetability.
9
CRUDE OIL 1 30
ACID NUMBER, mg NaOh/g
Precipitate in n-pentane
INTERFACIAL TENSION
25
Insoluble Asphaltene
Filter
Fraction
Soluble
Saturated, Aromatic 0.1 20

and Polar Cpds
Clay-gel adsorption High pressure liquid
chromatography chromatography
15
Acid Number
% Saturated Cpds %Aromatic Cpds % Polar Cpds Interfacial Tension
0.01 10
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Acid Number Determination Wetability Effects
CRUDE OIL WETABILITY
FIG. 5 The relationship of the acid content (acid number) and FIG. 7 Acid number for 10 crude oils and the aromatic and polar
organic nitrogen content of crude oil on steel corrosion organic fractions. Acid number as mg NaOH/g of sample.
rate in crude oil/brine mixtures (4% NaCl brine at 5.2 MPa
13 1
CO2 pressure and 85 C).
ACID NUMBER, mg NaOh/g

0.1
Concentration, %wt
0.1
0.01
0.001
-1.1 0.01
CR = 0.0015 (%wt N x %wt S)
6
6
6
6
-76
-76
-76
-76
6
5-7
6-7
1-7
9-7
7-7
8-7
16
30
42
43
0.0001
0.001 0.01 0.1 1 10
CRUDE OIL IDENTIFICATION
Corrosion Rate, mm/y
FIG. 6 Chromatographic analysis of 10 crude oils for aromatic FIG. 8 Steel corrosion rate on a logarithmic scale for crude
and polar organic compounds, with the balance saturated oil–brine mixtures using different crude oils with the same
9 13
organic compounds. brine composition (4% NaCl solution).
25 300
Aromatic Compounds
Polar Compounds
20
COMPOSITION, %
15
CORROSION RATE, µm/y
10 200
40%
30%
ENT
150
20%
5
CONT
15%
100
10%
5%
BRINE
50
0 2%
0%
6
6
-76
-76
-76
-76
9-7
0
1-7
5-7
6-7
7-7
8-7
16
C03 C48 CL1 SJC

30
42
43
CRUDE OIL IDENTIFICATION CRUDE OIL
produced water content for a constant produced water composi- and pressure data, the gas composition data, and the fluid sample
tion is shown in figure 8 and figure 9.18 This compositional varia- analyses. The well fluids composition, particularly the gas, crude
tion also results in differences in the way the amount of brine in oil, and produced water analysis, must be correct.
a crude oil stream affects corrosion, as shown in figure 10.19 Six fundamental test principles must be followed to preserve
the petroleum chemistry for corrosion testing and to allow for
valid laboratory corrosion tests in petroleum environments:
Laboratory Corrosion Testing
The unique characteristics of petroleum chemistry have a major 1. A representative production environment for the area of
effect on corrosion test methodology, experimental techniques, interest, or the most potentially corrosive or highest risk
and considerations. The most important step preliminary to con- area in a production system, should be duplicated as
ducting corrosion tests is to ensure that the actual petroleum nearly as possible for all corrosion testing, and its compo-
chemistry that occurs in the production system is the one inves- sition should not be altered, except for the purpose of
tigated. This requires accurate field data and rigorous sampling investigating specific field or composition variables, for
techniques. No corrosion test in the petroleum environment can example, changes in produced water level, CO2 partial
be more precise than the accuracy of the production temperature pressure, and H2S partial pressure (field souring).
5. Great care must be taken to prevent oxygen contamina-

FIG. 9 Steel corrosion rate on a linear scale for crude oil/brine
tion during corrosion testing, unless oxygen is one of
mixtures using different crude oils with the same brine
the test variables.
composition (4% NaCl solution), showing different effects
13
6. Each individual corrosion test must be completed before
of increasing brine content.
the chemistry of the water phase in the test environment
is changed significantly by the corrosion process, or a
flow-through system must be used to maintain the solu-
tion chemistry.
CORROSION TESTING FOR HYDROCARBON

CORROSION RATE, µm/y
104 GAS SYSTEMS

40%
30%
The following discussion applies to corrosion testing of hydro-
ENT
103
20% carbon gas systems and to the gas phase used for produced or
CONT
15% condensed water and crude oil system corrosion testing.
102
10%
5% Accurately reproducing the composition of the concurrently
BRINE
101
2% produced water phase is the primary concern with corrosion
0%
100 testing for hydrocarbon gas systems. The concentration of corro-
P01 E16 E08 C03 C48 CL1 SJC
CRUDE OIL sive gases in the water phase must be accurately simulated, and
simple equalizing of the partial pressure with the production
environment is not sufficient. As stated previously, gas produc-
tion wells are generally at high pressure. It is the high pressure
FIG. 10 The change in corrosion rate of steel in crude that causes the error with the use of partial pressure as the deter-
oil–produced water mixtures with increasing produced minant of acid gas concentration in the liquid water phase. This
water content showing the three general types of error is not as great for surface facilities operating at much lower
13
behavior observed. pressures.
Using equality of gas fugacity rather than partial pressure
0.32
to reproduce the production environment in the corrosion test
0.28 accounts for the effect of nonideality in the solubility of the gas
CORROSION RATE, mm/y
in the water phase at increasing total pressure. For example, a

0.24
test conducted at 20 psi total pressure of pure CO2 will not
CRUDE OIL A
0.20 result in the same CO2 concentration in the water phase as
20 psi CO2 partial pressure in a well with a total pressure of
0.16
CRUDE OIL B 5,000 psi with CH4 as the other gas. Significantly less CO2 is
0.12 dissolved in the water phase at the high-pressure well than in
the low-pressure test, even though the partial pressures are the
0.08
same. This can have a major effect on the application of corro-
0.04 CRUDE OIL C sion test results to the operating system, because the concentra-
tion of acid gas dissolved in the water phase strongly affects its
0
0 10 20 30 40 50 corrosivity.
PRODUCED WATER CONTENT, % Care is required to ensure that unwanted oxygen is
removed from the gas phase to prevent it from being intro-
duced into the water phase. Oxygen contamination in the water
2. The composition of corrosive gases in the test solution phase, even at a level of 50 ppb, can result in significant errors
should be calculated on the basis of gas fugacity not partial in the test results. Anaerobic gases should be used wherever
pressure for correlation with the production environment. possible. If oxygen removal from the test gas is required, this
The higher the total pressure of the production environ- can be accomplished by passing the gas through commercial
ment, the more important this becomes. oxygen removal cartridges, with final oxygen removal being
3. For crude oil corrosion tests, the actual production accomplished by passing the prescrubbed gas through a nickel
crude oil should be used for all corrosion testing, and chloride (NiCl2)–catalyzed 10,000 ppm solution of hydrazine
oxygen must not be allowed to contact the crude oil at chloride.
any time before corrosion testing. When H2S or gas mixtures containing H2S are used, the
4. Artificially produced water may be used. If, however, supplied gas has rarely any oxygen. These situations do require
crude oil is produced in service, the artificially produced removal of oxygen from the test solution and the test cell gas
water must be intimately contacted with the crude oil space before introduction of the H2S-containing test gas. Oxygen
before testing to ensure that the soluble organics from remaining in the test cell can react with the H2S to form oxy-
the crude oil are present in the test solution. sulfide compounds, which can greatly affect corrosion.
CORROSION TESTING FOR PRODUCED WATER

SYSTEMS FIG. 11 The effect of exposure to air on the titration curve for
acidic compounds extracted from 200 mL of a crude oil
The following discussion applies to corrosion testing in produced
with 10 mL of 0.06 M NaOH using 0.01 M HCl as the
or condensed water systems and to the liquid water phase used
titrant.
for hydrocarbon gas and crude oil system corrosion testing.
Produced water is an extremely complex chemical solution
that can include minerals dissolved from formation rocks, and
water-soluble organics from the hydrocarbon phase. Simulated 9
produced water used in corrosion testing must reproduce this
complexity. Good initial analysis of the produced water to be 8
tested is essential for success of the test program. C48 CRUDE OIL
Complete removal of unwanted oxygen from the solution 7 NOT EXPOSED TO AIR
before testing is vital, because oxygen contamination can result
pH
in significant errors in the test results. The test solution is best 6
deaerated by purging with the test gas. Purging times must be
sufficient to lower the oxygen concentration to less than 20 ppb. 5
The actual purge time required will vary with the solution con- C48 CRUDE OIL
centration and temperature. A hydrazine salt solution can be 4 EXPOSED TO AIR
DURING SHIPMENT
added to the test solution before its use to remove any residual
oxygen and maintain the solution in a reducing condition for the 3
duration of the test period, if this is required.
The test gas must be in equilibrium with the test solution 2
0 10 20 30 40 50
before corrosion testing begins. Because chemical equilibrium
0.01 M HCl, ml
between the gas phase and the water phase, particularly for CO2,
can require 4 to 8 h, purging overnight before testing begins is
recommended. If the gas and water phases are not at equilib- probably originated from the CO2 in the crude oil reacting with
rium, errors in the corrosion test results are possible. Caution the NaOH. The crude oil sample that was exposed to air contains
must be exercised, however, if volatile components in the test 1.5 milliequivalents per liter of acidic compounds that are not
solution could be stripped out by the purge gas. The primary present in the unexposed sample. This phenomenon does not
goal is to generate a test solution that accurately simulates the occur for all crude oils, but it is not possible at this time to know
production environment. which crude oils will be affected.
CORROSION TESTING FOR CRUDE OIL SYSTEMS PREVENTING CHANGES IN SOLUTION CHEMISTRY
The actual production of crude oil must be used for all testing to Contamination of the test solution with corrosion products is a
evaluate corrosion in crude oil, and oxygen must never be very real problem, particularly for corrosion testing with carbon
allowed to contact the crude oil at any time. The crude oil sam- and alloy steel. In designing the corrosion test program, calcula-
ples used in corrosion tests must be obtained in a manner tions using an estimated corrosion rate should be made to deter-
designed to prevent contact of the crude oil with air. The sample mine the solution volume and maximum exposure time for the
container must be purged with inert gas before filling with crude test. During the test, and at test termination, solution samples
oil, and the crude oil must be shipped under positive inert gas should be taken and analyzed to ensure that no significant
pressure. The sample container construction must be type 316 changes in solution chemistry occurred that could affect the
stainless steel or a material of greater corrosion resistance, or the results. The formation of one mole of ferrous ion will generate
container must be lined with an inert material. The crude oil two moles of bicarbonate in a sweet environment. For many pro-
sample must be stored under an inert gas blanket. The crude duced water compositions, this is not necessarily a problem. For
oil must be transferred from its shipping container into the test condensed water, however, the bicarbonate can result in a signifi-
cell using inert gas pressure or vacuum. cant increase in solution pH. As a general guide iron concentra-
The extreme measures to ensure the complete exclusion of tions should not be allowed to exceed 10 ppm during a test.
oxygen are needed because oxygen can react with some crude This assumes that there is no dissolved iron in the produced
oils to form organic acids that were not present in the original water, however, in which case the requirement becomes to not
crude oil, and could alter the test results. Figure 11 shows the allow significant changes in the iron concentration during the
effect air exposure (oxygen) can have on the concentration of test period. Many produced waters do contain dissolved iron,
acid compounds in a crude oil. Acids in the crude oil sample but care must be exercised to ensure that the iron concentration
were extracted with 0.06 M sodium hydroxide (NaOH), which analyzed is actually contained in the produced water and is not
was then titrated with 0.01 M hydrochloric acid (HCl). The an extraneous artifact resulting from tubular corrosion.
crude oil sample not exposed to air shows a titration curve that Maintaining the dissolved acid gas concentration in the
implies that carbonate–bicarbonate is the titrated species, which solution during the test period can be a problem, particularly
when testing carbon and alloy steel for periods of more than The field data are evaluated as they relate to known corro-
30 days. This is generally overcome by rapid stirring and sparging sion information and corrosion prevention practices. At this
gas below the liquid surface. Autoclave testing is a particularly dif- point, a decision is made on the possibility of sulfide stress corro-
ficult problem in that the liquid volumes are small. One effective sion cracking, including consideration of the possibility for
method for maintaining the solution dissolved acid gas con- future H2S occurrence, even though it is not presently contained
centration is to recirculate the test solution and allow it to fall in the produced fluids. If sulfide stress corrosion cracking is a
through the gas phase when it reenters the autoclave. concern, only resistant steels are passed to the corrosion testing
phase.
The corrosion tests are conducted to determine the corro-
Application of Corrosion Testing to sion rate break produced water level for steel, which is defined as
the sudden increase in the corrosion rate between two produced
New Production water levels when testing in a series of produced water levels.20
An approach utilizing corrosion testing for application to new Generally, only one or two of the steels will need to be tested,
production is given in the logic diagram shown in figure 12.20 because there is no significant difference in the corrosion rate
Steels, including corrosion testing of steels, are appraised before break produced water level measured for the various carbon and
any consideration is given to alloys. This is done because the low alloy steels commonly used in crude oil service. The corro-
very heavy cost penalty for alloys dictates that steels generally sion rate break produced water level is determined from
should be used if technically feasible. corrosion tests conducted at 10% by volume produced water
The first step is to obtain valid field production data and increments starting with 100% crude oil until a high corrosion
samples. As discussed previously, no corrosion test is any more rate is obtained or the expected produced water limit for the field
accurate than the accuracy of the temperature, pressure, and com- is reached, or to 90% produced water level. If a corrosion rate
position data, and the sampling methodology. The well fluid com- break is observed, additional corrosion tests are conducted at 2%
position, particularly the gas analysis and produced water analysis, produced water increments between the two produced water lev-
must be reasonably accurate. The crude oil samples for use in the els that form the break.20 An example of the results from this
corrosion tests must be obtained as previously described. type of test sequence is shown in figure 13.20
FIG. 12 The logic diagram for new field corrosion testing to determine the corrosion rate break produced water level for steel corrosion,
corrosion inhibitor application, and alloy selection.
ANALYZE TEST CORROSION INHIBITORS

DETERMINE THE STEEL
CORROSION DATA AT 5% TO 10% PRODUCED
CORROSION RATE BREAK
FOR DOWNHOLE WATER LEVEL ABOVE THE
PRODUCED WATER LEVEL
CONDITIONS CORROSION RATE BREAK
CAN
OBTAIN LOCALIZED CORROSION NO STEEL
FIELD DATA TESTS FOR ALLOYS AT BE
AND DOWNHOLE CONDITIONS USED
CRUDE OIL ?
SAMPLES YES
SPECIFY
SPECIFY 1. STEELS FOR USE IN

TUBULARS,
ALLOY(S) FOR USE IN WELLHEADS AND
TUBULARS, WELLHEADS FACILITIES.
AND 2. PRODUCED WATER
FACILITIES CONSTRUCTION LEVEL WHERE
CORROSION
INHIBITOR IS REQ'D.
3. CORROSION
INHIBITOR TO USE.
relatable to the intended service environment. Following the six

FIG. 13 Change in the corrosion rate of steel in crude basic principles given here will aid immensely in obtaining suc-
oil–produced water mixtures with increasing produced cessful results. The preventive corrosion engineering technique
water content, showing a corrosion rate break at to determine the corrosion rate break produced water level for
approximately 7% produced water. steel, corrosion inhibitor treatment requirements, and alloy
1 selection can be used to minimize the cost of corrosion protec-
(CORROSION RATE AFTER 24 HOUR EXPOSURE) tion while also maximizing its effectiveness.
(71ºC, 120 psi CO2, 0.2 psi H2S)
CORROSION RATE, mm/y
0.1
References
1. Petroleum and Natural Gas Industries—Materials for Use in H2S-
Containing Environments in Oil and Gas Production, ANSI/NACE
MR0175/ISO 15156, ISO-ANSI-NACE International Standard,
0.01 CORROSION RATE BREAK
PRODUCED WATER LEVEL
2nd ed. (Houston, TX: NACE International, 2009).
2. D. A. Shock and J. D. Sudbury, “Prediction of Corrosion in Oil

and Gas Wells,” in Carbon Dioxide Corrosion in Oil and Gas
0.001 Production, ed. L. E. Newton et. al. (Houston, TX: NACE
0.10 1.0 10 100 International, 1984), 394–401.
PRODUCED WATER CONTENT, %
3. C. de Waard and D. E. Milliams, “Carbonic Acid Corrosion of
Steel,” Corrosion 31, no. 5 (1975): 177–181.
The corrosion rate break tests are followed by tests for cor- 4. C. de Waard, U. Lotz, and D. E. Milliams, “Predictive Model for
rosion inhibitor effectiveness at a produced water content CO2 Corrosion Engineering in Wet Natural Gas Pipelines” (paper
above the corrosion rate break level. At this point, the decision presentation, Corrosion/91, paper 577, NACE International,
Cincinnati, OH, March 11–15, 1991).
is made on whether or not steel can be used, based on the cor-
rosion rate data and corrosion inhibitor effectiveness coupled 5. A. Dugstad, L. Lunde, and S. Olsen, “Dewing Corrosion: A
with estimates of future produced water levels during the life of Possible Problem Area for Pipelines Transporting Unprocessed
the field. Gas over Long Distances” (paper presentation, 5th International
If steel can be used, the corrosion rate break data are Conference on Mulitphase Production, British Hydrodynamics
Research Group, Cranfield, UK, 1991).
employed to specify:
6. S. Olsen and A. Dugstad, “Corrosion under Dewing Conditions”
• the steels to use for tubulars, wellheads, and facilities; (paper presentation, paper 472, NACE International, Cincinnati,
OH, March 11–15, 1991).
• the produced water level at which the injection of corrosion
inhibitor is required; and 7. R. Nyborg, A. Dugstad. and L. Lunde, “Top-of-the-Line Corrosion
and Distribution of Glycol in a Large Wet Gas Pipeline” (paper
• the corrosion inhibitor to use when the corrosive produced
presentation, Corrosion/93, paper 77, NACE International,
water level is reached. Houston, TX, 1993).
If steel cannot be safely used, alloys must be evaluated. 8. J.-L. Crolet and M. R. Bonis, “A Tentative Method for Predicting
The consideration of sulfide stress corrosion cracking must be the Corrosivity of Wells in New CO2 Fields,” Advances in CO2
Corrosion (Houston, TX: National Association of Corrosion
made for the alloys in the same manner as for steels. The pro-
Engineers, 1985), 2:23–38.
duction environment must be duplicated in alloy corrosion
tests in the same manner as for steels. Standard corrosion tests 9. J.-L. Crolet and M. R. Bonis, “pH Measurements in Aqueous CO2
modified to use the production environment are conducted for Solutions under High Temperature and Pressure,” Carbon Dioxide
the alloys with due consideration given to the probable failure Corrosion in Oil and Gas Production, ed. L. E. Newton et. al.
(Houston, TX: NACE International, 1984), 178–184.
modes—for example, crevice and pitting corrosion for stainless
steels. On completion of this test sequence, the alloy or alloys 10. G. Schmitt and D. Engels, “SEM/EDX Analysis of Corrosion
to use for tubulars, wellheads, and facilities construction are Products for Investigation of Metallurgy and Solution Effects in
specified. CO2 Corrosion” (paper presentation, Corrosion/88, paper 149,
NACE International, St. Louis, MO, March 21–25, 1988).
11. T. Murata, E. Sato and R. Matsuhashi, “Factors Controlling

Summary Corrosion of Steels in CO2-Saturated Environments,” Advances in
CO2 Corrosion (Houston, TX: NACE International, 1985), 1:64–71.
Petroleum chemistry is complex and sensitive to error when
translated to the laboratory. Great care must be taken when 12. K. Videm and A. M. Koren, “Corrosion, Passivity, and Pitting of
designing and conducting corrosion tests for the petroleum envi- Carbon Steel in Aqueous Solutions of HCO3 , CO2, and Cl ,”
ronment to ensure that the corrosion measurements made are Corrosion 49, no. 9 (1993): 746–754.
13. H.-J. Neumann, B. Paczynska-Lahme, and D. Severin, Geology of 17. J. S. Smart, “Wetability: A Major Factor in Oil and Gas System
Petroleum, vol. 5, Composition and Properties of Petroleum Corrosion” (paper presentation, Corrosion/93, New Orleans, LA,
(New York: Halsted Press, 1985). March 7–12, 1993).
14. E. C. Donaldson, “Characterization of the Crude Oil Polar 18. K. D. Efird and R. J. Jasinski, “Effect of the Crude Oil on Corrosion
Compound Extract” (U.S. Department of Energy Publication of Steel in Crude Oil/Brine Production,” Corrosion 45, no. 2
DOE/BETC/RI-80/5, Washington, DC, October, 1980). (1989): 165–171.
15. L. R. Snyder, “Petroleum Nitrogen Compounds and Oxygen 19. K. D. Efird, “Predicting Corrosion of Steel in Crude Oil
Compounds,” Accounts of Chemical Research 3, no. 9 (1970): Production,” Materials Performance 30, no. 3 (1991):
290–299. 63–66.
16. H. H. Hasiba and F. W. Jessen, “Film Forming Compounds from 20. K. D. Efird, “Preventive Corrosion Engineering in Crude
Crude Oils, Interfacial Films and Paraffin Deposition,” Journal of Oil Production” (paper presentation, Offshore Technology
Canadian Petroleum Technology 7, no. 1 (1968): 1–12. Conference, Houston, TX, May 6–9, 1991).
251
Chapter 16 | Organic Liquids
C. Sean Brossia1
Description of Environment 100 ppm water in acetonitrile results in a water concentration of

more than 4 mM).
OVERVIEW Organic liquids are classified in a variety of ways. A com-
Organic liquids are used in a wide variety of industrial applica- mon classification scheme is based on the nature of the bonding
tions. They can be characterized as liquids that consist of one or between molecules during solvation. Using this classification
more carbon atoms joined to other atoms through covalent bonds. approach, three general categories exist: protic liquids, nonpolar
Common atoms included in organic molecules are hydrogen, oxy- aprotic liquids, and dipolar aprotic liquids. Protic liquids (e.g.,
gen, nitrogen, sulfur, and halogens. Both the rate and yield of cer- alcohols, carboxylic acids, amines, amides) are those that can
tain reactions have been found to greatly increase when provide protons to other molecules. Solvation in protic organic
performed in organic liquids. Thus, they are widely used in the solvents occurs through dipole-dipole interaction, ion-dipole
chemical process industry for synthesis. With an increase in the interaction, and hydrogen bonding. These liquids are generally
use of organic liquids, increases in observed corrosion problems miscible with water (another protic liquid) and can solvate both
associated with the exposure of materials to them also have organic and inorganic acids. Nonpolar, aprotic liquid molecules
occurred. In some cases, failures involve an unacceptably large (e.g., aromatic and aliphatic hydrocarbons) interact through
loss of metal or degradation of material properties. In many other weak van der Waals bonds and have little solvating ability. The
cases, however, the major issue is discoloration, contamination, or protons in these liquids do not dissociate to any measurable
degradation of the organic solution resulting from corrosion of extent. Dipolar, aprotic liquid molecules (e.g., acetonitrile, alde-
the processing vessel, as the solution is the product of commercial hydes, esters, ethers, dimethyl sulfoxide, tetrahydrofuran, dime-
interest. For example, many pharmaceuticals are synthesized in thylformamide) interact through ion-dipole and dipole-dipole
organic solutions in large vessels. For these applications, the corro- forces and usually strongly solvate cations and tend to be poor
sion resistance requirements for materials used are stringent. The acceptors of electrons and poorly solvate anions in solution.
introduction of metals into a product can lead to rapid degrada- Organic solvents also may have functional groups that are either
tion of the product as well as to health and safety concerns. hydrophobic, which repel water molecules, or hydrophilic, in
Although corrosion in pure organic liquids can occur, many which case the functional groups readily react with water. It has
corrosion problems in organic liquids involve solutions with been shown that the predominant interaction of a metal with an
multiple components. For example, Schindelholz et al.1 examined organic adsorbate is through its functional groups.2
unusually high corrosion rates of Alloy 22 in organic solutions at The wide variety of organic liquids leads to complexity in
room temperature and found that the prime cause was due to the analysis of corrosion problems. In addition, the large number
hydrogen chloride (HCl) formation from a reaction between of different liquids leads to difficulties because of the limited
ethyl aluminum dichloride and ethanol when combined with a physical and chemical data on specific liquids. This has ramifica-
2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Furthermore, a tions both for the recording of corrosion data and for the devel-
solution containing ethanol, water, oxygen, and HCl contains opment of a broad-based understanding of the important
four components. Some of the components may be present at corrosion processes. The lack of physical and chemical informa-
small concentrations, but these can have dramatic effects. This tion is a limiting factor in any broad description of behavior,
often is the case with water because of its low molecular mass such as found in this chapter. Also, while many testing consider-
compared with many organic liquids. Small mass percentages of ations can be generalized for organic liquids, the corrosion
water can represent significant concentrations in moles/L (e.g., behavior of materials in nonaqueous solvents is not nearly as
well understood as in aqueous solutions. As a result, appropriate
1
INVISTA, 16945 Northchase Dr., Houston, TX 77060, USA http://orcid.org/ testing and accurate interpretation of the results obtained can be
0000-0002-0522-1123 challenging.
DOI: 10.1520/MNL202NDSUP20190024
TYPES OF CORROSION solution resistance between the reference electrode and the work-
The types of corrosion (i.e., the morphology of attack and the ing electrode. The conductivity of organic liquids is often less
oxidation process) that can be encountered in organic liquids than that of pure water,5 as shown in figure 1. The resulting high
are essentially the same as those observed in aqueous solutions. solution resistance can result in the development of large ohmic
The solution chemistry and solution electrochemistry may be potentials during the passage of even small currents. These
different, but the types of fundamental corrosion processes that ohmic potentials reduce the amount of the applied potential at
can occur remain the same. An excellent review of examples of the metal–solution interface and can affect the current–potential
corrosion in various organic solutions can be found in the work distribution on an electrode. Because the amount of the error
of Heitz.3 In addition to a review of the fundamental principles changes as the applied current changes, a distorted current–
involved, Heitz critically evaluates the literature published before potential relationship can result. More information on ohmic
1973 and describes a number of industrial case histories of com- drop and ways to minimize or compensate for its effects can be
ponent failures due to corrosion in organic solutions. Kelly and found in chapter 8, “Electrochemical Tests,” in this manual.6
Moran4 summarized much of the work in aprotic liquids and One common method used to minimize ohmic drop in organic
put forth a general description of the effect of water on passiv- liquids is to add a supporting electrolyte. The ideal supporting
ation processes. That said, many organic liquids are noncorro- electrolyte is a substance that substantially increases the conduc-
sive, particularly to carbon steel. tivity of the solution without affecting the reactions that occur.
Because organic liquids do not solvate many salts in high con-
LIMITS ON COVERAGE OF SECTION centrations, often only a small amount of supporting electrolyte
Because of the wide variety of organic liquids, specific informa- can be added before reaching saturation. Supporting electrolytes
tion relevant to each one cannot be covered in limited space. The are discussed in more detail in the section “Important Experi-
focus of this chapter will be primarily on corrosion of metals in mental Variables.”
the liquid phase, although many of the comments are applicable Another approach that has been used with some success has
to nonmetals as well as vapor phase attack. Because corrosion in been through the utilization of microelectrodes. Gui and Sridhar7
organic liquids is not fundamentally different than corrosion in and Gui, Sridhar, and Beavers8 utilized microelectrodes to inter-
aqueous solution, testing procedures for types of corrosion gen- rogate the electrochemistry of steel in fuel-grade ethanol in an
erally are similar. Thus, only unique considerations with respect
to testing in organic liquids will be considered.
FIG. 1 Comparison of electrolyte conductivity (S/m) of various
VARIABLES THAT AFFECT CORROSION 5
liquids with HCl added as a supporting electrolyte.
Corrosion in organic liquids is not fundamentally different from
corrosion in aqueous solutions, and therefore, all of the variables
that affect corrosion in aqueous solutions can affect corrosion in
organic solutions. These include temperature; redox potential;
presence and concentration of salts, acids, and bases; and fluid
velocity. A number of variables (that are not possible in aqueous
solution), however, can be important in organic solutions. The
most important of these will be covered in the next section.
Aspects Making Testing Unique

Several aspects to conducting electrochemical tests in organic
liquids often are not encountered or important while testing in
aqueous solutions. These include effects resulting from low solu-
tion conductivities, the importance of the water concentration in
the solution, the existence of an extremely wide variety of liquid
compositions, the complexity of products from electroactive
organic liquids, and a lack of thermodynamic data.
The low conductivity associated with most organic liquids
can give rise to experimental problems with conducting electro-
chemical experiments. During electrochemical experiments in
which a current is applied, the potential measured is the sum of
the actual potential difference between the working and the ref-
erence electrodes plus the ohmic potential developed in the solu-
tion resulting from the passage of current through the solution,
which exhibits a finite resistance. This ohmic potential is also
known as IRS, where I is the current passing, and Rs is the
ORGANIC LIQUIDS 253
attempt to elucidate the underlying mechanisms responsible for

observed stress corrosion cracking (SCC) behavior. The use of FIG. 3 Effect of applying IR correction based on electrochemical
microelectrodes attempts to reduce the ohmic potential drop impedance spectroscopy results to polarization data for
9
(IRS) by reducing the area of the electrodes. Thus, at a given cur- steel in simulated fuel grade ethanol.
rent density, the absolute current is lower, thereby making the
error due to the ohmic potential drop smaller. Gui et al.8 used
this approach primarily to avoid using a supporting electrolyte,
which was thought to alter the polarization behavior that was of
interest. In addition, the authors also moved the reference elec-
trode as close as possible to the working electrode to help mini-
mize R. By using this combination of approaches, the authors
were able to explore the effects of different environmental varia-
bles on the polarization behavior of carbon steel in ethanol-
gasoline mixtures. A summary of the key potentials (i.e., open
circuit, repassivation, and pitting potentials) from these measure-
ments is shown in figure 2.
Gui and Sridhar7 and Gui, Sridhar, and Beavers8 as well as
Cao, Frankel, and Sridhar9,10 also utilized electrochemical imped-
ance spectroscopy (EIS) to measure the solution resistance to
perform a correction to the observed polarization behavior for
ohmic drop. In particular, Cao, Frankel, and Sridhar9,10 found
that using EIS measurements before and after cyclic polarization TABLE 1 Weight Loss of Aluminum in Organic Acids
5
tests to estimate IR drop tended to result in overcompensation at

higher currents. As is shown in figure 3, at current densities
Acid Concentration, %
above approximately 100 lA/cm2 the shown polarization behav- Acid (Remainder Water) Mass Loss, g/m2 day
ior curves downward, thus making the data unreliable. Although Acetic 99.5 0.4
the correction was not perfect, this approach was successful in Acetic 99.94 990.0
helping to identify the effect of aeration on the polarization Propionic 99.5 2.0
behavior of steel in simulated fuel grade ethanol. The results Propionic 99.4 2,650
were able to better delineate in what ways that aeration resulted
in lower pitting damage compared with the deaerated case.
water concentration. Thus, even though each acid would be con-
Water concentration in organic liquids is difficult to control
sidered commercially pure, dramatic differences in corrosion rates
and measure at low levels. Even small amounts of water, however,
resulting from small water additions are observed. This also can
can have dramatic effects on the corrosion behavior, as shown in
be true for other impurities that often are present in organic
table 1. In this case, the corrosion rate of aluminum decreases by
liquids. Thus, the measurement and control of water levels can be
three orders of magnitude because of a 0.3 mass % increase in the
a key aspect to corrosion testing in organic liquids.
A popular technique to measure water content is the Karl
Fischer titration method.11 This method can reliably analyze
FIG. 2 Effect of oxygen concentration in the gas phase on the water contents as low as 100 ppm (0.01 mass %). Aliquots of
key potentials of carbon steel as a microelectrode solution can be taken before, during, and after an experiment to
measured against an ethanol-based silver–silver chloride follow any changes in water content. Such changes can occur
reference electrode using the cyclic potentiodynamic because of the tendency of some organic liquids to absorb water
8
polarization method in simulated fuel grade ethanol. from the ambient atmosphere. For example, it has been found
that the water content of a 100 mL sample of methanol, exposed
to laboratory air at 25 C with a relative humidity of approxi-
mately 55%, increased from 0.035 mass % to 0.42 mass % in 2 h,
as shown in figure 4.12 This illustrates the need for incorporating
a sealed experimental cell or a dry glove box when working at
low water levels. By using one or both of these, water absorption
can be minimized and water levels of 100 ppm and below can be
realized in the pure organic liquid. Care must be taken when
adding other components to the anhydrous liquid, as most salts
as well as electrodes also can add appreciable amounts of water
to the solution, which then is difficult to remove. Also, extremely
dry solutions can sometimes pose a safety hazard if suddenly
exposed to air or water.
to be considered when testing in such organic liquid mixtures,

FIG. 4 Increase in water concentration in methanol due to which typically are not considered in aqueous solutions. First,
12
absorption from the atmosphere at ambient conditions. the possibility exists that when two or more liquids are com-
bined, they are either immiscible or have limited miscibility.
This results in the formation of multiple liquid phases (phase
separation) in which the properties of each phase could be sig-
nificantly different from others. The net result is that testing in
mixtures can be difficult. The difficulty arises in trying to deter-
mine which phase or composition is detrimental to material
behavior and also may involve partitioning of dissolved species
between the various phases present. The possibility also exists
that it is not an individual phase, but rather the interface
between two phases in solution that is deleterious. Multiphase
solutions cause special problems, such as concentrations of
aggressive species into one phase (e.g., HCl into the aqueous
phase of a HCl/water/dioxane mixture),3 specific adsorption of
one phase at the metal surface, and preferential attack at the
phase boundary (akin to waterline attack). Additional discus-
sion of multiphase attack is outside the scope of this chapter
but can be found in Heitz’s review.3
Organic liquids encompass an extremely wide variety of One important complication for the study of corrosion in a
compounds. They can be classified into two main categories: large variety of organic liquids is the paucity of thermodynamic
aprotic (which are generally water insoluble) and protic (which data. Thus, an equivalent to Pourbaix diagrams,13 used widely in
are generally water soluble). Many solution properties, such as aqueous solutions, has not been extensively developed for
solvating power, depend on the primary functional groups of the organic liquids. In fact, pH in organic liquids is not relevant in
organic liquid. Thus, the protic nature of a given organic liquid aprotic organic solvents because there is no readily available
will determine the solubility of various impurities and corrosion hydrogen. In nonaqueous solutions, however, it is possible to
products. Even within a type of organic liquid, important differ- generate more powerful proton donors than the hydronium ion
ences emerge among individual liquids. For example, the corro- found in aqueous solutions by way of the following reaction:
sion rate of iron decreases in monocarboxylic acids as the chain
length increases (fig. 5).3 These differences among similar organic B þ H þ $ BH þ : (1)
liquids add another layer of complexity to the corrosion phe- The strength of these possibly extremely strong acids in
nomena as compared with aqueous solution. nonaqueous solutions is measured by the Hammett acidity func-
Cosolvent interactions are related to liquid composition tion,14 which is defined as follows:
effects. In many applications, a mixture of liquids (organic/
organic, organic/inorganic) is of interest. Several aspects need þ ½BH þ
H0 ¼ pKBH log , (2)
½B
where:
FIG. 5 Corrosion rate (mm/y) of iron in mono-carboxylic acids of B ¼ the nonaqueous solvent.
different chain lengths (i.e., formic, acetic, propionic,
3 No standard metal–solution potential difference has been
butyric).
defined for all liquids. Some of the behavior in organic liquids
can be explained by using the concept of Lewis acids and bases
employed in aqueous chemistry. A Lewis acid is an electron pair
acceptor, and a Lewis base is an electron pair donor. All the usual
ligands can be considered to be Lewis bases and metal ions can
be considered to be Lewis acids.
Because of these complications, thermodynamic data in the
literature pertaining to specific material–aqueous solution sys-
tems (e.g., Pourbaix diagrams) may not necessarily be valid for
the same material in organic liquids. Some efforts have been
made to develop electromotive series in different liquids, as
shown in figure 6. The reference point is given by the ferrocene/
ferriciniumþ couple. The selection of a reference electrode is dis-
cussed later in this chapter. In general, the order of reversible
potentials is maintained from aqueous solutions, although the
ORGANIC LIQUIDS 255
FIG. 6 Electromotive series for the redox reactions associated

Important Environmental Variables
with different materials in water and organic media. The environmental variables that influence corrosion testing in
organic liquids include metal, alloy, or nonmetallic material in
contact with the organic solution, solution conductivity, solution
acidity, water content of the solution, presence and stability of
oxide or other preexisting films, type and concentration of surface
contaminants or inclusions, functional group and concentration
of organic solvent, solvent oxidation or reduction products, type
and concentration of supporting electrolyte, applied potential,
possible mechanistic paths for passivation, and temperature. As in
all corrosion testing, matching the test environment to the actual
service environment is critical for obtaining useful information. In
addition, by studying the effects of these variables on the corrosion
processes, better insight into the controlling mechanisms, as well
as the sensitivity of the corrosion processes to changes in the
service environment, can be gained.
As noted, the high resistances often associated with organic
solutions can distort electrochemical measurements. To mini-
numerical values can change appreciably. That is, in most envi- mize these ohmic losses, supporting electrolytes are often used.
ronments, the redox potential for silver, given by Ideally, supporting electrolytes dissociate and increase the solu-
tion conductivity without altering the corrosion process under
Ag $ Ag þ þ e (3) study. A commonly used electrolyte is lithium perchlorate
(LiClO4) in concentrations ranging from 10 to 500 mM. The per-
typically will be at more positive potentials than the correspond- chlorate anion is thought to be inert in most solutions and is
ing redox reaction for hydrogen, given by weakly adsorbing to surfaces. Thus, LiClO4 is not expected to
affect the electrochemical reactions considered in most organic
H2 $ 2H þ þ 2e : (4)
liquids. The addition of 0.1 M LiClO4 as a supporting electrolyte
The absolute value and the relative difference between differ- to methanol can increase the conductivity from 106 S/cm5 to
ent redox reactions, however, are not constant and can vary 6 103 S/cm, thereby reducing the ohmic resistance by a factor
significantly. of 200. This reduction allows the experimenter to more easily
Finally, as is the case for water, organic liquids have a compensate for the ohmic drop. For fundamental studies of cor-
limited range of electrochemical stability. The products of elec- rosion in organic liquids, the addition of a well-chosen support-
trochemical reactions involving organic liquids often are electro- ing electrolyte is a reasonable approach to allow electrochemical
active and can become involved in the electrochemical or information to be gathered. For more applied measurements, the
chemical reactions that are of interest. Although solution oxida- addition of any supporting electrolyte salt should be considered
tion or reduction also can occur in aqueous solutions, the prod- carefully and comparison tests (e.g., coupon exposures) should
ucts are simple bases or acids (i.e., Hþ and OH). The products be performed to verify the absence of an effect of the supporting
resulting from electroactive organic liquids, however, usually are electrolyte on the corrosion process. If a supporting electrolyte is
a mixture of complex organic acids. These complex organic acids not added, caution must be used in the gathering and interpreta-
can combine with other ions in solution and form other chemi- tion of electrochemical data. In some cases, if a supporting elec-
cals that could be even more aggressive than the acid from which trolyte cannot be added and the solution resistance is high, the
they were derived. This has been shown to be an issue in metha- performance of meaningful electrochemical measurements is
nol by Smialowska and Mankowski,15 who found that galvano- extremely difficult.
static polarization of stainless steel in pure methanol resulted in Acids have often been used as supporting electrolytes.5
the formation of formic acid as follows: Strong acids—for example, sulfuric acid (H2SO4), HCl, and nitric
acid (HNO3)—generally enhance the conductivity of organic sol-
CH3 OH ! CH2 O þ 2H þ þ 2e , (5) utions greatly. Some organics, however, are susceptible to degra-
dation in acids. When water is present, acid hydrolysis becomes
CH2 O þ H2 O ! HCOOH þ 2H þ þ 2e , and (6) an additional degradation pathway.16 Also, the acidity of the
solution can have a controlling effect on the corrosion behavior
HCOOH ! CO2 þ 2H þ þ 2e : (7) of metals in organic solutions. For example, a recent review4 of
the literature on the corrosion of metals in aprotic liquids
The observed oxidation current was a mixture of metal dissolu- has shown that corrosion behavior, and more specifically, the
tion and methanol oxidation, complicating comparisons of mate- mechanisms of passivity, are affected by the acidity of the solu-
rial loss and charge passed based on Faraday’s second law. tion. The mechanisms of passivation were classified into four
types: (1) air-formed film, (2) salt film, (3) chemisorption of the
liquid, and (4) oxide/oxyhydroxide formation. Acidity is deleteri- FIG. 7 Plot of dielectric constant versus dipole moment for
ous to all four passivation mechanisms in organic solutions. different nonaqueous environments illustrating in which
29
Hence, control of acidity is important. In addition to Hþ, acidity environments SCC has been observed.
also implies the presence of a corresponding anion. Its presence
can alter material behavior by adsorbing to the surface in addi-
tion to increasing the solution conductivity.
Thus, acids should not be considered as supporting electro-
lytes, because they influence the behavior observed, unless the
service environment contains acids, in which case they should be
included in the test solution. An additional passivation mecha-
nism has been proposed by Shifler, Moran, and Kruger involving
the formation of a passive electro-polymerized film (polymer
films in which the polymerization process is electrochemically
activated) on bare steel surfaces in dimethoxyethane (DME)/
LiAsF6 solutions at potentials above the oxidation potential of
DME.17 The complex electropolymerization mechanism for car-
bon steel in DME/propylene carbonate mixtures with LiAsF6 as
the supporting electrolyte depends on the following: (1) DME
concentration, (2) cationic intermediate adsorbed concentration dielectric constant is a measure of ionic species dissociation in
and degree of coverage, (3) LiAsF6 concentration, (4) applied the given solvent. It was further argued that the dipole moment
potential, (5) rate of iron cation dissolution, and (6) water can be related to the dielectric constant through the following:
concentration. Decreases in any of these factors will either

decrease the rate of electropolymerization or may prevent elec- ðe 1Þð2e þ 1Þ 4pN l2 g
¼ aþ , (8)
tropolymerization entirely.18 Numerous other investigators 9e 3 3kT
also have examined the role of electro-polymerized films as a
where:
means of metal passivation in dioxolane,19,20 ether,21–24 pyr-
e ¼ the dielectric constant,
role,25,26 and carbazoles/dicarbazoles with polyether chain sub-
N ¼ Avogadro’s constant,
stitution,27 and phenol.28 For clarification, table 2 contains the
t ¼ the molar volume,
physical data for many solvents commonly encountered. Table 2
l ¼ the dipole moment,
is not intended to be a complete list, but rather to provide the
g ¼ a correlation factor that relates how neighboring molecules
reader with a sense of the range of physical properties of
are orientated with each other,
organic solvents.
k ¼ Boltzmann’s constant, and
Interestingly, Sridhar29 put forth an argument that the phys-
T ¼ temperature.
ical properties of the nonaqueous liquid, in particular the dielec-
tric constant and the dipole moment, may provide some ability Environments that have low dielectric constants and low dipole
to predict when SCC of carbon steel might take place. As shown moments, thus, are less likely to cause cracking because of the
in figure 7, nonaqueous systems that have higher dielectric low amount of dissociation of any ionic species present as well as
constants also coincide with observed cracking behavior. The low polarity (dipole moment). This at least sets the foundational
TABLE 2 Some Typical Physical Properties of Selected Solvents at 25 C
Solvent M.W., g/mole Density, g/cm3 Dielectric constant, e Viscosity, cP Dipole Moment (Debye) Formula
Water 18.0152 0.997044 78.30 0.8904 1.87 H2O

Methanol 32.042 0.7864 32.66 0.5513 2.87 CH4O
Propylene carbonate 102.090 1.1951 64.92 2.53 4.94 C4H6O3
Dimethoxyethane 76.95 0.859 7.20 0.455 1.07 C3H8O2
Tetrahydrofuran 72.12 0.880 7.58 0.46 1.71 C4H7O
Dioxolane (1,3-D) 74.079 1.0640 (20 C) 7.13 0.589 1.47 C3HA
Acetonitrile 41.052 0.88649 35.95 0.341 3.53 C2H3N
Dimethysulfoxide 78.129 1.09537 46.45 1.991 4.06 C2H6OS
Dimethylformamide 73.094 0.94873 36.71 0.802 3.24 C3H7ON
Pyrrole 67.09 0.9691 (20 C) 7.5 @ 17 C C4HSN
Phenol 94.11 1.07 4.3 @ 10 C C6H5OH
ORGANIC LIQUIDS 257
stage from which different systems exhibit differences in crack-

ing behavior. FIG. 8 The effect of water content on the anodic polarization of
35
As noted, when mixtures of nonaqueous liquids have been nickel in methanol containing 1 M H2SO4.
combined, unexpected corrosion results have occurred. Schindel-
holz et al.1 investigated why high corrosion rates for Alloy 22
where observed during pharmaceutical production. To deter-
mine what was causing this, the authors systematically varied
each main compositional variable in different combinations. In
addition, they also conducted controlled negative tests to prove
that other combinations and variables did not cause corrosion
rates as high as 25 mm/y at room temperature. Because of this
disciplined approach, they identified that the key was a reaction
between ethyl aluminum dichloride and ethanol when combined
with a 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. As this work
illustrates, when investigating mixed solvents, it is critically
important to examine each component in isolation as well as in
combination, which requires a more complex and rigorous test-
ing approach than typically is needed in aqueous environments.
The supporting electrolyte, which frequently is added, also
may play an integral role in passivation processes. In supporting
electrolytes, increasing the size of the counter-ions may lead to a
decreased film mobility and polyvalent ions, acting as stronger
acids, may enhance the formation of cross-links between chains
FIG. 9 The effect of water content on the anodic polarization of
and electrolyzed films.30 It has also been observed that AsF6-, 39
iron in propylene carbonate at 25 C.
added as a supporting electrolyte, can be an integral component
of the polymerization process on iron24 and carbon steel17 in
DME. The use of either tetrabutylammonium perchlorate
(TBAP) or LiClO4 as supporting electrolytes leads to alloy break-
down around the solvent oxidation potential.31 The oxidation of
aluminum was found to be influenced by the nature of the pas-
sivation mechanisms in nonaqueous solutions, which depended
on the kind of electrolyte salt.32
The water concentration in the experimental testing solu-
tion should duplicate as accurately as possible the water concen-
tration found in the actual service solution. This is because the
concentration of water present in the testing environment affects
material behavior and the solvating ability of the solution. The
presence of water in minimal concentrations (0.1–0.5 mass %) in
acidified protic organic liquid solutions leads to the passivation
of several materials. For example, iron, stainless steel, and nickel
exhibit this behavior in methanol,33–35 as shown in figure 8.
Water concentrations outside this range generally lead to
increased corrosion rates.34,35 In neutral aprotic organic solu-
tions, water in any concentration, except in high concentrations
(i.e., 80 þ mass %), tends to be deleterious. For example, iron
and nickel in neutral dimethylsulfoxide were passive only when
the water content was low (0.02 mass % for iron and 0.01 mass
% for nickel).36,37 Iron in neutral propylene carbonate solutions hydrogen bonds to form between the water hydrogen and the
exhibits similar behavior,38,39 as shown in figure 9. For other ether oxygen. Water added to DME increases the passive range
materials and liquids, for example, molybdenum and chromium of steel, as shown in figure 10, by several hundred millivolts17 and
in methanol and dimethylformamide, and iron in acidified dime- of iron by contributing to hydrogen bonding or as a Lewis acid.41
thylformamide, no clear dependence upon water content is Thus, as stated earlier, water content needs to be closely moni-
observed.35,40 Additionally, water can decrease the solvation abil- tored and controlled.
ity of organic liquids, thus inhibiting the solvation of impurities The preexistence of a surface film can affect testing in
and corrosion products. In contrast, anhydrous ethers cannot organic solutions in several ways. In the absence of aggressive
form hydrogen bonds, but the small additions of water allow species, an air-formed film can be protective even under anodic
influence the corrosion rate. For example, the corrosion rate of

FIG. 10 The effect of water content on the anodic polarization of iron in monocarboxylic acids of different chain lengths was stud-
17
carbon steel in DME at 25 C. ied and showed that as the chain length increased, the corrosion
rate decreased.3 Often, organic liquids contain impurities, such
as water, acids, and metal ions. Although these impurities gener-
ally have low concentrations in commercially purchased organic
liquids, these concentrations could still be significant. For exam-
ple, nickel in dimethylsulfoxide was passive only when the water
concentration was below 100 ppm. Therefore, the testing solu-
tion may need to be purified such that the experimental testing
solution closely matches the service solution. In contrast, some
corrosion problems develop because of the presence of impuri-
ties, so that an initially pure liquid may need to have impurities
added to mimic the attack observed. Additionally, if accelerated
testing is desired, care should be taken to ensure that the corro-
sion mechanisms and the location of the corrosion attack (e.g.,
vapor phase, immersed phase, etc.) accurately mimic in-service
observations.
In most organic solutions, the nature of the cathodic pro-
cess is unclear. In aqueous solutions, water reduction is the most
common cathodic reaction, with the reduction of dissolved oxy-
polarization. Examples of this include iron in propylene carbon- gen also being very important. The electrochemical reduction of
ate38,39 and ferritic stainless steel (Fe-18%Cr) in methanol.42 The many organics is very sluggish, however, and usually poorly
presence of competing mechanisms may also contribute to characterized. Often, the reduction of residual water is assumed
breakdown of metals and alloys in multicomponent organic mix- to be the predominant cathodic reaction. The role of molecular
tures as observed for steel in PC-DME mixtures.43 Propylene car- oxygen on the corrosion process in organic solutions has not
bonate interferes with DME electro-polymerization by solvating been characterized. Its solubility, however, is nearly 10 times
organic cations or cationic radical, or by contaminating the poly- higher in methanol than in water,3,50 making it a potentially
mer to form pores that allow charge and ionic species to pass much more influential oxidant. Additionally, aliphatic ethers are
through. Adding water to PC-DME mixtures allows for the pos- slowly converted to unstable peroxides when in contact with
sibility of aqueous passivating mechanisms that further compli- oxygen or air, leading to an unsafe condition that could induce a
cate solvent interactions and competition.18 Even if aggressive violent explosion during distillations.16 Deaeration by the passage
species are present in the solution, however, the air-formed film of an inert gas through the solution must be performed with care
may be protective until sufficient anodic polarization is achieved. to avoid the selective evaporation of the liquid. For low-boiling-
This creates the need for a testing technique that permits point liquids, such as methanol, this is of particular importance.
removal of the film, enabling examination of the base metal. This For high-boiling-point liquids, such as propylene carbonate, the
can be accomplished by using a stylus to scratch the surface, passage of ultrahigh-purity nitrogen through the solution for
thereby removing any preexisting protective film to expose new extended times can be used to selectively evaporate the water,
metal. By monitoring the current over time, the corrosion behav- leading to higher purity solutions, even after the addition of elec-
ior of the material in the absence of any preexisting film can be trolytic salts.39 The study of solution electrochemistry on plati-
observed. The long-term stability of air-formed oxides in organic num often can give insight into the nature of the cathodic as well
solutions is not known, and thus, the corrosion processes that as anodic reactions.
occur on bared surfaces may be the most relevant to the service Temperature affects corrosion testing in organic liquids in
conditions. In aqueous solution, cathodic polarization often is that the reaction rates, charge transport diffusional coefficient,
used to remove air-formed films. Extensive work in the literature and rate of liquid evaporation are increased and the potential for
on iron and ferrous alloys,44 as well as other materials,45 support ignition or explosion is greater. The effect of temperature on
the idea that this approach leads to an oxide-free surface. Such reaction kinetics, in general, follows the same principles that
information does not exist for oxide reduction in organic liquids. hold true for other heterogeneous chemical reactions.3 Corrosion
Many workers, however, cathodically polarize their samples rates of iron in monocarboxylic acids increase by a factor of 8 to
before performing electrochemical measurements.34,46–49 20 by increasing the temperature from 25 C to 80 C. Although
Because the composition and purity of the organic liquid this behavior is not unique to organic liquids, it is important to
can strongly affect the corrosion process, a key feature to testing realize that deviations in testing temperature compared with ser-
is the choice of an appropriate experimental testing solution. vice temperature could lead to erroneous conclusions. Elevated
This solution should be as close in composition and impurity temperatures also may lead to alternative reaction pathways,
concentrations to the service solution as possible, unless acceler- leading to other organic intermediate species. Temperature may
ated testing is desired. The composition of organic liquids can result in hysteresis in macroscopic polymer properties, such as
ORGANIC LIQUIDS 259
swelling, elasticity, and turbidity.30 If testing at elevated tempera- organic chemistry literature. This allows for an identification of
tures is called for, caution and appropriate safety preparations the expected by-products. Analysis of solutions after the expo-
are needed. sure will allow for a quantitative measurement of the degradation
rate of the liquid in the absence of any interaction with the cor-
roding materials. Comparison of the results with analyses of the
Laboratory Testing liquid exposed to metal coupons also may give insight into the
nature of the cathodic reaction that occurs.
The two types of laboratory testing are coupon testing and elec-
Water ingress during coupon testing must be monitored if
trochemical testing. This section discusses the special consider-
it is suspected that water concentrations are important in the sys-
ations for each type of testing when organic liquids are involved.
tem under study. During testing, seals can develop minute leaks,
allowing water levels to increase. Constant purging with an inert
COUPON TESTING
gas is an option if the boiling point of the solution is high. For
Exposure of coupons to the solution of interest with post-test
many organics, this is the case. For example, the boiling point of
evaluation according to accepted standards, such as ASTM G31,
propylene carbonate is more than 200 C. For low-boiling-point
Standard Guide for Laboratory Immersion Corrosion Testing of
liquids, such as methanol (b.p. ¼ 64.9 C), constant purging will
Metals, is the most directly applicable method of testing in
drive off liquid, increasing the concentration of the dissolved
organic liquids. Because of the general lack of data on corrosion
nonvolatile species with time.51
in organic liquids, coupon testing often takes on additional
importance. Although standard test practices have been devel-
oped mostly for aqueous solutions, the protocols are essentially ELECTROCHEMICAL TESTING
independent of the chemical nature of the environment, with For the most part, electrochemical testing in organic solutions is
minor exceptions. More detailed information on laboratory no different than such testing in aqueous solutions, The same
coupon testing can be found in ASTM G31. One of the most experimental arrangements are used, and the appropriate stand-
important caveats for such testing in organic solutions is the ards, such as ASTM G5, Standard Test Method for Making
need to check that the materials that make up the test apparatus Potentiostatic and Potentiodynamic Anodic Polarization Meas-
are not affected by the liquid. Many nonmetallics are degraded urements; ASTM G59, Standard Test Method for Conducting
by or preferentially absorb organic liquids, leading to dimen- Potentiodynamic Polarization Resistance Measurements; and
sional and mechanical property changes. If such materials are ASTM G61, Standard Test Method for Conducting Cyclic Poten-
used as spacers in a coupon exposure rack, unexpected experi- tiodynamic Polarization Measurements for Localized Corrosion
mental variability can result. For example, the nonmetallics Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys, are still
may act as getters for aggressive species, produce aggressive applicable (see section “Relevant ASTM Standards” in this chap-
species that normally would not be present, or produce inhibit- ter). Chapter 8 in this manual, “Electrochemical Tests,” should
ing agents that bias the results. Compounds that have been be consulted for other information on that subject. This section
used as mounting materials successfully in aqueous solution focuses on the special considerations in electrochemical testing
often do not perform well in either completely organic solu- in organic solutions.
tions or in mixed organic–aqueous solutions. Thus, a first step The most central difficulty in electrochemical testing of
in coupon testing is careful selection of the exposure rack and materials in organics is the choice of a suitable reference elec-
spacer materials. Often, information of this sort is available trode. Aqueous reference electrodes, such as saturated calomel
from the material manufacturer. For example, many nonmetal- (SCE), have been widely used in such studies,34,40,42,46,49,51,52 but
lics have been tested for weight loss or gain and mechanical can suffer from three types of problems. Because these reference
properties after exposure to a range of different types of organ- electrodes are in contact with the test solution, water can diffuse
ics (e.g., alcohols, aliphatics, aromatics) at ambient and elevated from the reference electrode into the test solution, thereby
temperature. Although these data can provide general guidance, changing the concentration of water during the test. The organic
accelerated tests in the environment of interest often may be liquid also will diffuse into the reference electrode, and may foul
warranted. the interface, leading to irreversible changes in its potential. Such
A second important aspect of laboratory coupon testing in a change cannot be detected easily, as it would be superimposed
organics is the possibility of an evolution of the solution compo- on any change in the potential of the working electrode. A sec-
sition during the test. These changes can be severe, especially at ond difficulty with using aqueous reference electrodes is the
elevated temperatures used to accelerate the corrosion process. development of a liquid junction potential. This potential devel-
Elevated temperature also will accelerate many organic liquid ops at the interface of the aqueous solution and the nonaqueous
degradation processes, including oxidation by ultraviolet (UV) solution because of the large difference in composition. Such
light. This can be severe in some instances. Thus, it is important potentials are extremely difficult to measure or calculate and
to run solution blanks simultaneously. In these tests, no coupon vary with time because of the interdiffusion of the two solutions.
is added to the solution under test, so its composition can be The third possible difficulty that may be encountered is reference
checked both before and after the testing to see whether any sig- electrode plugging. This is particularly troublesome when potas-
nificant changes in composition have occurred. Degradation sium chloride–based reference electrodes are used in perchlorate
reactions for many organics are well studied and available in the solutions. As the potassium diffuses out of the reference
electrode, precipitation of potassium perchlorate (KClO4) may

occur. FIG. 11 Effect of potential on measured carbon steel stress
Some research exists on organic liquid–based reference elec- corrosion crack growth rate and anodic dissolution in
10
trodes that have been successfully used in electrochemical simulated fuel grade ethanol.
studies.1,7–10,53–55 These include the Ag/AgClO4 (propylene carbon-
ate),53 Ag/AgCl (multiple),1,7–10,54 and numerous others, as detailed
in Ives and Janz.55 The Ag/AgClO4 reference electrode developed
by Kirowa-Eisner and Gileadi53 is easy to prepare, stable over
time, highly reproducible, and easily stored. This electrode has
been used successfully in conducting electrochemical experiments
in propylene carbonate solutions. Similarly, the Ag/AgCl (metha-
nol) reference electrode developed by Brossia and Kelly54 has simi-
lar characteristics and has been successfully employed in
electrochemical experiments conducted in methanol, ethanol,7–10
and other organic solutions.11 Using a reference electrode in which
the electrolyte is based on the testing solution will minimize con-
tamination of the testing solution as well as fouling of the refer-
ence electrode and the liquid junction potential.
Another aspect of electrochemical testing in organic solu-
tions is the isolation of the counter-electrode from the working
electrode. In aqueous solutions, this is often ignored, because the
predominant reactions at the counter-electrode are either oxygen
evolution (producing Hþ) or hydrogen evolution (producing
OH) during cathodic and anodic polarization of the working • ASTM E1064, Standard Test Method for Water in Organic
electrode, respectively. Liquids by Coulometric Karl Fischer Titration
Especially in a buffered solution, these reaction products • ASTM G1, Standard Practice for Preparing, Cleaning, and
have little effect. In an organic solution, however, the products of Evaluating Corrosion Test Specimens
the reactions at the counter-electrode are often more complex, • ASTM G5, Standard Test Method for Making Potentiostatic
and usually unknown. Thus, it is usually good practice to isolate and Potentiodynamic Anodic Polarization Measurements
the counter-electrode from the working electrode with porous
• ASTM G30, Standard Practice for Making and Using U-Bend
frits. This will minimize, but not eliminate, any effects of those
Stress-Corrosion Test Specimens
reaction products.
• ASTM G31, Standard Guide for Laboratory Immersion Corro-
STRESS CORROSION CRACKING TESTING sion Testing of Metals
Similar to what has been deployed to investigate SCC in aqueous • ASTM G38, Standard Practice for Making and Using C-Ring
environments, SCC testing in organic liquids also has been per- Stress-Corrosion Test Specimens
formed7–10,56–62 and in some cases, it has been combined with
electrochemical measurements to better elucidate the interaction
Bent-Beam Stress-Corrosion Test Specimens
between key electrochemical parameters and cracking behav-
ior.7–10,58–59,62 An example of the types of results that have been • ASTM G59, Standard Test Method for Conducting Potentiody-
generated are shown in figure 11.10 Cao et al.10 were able to deter- namic Polarization Resistance Measurements
mine that the rate of dissolution of carbon steel in simulated • ASTM G61, Standard Test Method for Conducting Cyclic
fuel-grade ethanol seemed to track similarly with potential as the Potentiodynamic Polarization Measurements for Localized
measured crack growth rate from compact tension SCC tests. Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based
Both crack growth rate and anodic dissolution rates peaked in Alloys
the same potential range as that observed for SCC in slow strain
• ASTM G100, Standard Test Method for Conducting Cyclic Gal-
rate tests. These various test methods were deployed following
vanostaircase Polarization
the same guidelines found for tests in aqueous systems but
accounted for complications such as IR drop arising from testing • ASTM G102, Standard Practice for Calculation of Corrosion
in ethanol. In this case, the authors used EIS to correct for the IR Rates and Related Information from Electrochemical
drop in their measurements. Measurements
• ASTM G129, Standard Practice for Slow Strain Rate Testing to
Evaluate the Susceptibility of Metallic Materials to Environ-
Relevant ASTM Standards mentally Assisted Cracking
• ASTM E203, Standard Test Method for Water Using Volumet- • ASTM G168, Standard Practice for Making and Using Pre-
ric Karl Fischer Titration cracked Double Beam Stress Corrosion Specimens
ORGANIC LIQUIDS 261
• ASTM G192 Standard Test Method for Determining the Crev-

FIG. 13 Effect of temperature on measured corrosion rates for
ice Repassivation Potential of Corrosion-Resistant Alloys Using
carbon steel in three organic liquids of slightly different
a Potentiodynamic-Galvanostatic-Potentiostatic Technique
composition obtained using electrical resistance
65
corrosion probes.
LABORATORY TESTING USING CORROSION
MONITORING TOOLS
Corrosion monitoring tools can offer a sensitive way in which to
study corrosion reactions in organic systems under controlled
laboratory conditions. Corrosion monitoring typically includes
the exposure of coupons and the use of electrochemically and
non-electrochemically-based probes. Corrosion coupons and
electrochemical test methods were discussed previously. One of
the most commonly used non-electrochemically-based corrosion
monitoring probes is the electrical resistance method. Corrosion
monitoring probes changes in electrical resistance have been in
use since the mid- to late-1950s.63,64 Because the sensing element
made of the material of interest is exposed to the environment
and experiences corrosion, its cross-sectional area will decrease,
resulting in an increase in the measured resistance. If this resis-
tance is monitored in real time and depending on the sensing the 316 stainless steel remains relatively constant over the entire
element shape and size, very small changes in corrosion rate can temperature range varying from 0.51 to 0.77 mm/y. Figure 13
be observed. Because no electron transfer occurs through the shows the effect of temperature on the corrosion rate of carbon
environment, electrical resistance probe measurements are not steel in an organic liquid with three different compositions. In the
hindered by high-resistivity media, such as organic liquids. In case of composition A, the corrosion rate was observed to steadily
fact, these probes often are used in the oil and gas industry and increase from 3.5 to 360 mm/y as the temperature increased from
also often are deployed to monitor corrosion under atmospheric 50 C to 200 C. In composition B, the corrosion rate remained rel-
conditions in which only an intermittent thin film electrolyte atively low (on the order of 1 mm/y) up to a temperature of
layer is formed. 120 C, at which point the corrosion rate suddenly increased dra-
Figure 12 and figure 13 show data obtained in a set of organic matically increasing to 854 mm/y at 125 C. In composition C, the
liquids consisting of nitriles and long-chain carboxylic acids. In corrosion rate increased steadily with increasing temperature simi-
figure 12, the corrosion rate for carbon steel and 316 stainless lar to composition A; however, the corrosion rates measured were
steel are compared over the temperature range of 70 C to 300 C considerably lower. At 50 C, the corrosion rate in composition C
using electrical resistance probes. As can be seen, in this system, was 1.5 mm/y and then increased to 4.1 mm/y at 200 C. As these
the corrosion rate of carbon steel is initially on the order of results indicate, a reasonable picture of corrosion behavior of dif-
1–2 mm/y until the temperature reaches approximately 125 C, at ferent materials and the effect of composition and temperature
which point it begins to increase significantly ultimately reaching can be obtained using this approach.
values over 100 mm/y at 300 C. In contrast, the corrosion rate of Electrical resistance probes, however, do experience issues
and confounding effects. If conductive surface scales or deposits
form, the resistance of the sensing element will tend to decrease,
FIG. 12 Effect of temperature on measured corrosion rates for providing a negative corrosion rate. Compensating for the change
carbon steel and 316 stainless steel in an organic liquid in metal resistance as a function of temperature also must be per-
65
obtained using electrical resistance corrosion probes. formed if tests are conducted at elevated temperatures.
Field Testing
The approach to field studies of corrosion in organic liquids is
no different than that used for aqueous corrosion. The choice of
coupon size, rack design, test length, and other variables is more
strongly influenced by the goals of the testing than by the testing
medium. Safety concerns also must be addressed. Different
organic liquids have different properties and safety issues, and
appropriate references and experts should be consulted. More
guidance on the general topic of field testing can be found in
ASTM G4, Standard Guide for Conducting Corrosion Tests in
Field Applications. The concerns expressed in the previous
section on laboratory coupon testing with regard to the effects of 7. F. Gui and N. Sridhar, “Conducting Electrochemical
the organic liquid on the nonmetallic components of the mount- Measurements in Fuel-Grade Ethanol Using Microelectrodes,”
ing hardware should be considered. Corrosion 66 (2010): 045005-1.
Because the corrosion behavior of materials in organic liquids 8. F. Gui, N. Sridhar, and J. A. Beavers, “Localized Corrosion of
can be influenced by low levels of water, minimizing the introduc- Carbon Steel and Its Implications on the Mechanism and
tion of water from the ambient atmosphere during the introduc- Inhibition of Stress Corrosion Cracking in Fuel-Grade Ethanol,”
tion of samples or probes should be carefully considered. For Corrosion 66 (2010): 125001-1–125001-12.
long-term testing at sites where there is a constant turnover of 9. L. Cao, G. S. Frankel, and N. Sridhar, “Effect of Oxygen on
solution, these effects may be small for a one-time insertion of Ethanol Stress Corrosion Cracking Susceptibility: Part 1.
coupons. If, however, a retractable electrochemical probe is used, Electrochemical Response and Cracking-Susceptible Potential
the solution with which it comes into contact should be flushed to Region,” Corrosion Science 69 (2013): 768–780.
allow it to sample the most relevant environment. 10. L. Cao, G. S. Frankel, and N. Sridhar, “Effect of Oxygen on
In all field testing, the effects of variability in the composi- Ethanol Stress Corrosion Cracking Susceptibility: Part 2.
tion of the stream being studied on the corrosion processes must Dissolution-Based Cracking Mechanism,” Corrosion Science 69
be considered. Because small changes in the composition in (2013): 851–862.
organic solutions can have dramatic effects on the corrosion rate
11. R. F. Milton and W. A. Waters, eds., Methods of Quantitative
as well as the stability of passive films, large transients in corro- Micro-Analysis, 2nd ed. (London: Edward Arnold, 1955).
sion rate may be experienced. Thus, it is important to comple-
ment the corrosion measurements with solution composition 12. C. S. Brossia, “Iron Corrosion in Methanol Solutions” (M.S. thesis,
measurements to develop an understanding of the role of stream University of Virginia, Charlottesville, VA, 1994).
composition on the corrosion behavior. In addition to ionic 13. M. Pourbaix, Atlas of Electrochemical Equilibria in Aqueous
composition, water concentrations and the level of liquid by- Solutions (Houston, TX: NACE International, 1974).
products should be monitored.
14. C. H. Rochester, “Acidity Functions,” in Organic Chemistry,
Monographs Series 17 (New York: Academic Press, 1970).
Summary 15. Z. Szklarska-Smialowska and J. Mankowski, Corrosion Science
Corrosion testing in organic liquids has taken on greater impor- 22 (1982): 1105.
tance in recent years because of the increase in the use of non- 16. R. T. Morrison and R. N. Boyd, Organic Chemistry (Boston, MA:
aqueous and mixed liquids in material and chemical synthesis as Allyn and Bacon, 1973).
well as energy production. Although the basic types of corrosion
processes are similar in both aqueous and organic liquid envi- 17. D. A. Shifler, P. J. Moran, and J. Kruger, Electrochimica Acta 38
(1993): 881.
ronments, special attention must be given to the direct applica-
tion of testing tools to organic testing because of the complexity 18. D. A. Shifler, P. J. Moran, and J. Kruger, in Proceedings of the
of organic systems. The wide variety of organic liquids and mix- Symposium on Passivity and Its Breakdown, PV 97-26, ed. Natishan
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Applications and Ambient Temperature Lithium Batteries,
ed. B. B. Owens and N. Margalit (Pennington, NJ:
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Materials and Applications
265
Chapter 17 | Titanium
Ronald W. Schutz1
Introduction strengthening is achieved through solid-solution alloying and stabi-

lization of two-phase structures. These alpha-beta and beta alloys
Application of titanium and its alloys in aerospace, marine, contain varying amounts of beta phase, which may be heat-treated
energy, chemical process, and other industrial sectors continues (aged) by precipitating the fine-alpha phase to achieve higher
to expand. This has been motivated, in part, by trends in strength levels. The first 16 alloys listed are typically used in the
decreasing cost and increasing commercial availability of tita- annealed (nonaged) metallurgical condition. Further details on the
nium mill products, improved designer and user knowledge and metallurgy and mechanical–physical properties of titanium alloys
familiarity, and titanium’s attractive combination of engineering can be found elsewhere.3–8
properties. These properties include, but are not limited to, rela-
tively low density and elastic modulus, a wide range of strength,
and exceptional corrosion resistance over a wide span of envi- Mechanism of Corrosion Resistance
ronmental conditions.1,2
Growing application of titanium and its alloys has led to The excellent corrosion resistance of titanium alloys results from
increased laboratory and in-process (in situ) corrosion testing the formation of chemically stable and resistant, highly adherent
for the purpose of evaluation and service qualification. Although and continuous, ultra-thin (on the order of 10-nm thick) tita-
titanium alloys are evaluated with the same basic test methodolo- nium oxide films on the metal surface. Because titanium metal is
gies used for other passive, film-forming corrosion-resistant highly reactive and has an extremely high affinity for oxygen,
alloys (CRAs), its unique metallurgy, windows of susceptibility, these beneficial surface oxide films form spontaneously and
and properties can require additional consideration of and instantly when fresh metal surfaces are exposed to air or mois-
adjustments in certain testing details. This chapter provides an ture, or both. In fact, a damaged oxide film generally can reheal
overview of relevant corrosion test methods and detailed guide- itself instantaneously if at least traces (i.e., parts per million) of
lines to ensure proper and meaningful evaluation of titanium oxygen or water (moisture) are present in the environment.
alloy corrosion resistance and environmental behavior. However, anhydrous conditions in the total absence of a source
of oxygen (or water/moisture) may result in titanium corrosion,
because the protective film may not be regenerated if damaged.
The nature, composition, and thickness of the protective
Commercial Titanium Alloys surface oxides that form on titanium alloys depend on environ-
The designations and nominal compositions of various commercial mental conditions. In most aqueous environments, the oxide is
aerospace and industrial titanium alloys are listed in table 1. The typically and primarily titanium dioxide (TiO2), but may consist
first 11 alloys listed are titanium alloys primarily used in chemical of mixtures of several titanium oxides, including TiO2, Ti2O3,
or industrial applications in which corrosion resistance is the main Ti3O5, and TiO,9 depending on exposure conditions. Higher
design consideration. These alloys consist of single-alpha phase temperature (>500 C) oxidation in air tends to promote the for-
(hexagonal close-packed crystal structure) or near-alpha alloys con- mation and growth of the chemically resistant, highly crystalline
taining relatively small amounts of beta phase (body-centered cubic form of TiO2, known as rutile. Lower temperatures, oxidizing
crystal structure) in an alpha-phase matrix. The remaining alloys aqueous media, and anodizing favor generation of a less-crystalline
exhibit significantly higher strength and were developed primarily form of anatase TiO2, or a mixture of rutile and anatase.9,10 These
for aerospace service (except for Grade 29 titanium), although sev- naturally formed films typically are less than 10- to 30-nm thick
eral are finding application in industrial and energy service. Alloy and are invisible to the eye. The TiO2 oxide is highly chemical
resistant and is attacked by few substances, including hot, con-
1
Fellow-Corrosion and Energy Materials, TiCorr LLC, 410 Shadydale Dr., Canfield, centrated hydrochloric acid (HCl), sulfuric acid (H2SO4), sodium
OH 44406, USA hydroxide (NaOH), and (most notably) hydrogen fluoride (HF).
DOI: 10.1520/MNL202NDSUP20190027
TABLE 1 Various Commercial Titanium Alloys
Common Alloy Designation UNS Designation Nominal Composition, wt% ASTM Grade Ti Alloy Type
CP Grade 1 R50250 unalloyed titanium (commercially pure) 1 alpha

Ti-Pd R52400/R52250 Ti-0.15Pd 7/11 alpha
Ti- Lean Pd R52402/R52252 Ti-0.05Pd 16/17 alpha
Ti-Ru R52404/R52254 Ti-0.lRu 26/27 alpha
Grade 12 R53400 Ti-0.3Mo-0.8Ni 12 near-alpha
Ti-3-2.5 R56320 Ti-3Al-2.5V 9 near-alpha
Ti-3-2.5-Pd R56322 Ti-3Al-2.5V-0.05Pd 18 near-alpha
Ti-3-2.5-Ru R56323 Ti-3Al-2.5V-0.1Ru 28 near-alpha
Ti-6-4 R56400 Ti-6Al-4V 5 alpha-beta
Ti-6-4-ELI R56407 Ti-6Al-4V (0.13 % O max.) 23 alpha-beta
Ti-6-4-Ru R56404 Ti-6Al-4V-0.1Ru (0.13 % O max.) 29 alpha-beta
Ti-5-2.5 R54520 Ti-5Al-2.5Sn alpha
Ti-6-2-4-2 S R54620 Ti-6Al-2Sn-4Zr-2Mo-0.1Si near-alpha
Ti-550 Ti-4Al-2Sn-4Mo-0.5Si alpha-beta
Ti-6-6-2 R56620 Ti-6Al-6V-2Sn-0.6Fe-0.6Cu alpha-beta
Ti-6-2-4-6 R56260 Ti-6Al-2Sn-4Zr-6Mo alpha-beta
Ti-6-22-22 Ti-6Al-2Sn-2Zr-2Cr-2Mo-0.15Si alpha-beta
Ti-10-2-3 Ti-10V-2Fe-3Al near-beta
Ti-15-3-3-3 Ti-15V-3Sn-3Cr-3Al beta
Beta-21S R58210 Ti-15Mo-2.7Nb-3Al-0.2Si 21 beta
Ti-3-8-6-4-4 (Ti Beta-C) R58640 Ti-3Al-8V-6Cr-4Zr-4Mo 19 beta
Ti-13-11-3 Ti-13V-11Cr-3Al beta
This thin-surface oxide film is also a highly effective barrier to and common salt solutions of halides (i.e., chlorides), sulfates,
atomic and molecular hydrogen. With this hard rehealable silicates, phosphates, nitrates, and carbonates over the pH range
(ceramic-like) oxide film, titanium alloys exhibit elevated resis- of 3–12. Oxide film breakdown and the resultant corrosion of
tance to erosion, erosion-corrosion, and cavitation damage under titanium, however, occurs under moderate to strong reducing
high-velocity turbulent flow conditions.1 Note that this titanium acid conditions.
surface oxide film also may be substantially thickened for cos- Thus, severe general corrosion is possible in strong uninhib-
metic or coloration purposes or for enhanced corrosion protec- ited reducing acids, such as HCl, hydrobromic acid (HBr), H2SO4,
tion through thermal oxidation (heating of the metal in air at or phosphoric acid (H3PO4) solutions, particularly as acid concen-
higher temperatures) or by anodizing in certain aqueous salt tration or temperature, or both, increases.1,2 Severe attack of tita-
solution electrolytes at higher positive DC voltage, as described nium occurs in acidic aqueous fluoride (i.e., HF) solutions, even at
elsewhere. relatively low concentrations (>10 to 15 ppm free fluorides) and
The TiO2 film, being an n-type semiconductor, is electroni- temperatures. If other metallic ions that form stable fluoro-com-
cally conductive. As a cathode, titanium permits electrochemical plexes are also present, acidic fluoride attack may be inhibited (i.e.,
reduction of ions in an aqueous electrolyte. Conversely, high resulting in little or no free fluoride available) and may not occur.
resistance to anodic current flow through the passive oxide film Titanium hydride formation is predicted under strongly reducing
(i.e., significant anodic polarization) can be expected in most aqueous conditions (i.e., at highly cathodic or negative potentials)
aqueous solutions. Elevated anodic pitting (breakdown and and is dependent on solution pH.
repassivation) potentials in aqueous media can be expected with
many titanium alloys.
Passivity and good corrosion resistance of titanium can be Factors Affecting Passivity
expected under conditions in which these protective surface
oxides are thermodynamically stable. Pourbaix (potential-pH)
in Aqueous Media
diagrams for the titanium-water system.1,11 reveal that oxide film The passivation of titanium is favored and can be expanded in
stability occurs over a wide range of potentials, from highly oxi- aqueous reducing acid media by any factor that shifts the alloy
dizing to mildly reducing conditions. As a result, titanium alloys potential in the noble or positive direction (i.e., increased redox
can be expected to resist all natural waters (including seawater) potential) where oxide film stability is promoted. This beneficial
TITANIUM 267
ennobling influence may result from several factors including the OTHER METALLURGICAL FACTORS IN
following: AQUEOUS MEDIA
The nature of the oxide film on titanium alloys basically remains
• an increased surface oxide film thickness by anodizing or
unaltered in the presence of minor alloying constituents; thus,
thermal oxidation;
small additions (less than 1–2 wt%) of most commercially used
• anodic polarization of the alloy by impressed anodic current, alloying elements, or minor variations in interstitials (i.e., oxy-
or galvanic coupling to a more noble metal (i.e., precious/plat- gen, nitrogen, carbon, hydrogen) or trace alloy impurities (i.e.,
inum-group metals); iron) generally have little effect on the general corrosion resis-
• the presence of dissolved oxidizing species in the environment tance of titanium in passivating environments. Under active
acting as cathodic depolarizers; and (nonpassive) conditions (i.e., in strong reducing acids) in which
• the presence of certain alloying elements in titanium that titanium exhibits significant general corrosion, certain alloying
decreases the cathodic (hydrogen) overvoltage, thereby depo- elements, such as iron or sulfur, or both, may accelerate corro-
larizing the cathodic process. sion. Thus, minor variations in alloy chemistry may be of signifi-
cance only under conditions in which the passivity of titanium is
The last two factors listed are most commonly encountered borderline or when the metal is fully active. Increasing alumi-
and can dramatically influence titanium alloy performance in num content generally diminishes alloy corrosion resistance in
reducing acid solutions. Dissolved reducible (oxidizing) species strongly reducing or oxidizing acid media. Higher vanadium
in solutions are common in many chemical process streams, content also can result in higher corrosion rate in strong oxidiz-
whether intentionally added or present as minor background ing acids, especially as temperature increases.
contaminants. Some common oxidizing inhibiting species in Weldments and castings of the first 11 titanium alloys listed
reducing acid solutions include iron (Feþ3), copper (Cuþ2), in table 1 generally exhibit corrosion resistance similar to that of
nickel (Niþ2), titanium (Tiþ4), chromium (Crþ6), oxygen (O2), their unwelded, wrought counterparts.1 These titanium alloys con-
chlorine (Cl2), and nitrate (NO32) ions. For example, it is not tain so little alloy content and second phase that metallurgical
uncommon for upstream steel component corrosion to produce instability and thermal effects are not substantial. Protected by the
ferric corrosion products (i.e., Feþ3 ions), which contaminate same surface oxide film, titanium weldments and associated heat-
process streams. Several parts per million concentration or more affected zones will exhibit passive behavior (insignificant corro-
of any of these species may partially or fully passivate titanium sion) for the same conditions under which the wrought base metal
alloys in reducing aqueous media depending on acid concentra- is passive. However, under marginal or active corrosion conditions
tion and temperature and should be taken into account when (for corrosion rates 0.10 mm/y, or 4 mils/y), weldments may
evaluating alloy corrosion resistance. experience accelerated corrosion attack relative to the base metal,
These same oxidizing species can also stimulate and aggra- depending on alloy composition.15,16 Microstructural and crystallo-
vate crevice corrosion of titanium in hot salt solutions. By depo- graphic texture, which often exists in many commercial titanium
larizing the cathodic process on open-metal surfaces exposed to products, generally produces little or no effect on general or crev-
bulk solution, these oxidants effectively increase the potential dif- ice corrosion test results. Thus, sample orientation or end-on
ference between creviced and noncreviced metal surfaces, thereby (edge) grain texture effects are generally minor or insignificant in
driving the crevice cell.1,12–14 This explains why hot iron(III) these two test modes. Unlike many metals, the introduction of
chloride (FeCl3) solutions, Cl2-saturated solutions, or oxygen- severe cold work (plastic deformation/damage) has little impact
ated/aerated brines are often selected as test media for acceler- on passivity, and generally it does not alter the basic corrosion
ated test screening of alloy crevice corrosion resistance. Again, resistance of titanium alloys.
it is vital that these common minor background species be Although little effect of heat treatment or annealing is
accounted for in any crevice corrosion tests involving simulated observed with the leaner-alloy industrial titanium alloys (the first
laboratory environments. 11 listed in table 1), certain heat treatments (e.g., aging) may
The last factor addresses certain alloying element additions affect the corrosion resistance of higher strength alpha-beta and
to titanium that also may enhance passivation in reducing acid beta titanium alloys in reducing acid environments. Evaluation
solutions through cathodic depolarization (reduced hydrogen of stress corrosion cracking (SCC) resistance of titanium alloys,
overvoltage on metal surfaces). This simultaneously enhances in contrast, does require attention to, and can be highly depen-
the alloys resistance to crevice corrosion in hot salt solutions, dent on, alloy composition, heat treatment, microstructure,
because the solutions within an active crevice are essentially dea- product processing, crystallographic texture, and orientation.
erated reducing acids. Alloying elements commonly added to Although the leaner alloyed industrial alloys (the first 11 listed in
commercial titanium alloys to achieve these improvements table 1) are generally SCC resistant in aqueous environments,
include the precious metals (i.e., 0.04 wt% palladium [Pd] most higher strength titanium alloys generally exhibit SCC sus-
or 0.08 wt% ruthenium [Ru]), nickel (Ni; 0.5 wt%), and ceptibility in the form of KIC or Kc reduction (i.e., KISCC or
molybdenum (Mo; 3.5 wt%). Alloys incorporating these alloy- KSCC) or increased environmental crack growth rates. With the
ing additions for corrosion resistance enhancement in table 1 exception of a few, unique Ti alloys in sensitized conditions (e.g.,
include titanium Grades 7, 11, 12, 16, 17, 18, 19, 21, 26, 27, 28, Ti-13-11-3), most commercial Ti alloys will not exhibit SCC in
and 29, and the Ti-6-2-4-6 alloy. stressed smooth or notched samples or component configurations
when exposed to aqueous media. For this reason, aqueous SCC Role of Hydrogen
testing of titanium alloys is often conducted through loaded pre-
cracked fracture mechanics or slow strain rate to failure tests. Tita- Titanium alloys are generally highly resistant to penetration by
nium alloying elements that decrease SCC susceptibility include gaseous (diatomic) hydrogen and nascent (atomic) hydrogen
molybdenum, vanadium, niobium, and tantalum, and precious because of the surface oxide barrier film. In hydrogen gas expo-
metals (palladium and ruthenium) in high-temperature halide sures, traces of moisture or oxygen are sufficient to maintain this
media. Reduced SCC resistance may stem from increasing alumi- protective film, whereas anhydrous gas can lead to hydrogen
num (>5 wt%), silicon, chromium, and manganese content in absorption, particularly as hydrogen gas pressures and tempera-
these alloys, as well as oxygen (0.2 wt% in unalloyed titanium, ture increase. Excessive cathodic charging of atomic hydrogen
or >0.13 wt% in higher strength alloys) and other interstitials. In on titanium metal surfaces through galvanic coupling with active
alloys containing more than 5 wt% aluminum, this SCC suscepti- metals or impressed cathodic currents may induce excessive
bility (typically in aqueous chlorides) may stem from ordering and hydrogen uptake, depending on solution pH and temperature.
precipitation of Alpha-2 (Ti3Al) intermetallic phase, which pro- Active corrosion of titanium in reducing acids, within active
motes lower energy planar slip along certain near-basal-oriented crevices, or exposure to high-temperature strongly alkaline solu-
alpha grains. The influence of these metallurgical factors on tita- tions in which the oxide film is compromised also can result in
nium alloy SCC behavior is discussed in detail elsewhere.1,17–20 significant hydrogen pickup. Metallic iron embedded or galled
Titanium alloys are generally not susceptible to sulfide stress into titanium metal surfaces can provide “windows” for
cracking (SSC) in H2S- and sulfide-rich or sulfur-containing enhanced penetration of hydrogen. Conversely, surface treat-
environments (e.g., sour gas/oil well fluids). This inherent SSC ments that increase oxide film thickness, such as anodizing and
resistance stems from the fact that formation of TiS corrosion thermal oxidation, tend to thwart hydrogen absorption.
products is not thermodynamically favored, such that stability of In alpha and alpha-beta alloys, excessive hydrogen uptake
titanium’s protective oxide surface film will prevail even at can induce the precipitation of the titanium hydride phase in the
higher service temperatures. In these cold and hot sour brine ser- alpha phase. These acicular-shaped (needle-like) hydrides (fig. 1)
vice environments, resistance to chloride-induced SCC is a more when viewed in cross section are actually platelets and are a rela-
relevant issue for titanium alloys. tively brittle phase. In most cases, small amounts of hydride pre-
As a rough guide, the corrosion fatigue resistance of tita- cipitates are not detrimental from an engineering standpoint, but
nium alloys generally parallels its relative SCC behavior in a they can cause severe reduction in alloy ductility and toughness
given environment. As such, the first 11 titanium alloys listed in when present in greater amounts. For example, hydride precipi-
table 1 generally exhibit minimal degradation in S-N and fatigue tates can be observed in Grade 2 titanium microstructures at
crack growth resistance (i.e., minimal corrosion fatigue) in most hydrogen concentrations above approximately 40–100 ppm at
environments where metal passivity occurs. Conversely, environ- room temperature, depending on the amount of background
mental knockdown in fatigue life may be expected in situations beta phase and interstitials present.
in which crevice corrosion or SCC are possible. These precipitates do not result in gross embrittlement of
Because of the protective oxide film, titanium alloys gener- Grade 2 titanium until hydrogen levels in excess of 500–600 ppm
ally exhibit anodic pitting (breakdown and repassivation) poten- are reached. Because hydrogen solubility increases dramatically
tial values that are elevated and well above those of most with temperature, hydride embrittlement may not be observed at
corrosion engineering metals (i.e., > > þ l V). For example, pit-
ting potentials in sulfate and phosphate solutions exceed þ80 V FIG. 1 Photomicrograph of severely hydride unalloyed titanium
(versus SCE), and are typically in the þ2 to þ 10 V range in chlo- at 200. Note the acicular (needle-like) titanium hydride
ride media depending on alloy composition, brine pH, and tem- precipitate.
perature. As a result, spontaneous pitting of titanium alloys in
most aqueous environments does not occur and usually is not of
engineering concern in the majority of applications. However,
relatively low anodic pitting potential values near or just below
þ1.0 V, which decrease with increasing temperature and acidity,
may be observed in pure bromide or iodide salt solutions. Studies
have shown that increasing almost any alloying element reduces
anodic repassivation potential values in titanium,21 whereas
molybdenum, niobium, and zirconium generally have neutral or
slightly beneficial influences. Unlike the intrinsic, conservative
anodic repassivation potential value, the extrinsic anodic break-
down pitting potential is highly dependent on metal surface con-
ditions. Roughened, mechanically damaged, ground, and
sandblasted surfaces reduce values, whereas well-pickled, ther-
mally oxidized, and anodized surfaces elevate alloy anodic break-
down potentials.7
TITANIUM 269
higher temperatures. If significant absorption has occurred, high solubility for hydrogen and, therefore, high hydrogen toler-
embrittlement may manifest upon cooling as the hydride phase ance. As such, embrittlement generally is not associated with
precipitates. Hydrogen solubility and tolerance generally increase hydride precipitation. Significant losses in ductility or formability
with increasing volume percent beta phase in alpha-beta alloys. do not occur below hydrogen levels of several thousand parts per
In Ti-6Al-4V, for example, hydride precipitates are not formed million, although the tolerance to hydrogen decreases somewhat
below approximate hydrogen levels of 600–1,000 ppm, depend- in the aged (high-strength) condition where fine alpha phase pre-
ing on product microstructure. cipitates are also present. In addition, hydrogen atom diffusivity
Although uniaxial tensile properties may experience little (mobility) within the beta alloy is typically several orders of mag-
effect from increasing hydrogen levels, biaxial or triaxial stress nitude above that in alpha titanium even at room temperature.
properties, such as bend ductility, cold-drawing limits, and impact
toughness in alpha and near-alpha alloys may be sensitive to
hydrogen levels.21–24 In alpha and especially alpha-beta alloys, Relevant Forms of Titanium
hydrogen contents above critical levels (i.e., > 80–120 ppm) can
result in sustained-load cracking (SLC), which dramatically
Corrosion
reduces useful maximum service loads (reduced fracture resis- It is important to know where titanium might exhibit susceptibil-
tance) in notched or cracked components under slow strain rate ity to corrosion attack to establish which corrosion test methods
or constant tensile load situations,22–26 Beta titanium alloys have a may be applicable or relevant to titanium alloys. Table 2 presents
TABLE 2 Environments in which Corrosion and Environmental Susceptibility of Titanium Alloys Has Been Observed
Environment Corrosion Mode of Concern Susceptible Ti Alloys Conditions Promoting Susceptibility
Strong reducing acids (HCl, HBr, HI, general corrosion/etching, and all Dependent on alloy composition, acid concentration, and
H2SO4, H3PO4, and especially HF) possible by-product hydrogen temperature, and presence of inhibitive oxidizing species.
absorption
Higher temperature halide (chloride crevice corrosion Alloys without Pd or Ru, or Dependent on alloy composition, brine pH and
and bromide) and sulfate solutions alloys with <3.5 % Mo or temperature. Requires severe, tight crevices.
< 0.5 % Ni
Pure bromide/iodide solutions anodic pitting all Dependent on alloy composition and surface, and
solution pH and temperature.
High-temperature strongly alkaline hydrogen absorption all Occurs at pH > 12 and >75 C.
solutions
High-temperature sour brine (sulfide/ galvanically induced hydrogen all Requires galvanic coupling to an active metal/alloy and
H2S-rich) absorption >75 C.
Anhydrous hydrogen gas hydrogen absorption all Occurs at higher temperatures, and gas pressures if
water- or oxygen-free.
Anhydrous methanol stress corrosion cracking all Occurs when water content is below 2–3 wt%, and is
most severe near room temperature.
Red-fuming nitric acid or nitrogen stress corrosion cracking and/or all Dependent on water and/or oxygen content.
tetroxide pyrophoric reaction
Halide salt residues at high hot salt stress corrosion cracking Higher strength Ti alloys Dependent on alloy composition, stress load,
temperatures (>230 C) temperature, and exposure time.
Chlorinated hydrocarbons stress corrosion cracking Higher strength alpha- beta Dependent on alloy composition and condition.
and beta alloys
Halide (chloride, bromide) salt stress corrosion cracking Higher strength alpha-beta Dependent on alloy condition, brine pH and temperature,
solutions and beta alloys and test method.
Liquid cadmium and mercury, and liquid or solid metal embrittlement all Requires direct, intimate contact with fresh unfilmed
solid silver (>230 C) and cadmium metal surface under high stress.
Dry chlorine gas general corrosion and/or all Occurs when water content is below 0.5–1.0 wt%
ignition/burning depending on temperature.
Pure oxygen gas and liquid oxygen ignition/burning all Dependent on alloy composition, component thermal
(LOX) mass, and gas pressure. Ignition in LOX requires impact
damage threshold.
Warm alkaline peroxide solutions general corrosion all Dependent on peroxide solution composition, pH, and
temperature.
High-temperature air or oxygen- metal oxidation, wastage, and/or all Dependent on alloy composition, temperature, and
containing gas exposures (>600 C) embrittlement exposure time.
a list of specific environments in which some form of corrosion

susceptibility has been observed on titanium alloys in laboratory FIG. 2 Typical Huey test apparatus with water-cooled condenser
tests or service experience. The table shows the relevant mode of for conducting sample general corrosion (weight-loss)
corrosion degradation that can be expected, general scope of tita- tests up to the solution boiling point. Samples are
nium alloys susceptible, and comments on critical factors that typically suspended in the solution by Teflon string or
strongly influence each corrosion phenomenon. glass rods.
Based on table 2, the general forms of corrosion and corre-
sponding test methods relevant to titanium alloys include the fol-
lowing: general corrosion, crevice corrosion, anodic pitting, SCC,
hydrogen absorption or embrittlement, ignition or burning, and
oxidation. The following sections will provide methods and
guidelines for testing and evaluation of these seven basic forms
of titanium alloy corrosion damage.
Test Methods for Evaluation of

Corrosion Damage
GENERAL CORROSION TESTING
General corrosion rates for titanium alloys can be determined
from measurements of changes in component or test coupon
mass (i.e., typically weight loss, and sometimes weight gain),
dimensional change, or electrochemical methods. Electrochemi-
cal anodic and cathodic polarization testing is often used to sup-
plement weight loss testing. Polarization testing can identify
whether the alloy is truly fully passive or possibly metastable;
this is often not discernible from weight loss tests alone. The
immersion test procedures described in ASTM G1, Standard
Practice for Preparing, Cleaning, and Evaluating Corrosion Test shiny gray specimen that is ready for weighing. The abraded sur-
Specimens, and ASTM G31, Standard Practice for Laboratory face finish can be obtained by wet grinding with fine-grit silicon
Immersion Corrosion Testing of Metals, apply, provided that sev- carbide (SiC), aluminum oxide (Al2O3), or zirconium dioxide
eral modifications are observed1,27 These modifications focus on (ZrO2) abrasive paper after the cleaning step. A final deionized
test sample surface preparation and post-test sample-cleaning water rinse and drying would prepare the specimens for weigh-
procedures. A typical laboratory test apparatus for weight-loss ing and testing. Prepared and weighed titanium samples may be
immersion testing in acid solutions at or below the boiling point stored in open air before exposure for several days without sig-
is shown in figure 2. nificantly affecting sample weight.
The type of sample surface finish tested should resemble the A mechanically abraded or polished coupon surface finish is
one expected in service. For many titanium alloys, depending on highly recommended over pickled finishes when corrosion test-
product form, this is frequently the pickled finish, although sanding titanium alloys containing readily reducible (noble) alloying
blasted, ground, or machined surfaces also are common. The ini- elements. These alloys include those containing platinum group
tial degreasing of test samples should avoid chlorinated organic metals (Pd, Ru, Pt) and other metals (Ni, Cu), which may readily
solvents (with higher-strength titanium alloys), anhydrous/neat plate back in pure form onto titanium coupon surfaces during
methanol, or hot alkaline cleaners. Acceptable cleaning solvents the final pickling step. These plated metal residues can ennoble
include methyl-ethyl ketone (MEK), acetone, most alcohols, coupon test surfaces and may not represent the most conserva-
benzene or toluene, and most detergent solutions. The pickled tive test methodology.
finish can be prepared by pickling the metal in a 35 vol% nitric Consideration should be given to the presence of certain
acid (HNO3) to 5 vol% HF solution (based on 48 wt% HF and test solution contaminants that may significantly affect the cor-
70 wt% HNO3 stock acid solutions, with the balance being water) rosion rate. More specifically, contamination of acid media with
at 20–55 C for 0.5–5 min or more. Typically, 0.005–0.05 mm transition metal ions, such as ferric, nickel, cupric, and chromate
(0.2–2 mils) of sample surface is removed in this process, ions, and other oxidizing species should be avoided because these
depending on surface requirements. More dilute solutions, such ions act as cathodic depolarizers and inhibit corrosion in most
as 12 vol% HNO3 to 1 vol% HF, also can be used if slower pick- acid media. In nitric acid testing, dissolved silicon, Tiþ4, Feþ3,
ling rates are desired. In any case, a minimum 7:1 HNO3 to HF and most precious metal ions are fairly effective inhibitors and
stock acid vol% ratio should be maintained to avoid excessive will lower corrosion rates. In strong nitric acid media, it is best
uptake of hydrogen in titanium alloys during pickling. After to avoid prolonged testing in glass, and the accumulation of dis-
pickling, a quick rinse in deionized water and air drying leaves a solved Tiþ4 corrosion product, which inhibits corrosion. This
TITANIUM 271
can be counteracted by frequent solution change or refreshment. results in acceptably small weight losses in sample coupons.
In most reducing acids, such as HC1, H2SO4, or H3PO4 (but not Weight losses in the 10-4 g range may be incurred when light
HF), testing in glass flasks is acceptable. The Tiþ3 ion corrosion sandblasting (<5 s exposure) is used, and these can be corrected
product normally formed and dissolved in a reducing acid for by exposing an untested titanium specimen to the same blast-
medium has minimal effect on corrosion except at near-saturated ing procedure and correcting for its weight loss. A final rinse in
concentrations; but the mild oxidizing agents mentioned earlier, distilled water after sandblasting leaves the dried specimen ready
such as the transition metal ions (particularly those in higher for weighing. Titanium specimens that have been exposed to hot,
oxidation states), may inhibit corrosion at concentrations above strong reducing acids in which the corrosion rate is quite high
several parts per million. It is recommended that the solution generally exhibit chemically roughened, matte-gray hydride
be constantly refreshed or changed at least every 24 h (or more metal surfaces, which may not require surface cleaning.
frequent) in corrosion tests where foreign ions are generated Immersion testing will generate weight loss (or weight gain)
from corrosion processes to minimize their effects. It is also criti- data for corrosion rate determination. Also, corrosion current
cal that the degree of aeration (dissolved oxygen level) and other measurements for corrosion rate calculation can be obtained
background chemistry variables in the test media that influence from standard electrochemical polarization tests (see ASTM G5,
titanium passivity be taken into account to achieve valid and Standard Reference Test Method for Making Potentiostatic and
relevant test results. Potentiodynamic Anodic Polarization Measurements, and the
The presence of surface corrosion products on titanium after ASM Metals Handbook28).
testing depends on the environment to which the titanium was Corrosion rates in millimeters per year (mm/y) for titanium
exposed. Removal of these products, when formed, is necessary for alloys can be calculated from sample weight loss data as follows:
obtaining the proper weight loss data, and the correct corrosion
ð8:76 104 ÞðWÞ
rate. In media where the titanium has remained essentially passive, Corrosion rate ðmm=yÞ ¼ , (1)
ðdÞðAÞðtÞ
such as near-neutral brines, the original shiny metal luster usually
will still exist, and the specimens need only be rinsed in distilled where:
water before their final weighing. Most deposits from the medium d ¼ alloy density in g/cm3,
that adhere to the specimen surface and are nontitanium corrosion A ¼ sample surface area in cm2,
products may be cleaned off in a warm (<65 C) 25 vol% HNO3 to t ¼ exposure time in h,
25 vol% HC1 ratio solution or a 50 vol% HNO3 solution based on W ¼ weight change in g.
stock acids. Other compatible post-test acid cleaning solutions
Corrosion rates in mpy (thousandths of an inch per year) can be
include 10 wt% HC1 or H2SO4 inhibited with a minimum of
derived using the formula:
1,000 wppm ferric (Feþ3), cupric (Cuþ2), chromate (Crþ6), or
molybdate (Moþ6) ions heated up to about 70 C. These are gener- Corrosion rate ðmpyÞ ¼
ð534,700ÞðWÞ
, (2)
ally oxidizing inhibitor additions that maintain titanium passivity ðdÞðAÞðtÞ
during exposure to these dilute reducing acid cleaning solutions. where:
Traditional filming or adsorption-type acid corrosion inhibitors W ¼ weight change in g,
used for ferrous alloys (e.g., amines, quaternary salts, cyclic imines, d ¼ alloy density in g/cm3,
aldehydes) generally are not effective for titanium. Siliceous scales A ¼ sample surface area in in.2,
may be removed in warm (<65 C) solutions containing < 20 % t ¼ exposure time in h.
NaOH inhibited with 1 wt% sodium nitrate (NaNO3), sodium
hypochlorite (NaOCl), sodium dichromate (Na2Cr2O6), or sodium A list of density values for common commercial titanium alloys
molybdate (Na2MoO4). The use of strong, uninhibited mineral is given in Table 3.
acids such as HCl, H2SO4, H3PO4, and especially HF are not rec-
ommended for cleaning, because they will corrode the metal sam- TABLE 3 Room Temperature Density Values for Some Common
ples, which also explains why the electrolytic cleaning method Commercial Titanium Alloys
mentioned in ASTM G1 is not used.
In media in which the titanium does have a low but finite
Alloy Density, g/cm1
corrosion rate and where the dissolved titanium in solution
Ti Gr.l, 2, or 3 4.51
hydrolyzes back onto the surface of the specimen (such as dilute
Ti Gr.7, 11, 16, 17, 26, or 27 4.51
hot-reducing acids) or in strongly oxidizing media (such as boil-
Ti Gr.12 4.52
ing concentrated HNO3), a titanium oxide–hydroxide corrosion
Ti Gr.9, 18, or 28 4.48
product may build up slowly on the surface. This oxide film or
Ti Gr.5, 23, or 29 4.42
deposit is not soluble in common mineral acids and cleaning sol-
Ti-6-2-4-6 4.68
utions. The more desirable means of cleaning the specimen of
Ti-10-2-3 4.64
titanium corrosion product or even stubborn nontitanium
Ti-15-3-3-3 4.78
deposits is a fine-grit- or glass bead-blasting procedure. Tests
Ti-3-8-6-4-4 (Ti Gr.l9) 4.82
run in the laboratory suggest that the use of 180-grit or finer sil-
Ti Gr.21 4.93
ica or alumina sand to lightly grit-blast off titanium surfaces
Corrosion rates in mm/y can be calculated from electro-

chemical measurements by using the formula: FIG. 3 Typical example of crevice corrosion of titanium in hot
chloride brines. (A) Irregularly shaped crevice corrosion
ð3:3Þðicorr ÞðEWÞ attack on Grade 2 titanium tubing. (B) Photomicrography
Corrosion rate ðmm=yÞ ¼ , (3)
d of cross section through crevice corrosion site in Grade 2
where: titanium showing the titanium oxide corrosion product
icorr ¼ the measured corrosion current in mA per cm2, cap and irregular attack profile (100 magnification).
d ¼ alloy density in g/cm3

EW ¼ the equivalent weight (atomic weight/valence state)
for titanium.
The equivalent weight for titanium is 16 g per equivalent under
reducing acid conditions (Ti to Tiþ3 species), and 12 g per equiv-
alent under oxidizing conditions (Ti to Tiþ4 species). The corro-
sion current (icorr ) value is typically determined from Tafel slope
extrapolation or linear polarization methods.28–30
The use of weight loss measurements and the alloy densities
cited here assume the standard gravity state at the Earth’s surface
and should be reconsidered when testing under varying gravity
scenarios at other universe locations. In these cases, it may be
beneficial to measure changes in test coupon mass using dimen-
sional parameter changes to calculate true corrosion rates. This
approach also may provide more accurate corrosion rates in
instances in which severe uniform corrosion attack has occurred
in the test exposure.
CREVICE CORROSION TESTING

Crevice corrosion is a form of localized attack of titanium alloys
that may occur in higher temperature (>70 C) chloride, bro-
mide, iodide, fluoride, and sulfate-containing solutions; its occur-
rence is highly dependent on alloy composition, solution pH,
and temperature. Crevice attack on titanium requires the pres-
ence of large and severe (tight) crevices, such as gasket-to-metal
flange joints or seals, tube-to-tube-sheet joints, metal-to-metal
joints, or adherent process stream deposit or scale crevice for- because titanium is highly crevice resistant and requires a rela-
mers found in service. Attack typically takes the form of irregu- tively large, deep creviced surface area for crevice corrosion initia-
larly shaped craters or pits, with voluminous, off-white, light tion. The larger creviced surface area and depth of the sheet/plate
gray, or sometimes black corrosion product caps, as pictured in coupon sandwich-type assembly, illustrated in figure 4, dramati-
figure 3. Metal surfaces adjacent to active crevices may display cally increases susceptibility to attack and is most commonly used.
vivid oxide film coloration from hydrolyzed acidic crevice solu- This method uses a test assembly in which thin gasket sheets
tions. The mechanism for titanium alloy crevice corrosion gener- (typically PTFE, FEP, or other polymeric gasket material, or
ally is similar to that for stainless steel and nickel alloys, in which sealant, of interest), or highly polished ceramic wafers, are inter-
oxygen-depleted reducing acid conditions develop within tight spersed between flat metal sheet or plate coupons to produce the
crevices as detailed elsewhere.1,31 desired number of metal-to-metal or metal-to-gasket crevices, or
Crevice corrosion testing of titanium alloys generally aims both. Coupons are typically 1 in. by 1 in. (25 mm by 25 mm) or
at determining go/no-go performance information. The rate of larger to create large, deep creviced surfaces. Each test assembly is
crevice corrosion is of little practical interest, because crevice fastened together with a centerline titanium bolt and nut and
attack generally is insidious and rapid and, therefore, cannot be tightened down to a torque of 25 to 90 in.-lb (2.8 to 10.1 m-N) to
tolerated in any form. Many crevice test assemblies have been create tight, severe crevices. The titanium assembly bolts and nuts
used, including the multiple-crevice (serrated) washer (ASTM may be of the same titanium alloy being tested, or covered with an
G78, Standard Guide for Crevice Corrosion Testing of Iron-Base insulating PTFE sleeve or tape wrap to avoid galvanic interfer-
and Nickel-Base Stainless Alloys in Seawater and Other Chloride- ences. Ceramic washers also may be incorporated, if needed, to
Containing Aqueous Environments), the Dutchman or spool rack electrically isolate the assembly bolting.
(ASTM G4, Standard Guide for Conducting Corrosion Coupon It is important that coupon surfaces be flat and, especially,
Tests in Field Applications) assembly, and the sheet (or thin-plate) as smooth as possible (low root mean square roughness) to mini-
sandwich-type assembly. The multiple-crevice (serrated) washer mize crevice gap and volume and, thereby, stimulate initiation.
generally is not a conservative test and is not recommended, Highly roughened sandblasted or ground surfaces exhibit
TITANIUM 273
weight gain is often measured in this situation. In addition to

FIG. 4 Typical crevice test assembly for crevice corrosion testing visual examination and weight change measurements, monitoring
of titanium alloy sheet or plate coupons. Sequence of of creviced specimen potential32,33 and current34 has been used to
coupons and gasket sheets can be modified to form a limited extent to identify the initiation of crevice corrosion.
gasket-to-metal or metal-to-metal crevices. Examination of polished and etched metallurgical sections
through pitted areas of creviced coupons may provide additional
information regarding depth and attack mechanism.
PITTING POTENTIAL TESTING

The susceptibility of an alloy to pitting on openly exposed surfa-
ces (in the absence of crevices) in a given solution and fixed tem-
perature is normally assessed by determination of anodic pitting
potential values. The two pitting potentials of interest are (1) the
extrinsic, surface-dependent anodic breakdown potential (Eb); and
(2) the conservative, intrinsic anodic repassivation potential (or
protection potential, Eprot) that defines the minimum potential at
which pitting is possible in the test environment.
The anodic breakdown potential of titanium alloys is typi-
cally determined by the potentiodynamic (potential scan) tech-
nique (ASTM G3, Standard Practices for Conventions Applicable
reduced crevice corrosion susceptibility compared to finer, to Electrochemical Measurements in Corrosion Testing, and
smoother, and more polished surfaces. Although a 220-grit wet- ASTM G5) at slow scan rates (0.5 mV/s). Because this value is
ground coupon surface finish may be considered a minimum sensitive to sample surface condition, it is vital that the represen-
requirement, a 400-grit finish or finer is recommended for most tative metal surface anticipated in service be tested. Conversely,
conservative test results. Preparation of crevice test coupons fol- titanium alloy repassivation potential may be measured by a gal-
lows the same procedures as that for general corrosion test cou- vanostatic method,35 the constant potential-surface scratch
pons. It is also vital that only the virgin grade of fluoropolymer test,28,30,35 or reverse scan potentiodynamic method. The galva-
gaskets (e.g., PTFE, FEP) be used in these tests, because nonvir- nostatic method is quick, easy, and generally preferred. It
gin (reprocessed) grades may release soluble fluorine–fluoride involves impressing a constant anodic current density of approx-
compounds within crevices during test exposures that may imately þ200 mA/cm2 on the specimen for at least several
falsely stimulate localized attack. minutes before measuring the sample polarization potential rela-
Laboratory crevice testing is usually conducted in glass tive to a reference electrode. This potential, once stabilized and
flasks and vessels, titanium alloy autoclaves, or other CRA auto- corrected for electrolyte IR drop, represents the anodic repassiva-
claves. The minor presence of background or contaminating tion potential. The constant potential-scratch method is more
metal ion species or other oxidizing species may aggravate crev- tedious and time consuming, involving trial iterations for brack-
ice attack. Thus, it is also vital that suitable test vessels be selected eting the critical potential. Potentiodynamic scan reversal
and that the representative degree of aeration, pH, and other (ASTM G61, Standard Test Method for Conducting Cyclic Poten-
aspects of background solution chemistry be controlled and sim- tiodynamic Polarization Measurements for Localized Corrosion
ulated. Although crevice corrosion can initiate within the first Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys) after scan-
several hours of exposure, a minimum test duration of 30 days is ning anodically to induce breakdown pitting may produce
recommended to develop a sufficient degree of attack for detec- ambiguous results with nonreproducible, scan rate–dependent
tion and measurement purposes. repassivation potential values.
Post-test evaluation of crevice test coupons may require The exceptionally high anodic pitting potentials of titanium
removal of titanium oxide–hydroxide corrosion products (see fig- alloys in most aqueous solutions means that (1) oxidizing acid
ure 3) if crevice attack has occurred. Common mineral acids and solutions, such as FeCl3 or Fe2(SO4)3 solutions (ASTM G28,
reagents will not dissolve these adherent, tenacious deposits. A Standard Test Methods for Detecting Susceptibility to Intergranu-
light (>l20 grit and <5 s) grit-blasting or glass-bead blasting of lar Attack in Wrought, Nickel-Rich, Chromium-Bearing Alloys,
coupon surfaces will readily remove these scales and facilitate and ASTM G48, Standard Test Methods for Pitting and Crevice
visual examination of pitted surfaces (per ASTM G46, Standard Corrosion Resistance of Stainless Steels and Related Alloys by Use
Guide for Examination and Evaluation of Pitting Corrosion) and of Ferric Chloride Solution) cannot be used to identify critical pit-
permit sample weighing after water rinsing. Creviced coupon sur- ting parameters; and (2) potential range or power requirements
faces are often highly colored after hot aqueous exposures, but for potentiostats/galvanostats are greater than that for most
reveal no visible pits or localized attack after sandblasting. This is other common metals and alloys. In chloride solutions, for
indicative of slight growth and thickening of a protective titanium example, a potentiostat or galvanostat with an impressed sample
oxide film on creviced surfaces, which is considered quite normal potential output range as high as þ10 to þ 12 V may be required
and acceptable from a performance standpoint. Slight coupon for pitting potential determinations. Practical counter-electrodes
for these electrochemical techniques include glassy carbon and Selection of a suitable SCC test method for titanium alloys
platinum wire and mesh. is primarily determined by the nature of the stress cracking data
or design information desired, and by the chemical nature of the
STRESS CORROSION CRACKING TESTING test environment relative to titanium alloy passivation. For sim-
SCC test methods commonly used for metals36 are applicable to ple go/no-go assessment of SCC with no quantitative cracking
titanium alloys, as long as relevant mechanical and physical parameters, the least costly, simpler category 1 tests may be ade-
properties are accounted for. This means selecting applied quate if SCC initiation (incubation) periods are not too long.
stresses based on alloy strength or elastic modulus values for the The data typically are considered in terms of specimen stress
appropriate sample orientation, which is corrected for test tem- level versus time to failure, as shown in figure 5A. Category 3
perature when appropriate. The smaller spread between yield SSRT test results are generally assessed as comparisons or ratios
and ultimate strength, and the lower plastic strain limits exhib- of test sample ductility (total elongation or reduction in area) or
ited by titanium alloys compared with most common CRAs also time-to-failure values to those from a reference (control) sample
means limiting applied sample stresses values to approximately (tested in air or inert gas), providing some degree of relative SCC
105% yield strength in static- or deflection-loaded (e.g., tensile, susceptibility. Confirmation of SCC occurrence, however, must
U-bend, C-ring, bent-beam) tests. Because many titanium alloy entail examination of SSRT specimen post-test fracture surfaces
products can exhibit significant crystallographic texture depend- for indications of any SCC (i.e., low-energy fracture mode), such
ing on alloy type and processing history, it is advisable that SCC as relative extent of any cleavage, intergranular cracking, or sec-
susceptibility be evaluated with regard to sample orientation as ondary cracking over the total fracture area.
well. In alpha and alpha-beta titanium alloy mill products, for If fracture mechanics design information (i.e., KISCC, KSCC,
example, greater susceptibility is often associated with the direc- JIC, Jc, KJ) is sought, then the more sophisticated and costly cate-
tion along the hexagonal closed-packed basal plane intensifica- gory 2 fracture tests per ASTM E399 or ASTM E1820 specifica-
tion (e.g., T-L direction in unidirectional processed products). tions (using compact-tension [C-T] or single-edge notch bend
Test methods to assess the SCC resistance of titanium alloys [SENB]-type test specimens) are the preferred choice. As indi-
can be grouped into three basic categories: cated in figures 5B and 5C, KISCC results for titanium alloys are
stress and time dependent, such that KISCC values may be plotted
• Category 1 tests use smooth, statically loaded specimens, such
as a function of time to failure to reveal true, conservative KISCC
as U-bend, C-ring, bent-beam, and direct-tension test speci-
values. These may involve bolt- or wedge-open-loaded fracture
mens (per ASTM G30, Standard Practice for Making and Using
specimens (see ASTM E1681 or ASTM G168), which should be
U-Bend Stress-Corrosion Test Specimens; ASTM G38, Standard
tested for at least 24–100 h, or by rising (increasing) load steps
Practice for Making and Using C-Ring Stress-Corrosion Test
applied to fracture specimens as described by ASTM F1624, Stan-
Specimens; ASTM G39, Standard Practice for Preparation
dard Test Method for Measurement of Hydrogen Embrittlement
and Use of Bent-Beam Stress-Corrosion Test Specimens; and
Threshold in Steel by the Incremental Step Loading Technique.
ASTM G49 Standard Practice for Preparation and Use of
Sufficient hold time at each stress-intensity level (applied load
Direct Tension Stress-Corrosion Test Specimens (superseded),
step) tested should be considered relative to load step size to
respectively).
ensure that the plateau shown in figure 5B will be reached. Step
• Category 2 tests are fracture mechanics tests that use notched load hold times on the order of 20 min to 2 h should be considered
and fatigue precracked specimens that are statically or to manifest SCC effects in aqueous environments. A more practi-
dynamically loaded, such as cantilever beam, compact tension, cal modified version of the rising step method and ASTM E399
and double cantilever beam specimens. These tests are con- test protocol, which identifies a singular Kscc value from each test
ducted per ASTM E399, Standard Test Method for Linear- specimen, is the continuous rising-K test conducted on these frac-
Elastic Plane-Strain Fracture Toughness of Metallic Materials; ture specimens, which involves loading at a slow displacement
ASTM E1820, Standard Test Method for Measurement of rate. In aqueous media, specimen loading can be initiated at
Fracture Toughness; ASTM E1681, Standard Test Method for 15–20 MPa m0.5 to reduce testing time, to which a subsequent
Determining Threshold Stress Intensity Factor for Environment- constant rising-K rate in the typical range of 0.3 to 1.0 10-3 MPa
Assisted Cracking of Metallic Materials; and ASTM G168, Stan- m0.5 s-1 is applied to the specimen. As with other rising-K or K-
dard Practice for Making and Using Precracked Double Beam load testing, the critical KSCC (or threshold K) is derived in cases
Stress Corrosion Specimens. in which the load curve drops sharply and an increase in CMOD
• Category 3 tests use smooth (or notched, but not precracked) data measurements (i.e., discernable crack growth) coincide.
tension specimens that are dynamically axially loaded in ten- It is important to recognize that K values derived from the
sion and strained to failure at very low strain rates. The slow elastic fracture mechanics tests (ASTM E399, ASTM E1681, ASTM
strain rate tensile (SSRT) test is typically conducted in accor- G168, and ASTM F1624) will be highly dependent on fracture
dance with ASTM G129, Standard Practice for Slow Strain Rate specimen geometry and type and, especially, specimen thickness.
Testing to Evaluate the Susceptibility of Metallic Materials to With most relatively plastic titanium alloy materials, plane stress
Environmentally Assisted Cracking, or NACE TM0198-2011, effects (i.e., crack tip blunting) can result in artificially lower Kc
Slow Strain Rate Test Method for Screening Corrosion Resistant and KSCC values. As such, it is highly recommended that all frac-
Alloys for Stress Corrosion Cracking in Sour Oilfield Service. ture specimen thicknesses (B value) be maximized for the product
TITANIUM 275
fracture mechanics test methods may be observed at test specimen

FIG. 5 Various types of SCC test data presentation: (A) typical thicknesses below approximately 19–25 mm depending on partic-
for category 1 tests; (B) and (C) typical for category 2 ular alloy strength and toughness properties and metallurgical
tests. condition. Those same specimens measured by elastic-plastic test
methods (e.g., J-testing) generally produce significantly higher
toughness, with reduced sensitivity to variations in specimen size
and thickness.
SSRT testing of smooth specimens (ASTM G129 or NACE
TM0198-2011) is a highly sensitive, rapid, most discriminating,
and conservative SCC test method for titanium alloys. In some
cases, this SCC test may be too conservative from a design or use
standpoint because the surface-oxide film is continuously being
broken during straining to failure. This method is particularly
useful for rapid alloy screening and sorting, and provides a rela-
tive or semiquantitative sense of alloy SCC susceptibility. Dis-
criminating strain rates for titanium alloys in aqueous and
methanolic solutions lie within the 10-5 to 10-7 s-1 window. A
practical strain rate traditionally used effectively in aqueous and
methanolic test media is 4 10-6 s-1. It is also recommended that
specimen test gage sections and diameters be sufficiently large in
coarser-grain titanium alloy product forms (e.g., beta annealed
alpha-beta alloy condition) to avoid scatter and variability in
resultant test strain values.
The selection of an appropriate SCC test method for titanium
alloys may be based on the particular type of environment to be
tested. In environments in which alloy repassivation (oxide film
formation) is favored, and in which stage I subcritical cracking
generally is not observed, category 2 and 3 tests are more severe
and discriminating than category 1 tests. This is the case for aque-
ous media, including salt water and brines, and chlorinated
organic solvents in which cracking failure of category 1 specimens
generally is not observed at near-ambient temperatures. One must
provide initial or continued local oxide film breakdown, such as in
category 2 and 3 tests, to expeditiously initiate and manifest
potential SCC tendencies in these alloys. Exceptions to this rule
include those few titanium alloys that may exist in highly sensi-
tized metallurgical conditions. For example, alloys susceptible to
SCC in ambient neutral salt water in smooth or notched samples
include step-cooled Ti-8Al-lMo-lV and Ti-13V-11Cr-3Al alloys.
Highly stressed category 1 test specimens also may be applicable
for testing in hot aqueous halides or chlorinated solvents, where
higher temperatures may overcome SCC activation barriers in cer-
tain alloys after sufficient exposure periods.
For environments in which stage I subcritical cracking
form tested so that plane-strain conditions are approached or behavior occurs and repassivation is not favored, category 1, and
achieved to obtain more representative K values. Furthermore, lig- sometimes category 3, testing is generally preferred over category
ament size should be maximized where possible, such that C-T 2 testing for practical reasons. These environments include
and B 2B-type SENB specimen geometries are preferred over methanol, red-fuming nitric acid and dinitrogen tetroxide
B B-type SENB specimens where possible. Fracture mechanics (N2O4), certain liquid and solid metals, molten salts, and hot
parameters derived from elastic-plastic fracture-based testing salt, as listed in table 2. Note that category 2 testing is not physi-
methods (e.g., J-R testing per ASTM E1820) are less sensitive to cally applicable to the evaluation of solid metal embrittlement
this effect and should be considered when component cross-sec- and hot salt SCC in these alloys. Note also that hot salt SCC test-
tion or specimen thicknesses are relatively small and serious plane ing of titanium should follow the guidelines and procedures pro-
stress conditions prevail. In the case of the higher strength (but vided in ASTM G41, Standard Practice for Determining Cracking
still reasonably plastic) Ti-6Al-4V alloy, for example, substantial Susceptibility of Metals Exposed under Stress to a Hot Salt
reductions in fracture toughness (K) values measured using elastic Environment.
HYDROGEN TESTING sample is galvanically coupled to the titanium alloy sample, such
Testing to determine the susceptibility of a titanium alloy to that a specific anode-to-cathode surface area is tested. Impressed
hydrogen uptake and embrittlement should simulate conditions cathodic charging tests are performed in electrolytic cells con-
expected in service. In hydrogen gas atmospheres, simple coupon taining a specific electrolyte. A power supply (potentiostat or gal-
exposures for as long as is deemed practical are recommended to vanostat) impresses a constant potential or current on the cell,
ensure significant uptake, if it occurs. The gas atmosphere must such that the titanium is cathodic relative to an inert counter-
duplicate exact gas chemistry, particularly with respect to water electrode, such as graphite or platinum. A reference electrode
and oxygen content. Mere traces of moisture, for example, will also can be used to control or to measure the polarization poten-
effectively inhibit hydrogen absorption by titanium in dry hydro- tial of the test cathode. There are no standardized test methods
gen gas and possibly cause test interference. or setups for cathodic charging studies; therefore, they are
Galvanic coupling tests or cathodic charging tests also can designed to best simulate conditions anticipated in service. Two
be conducted to evaluate susceptibility to hydrogen uptake. For a examples of typical laboratory charging cell setups are depicted
given electrolytic media, an active metal (e.g., iron, aluminum) in figures 6A and 6B. Note the presence of a porous diaphragm
FIG. 6 Typical examples of laboratory cell setups for cathodic charging tests on titanium alloys. (A) Typical cell setup for short-term
cathodic charging of titanium samples at constant current in hot acidic electrolytes. (B) Typical cell setup for longer-term cathodic
charging of titanium samples at constant potential in seawater and brines.
TITANIUM 277
(e.g., glass wool, sintered glass frits) in these cells to minimize

unwanted intermixing of cathode or anode by-products and FIG. 7 Generalized test time dependence of KISLC values
catholyte contamination. Catholyte refreshment should be con- measures for high-strength titanium alloys compared with
sidered to maintain representative electrolyte composition and their KIC and KISCC values.
pH, especially if higher current densities and longer charging
times are involved.
The surface condition of the test sample is a critical variable
in all hydrogen uptake tests. Studies have shown that abraded
or sandblasted surfaces absorb hydrogen more readily than as-
pickled surfaces.1 Thickening of the surface oxide film by anodiz-
ing or thermal oxidation further retards absorption. The actual
surface finish anticipated in service should be evaluated.
After test exposure, sample evaluation for hydrogen may
include smooth or notched tensile, bend, ductility/cold formabil-
ity, or impact Charpy tests, hydrogen analysis, or cross-sectional
microstructural examination. Uniaxial, smooth specimen tension
testing is generally of little value in manifesting the subtle
embrittling effects of increasing hydrogen content. Titanium
alloys tend to exhibit susceptibility under biaxial or triaxial stress fused within a chamber to reversibly release the absorbed hydro-
states; therefore, bend tests, cup-forming tests, or notched ten- gen, which is subsequently measured. LECO hydrogen analyzers
sion tests are generally more sensitive to hydrogen effects. offer measurement resolution on the order of 65 wppm at sam-
Impact toughness testing can be an especially sensitive indicator ple hydrogen levels below 200 wppm. It is critical to note that
of hydrogen effects in alpha alloys, whereas slow strain rate the analyzed hydrogen content may be directly dependent on the
methods are suitable for alpha-beta alloys.22,23,26 Because hydro- test sample thickness tested if a nonhomogeneous distribution
gen content has relatively little effect on alloy hardness, macro- (i.e., hydrogen gradient or surface film) of absorbed hydrogen
or microhardness testing is generally of little use. exists within the sample. If the hydrogen is uniformly distributed
Some titanium alloys may be susceptible to SLC, also known or diffused through the sample cross section (which is often not
as delayed cracking. This can occur on alpha, alpha-beta, and the case), no sample thickness dependence exists, and the hydro-
aged beta alloys that are highly stressed in tension for sustained gen content may be directly used to predict or correlate with
periods. SLC susceptibility increases with increasing internal metal behavior and properties.
hydrogen content, increasing alloy aluminum or oxygen equiva- Because hydrogen chemical analysis only provides the total
lency, decreasing strain rate, and increasing triaxial tensile stress hydrogen content in a specific localized specimen location, test
state and stress intensity.24,37 Highest susceptibility generally specimens are often metallurgically cross-sectioned and examined
occurs at or somewhat below room temperature24 and dimin- for the titanium-hydride phase to determine the hydrogen distri-
ishes at higher temperatures. bution. This technique, which is useful only in alpha and near-
SLC test severity increases (to the right) according to the alpha titanium alloys, where hydrides may precipitate because of
following types of test specimens: smooth tensile < < notched limited alpha phase solubility. This procedure involves wet-abra-
tensile < < loaded precracked specimen. For determination of sive wheel- or saw-cutting through the sample cross section, wet-
fracture toughness thresholds (KSLC), ASTM F1624 may be use- grinding down below any worked or heat-affected metal, and
ful, whether a specimen is loaded in increasing steps or using a hand-polishing down through abrasive papers and slurry or cloth
continuous rising load at a slow rising-K rate (e.g., 0.3 to wheels down to 0.05 lm alumina. Sample edge retention is vital in
1.0 10-3 MPa m0.5 s-1). Typical KISLC data dependence with test this hand-polishing technique. Final, very light etching with an
time (i.e., time-to-failure) is depicted in figure 7 with respect to HF/HNO3-type etch (i.e., Kroll), or even a 1 wt% HF acid etch,
KIC (air) and KISCC (salt water). Approximate test time scale typ- should reveal the acicular hydride precipitates (fig. 1), if present,
ically ranges anywhere from several hours to a day.24,37 Because which tend to etch out first. Intermediate electropolishing fol-
alloy microstructure and, especially, product crystallographic tex- lowed by etching also may be employed if sample edge (surface)
ture strongly influence SLC susceptibility, it is important to con- retention is not critical or of interest. Basic guidelines and proce-
sider the sample orientation of interest for testing. Examination of dures for preparation of titanium alloy samples for metallographic
post-test specimen fracture surfaces should reveal low-energy fac- examination can be found in Metallography and Microstructure.38
ets of quasi-cleavage under high-magnification scanning electron Microscopic examination of hydride phase precipitates is typically
microscopy examination if SLC has occurred. conducted at magnifications of 200 to 1,000, depending on
Hydrogen analysis of coupons is performed according to hydride phase size and quantity.
ASTM E1447, Standard Test Method for Determination of Hydro-
gen in Titanium and Titanium Alloys by Inert Gas Fusion Ther- IGNITION TESTING
mal Conductivity/Infrared Detection Method, whereby a small Titanium alloys can be susceptible to ignition or burning, or
(0.12 g) metal sample extracted from a titanium test coupon is both, in few specific gas environments, such as pure gaseous or
liquid oxygen, oxygen-enriched gas mixtures, and dry chlorine focused on the metal test sample. Although less relevant to high-
gas.1 These highly exothermic reactions generally increase with impact ignition sensitivity in titanium alloys found in LOX,39
increasing gas pressure, concentration, flow rate, and tempera- tensile rupture of test samples within pressurized test vessels has
ture. Normally, the nonreactive, protective surface oxide film on been employed most commonly for testing in oxygen-rich gas
titanium must be removed, damaged, or penetrated for ignition mixtures41–43 and dry chlorine gas.44 A typical ignition test setup
and reaction to occur. In the case of oxygen gas, burning is sus- using tensile rupture is depicted in figure 8.
tained only if the local metal surface temperature remains at or Continuous measurement of gas pressure and test sample
above the alloy’s melting point, above which formation of the temperature can provide an indirect means of assessing ignition
protective oxide film is not possible. Any factor that removes occurrence. Go/no-go assessment of ignition is usually based on
local heat generated, such as increased metal thermal conductiv- post-test visual examination of sample fracture surfaces for melt-
ity or section thickness (i.e., increased thermal mass), will inhibit ing or oxide scaling, or both. More sophisticated burn testers
or diminish ignition and burning tendencies. may incorporate continuous video monitoring and pyrometers,
Although no standard metal ignition tests exist, testing tra- or other heat sensors to track the ignition or burn event.
ditionally has been aimed at identifying ignition and sustained Burning or sustained combustion testing of titanium alloys
burning thresholds of a metal as a function of gas pressure, con- typically involves intentional localized heating of a test sample at
centration, and temperature. Ignition and burning tests may be one end or location to a temperature above its melting point.
categorized as either static or dynamic, depending on whether This localized focused sample heating can be achieved by laser,
the reaction gas is nonflowing (static) or continuously flowing electron beam, electric arc, electrical resistance, or plasma arc
past the test sample through a test chamber. Because increased methods. Once sample ignition is induced, the ignition heating
gas flow rate exacerbates metal ignition and burning, the source is removed, and duration and extent of sustained sample
dynamic tests tend to produce more conservative thresholds. burn is measured. A typical burn test has used a 4-in. (102-mm)
Ignition tests must incorporate a means of breaking or long, 0.125-in. (3.18-mm) diameter test sample (rod) that is
removing the surface oxide film and exposing fresh metal surface ignited on one end by electric arc.43 The rod length remaining
on the sample. This can be achieved by a variety of methods,39 after the test is measured and used to rate alloy burn susceptibil-
including tensile straining to fracture, puncture, impact, severe ity. Design details and setup of static and flow (dynamic) burn
surface abrasion or scratching, severe plastic straining, explosive testers are presented in figure 9 and figure 10, and are discussed
shock, or high-energy beams (i.e., laser)40 or electric sparks in more detail in Mcllroy and Zawierucha.45 Test sample size,
FIG. 8 Typical ignition test setup for titanium samples using tensile rupture.
TITANIUM 279
geometry, and section thickness directly influence burn suscepti-

FIG. 9 Static burn testing using promoted metal sample bility and must be standardized for comparative tests and speci-
43
ignition. fied in all cases.
UPPER
3.18 MM ROD SECTION
SAMPLE OF TEST OXIDATION TESTS
CHAMBER Although titanium alloys are highly resistant to oxidation up to
(SS)
moderate temperatures, colored protective surface oxide films
OXYGEN
INLET
form in the air at 370–595 C. Depending on exposure time at
temperature and alloy composition, oxide film or scale growth
COPPER
COPPER may become excessive and unacceptable for engineering purposes
SHIELD
SUPPORT above 620 C. In terms of titanium alloy content, increasing
OIL
THERMO- PROMOTER
vanadium, manganese, and zirconium concentrations are gener-
COUPLE IN CRUCIBLE ally detrimental, whereas increasing molybdenum, niobium, sili-
LOCATIONS
T.C. LEAD con, and chromium concentrations tend to retard oxidation.
CRUCIBLE SEAL RING Elevated aluminum content, as in the titanium aluminide interme-
tallics, markedly enhances oxidation resistance, elevating titanium
alloy use windows by several hundred degrees Fahrenheit.
CLAMP In addition to surface oxide film growth or scale formation
when thermomechanically processed or heat-treated in air at ele-
vated temperatures, titanium alloy products can experience oxy-
gen enrichment of metal surfaces beneath the titanium-oxide
EXPENDABLE LOWER
CERAMIC SECTION
scale. These hard, brittle metal surface layers, known as the alpha
FIBER OF TEST case, represent a diffused-in gradient of interstitial oxygen (and
BASE CHAMBER
(SS)
possibly nitrogen or carbon in other exposures) into the metal
surface. This diffusion-based time- and temperature-dependent
phenomenon becomes significant above 540–590 C, depend-
ing on alloy type. It severely reduces metal formability, ductility,
INSTRUMENTATION
AND ELECTRICAL and, particularly, fatigue life, in particular as metal section thick-
CONNECTIONS ness is reduced. Typical examples of alpha case formed on an
FIG. 10 Typical dynamic, flowing gas metal burn tester showing (A) overall equipment setup and (B) details of reaction chamber internals
45
for ignition and burning of metal test specimens.
PRESSURE CHECK
VALVE 3.2 mm COPPER
GAUGE EMERGENCY MONEL ROD
ISOLATION SHIELD
PRESSURE STOP VALVE PRESSURE
VALVE REGULATOR LOCKING
SWITCH SCREW
COPPER
SUPPLY GAS SLEEVE
BURSTING MASS CERAMIC INSULATED
DISC FLOW METER BLOWDOWN COPPER CONDUCTOR
VALVE
DIGITAL
OUTPUT
SHEATHED
WELDER ARC
+ THERMOCOUPLE
POWER SUPPLY
METAL TEST
SAMPLE CARBON STEEL
− PROMOTER
CARBON
ELECTRODE
NEEDLE REACTION
ELECTRONIC WATER COOLING ALUMINUM OXIDE
VALVE CHAMBER
CHECK VALVE COIL SPHERES
(A) (B)
FIG. 11 Cross-sectional photomicrographs showing thin surface layers of alpha case (diffused-in oxygen) on a Ti-6Al-4V wrought product
heat-treated in air (A) below (200) and (B) above its beta-transus temperature (100).
alpha-beta titanium alloy surface after heating in air for 1 h just typically is not observed with titanium alloys. Mechanical testing
below and above its beta-transus temperature are shown in the of samples after thermal exposure (i.e., tensile, bends, S-N fatigue
magnified cross section in figure 11. testing) may be of interest to assess extent of oxidation wastage
Simple static oxidation testing of titanium alloys can be and surface diffused-in interstitial embrittlement. Knoop or
conducted per ASTM G54, Standard Practice for Simple Static Vickers microhardness profiles of mounted and polished sample
Oxidation Testing (withdrawn 2002), with a few distinct consid- cross sections may be useful in identifying heavy alpha-case layer
erations relative to post-test evaluation. Descaling of titanium depth, because these oxygen-rich layers are substantially harder
samples after test exposure may employ mechanical scale than the metal matrix.
removal or hot alkaline solution descaling. A light fine sand grit
or a glass-bead blast for several seconds are both good mechani-
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Methodology on the Promoted Ignition-Combustion Behavior
42. F. E. Littman and F. M. Church, “Reaction of Titanium with Water of Carbon Steel and 316L Stainless Steel in Oxygen Gas
and Aqueous Solutions” (Final Report, SRI Project No. SD-2116, Mixture,” Flammability and Sensitivity of Materials in
Stanford Research Institute, Menlo Park, CA, June 1958). Oxygen-Enriched Atmospheres, vol. 4, ASTM STP1040
(West Conshohocken, PA: ASTM International, 1989),
43. P. Krag and R. Henson, “An Ignition Resistant Titanium Alloy for 38–53.
Acid Pressure Oxidation Applications,” in Proceedings of the
283
Chapter 18 | Corrosion Testing of Nonmetallic Coatings
William L. Mankins1
Introduction Additional types of coatings exist, which are hybrids of

these groups, and may be appropriately classified as metallic
A large number of tests exist for establishing the reliability of coatings or composite materials.
nonmetallic protective coatings on metal substrates. Definitions,
fundamentals, methodology, and practical examples are offered
COATINGS AND COATINGS SYSTEMS
for a better understanding of tests for protective coatings and to
The term “coatings” implies that there is a supporting structure
demonstrate that well-defined tests alone are not adequate with-
or substrate—an obvious point sometimes overlooked. The fail-
out rational application and interpretation.
ure of otherwise-acceptable coatings may be due to the substrate.
FOCUS OF TESTING The machined, molded, or polished substrate may contain
Materials tests and standards of nonmetallic organic and inor- defects or trapped impurities that affect performance of the coat-
ganic coatings systems on metallic substrates are described. ings system. A coatings test may assess the substrate properties.
Coating systems may provide many properties in addition to Likewise, the cleaning, surface preparation, and pretreatment
corrosion resistance (e.g., appearance and insulation). Although methods influence the coatings system performance. Use of the
test methods exist for a wide variety of coatings characteristics, term coatings system is intended to emphasize these interdepen-
the primary nonmetallic coatings tests addressed herein evaluate dent properties. Most tests evaluate whole coatings systems, with
corrosion resistance, adhesion, and physical or chemical an emphasis on a particular component or processing step.
durability. (Conversely, the term film is appropriate when a coatings mate-
rial can be evaluated independent of the substrate.)
NONMETALLIC COATINGS MATERIALS
Two broad groups of nonmetallic coatings materials are
considered: Fundamentals
1. Organic, including formulations containing dispersed TESTS/STANDARDS, APPLICATION/SELECTION,
inorganic or metallic materials: Examples include clear AND SPECIFICATIONS
coatings, typical paints, metal flake coatings, and organic- Corrosion inspection programs include those sponsored by the
based galvanic (zinc-rich) coatings. National Association of Corrosion Engineers (NACE Interna-
2. Inorganic, which may be modified by organic and metal- tional) and the Society for Protective Coatings (SSPC); both
lic materials. Examples include phosphates, anodic coat- societies have training and certification programs aimed at
ings, oxides, carbides, nitrides, borides, silicides, and improving quality control. They introduce inspectors, users,
inorganic-based galvanic (zinc-rich) coatings. Most of blasters, manufacturers, owner’s representatives, specifiers, and
these inorganic coatings are applied to the metallic sub- technical salesmen to the basics of corrosion control, paint
strates by a combination of thermal or chemical pro- inspection, and project management in a way that has resulted in
cesses. Some, such as anodic coatings, are formed by savings of billions of dollars in costly mistakes.
reactions on the surface. Tests and standards are intended to provide a means for
determining the appropriateness of materials for the users’ pur-
poses, for example, when a user requires excellent performance
at low cost. The requirement must be translated to a set of tests
1
Metallurgical Services, Inc., 594 Fairwood Rd., Huntington, WV 25705, USA
and standards, collectively known as specifications, agreeable to
The author acknowledges the previous author of this chapter, Richard D. Granata, the supplier and user, often on a contractual basis. Achieving an
Florida Atlantic University, Boca Raton, FL. agreement accrues benefits to both supplier and user; an efficient
DOI: 10.1520/MNL202NDSUP20190035
and effective agreement yields a competitive result. The major CORROSIVE ENVIRONMENTAL EXPOSURE
specification or objective in the context of corrosion testing is Corrosion occurs when all components of the process are present
service life. Tests and standards must be selected and applied to (anode, cathode, electrolyte, and intimate contact of the compo-
satisfy user specifications (service and lifetime requirements). A nents) and capable of reaction (see preceding section). Basic test
difficulty is the often-unsatisfactory relationship between long- conditions include exposure of the coatings systems to an elec-
term field service results to laboratory tests and standards results. trolyte containing reducible species (typically oxygen or hydro-
Application and interpretation of tests for nonmetallic corrosion gen ion). More sophisticated testing would include closely
protective coatings is a dynamic, evolving process of satisfying replicating known corrosive conditions, such as wet–dry cycles
specifications, including both short-term tests and long-term ser- and multicomponent and multiphase chemical environments.
vice performance. It is important to understand the limitations Immersion, salt spray, and a partial pressure of sulfur dioxide
of tests and standards results. corrosion tests correspond to water tank, marine, and combus-
tion exhaust service environments, respectively. An important
relationship exists between the corrosive environment used in
ELECTROCHEMICAL MECHANISM OF CORROSION the test procedures and the product’s intended service use.
A typical corrosion process, the reaction of iron with hydro-
chloric acid (HCl) under anaerobic conditions, is represented by CORROSION EFFECTS
the following equation: Distinction should be made between degradation because of cor-
Fe þ2HCl ¼ FeCl2 þ H2 ðgÞ, (1) rosion and other processes. Corrosion can cause loss of coatings
adhesion, such as occurs with cathodic disbondment, blistering,
which indicates that the acid reactant and the ferrous chloride or undercutting. Although adequate adhesion is necessary,
(FeCl2) corrosion product exist largely in the ionic state in aque- greater adherence does not correspond to greater corrosion resis-
ous solution. The probability of this reaction occurring by the tance. Exposing a coatings system to water can reduce the adhe-
mechanism implied in the equation is very low because too sion (wet adhesion), which is regained upon drying. Unless
many species must meet simultaneously. Conceivably, this reac- permanent damage occurs during the low-adhesion period, no
tion occurs in two independent steps: corrosion degradation results. The same may be true for other
properties such as flexibility. Initial properties and property
Anodic Reaction: Fe 2e ¼ Feþþ ðaqÞ changes due to a corrosion environment may relate to corrosion
(2)
Cathodic Reaction: 2Hþ ðaqÞ þ 2e ¼ H2 ðgÞ: protective properties. Clearly defining the relationship between
measured properties and the intended use of the protective coat-
In these two reactions, electron loss occurs at one site ings is important.
and electron gain occurs at another with the electrons linking
the reactive sites through the conductive metal phase (Fe ) and NONCORROSIVE EFFECTS
the ions linking the reactive sites through the aqueous (aq) phase. Many tests for coatings systems provide useful information
The overall reaction takes place at a rate determined by the related to service requirements involving salts, fogs, immersion,
more difficult of these two steps. This simple concept—that is, scribes, radiation, heat, chemical, cold, and pressure transients.
independent anodic and cathodic half-reactions—is the basis of Whether such tests are applicable to the service intended for the
the electrochemical mechanism of corrosion. The mechanism coatings must be established, and the test results must be inter-
has profound effects on the corrosion protective properties of preted in the context of corrosion protection performance. Ultra-
nonmetallic coatings materials. Some tests exploit the electro- violet (UV) resistance is not a useful property for the interior of
chemical mechanism to determine specific corrosion susceptibili- water storage tanks. Long-term 100% relative humidity and
ties of coatings systems, such as cathodic disbondment and water immersion resistances are not necessarily appropriate for
pinhole detection. Coatings that are permeable to oxygen may be outdoor desert or climate-controlled indoor environments.
vulnerable to damage because of the following alternative Selecting tests without regard for the coatings’ use may be detri-
cathodic reaction: mental to the development or qualification of a satisfactory coat-
ings system.
O2 þ 2H2 O þ 4e ¼ 4OH : (3)
This reaction is capable of causing high local pH and chemi-

cal degradation of the polymer or adhesive bonds. Thermody- Tests and Standards: Selection,
namically, this cathodic (reduction) reaction takes precedence Application, and Interpretation
over the hydrogen ion reduction reaction whenever oxygen is
present at the cathodic reaction site. AVAILABLE TESTS AND STANDARDS
A more accurate representation of the combined corrosion New and existing tests and standards are under continuous
reaction for an oxygen-deprived cathode follows: development and revision. ASTM is a leader of tests and stand-
ards; other contributors, with various emphasis on specifications,
Fe þ 2Hþ ðaqÞ þ 2Cl ðaqÞ ¼ Feþþ ðaqÞ þ 2Cl ðaqÞ þ H2 ðgÞ: are the federal government with Federal Test Method Standard
(4) 141C (supersedes 141A and 141B), state government agencies,
CORROSION TESTING OF NONMETALLIC COATINGS 285
NACE International, Society of Automotive Engineers (SAE), Altmayer3 compiled a table of 13 applicable corrosion tests for 30
Steel Structures Painting Council (SSPC), National Coil Coaters metallic, inorganic, and organic coating/substrate combinations.
Association (NCCA), International Standards Organization The most commonly used tests are salt spray (ASTM B117-19,
(ISO), and foreign systems (DIN), as well as commercial (e.g., Standard Practice for Operating Salt Spray (Fog) Apparatus), acetic
automotive, architectural, electronics), proprietary, and military acid salt spray (ASTM G85-19, Standard Practice for Modified Salt
organizations. A comprehensive listing of these tests and stand- Spray (Fog) Apparatus, Annex Al [formerly ASTM B287]), and
ards is not the intent of this document. the 100% humidity test (ASTM D2247-15(2020), Standard Prac-
Gaynes1 and Munger2 give descriptions and the framework tice for Testing Water Resistance of Coatings in 100% Relative
for effective use of tests and standards. Gaynes1 provides detailed Humidity). A condensed listing with brief descriptions of tests
descriptions including photographs, cross-listing ASTM to fed- selected from Altmayer,3 Mazia,4 ASM International,5,6 and
eral tests and a broader perspective encompassing the federal others is given in table 1. Additional tests are listed in table 2,
standard, miscellaneous tests, and some caveats of traditional which is an edited and revised listing by Munger.2 Hess7 provides
testing. Munger2 offers practical material directed toward large an important auxiliary reference to aid in identifying the causes
structures and provides a listing based on ASTM standards. of paint film defects.
TABLE 1 Brief Descriptions of Selected Protective Coating Tests for Metal Substrates
Test Description and Remarks
Salt Spray (ASTM B117-19) Most widely specified test. Atomized 5% sodium chloride, neutral pH, 35 C*, follow details of ASTM B117-19, Appendix XI.
Emphasizes wet surfaces (nondrying), high oxygen availability, neutral pH, and warm conditions. Control or comparative specimens
should be run simultaneously. Corrosivity consistency should be checked as described in ASTM B117-19, Appendix X3. Notes: May be
the most widely misused test. Requires correlation to service tests for useful results. Do not assume correlation exists. *Note that
dissolved CO2 concentration at 0 C is three times that of concentration at 35 C and can affect corrosion.
_____________________________________________________________________________
100% Relative Humidity Widely used test. Condensing humidity, 100% relative humidity (RH), 38 C. Emphasizes sensitivity to water exposure.
(ASTM D2247-15(2020) ______________________________________________________________________________
Acetic Acid-Salt Spray Widely used test. Atomized 5% sodium chloride, pH 3.2 using acetic acid, 35 C. More severe than ASTM B117-19. The lower pH and
(ASTM G85-19, Annex A1 the presence of acetate affect the solubility of corrosion products on and under the protective coatings.
[formerly ASTM B287]) ______________________________________________________________________________
Sulfur Dioxide-Salt Spray Atomized 5% sodium chloride, collected solution pH ¼ 2.5–3.2, 35 C, SO2 metered (60 min x 35 cm3/min per m3 cabinet volume),
(ASTM G85-19, Annex A4) four times per day. ______________________________________________________________________________
Copper Accelerated Salt Spray Atomized 5% sodium chloride, pH 3.2 with acetic acid, 0.025% cupric chloride-dihydrate, 35 C. Galvanic coupling because of copper
(ASTM B368-09(2014)) salt reduction to copper metal. More severe than ASTM B117-19.
_______________________________________________________________________________
FACT (formerly ASTM B538) Testing anodized aluminum specimens. Electrolyte as in salt-spray or CASS test. Specimen is made the cathode to generate high pH
at defects. _______________________________________________________________________________
Accelerated Weathering Exposure of coated specimens to effects of ultraviolet (UV) radiation experienced in outdoor sunlight condition which may be
combined with other exposures such as moisture and erosion. Exposure cabinets use carbon arc (ASTM D822/D822M-13(2018)),
xenon lamp (ASTM G26-70 [historical version]), or fluorescent lamp (ASTM G53-96).
_____________________________________________________________________________
Lactic Acid On substrates of brass and copper alloys, determines coatings porosity and resistance to handling (perspiration). Consists of
immersion in 85% lactic acid solution, drying and incubating above acetic acid vapors for 20 h to reveal discoloration spots at failure
points or delaminations.
Acidified Synthetic Seawater Atomized synthetic seawater (ASTM D1141-98(2013)) with 10 mL glacial acetic acid per L of solution, pH 2.8 to 3.0, 35 C. More
Testing (SWAAT) (ASTM G85-19, severe than ASTM D117-19. The lower pH and the presence of acetate affect the solubility of corrosion products on and under the
Annex A3-01(2019) protective coatings.
[formerly ASTM G43])
Electrographic and Chemical Pores and active defects in nonmetallic coatings can be revealed by color indication or deposit formation. On nickel substrates,
Porosity Tests dimethylglyoxime, or steel, potassium ferricyanide (ferroxyl test) indicator can be applied to surface on filter paper while substrate
is made the anode. Alternatively, a substrate immersed in acidic copper sulfate can be made the cathode to form copper nodules at
conductive coatings defects. _____________________________________________________________________________
Adhesion (ASTM D3359-17) Knife and fingernail test consists of cutting through the coating with knife or awl and dislodging coating with thumbnail or fingernail
(pass/fail). This test consists of “X” scribes or parallel cross-hatches followed by adhesive tape stripping of loosened coating.
_____________________________________________________________________________
(continued)
TABLE 1 (continued)
Test Description and Remarks
T-Bend Adhesion Combined flexibility and adhesion test consists of clamping end of coated flat metal panel in vise or similar tool, bending (convex)
(ASTM D4145-10(2018)) through 90 , reclamping to bend through 180 to give “0T” bend (where “T” is panel thickness and # (zero, 1, 2, …) is the number of
panel thicknesses). Rebending over the 180 bend gives an “IT” bend. Adhesive tape is pressed down along edge of bend and any
loose coating stripped off. Cyclic testing consisting of short salt exposure, short drying period followed by longer period of high
humidity. Undercutting from the scribe is also measured.
Exterior Exposure Method for conducting exterior exposure tests of paints on steel. Well-defined exposure setup, not necessarily equivalent to service
(ASTM D1014-18) tests.
Service Test/Data Performance data of coatings systems under use conditions. Slowest evaluation method: provides tangible results.
TABLE 2 Coatings Tests and Methods Pertinent to Corrosion Protection
Standard Title of Standard
NACE TMO174-2002 Laboratory Methods for the Evaluation of Protective Coatings and Lining Materials on Metallic Substrates in Immersion Service
ASTM B117-19 Standard Practice for Operating Salt Spray (Fog) Apparatus
ASTM B368-09(2014) Standard Test Method for Copper Accelerated Acetic Acid-Salt Spray (Fog) Testing (CASS Test)
ASTM B457-67(2018) Standard Test Method for Measurement of Impedance of Anodic Coatings on Aluminum
ASTM C536-83(2018) Standard Test Method for Continuity of Coatings in Glassed Steel Equipment by Electrical Testing
ASTM C743-87(2018) Standard Test Method for Continuity of Porcelain Enamel Coatings
ASTM D522/D522M-17 Standard Test Methods for Mandrel Bend Test of Attached Organic Coatings
ASTM D523-14(2018) Standard Test Method for Specular Gloss
ASTM D610-08(2019) Standard Practice for Evaluating Degree of Rusting on Painted Steel Surfaces
ASTM D662-93(2019) Standard Test Method for Evaluating Degree of Erosion of Exterior Paints
ASTM D714-02(2017) Standard Test Method for Evaluating Degree of Blistering of Paints
ASTM D822/D822M-13(2018) Standard Practice for Filtered Open-Flame Carbon-Arc Exposures of Paint and Related Coatings
ASTM D823-18 Standard Practices for Producing Films of Uniform Thickness of Paint, Varnish, Lacquer, and Related Products on Test Panels
ASTM D870-15(2020) Standard Practice for Testing Water Resistance of Coatings Using Water Immersion
ASTM D968-17 Standard Test Methods for Abrasion Resistance of Organic Coatings by Falling Abrasive
ASTM D1014-18 Standard Practice for Conducting Exterior Exposure Tests of Paints on Steel on Metal Substrates
ASTM D1186-01 (withdrawn 2006, Standard Test Method for Nondestructive Measurement of Dry Film Thickness of Nonmagnetic Coatings Applied to a Ferrous Base
replaced by ASTM D7091-20) (Withdrawn 2006)
ASTM D1400-00 Standard Test Method for Nondestructive Measurement of Dry Film Thickness of Nonconductive Coatings Applied to a Non-Ferrous
(withdrawn 2006, replaced by Metal Base (Withdrawn 2006)
ASTM D7091-20)
ASTM D1567-89(1995) Standard Test Method for Testing Detergent Cleaners for Evaluation of Corrosive Effects on Certain Porcelain Enamels
(withdrawn, no replacement)
ASTM D1653-13 Standard Test Methods for Water Vapor Transmission of Organic Coating Films
ASTM D1654-08(2016)e1 Standard Test Method for Evaluation of Painted or Coated Specimens Subject to Corrosive Environments
ASTM D1735-14 Standard Practice for Testing Water Resistance of Organic Coatings Using Water Fog Apparatus
ASTM D2197-16 Standard Test Method for Adhesion of Coatings by Scrape Adhesion
ASTM D2247-15(2020) Standard Practice for Testing Water Resistance of Coatings in 100% Relative Humidity
ASTM D2248-01a(2018) Standard Practice for Detergent Resistance of Organic Finishes
ASTM D3258-04(2019) Standard Test Method for Porosity of White or Near White Paint Films by Staining
ASTM D3273-16 Standard Test Method for Resistance to Growth of Mold on the Surface of Interior Coatings in an Environmental Chamber
ASTM D3276-15e1 Standard Guide for Painting Inspectors (Metal Substrates)
ASTM D3359-17 Standard Test Methods for Rating Adhesion by Tape Test
ASTM D3361/D3361M-13(2018) Standard Practice for Operating Open-Flame Carbon-Arc Exposures of Paint and Related Coatings
ASTM D3363-20 Standard Test Method for Film Hardness by Pencil Test
ASTM D4145-10(2018) Standard Test Method for Coating Flexibility of Prepainted Sheet
ASTM D4585/D4585M-18 Standard Practice for Testing Water Resistance of Coatings Using Controlled Condensation
(continued)
TABLE 2 (continued)
Standard Title of Standard
ASTM D4587-11(2019)e1 Standard Practice for Fluorescent UV-Condensation Exposures of Paint and Related Coatings
ASTM E376-19 Standard Practice for Measuring Coating Thickness by Magnetic-Field or Eddy Current (Electromagnetic) Test Methods
ASTM G8-96(2019) Standard Test Method for Cathodic Disbonding of Pipeline Coatings
ASTM G12-07(2013) Standard Test Method for Nondestructive Measurement of Film Thickness of Pipeline Coatings on Steel (Withdrawn 2013)
(withdrawn 2013, replaced by
ASTM D7091-20)
ASTM G42-11(2019)e1 Standard Test Methods for Cathodic Disbonding of Pipeline Coatings Subjected to Elevated Temperatures
ASTM G53-96 (withdrawn, Standard Practice for Operating Light- and Water-Exposure Apparatus (Fluorescent UV-Condensation Type) for Exposure of
replaced by ASTM G154-16) Nonmetallic Materials (Withdrawn 2000)
ASTM G60-01(2018) Standard Practice for Conducting Cyclic Humidity Exposures
ASTM G80-07 (withdrawn 2013, Standard Test Method for Specific Cathodic Disbonding of Pipeline Coatings (Withdrawn 2013)
replaced by ASTM G8)
ASTM G84-89(2020) Standard Practice for Measurement of Time-of-Wetness on Surfaces Exposed to Wetting Conditions as in Atmospheric
Corrosion Testing
ASTM G85-19 Standard Practice for Modified Salt Spray (Fog) Testing
ASTM G87-02(2018) Standard Practice for Conducting Moist SO2 Tests
ASTM G90-17 Standard Practice for Performing Accelerated Outdoor Weathering of Nonmetallic Materials Using Concentrated Natural Sunlight
ASTM G92-20 Standard Practice for Characterization of Atmospheric Test Sites
SAE J2334_201604 Laboratory Cyclic Corrosion Test (Stabilized April 2016)
2
Source: Revised from Munger, 310.
METHODS SELECTION All coupons are to be “scribed” using the procedures of

The large number of tests and possible test methods makes selec- ASTM D3359-17, Standard Test Methods for Rating Adhesion by
tion difficult. Suppliers, users, and testers and researchers all Tape Test, wherein the coating scratched or compromised
have different perspectives to narrow the selection process. through the entire thickness of the coating to expose the unpro-
Obtaining corrosion-resistance information enables a better tected substrate. Exposure times are variable, depending on test
focus. To aid in the selection process in which no universal and substrate. Additional corrosion tests (unscribed and ASTM
methodology exists, engage one or more from the following sec- D714, Standard Test Method for Evaluating Degree of Blistering of
tions: (1) survey of practices, (2) specific practice by a successful Paints) include hot humidity (ASTM D2247-15(2020), Standard
coatings industry participant, (3) service life testing philosophy, Practice for Testing Water Resistance Coatings in 100% Relative
or (4) a useful practical example involving cooperative efforts Humidity; 100 F/100% relative humidity), condensing humidity
through better understanding (methodology). (ASTM D4585/D4585M-18, Standard Practice for Testing Water
Resistance of Coatings Using Controlled Condensation), condens-
A SPECIFIC PRACTICE ing humidity/UV (ASTM G53-96 withdrawn, replaced by ASTM
The following tests constitute a generic test plan used by one indus- G154), water soak (ASTM D870-15, Standard Practice for Testing
trial service company for coated metal in laboratory performance Water Resistance of Coatings Using Water Immersion), and
testing. Typical test coupons, 4 in. by 12 in. (10.2 cm by 30.5 cm) detergent soak (ASTM D2248-01a(2018), Standard Practice for
are prepared with all surfaces uniformly coated. Before accelerated Detergent Resistance of Organic Finishes). Scribed samples are
corrosion testing, use one of the following procedures: prepared for ASTM D1654-08(2016)e1, Standard Test Method for
Evaluation of Painted or Coated Specimens Subjected to Corrosive
• ASTM B117-19, Standard Practice for Operating Salt Spray Environments, evaluation by scrape/rinse/dry or by rinse/blow-
(Fog) Apparatus off tape pull-off. Other noncorrosion tests (mainly adhesion) are
also performed including t-bend, wedge bend, conical mandrel,
• ASTM G85-19, Standard Practice for Modified Salt Spray
impact (direct/reverse), methyl ethyl ketone solvent rub test,
(Fog)
Olsen cup, gravelometer, pencil hardness, cross-hatch, dry film
• ASTM B68/B68M-19, Standard Specification for Seamless Cop- thickness, and loss of gloss. This battery of tests provides gener-
per Tube, Bright Annealed ous information about the coatings system, without establishing
• ASTM G85-19, A3-10(2019), Standard Practice for Modified a direct link to service data. The test battery is necessarily exten-
Salt Spray (Fog) Apparatus sive because the intent is to determine possible causes for service
problems. A clear relationship between service and test data is
The procedure selected from this list usually is defined from necessary for problem resolution. Discussion of each test proce-
the product specifications. dure is beyond the scope of this paper.
SURVEY OF PRACTICES and theoretical and empirical models.13–15 An open forum of all
A survey commissioned by the Federation of Societies for Coat- interested parties (mainly North American automotive and steel
ings Technology (FSCT) was performed by Steel Structures industries) was organized as the Corrosion Task Force of the AISI.
Painting Council (SSPC).8 The full report9 is available from This task force developed an improved laboratory-accelerated test
FSCT and contains useful details, including nonstandard tests for ranking the cosmetic corrosion resistance of coated automo-
and analyses. One portion of the report is particularly relevant to tive steel sheet products. This approach serves as a model for
methods selections; a compilation of 102 coatings test users’ methodology development in areas of nonmetallic coatings cor-
responses is shown in table 3, from which two conclusions are rosion testing.
drawn: (1) most respondents used only one or two tests; and
(2) the most prevalent test was salt spray. Salt spray testing is a Summary
crude approximation to highway environments involving deicing
compounds9 (see also the section, “Cooperative Practice Yielding • Many tests are available for evaluation of corrosion protective
Better Understanding”) and is more useful for marine systems.9 properties necessitating a test selection process.
Coatings users may approach quality assurance with fewer tests • Understanding the protective mechanisms of coatings systems
than formulators.9 Liu10 presents a discussion describing salt aids in developing methodologies for systems having long
spray test usefulness or uselessness based on years of experience lives.
(see chapter 23, “Automotive,” in this manual).
• The interpretation of the test results requires adequate corre-
lation to service life data.
SERVICE LIFE TESTING METHODOLOGY
In the previous example, no rationale is given for the selection or • Service results validation is difficult and often requires con-
application of the tests. Experience provides an important gage strictively long times.
for developing a useful set of tests. Dickie11 suggested that a • Successful case histories and experiences provide the best
methodology be developed to provide rational guidance for ser- means for useful evaluations until functional methodologies
vice life testing and proposed a general framework integrating are devised.
laboratory experiments, field exposure history, and theoretical
and empirical models. The central role of physical and chemical
models of degradation processes in service life prediction was References
examined11 and represents an important philosophical contribu-
1. N. I. Gaynes, Testing of Organic Coatings (Park Ridge, NJ: Noyes
tion to coatings testing. The methodology was first presented in Data Corporation, 1977), 293–312.
a somewhat-different form at an informal meeting of experts dis-
cussing coatings failure mechanisms.12 (Correlation of test results 2. C. G. Munger and D. V. Vincent, Chapter 12 in Corrosion
with service life is discussed in several chapters in this manual.) Prevention by Protective Coatings, 2nd ed. (Houston, TX: NACE
COOPERATIVE PRACTICE YIELDING BETTER 3. F. Altmayer, “Choosing an Accelerated Corrosion Test,” Metal
UNDERSTANDING Finishing, 69th Guidebook and Directory 99, no. 1A (January
AISI has taken a leadership role to develop and evaluate a meth- 2001): 579–585.
odology based on laboratory experiments, field exposure history, 4. R. D. Athey, “Testing,” Metal Finishing Organic Finishing
Guidebook and Directory 101, no. 10A (October 2003): 438.
TABLE 3 Compilation of Corrosion Tests and Standards Manual 5. M. H. Sandier, “Nonmetallic Coating Processes: Painting,” in
Metals Handbook, vol. 5, Surface Cleaning, Finishing and Coating,
Survey Results of 102 Users Responses Frequently Used Tests
9th ed. (Metals Park, OH: ASM International, 1990), 489–498,
527–531.
Test Respondents, %a
Salt Spray 52 6. F. Mansfeld, “Electrochemical Methods of Corrosion Testing,” in
Immersion 24 Metals Handbook, vol. 13A (Metals Park, OH: ASM International,
2003), 446.
Outdoor 22
Ultraviolet/Condensation 20 7. H. R. Hamburg and W. M. Morgans, eds., Hess’s Paint Film
Accelerated Weathering 14 Defects: Their Causes and Cure (London: Chapman and Hall,
Humidity/Condensation 10 1979).
Cathodic Disbondment 7
8. B. R. Appleman, “Survey of Accelerated Test Methods for
Adhesion 7 Anticorrosive Coating Performance,” Journal of Coatings
Atlas Cell Test (NACE TM0174) 4 Technology 62, no. 787 (August 1990): 57–67.
Other Physical Tests 4
9. B. R. Appleman, Survey of Accelerated Test Methods for Anti-
Other Chemical Tests 3
Corrosive Coating Performance (monograph prepared for
Flexibility 2
Corrosion Committee of Federation of Societies for Coatings
a
Multiple tests used (total greater than 100%). Technology, Blue Bell, PA, June 1990).
10. T. Liu, “Is the Salt Fog Test an Effective Method to Evaluate 13. H. E. Townsend, R. D. Granata, D. C. McCune, W. A. Schumacker,
Corrosion Resistant Coatings?” in Corrosion Control by Organic and R. J. Neville, Progress by the Automotive and Steel Industries
Coatings, ed. H. Leidheiser, Jr. (Houston, TX: NACE International, Towards an Improved Laboratory Cosmetic Corrosion Test, ACAP
1981), 247–254. Conference Proceedings, SAE P-250 (Warrendale, PA: SAE
11. R. A. Dickie, “Toward a Unified Strategy of Service Life
Prediction,” Journal of Coatings Technology 64, no. 809 (June 14. H. E. Townsend, “Development of an Improved Laboratory
1992): 61–64. Corrosion Test by the Automotive and Steel Industries,” in
Advanced Coatings Technology, Proceedings of the 4th Annual
12. W. Funke, H. Leidheiser Jr., R. A. Dickie, et al., “Unsolved ESD Conference (Ann Arbor, MI: The Engineering Society, 1994).
Problems of Corrosion Protection by Organic Coatings: A
Discussion,” Journal of Coatings Technology 58, no. 741 (October 15. Cosmetic Corrosion Lab Test, SAE J2334 (Warrendale, PA: SEA
1986): 79–86. International, 1997).
291
Chapter 19 | Metal-Matrix Composites
L. H. Hihara1
Introduction FIG. 1 Foamed particulate SiC/Al MMC (A). Each side of cube is
Metal-matrix composites (MMCs) are metals that are reinforced approximately 6 cm. Al2O3/Al MMC fabricated from
with fibers or particles that usually are stiff, strong, and light- woven Al2O3 fabric (B). Each side of square coupon
weight. The fibers and particles can be metal (e.g., tungsten), is 2.54 cm.
nonmetal (e.g., carbon or boron), or ceramic (e.g., silicon carbide
(SiC) or alumina (Al2O3)). The purpose for reinforcing metals
with fibers or particles is to create composites that have proper-
ties more useful than that of the individual constituents. For
example, fibers and particles are used in MMCs to increase stiff-
ness,1 strength,1 and thermal conductivity,2 and to reduce weight,1
thermal expansion,3 friction,4,5 and wear.6 Particulate MMCs can
even be foamed (fig. 1A) resulting in extraordinary properties,
such as extremely low density and excellent energy, vibration,
and noise absorption, with potential application for impact-
absorbing material for blast attenuation, fire-proof walls, and
sound barriers. MMCs can even be processed from woven
ceramic fabric (fig. 1B).
Selection of the matrix metal and reinforcement constituent
compounds, fly ash, graphite, mica, quartz, silicon, SiC, titanium
usually is based on how well the combination interacts to achieve
carbide (TiC), tungsten, tungsten carbide (WC), yttria, and zir-
desired properties. Interaction of the MMC with the environ-
con. The reinforcement constituents usually range from 10 to
ment is normally a secondary consideration; therefore, it is not
60 vol%. This review focuses on the corrosion properties of bulk
uncommon for MMCs to have low resistance to corrosion. It is
MMCs and does not cover corrosion protection of MMCs, sur-
also not uncommon for MMCs to have corrosion behavior sig-
face modification of MMCs, or MMCs used as coatings. Other
nificantly different from what might be expected based on the
reviews on corrosion of various types of MMC are available.7–14
normal corrosion behavior of the MMC constituents. The corro-
Methods and tests that can be used in a corrosion testing pro-
sion resistance of the MMC is usually inferior to that of its
gram to assess corrosion damage, determine corrosion mecha-
monolithic matrix alloy for one or more of the following reasons:
nisms, and study specific types of corrosion will be discussed.
(1) galvanic coupling of reinforcement constituent and matrix;
(2) formation of an interphase between the reinforcement con-
stituent and matrix; (3) microstructural contaminants and proc- Corrosion Susceptibility of MMCs
essing residuals in the MMC; and (4) microstructural changes
caused by the presence of the reinforcement constituents. The effect of different types of reinforcement constituents on
The corrosion behavior of aluminum, magnesium, lead, MMC corrosion behavior is discussed in this section. Because of
depleted uranium, stainless steel, titanium, copper, and zinc the limited amount of information on MMC corrosion behavior,
MMCs will be reviewed. Reinforcement constituents used in it is not feasible to have separate sections for effects of alloying
these MMCs include Al2O3, boron, boron carbide (B4C), calcium elements, effects of microstructure, and sensitivity to acidity/
alkalinity. MMCs are still relatively new and specialized materi-
als; therefore, only a limited number of corrosion studies have
1
Dept. of Mechanical Engineering, 2540 Dole St., University of Hawaii at Manoa, been conducted. Most studies relate the effects of the reinforce-
Honolulu, HI 96822, USA http://orcid.org/0000-0002-4777-4287 ment constituents to overall MMC corrosion behavior.
DOI: 10.1520/MNL202NDSUP20190037
ALUMINUM MMCS content was increased from 18 to 46 vol%, suggesting that corro-
Corrosion research has focused primarily on aluminum MMCs, sion rates increase as aluminum-boride cathodic sites increase. It
which is the only type of MMC that has become widely avail- was also noted that BF-matrix interface regions were preferen-
able.3 Aluminum has relatively good corrosion resistance and is tially corroded, but it was not determined whether matrix near
light weight. Its density is 2.7 g/cm3. Corrosion studies have been the interphase or the interphase was attacked. Others have found
conducted on aluminum MMCs reinforced with boron, graphite, that diffusion bonds in B/Al MMCs have been major sources of
SiC, B4C, silicon, Al2O3, mica, and fly ash. Corrosion of diffusion corrosion.21,22 This is discussed in the subsection “Effect of Diffu-
bonds, stress corrosion, and corrosion fatigue will also be sion Bonds and Microstructural Contaminants.”
discussed.
Effect of Graphite
Effect of Boron Continuous fiber Gr/Al MMCs (fig. 2) are known to have high
The primary use of boron/aluminum (B/Al) MMCs has been specific tensile strength and stiffness in the direction of the fiber
tubular struts in the mid-fuselage structure of the space shuttle. axis. Limitations of shear, compression, and transverse strengths
The use of B/Al MMCs instead of aluminum alloys (as planned of the MMCs, however, have restricted their use.5 Particulate
in the original design) resulted in a 44% savings in weight.15 Gr/Al MMCs also have been developed for potential use in
Boron filaments (BFs) consist of polycrystalline boron with tribological applications because of good resistance to wear and
a core of tungsten and tungsten borides, which form during seizure.25,26
processing.16 B/Al MMCs are usually fabricated by diffusion In the presence of water, carbon has a small domain of ther-
bonding BFs between aluminum foils.17 Aluminum borides (i.e., modynamic stability in potential-pH space.27 At active potentials,
AlB12 and AlB2) have been found at BF-matrix interfaces.18 it is thermodynamically possible to form methane (CH4) by the
Crystalline boron has good chemical resistance and is not following reaction:
attacked by strong acids and bases even though it is thermody-
namically unstable in water.19 Accordingly, BFs are relatively C þ 4Hþ þ 4e ¼ CH4 : (1)
inert in aqueous solutions. No observable degradation of the BFs This has not been confirmed, however.27 No CH4 was detected or
was observed after exposure to boiling, saturated, nickel chloride visual fiber degradation observed when pitch-based graphite fibers
solutions for 16 s,20 or to 3% sodium chloride (NaCl) solutions were cathodically polarized.28 At noble potentials, various carbon
containing 0.1% hydrogen peroxide (H2O2).21 compounds may form during carbon oxidation,27 but carbon
Pure boron (99.999%),22 as-manufactured (referred to as dioxide (CO2) and carbon monoxide (CO) are believed to be the
“virgin”) BF with tungsten core shielded,22,23 virgin BF with tung- dominant reaction products.28 During anodic polarization, pitch-
sten core exposed,23 and BF extracted from aluminum matrices based graphite fibers are oxidized to CO2 and CO with crevice
(not specified if tungsten core exposed)24 are noble to aluminum formation.28 Graphite compounds also form by the intercalation
in NaCl solutions. Therefore, galvanic corrosion of aluminum of ions between graphite planes during polarization.29 In the
coupled to pure boron or BF is thermodynamically possible. open-circuit condition or when coupled to aluminum, however,
Pure boron, however, is an insulator and cannot support electri- graphite fibers do not usually exhibit visual degradation.
cal currents under normal conditions. Cathodic and anodic cur- Graphite, which is an electrical conductor, can serve as an
rents were unmeasurable on pure boron (99.999%) electrodes in efficient cathode during galvanic corrosion in Gr/Al MMCs.
aerated NaCl solutions.22 The conductivity of BFs is many orders Czyrklis30 and others31–33 have found that the open-circuit
of magnitude greater than that of pure boron because of tungsten
and tungsten borides in the core.16 Galvanic currents, however,
were also unmeasurable between virgin BF and 2024 aluminum FIG. 2 Micrograph of Gr/6061-T6 Al MMC. Graphite fiber volume
or 6061 aluminum in 3.5% NaCl solutions.24 It was not specified fraction is approximately 50%.
whether solutions were aerated or deaerated and whether the
tungsten core of the BFs was exposed. Galvanic currents were
measurable between the aluminum alloys and BFs that were
extracted from the matrix.24 The extracted BFs were enveloped
by a 4-lm-thick layer of aluminum boride, which could not be
positively identified as AlB2 or AlB12. Galvanic currents mea-
sured between the aluminum alloys and aluminum boride
(boride species not specified) were similar to those between the
alloys and the extracted BFs. When the layer of aluminum boride
was removed from the extracted BFs, the galvanic current ceased,
indicating that the aluminum boride interphase is necessary for
galvanic corrosion. In addition, B/Al MMCs were noble to the
matrix alloy and active to the extracted BF and aluminum
boride, which coincides with the mixed-potential theory. The
corrosion rate of B/Al MMCs also increased when the BF
METAL-MATRIX COMPOSITES 293
potential of a Gr/Al MMC is noble to the matrix alloy in deaer-

ated NaCl solutions.30 The open-circuit potential of a particulate FIG. 4 Anodic polarization diagrams of ultrapure aluminum
Gr/Al MMC, however, was reported to be more active than the and 6061-T6 aluminum in deaerated 3.15 wt% NaCl
matrix material for a case in which the presence of graphite par- plotted with the cathodic polarization diagrams of
ticles caused a large increase in the anodic currents.33 Dull, Har- pitch-based graphite fibers (cross section exposed)
rigan, and Amateau34 conducted polarization experiments on in deaerated and aerated 3.15 wt% NaCl at 30 C.
various Gr/Al MMCs in NaCl solutions and found that dissolved Scan rate = 0.1 mV/s.
oxygen greatly increases the corrosion rate, indicating that the
main driving force for galvanic corrosion is oxygen rather than
proton reduction in aerated solutions. Using the zero-resistance
ammeter (ZRA) technique,35 Dash36 showed that the galvanic-
corrosion current density (iGALV) of a galvanic couple with a 5-
to-1 area ratio of pure aluminum to pitch-based graphite fiber
increased from less than 1 10-8 A/cm2 in deaerated 3.5 wt%
NaCl to 1.5 106 A/cm2 in aerated 3.5 wt% NaCl. Hihara and
Latanision37 also found that iGALV of galvanic couples consisting
of equal areas of 6061-T6 aluminum and pitch-based graphite
fiber was about 60 times greater in aerated 3.15 wt% NaCl solu-
tions compared to deaerated solutions where iGALV was equal to
about 3 106 A/cm2. The galvanic effect has also been reported 3.15 wt% NaCl with the cathodic polarization diagrams of pitch-
in particulate Gr/Al MMCs.38,39 based graphite fibers in deaerated and aerated 3.15 wt% NaCl.
Galvanic corrosion between Gr and the aluminum matrix As shown in the figure, proton reduction on graphite will polar-
(fig. 3) was also evident in atmospheric corrosion studies of a ize aluminum to noble potentials that are less than the pitting
50% nickel-coated Gr fiber/pure Al MMC exposed in agricul- potential EPIT, explaining the negligible galvanic-corrosion rates
tural, rainforest, marine, industrial, arid, and volcanic (with acid in deaerated solutions. Oxygen reduction on graphite, however,
rain) environments.40 The corrosion damage of the 50% nickel- polarizes aluminum into the pitting regime, which causes high
coated Gr fiber/pure Al MMC is contrasted with that of a 50% galvanic-corrosion rates in aerated, chloride-containing solu-
Al2O3/pure Al MMC exposed at the industrial site for the same tions. Figure 5 shows iGALV of 6061-T6 aluminum and ultrapure
exposure period (fig. 3). The annual corrosion rate of the MMC aluminum as a function of the area fraction of pitch-based
was approximately 500 times higher than that of pure Al at the graphite fiber (cross-section exposed) in aerated 3.15 wt%
marine site, and ranged from approximately 30 to 300 times NaCl.37 Both ultrapure aluminum and 6061-T6 aluminum are
higher in the agricultural, rainforest, industrial, and arid sites. represented by the same curve because they have similar gal-
Interestingly, the corrosion rate of the MMC was only approxi- vanic-corrosion behavior. Relatively new, nonequilibrium alumi-
mately 10 times higher than that of pure aluminum at the volca- num alloys containing approximately 20 at% molybdenum or 26
nic site; which was attributed to the dissolution of Ni, which may at% tungsten, with marked higher pitting potential (i.e., in excess
have had an inhibitive effect on the aluminum matrix in acidic of 1 V compared with pure aluminum) in chloride solutions
environments.41 The high corrosion rates of the MMC is likely have been studied as potential new alloys for Gr/Al MMCs.42,43
caused by oxygen reduction on the Gr fibers. The results have been promising, as graphite fibers in aerated
Figure 4 shows the anodic polarization diagrams of ultra- chloride solutions were incapable of polarizing the alloys to their
pure aluminum (99.999%) and 6061-T6 aluminum in deaerated pitting potentials, resulting in galvanic corrosion rates between
FIG. 3 Corrosion of the 50% nickel-coated Gr fiber/pure Al MMC (A) contrasted to 50% Al2O3/pure Al MMC (B) exposed at industrial site
for the same period.
FIG. 5 Graphs showing iGALV of ultrapure aluminum and 6061-T6 FIG. 6 Micrograph of SiCP/6061-T6 Al MMC. SiC volume fraction
aluminum as a function of area fraction Xc of graphite is 13%.
fiber and SiC in aerated 3.15 wt% NaCl at 30 C.
the fibers and alloys up to three orders of magnitude lower than

that with pure aluminum.42,43
Another cause of degradation in Gr/Al MMCs is the presence
of aluminum carbide (Al4C3). An Al4C3 interphase forms by the
reaction of aluminum and carbon.44 In Gr/Al MMCs, the forma- respectively.54 Therefore, galvanic corrosion between Al and SiC
tion of Al4C3 becomes substantial during processing at tempera- could be possible, but the degree will be highly dependent on the
tures much higher than the liquidus temperature.45 Portnoi et al.46 purity level of SiC.
showed that Al4C3 in Gr/Al MMCs readily decomposes in water, In deaerated, chloride-containing solutions, SiC/Al MMCs
producing CH4 and aluminum hydroxide Al(OH)3: and their matrix alloys passivate in the open-circuit condi-
tion.48,55 Proton reduction alone cannot polarize the composites
Al4 C3 ðsÞ þ 12H2 Oð1Þ ¼ 4A1ðOHÞ3 ðsÞ þ 3CH4 ðgÞ, (2)
or the matrix alloys to EPIT because oxygen reduction is required
The hydrolysis rate of hot-pressed Al4C3 (78% theoretical den- for this. Accordingly, in aerated, chloride-containing solutions,
sity) was measured to be approximately 1%/h.47 the open-circuit potentials of SiC/Al MMCs and their matrix
Aylor and Moran,48 who conducted polarization experiments alloys are nearly equal to pitting potentials.55
on Gr/Al MMCs in seawater, also hypothesized that diffusion of In aerated chloride-containing solutions, the degree of gal-
carbon into aluminum could lower the integrity of the passive vanic corrosion is strongly dependent on the type of SiC rein-
film, rendering it more susceptible to breakdown. Wielage49 forcement. Figure 7 shows the anodic polarization diagrams of
reported that the pitting potentials of various squeeze-cast Gr/Al ultrapure aluminum and 6061-T6 aluminum in deaerated 3.15
MMCs were approximately 20 mV more active than that of the wt% NaCl with the cathodic polarization diagrams of hot-
pure aluminum matrix material in a chloride solution. Al4C3 was pressed SiC, SiCMF (configurations with either carbon cores or
found at the Gr fiber-matrix interfaces. Shimizu, Nishimura, and carbon-rich surface exposed), pitch-based graphite fiber, and
Matsushima,50 however, found that pitting potentials of a squeeze- 6061-T6 aluminum in aerated 3.15 wt% NaCl. The figure shows
cast, short fiber Gr/6061 Al MMC had pitting potentials similar to that iGALV of 6061-T6 aluminum coupled to hot-pressed SiC (of
that of monolithic 6061 Al in a chloride solution. equal surface area) is about twice the normal corrosion current
density (iCORR) of 6061-T6 aluminum. When 6061-T6 aluminum
Effect of Silicon Carbide is coupled to SiCMF (of equal surface area), iGALV is about
The SiC/aluminum (SiC/Al) MMCs are reinforced with SiC par- 25 times greater than iCORR of 6061-T6 aluminum. The influence
ticles (P) (fig. 6), whiskers (W), fibers, or monofilament (MF). In of the carbon core and carbon-rich surface of the SiCMF is clearly
1988, an aluminum tube in the catamaran Stars and Stripes ‘88 seen in figure 7 where the polarization diagram of the SiCMF has
was replaced by a lighter SiCP/Al MMC tube having a 30.5-cm a stronger resemblance to that of pitch-based graphite than that
outer diameter.3 Lightweight mirrors for telescopes have also of hot-pressed SiC.47 Galvanic current between Nicalon SiC
been fabricated from SiCP/Al MMC foam.51 fibers and an aluminum alloy was also measured in an aerated
SiC is a semiconductor and its electrical resistivity depends NaCl solution.31 The galvanic current was 72 lA (specimen areas
on its purity. It ranges from about 1013 to 105 Xcm.52 Thus, in not given) and 15% of that between carbon fiber and the alumi-
the unpure state, the resistivity of SiC can be rather low. Some num alloy. If the SiC is of the p-type semiconductor, galvanic
SiCMF also have carbon cores and carbon-rich surfaces,53 with currents also can increase under illumination. This effect is
resistivities on the order of 102 Xcm.47 Consequently, in aque- shown in aerated 0.5 M Na2SO4 where the cathodic current
ous solutions, SiC can serve as an inert electrode for proton and density of a 20 vol% SiC/6092-T6Al increased because of photo-
oxygen reduction. Also, depending on doping and impurity lev- generated currents under illumination (fig. 8).54
els, SiC can be a p-type or n-type semiconductor which can For particulate-reinforced SiC/Al MMCs, the galvanic
induce cathodic or anodic photo-generated currents, corrosion behavior is likely to be more accurately represented
chloride-containing environments. Lore and Wolf57 found that

FIG. 7 Anodic polarization diagrams of ultrapure aluminum the degree of corrosion in SiCW/6061 Al MMCs exposed to chlo-
and 6061-T6 aluminum in deaerated 3.15 wt% NaCl ride-containing solutions is proportional to the SiC content.
plotted with the cathodic polarization diagrams of Metzger and Fishman7 reported the results of DeJarnette and
pitch-based graphite fiber, SiCMF, hot-pressed SiC, and Crowe who exposed 20 vol% SiCP/2024 Al MMCs and mono-
6061-T6 aluminum in aerated 3.15 wt% NaCl at 30 C. lithic 2024-T4 Al to aerated 3.5 wt% NaCl. The composite cor-
CS = cross section exposed. FS = fiber surface roded about 40% faster than the matrix alloy. Sun, Koo, and
exposed. Scan rate = 0.1 mV/s. Wheat58 and Modi et al.59 also reported that corrosion rates of
SiCP/Al MMCs were higher than that of the matrix alloys. Haw-
thorn60 showed that atmospheric corrosion rates (in rainforest
and marine environments) of SiCP/6092 Al MMCs generally
increased as the content of black SiC increased from 5, 10, 20,
40, to 55 vol%. The corrosion rate of an SiCP/6092 Al MMC
reinforced with 55 vol% high-purity green SiC was consistently
lower than that reinforced with 55 vol% lower-purity black SiC.
The high-purity green SiC should have higher electrical resistiv-
ity resulting in lower galvanic corrosion compared with the
MMC reinforced with the lower purity black SiC.
Griffiths and Turnbull61 found no evidence of galvanic cor-
rosion in SiC/6061 aluminum MMCs with 20–30 wt% (17–27
vol%, respectively) SiC particles. Rather, they showed that diffu-
FIG. 8 Cathodic polarization diagram of the 20 v% SiC/6092-T6
sion-limited oxygen reduction on SiC/Al MMCs in an NaCl
Al MMC exposed to air-exposed 0.5 M Na2SO4 at 20 C in
solution was significantly greater than that of the monolithic
the dark with four periods of illumination.
alloy, which could not be attributed to the SiC content but could
be attributed to the increase in intermetallic particles in the
MMC. Hence, it is possible that the increase in corrosion rates of
the MMCs in comparison to the monolithic alloys could be the
result of oxygen reduction on intermetallics. Aziz and Zhang62
and Aziz63 also reported that 17.5% SiC/5A06 Al MMCs cor-
roded faster than the monolithic alloy in aerated 3.5 wt% NaCl,
and attributed the higher rates to the high uniform density of
cathodic (Al (Mn, Fe)) and anodic (Al (Si, Mg)) intermetallics
with respect to the monolithic matrix alloy as well as cervices at
SiC-Al interfaces. Qian et al.64 reported that the corrosion rate of
25 % SiCP/2124 MMCs in naturally aerated 0.6 M NaCl solution
at room temperature were higher when the SiC particles were
by comparison to the hot-pressed SiC data, as opposed to the larger (3 lm vs. 0.7 lm). The formation of intermetallics at the
SiCMF and Nicalon SiC fiber data. From the polarization data in SiC/Al interface was significantly reduced for the smaller 0.7 lm
figure 7, galvanic-corrosion rates were calculated for ultrapure SiC, thus reducing active sites for corrosion initiation. Some
aluminum and 6061-T6 aluminum coupled to hot-pressed SiC observations contrary to these, however, have been made. Sun
exposed to aerated 3.15 wt% NaCl.37 Figure 5 graphically shows et al.58 reported that the degree of corrosion increased with SiC
iGALV as a function of hot-pressed SiC area fraction. Galvanic particle content, but the intermetallic content was relatively con-
corrosion between hot-pressed SiC and 6061-T6 Al would stant. Cheng et al.65 showed that the cathodic current density of
not exceed the normal corrosion rate of 6061-T6 Al in aerated 15% SiCP/7075 Al MMC was lower than that of the base alloy in
3.15 wt% NaCl until the SiC volume fraction exceeds approxi- 3.5 wt% NaCl, indicating that oxygen reduction was lower on the
mately 0.3. Hence, based on figure 5, galvanic corrosion of MMC compared with the base alloy. The characteristics of the
particulate SiC/Al MMCs would increase with SiC content and SiCP or intermetallics, however, were not described.
become relatively noticeable only at higher SiC volume frac- SiC particles in SiC/Al MMCs have little effect on passive
tions—for example, in the electronic-grade MMCs with 35 to currents. In a chloride-free, sodium tetraborate-boric acid solu-
55 vol% SiC. tion of pH 8.4, the passive current of a SiCW/6061 Al MMC was
Dı́az-Ballote et al.56 showed via electrochemical microscope only slightly greater than that of monolithic 6061 aluminum.66
that SiCP was electrochemically active and oxygen reduction In deaerated 0.1 N NaCl, the passive current densities (at poten-
occurred over SiCP in an Al alloy (13.5% Si, 9% Mg, balance Al) tials less than EPIT) of 20 vol% SiCW/2024 Al and 20% vol%
MMC exposed to aerated 0.1 N NaCl. Experimental results have SiCW/6061 Al MMCs were actually slightly less than that of their
generally indicated that the corrosion rate of particulate and monolithic matrix alloys. The passive current densities were on
whisker SiC/Al MMCs increases with SiC content in aerated, the order of 105 A/cm2.55
SiC generally has little effect on EPIT,31,48,50,55,61,67–70 indicat- ranging from 0.1–1,000 Xcm.84 Hence, it is possible that B4C
ing that the presence of SiC particles does not degrade the pitting can serve as cathodic sites and induce galvanic action with the
resistance of passive films on aluminum. In one example, how- aluminum matrix. In some particulate 20% B4C/6092-T6 Al
ever, the pitting potential of a 20 vol% SiCW/2024 Al MMC was MMCs (fig. 9), sporadic graphite particles identified by Raman
depressed by about 0.1 V.55 Contrary to the relatively invariable spectroscopy (fig. 10) have been found to be mixed in with the
behavior of EPIT, pit morphology is indirectly affected by the B4C particles.85
presence of SiC particles. Trzaskoma71 found that pits on SiCW/ In particulate 16% B4C/1100 Al MMCs exposed to 0.5 M
Al MMCs were notably more numerous and much smaller in K2SO4, Han, Gallant, and Chen86 reported that B4C supported O2
size compared with pits on wrought and powder-compacted and/or H2O reduction, which was verified by the deposition of
monolithic alloys during anodic polarization in 0.1 N NaCl. The copper oxides on the B4C because of the alkalinization of the solu-
pits nucleated at intermetallic particles (not SiC), which are tion. Han and Chen87 also showed that the corrosion rate increased
smaller and more numerous in the MMCs than in the mono- with B4C content and that galvanic currents could be measured
lithic matrix alloys.71 Apparently, SiC whiskers71 and particles61 between bulk B4C and 1100 Al in aerated 3.5 wt% NaCl.
enhance the precipitation of the intermetallic phases. The pres- Dikici and Tekmen78 also reported an increase in corrosion
ence of SiC, therefore, may increase the number of intermetallic rates as the B4C content was increased from 10% to 30% in par-
pit-nucleation sites but does not weaken the resistance of the ticulate B4C/Al (5% Cu) MMCs exposed to aerated 3.5% NaCl
passive film, as gauged by pitting potentials. Others have also solution, but attributed this increase to the formation of CuAl2
observed pit nucleation at dendrite cores,70 near eutectic sili- precipitates that served as cathodic sites. The CuAl2 precipitates
con,69,72 and intermetallic particles72 in various SiC/Al MMCs. formed on the B4C-Al interface.
The corrosion behavior of particulate SiC/Al MMCs is also Relatively large, circular, localized anodic regions formed on
sensitive to processing. The SiC particles have an indirect effect particulate 20% B4C/6092-T6Al MMCs immersed in near-neutral,
on corrosion behavior by altering the condition of the matrix chloride-free, 0.5 M Na2SO4 solution exposed to air at room tem-
metal. Processing conditions and the presence of SiC particles perature within 40 h.88 The localized anodic sites were approxi-
can affect void content,73 dislocation density,74 and the precipita- mately 300–400 lm in diameter and significantly larger than the
tion of active phases75 in aluminum matrices. Paciej and Agar- reinforcement size (10–20 lm). The rapid corrosion of the
wala73 found that certain solution heat treatments and high MMC in the sodium sulfate solution indicated that there was a
extrusion ratios improved corrosion resistance of a 20% SiCP/ galvanic coupling effect between the Al matrix and B4C reinforce-
7091 Al MMC. Bhat, Surappa, and Sudhaker Nayak76 reported ment network. The anodic region grew and spread out into the
that extrusion improved the corrosion resistance of cast MMCs surrounding cathodic regions. Near the center of the localized
by reducing the amount of pores and agglomerates of SiC par- anodic region, the solution was most acidic with a pH close to 5.
ticles; and Ahmad and Abdul77 found that the T4 temper The pH rose to approximately 8.5 in the surrounding cathodic
improved corrosion resistance over O and F tempers because of regions. It was hypothesized that the localized acidification of the
a finer, more homogenous distribution of secondary phases. solution is enhanced by the formation of microcrevices created by
Dikici and Tekmen,78 however, observed increasing corrosion reinforcement particles left in relief as the matrix corroded. The
rates with increase in cold work from 4–50% reduction in area results do not preclude the possibility of the formation of short-
(before aging) in 10% and 20% SiC/Al (Si-Mg based) MMCs. range, microgalvanic cells between individual B4C particles and
The effect of the cold working had a greater influence on the cor- the surrounding matrix; however, the formation of macro anodic
rosion behavior compared to the SiC content (10% vs. 20%). It and cathodic regions seemed to dominate the corrosion process.
has been suggested that corrosion near the SiC-Al interface could Because of the amphoteric properties of aluminum, the anodic
be caused by high dislocation density because of a mismatch of and cathodic regions flip-flopped with time.
the coefficient of thermal expansion between SiC and alumi-
num,47,69,79 segregation of alloying elements to the SiC-Al inter-
FIG. 9 Particulate B4C/6092 Al MMC with sporadic graphite
face,80 or the formation of Al4C3, which hydrolyzes in water. SiC
particle (arrow) identified by Raman spectroscopy
reacts with molten aluminum to form Al4C3 if the silicon activity
amongst B4C particles.
is low.81 Al4C3 has been identified as a source of corrosion for
MMCs reinforced82 with particles83 and SiC Nicalon fibers.31
Effect of Boron Carbide

B4C has low density and relatively high hardness and often used
in ballistic armor. B4C also has good neutron shielding proper-
ties and, therefore, B4C/Al MMCs have found utility in nuclear
applications as neutron absorber materials. B4C is a p-type semi-
conductor (without deliberate doping) and has high electrical
resistivity (i.e., 1010 Xcm) at room temperature.82 The electri-
cal resistivity of commercially available hot-pressed or reaction-
bonded B4C, however, has been reported to be relatively low,
FIG. 10 Raman spectra of bulk B4C, B4C particles in B4C/Al MMC (fig. 9), bulk graphite, and graphite particle in B4C/Al MMC (fig. 9).
1 900 B4C bulk

Raman intensity
1 800
1 700
1 600
1 500
1 400
1 300
1 200
1100
1 000
900
800
700
600
500
400
300 800
200
100
4000 3500 3000 2500 2000 1500 1000 500
B4C 20p5
800
Raman intensity
600
400
200
4000 3500 3000 2500 2000 1500 1000 500

Raman shift (cm–1)
Graphite
2000
Raman intensity
1500
1000
500
3000 2800 2600 2400 2000 2000 1800 1600 1400 1200
2500 B4C BR 3
2000
Raman intensity
1500
1000
500
3200 3000 2800 2600 2400 2000 2000 1800 1600 1400 1200 1000
Raman shift (cm–1)
Effect of Silicon matrix corroded, aluminum-doped Si (p-type) surfaces became

Silicon/aluminum MMCs have been used for electronic packag- exposed, which served as efficient cathodic sites in contrast to the
ing materials because of (1) the relative ease of machining com- lesser-doped interior regions of the Si particles. Hence, with time,
pared with other MMCs with harder reinforcements (e.g., SiC), as more Si particles were left in relief as the matrix corroded, a
and (2) the relatively low coefficient of thermal expansion com- large cathodic network formed polarizing the MMC to the alumi-
pared with monolithic aluminum. The electrical resistivity of num pitting potential. The p-type semiconductor behavior was
pure silicon is 2.3 105 Xcm, but can be much lower for verified by the observation of instantaneous increases in cathodic
impure Si (e.g., four to five orders of magnitude lower for boron- currents on partially corroded (to expose the aluminum-doped Si
doped Si).89 Hence, galvanic corrosion with Si could be possible surface) Si/Al MMCs upon illumination.91
depending on the purity.
Open-circuit potential measurement of 40 wt% Si/pure Al Effect of Alumina
MMCs exposed to aerated 3.15 wt% NaCl indicated various Particles and both short and continuous Al2O3 fibers have been
degrees of oxygen-reduction activity on the Si/Al MMC speci- used to reinforce aluminum alloys. A short type of Al2O3 fiber
mens.90 For some specimens, the corrosion potentials indicated has been used to reinforce diesel-engine pistons.92
that the specimens were not polarized to the aluminum pitting The resistivity of Al2O3 (99.7% pure) is greater than about
potential by oxygen reduction after 1 h of immersion. Therefore, 1014 Xcm,93 and therefore galvanic corrosion between Al2O3
to further investigate the susceptibility of the Si/Al MMCs to pit- fibers and aluminum is unlikely. In alkali and acidic solutions,
ting corrosion in aerated 3.15 wt% NaCl, the corrosion potentials Al2O3 is thermodynamically unstable94; however, the short type
were monitored for 120 h, at which time all of the samples equili- of Al2O3 fibers are resistant to hot concentrated alkalis and most
brated to that of the aluminum pitting potential. The initial vari- hot acids.95 It can be assumed for practical purposes that Al2O3
ability of the corrosion potential was likely associated with the fibers are inert in aqueous solutions that Al2O3/Al MMCs are
amount of iron-containing intermetallic particles contained within likely to be exposed.
the exposed specimen surface, and the degree and amount of Si The Al2O3 reinforcements usually do not have significant
particles in relief. The iron-containing intermetallic particles were effects on pitting potentials in chloride solutions,31,50,67–69,96
found to serve as effective cathodic sites.91 Also, as the aluminum although passive current densities below the pitting potential
have been reported to increase with Al2O3 content.96,97 Microbial pitting potentials by approximately 20 to 30 mV compared with
corrosion was also more significant on particulate MMCs com- the monolithic matrix alloys, suggesting that the presence of
pared with the monolithic alloy, indicating that the Al2O3/Al mica particles may slightly weaken the passive aluminum film.
matrix interface may have aided biofilm formation.98 Corrosion behavior was affected by the precipitation of second-
Formation of interphases (incorporating aluminum, oxygen, ary phases. In some cases, precipitates were preferentially
and alloying elements) as well as intermetallics have been attacked. Pits around and away from mica particles, interfacial
observed in some Al2O3/Al MMCs. Preferential corrosion near corrosion of the mica-matrix interface, and exfoliation of mica
fibers and particles is sometimes noticed. particles also were observed. Values of iCORR (extrapolated from
Continuous Al2O3 fibers in an aluminum (2% Li) MMC polarization diagrams) for nondeaerated 3.5 wt% NaCl ranged
(containing 50 vol% of fibers)99 were enveloped by a 2- to 3-lm- from about 3 to 10 lA/cm2, which was slightly less than that of
thick Li2O/5Al2O3 interphase, which formed during processing the monolithic matrix alloys. Weight-loss data that were mea-
of the composite.7 The corrosion resistance of the Al2O3/Al (2% sured over a 32-day period showed that the MMCs corroded at
Li) MMC was compared to that of 6061-T6 aluminum and higher rates than that of the alloys, contradicting trends observed
2219-T87 aluminum in eight accelerated-corrosion tests that in iCORR data. The mica MMCs corroded at rates ranging from
often are used for wrought aluminum alloys. Most of the test approximately 3.0 to 5.5 mg/dm2/day1, which was approxi-
environments contained chlorides. In most cases, weight-loss mately 1.5 to 2.0 times that of the monolithic alloys. The discrep-
data showed that the corrosion rate of Al2O3/Al (2% Li) MMCs ancy in the trends of the weight-loss and iCORR data could have
was slightly higher than that of 6061-T6 aluminum, but signifi- resulted from several possibilities. Some of the weight loss could
cantly lower than that of 2219-T87 aluminum. No severe interfa- be due to nonelectrochemical reactions, such as the dissolution
cial corrosion was observed. of dissolvable phases and the exfoliation of mica particles. The
Continuous fibers in an aluminum (2% magnesium) MMC100 values of iCORR were extrapolated from polarization curves that
were enveloped by a thin layer of MgAl2O4 through which bond- were generated after relatively short exposure times, whereas the
ing between fiber and matrix was made. Near the fibers, iron was weight loss was assessed over a 32-day period.
detected and magnesium concentrations reached levels of about
10%, suggesting that Mg2Al3 clusters were present. Pits were Effect of Fly Ash
found near the fibers after the composites were exposed to NaCl Prototype fly ash MMC castings were developed109 to combat the
solutions containing H2O2. Yang and Metzger.100 attributed the relatively high cost of MMCs, which has been a major impedi-
pits to corrosion of Mg2Al3, which is rapidly attacked at low ment toward their widespread application. Fly-ash particles are
potentials. No attack of the MgAl2O4 interphase was observed. waste by-products of combustion in coal-based power genera-
On a 60% Al2O3/Al (2% Cu)-T6 MMC exposed to aerated tion,109 and primarily composed of SiO2, Al2O3, and Fe2O3, as
3.15 wt% NaCl, corrosion initiated around intermetallic precipi- well as other oxides. Fly ash, therefore, should be electrically
tates that formed on the continuous alumina fibers.97 The precip- insulating and not promote galvanic corrosion.
itates that served as cathodic sites contained on average Ramachandra110 exposed 5, 10, and 15 wt% fly ash/Al
approximately 60% Al, 10% Fe, and 30% Cu. (12%Si) MMC to ASTM B117, Standard Practice for Operating
Preferential corrosion in the proximity of an unspecified type Salt Spray (Fog) Apparatus. The fly ash had an average particle
of Al2O3 fiber in a 6061-T6 Al MMC was observed by Agarwala.101 size of 10 lm, and consisted of SiO2 (30 wt.%), Al2O3 (58%),
The MMC was exposed to 3.5 wt% NaCl (deaeration or aeration Fe2O3 (8%), TiO2 (3%), and carbon (carbon determined by froth
was not specified) for a 500-h period. No correlation was made floatation). The form of the carbon was not specified. After 10
between the microstructure and the region of corrosion. days in the ASTM B117 test, the weight loss of the fly ash MMCs
Selective attack in the vicinity of Al2O3 particles have been was 10% (5 wt% fly ash MMC), 50% (10 wt% fly ash MMC), and
observed during anodic polarization102 and in the open-circuit 80% (15 wt% fly ash MMC) higher than the base Al (Si 12%)
condition69 in chloride solutions. alloy. Corrosion initiated around the fly ash particles.
Effect of Diffusion Bonds and Microstructural Contaminants

Effect of Mica B/Al and Gr/Al MMCs have been fabricated using techniques
Mica/aluminum (mica/Al) MMCs have been developed for in which aluminum foils, filaments, and precursor wires have
potential use in applications in which good antifriction, seizure been consolidated by diffusion bonding. The diffusion bonds, if
resistance, and high-damping capacity are required.103 of low integrity or if contaminated, may cause severe corrosion
Muscovite (KAl3Si3O10(OH)2) mica particles that are less damage.
than about 70 lm in size are used in mica MMCs.104 Galvanic Sedriks, Green, and Novak22 and Bakulin, Ivanov, and
corrosion between aluminum and muscovite should not be a Kuchkin21 found that ECORR of B/Al MMCs was active to that of
problem since muscovite is an insulator with resistivities that their monolithic matrix alloys in aerated NaCl solutions. That
range from about 1013 to 1017 Xcm.105 Muscovite is insoluble in behavior does not appear to comply with the mixed-potential
cold water.106 It has been reported, however, that muscovite par- theory. Bakulin et al.,21 however, found that hot-pressed stacks of
ticles have a tendency to absorb moisture and then swell.107 aluminum foil processed in the same way as the MMC (but with-
Mica particles were cast in various aluminum alloys.107,108 In out the BFs) have ECORR values that are active to the MMCs.
3.5 wt% NaCl solutions, the presence of mica particles depressed The only difference between the monolithic aluminum and the
hot-pressed stacks of aluminum foil was crevices in the diffusion Effect of Reinforcement Constituents on Stress Corrosion
bonds between adjacent foils. The crevices, which are sources of in Al MMCs
additional anodic sites, can polarize the stacks to active poten- Stress corrosion studies have been conducted on continuous-
tials. Thus, the B/Al MMCs are actually noble to the matrix fiber reinforced and particle-reinforced Al MMCs.
material processed in the same way, and the ECORR values actu- Studies have been conducted on unidirectional, continuous-
ally coincide with the mixed-potential theory. Sedriks et al.22 fiber Gr/6061 Al,117 BF/2024 Al,22 BORSIC/2024 Al, BORSIC/
found that increasing the volume fraction of BF caused anodic 6061 Al,118 and Nextel (Al2O3, SiO2, B2O3)/6061 Al119 MMCs.
current densities (w.r.t. matrix area) to increase. This implies Stresses have been applied either parallel or perpendicular to the
that BF-matrix interfaces, which increase with BF content, were fiber axis of unnotched specimens. The Gr/6061 Al MMCs were
also sources of anodic sites. Evans and Braddick111 also reported stressed parallel to the fiber axis in natural sea water. At high
that BF-matrix interface regions were severely attacked in an stresses, failure was stress-dependent and occurred in less than
oxygenated NaCl solution. These reports indicate that the BF- 100 h. At lower stresses, failure was primarily caused by extensive
matrix and foil-foil interfaces are major causes of corrosion. corrosion, and therefore was relatively stress-independent. BF/
Gr/Al MMCs that were fabricated by the Ti-B vapor deposit 2024 Al MMCs stressed parallel to the fiber axis at 80% fracture
method112 go through a processing sequence where a tow of strength in an NaCl solution did not fail in 1000 h, but failed
graphite fibers is infiltrated with molten aluminum and solidified after 500 h when H2O2 was added to the NaCl solution. Exten-
as a precursor composite wire. Bunches of wires are then diffusive intergranular matrix corrosion and broken filaments at ran-
sion bonded to consolidate larger components such as plates and dom sites were observed. The monolithic matrix alloy failed
bars. Some of these composites have been susceptible to exfolia- within 10 h under similar conditions. For BF/2024 Al MMCs
tion (fig. 11), which is the disbonding of precursor wires and alu- stressed perpendicular to the fiber axis at 90% yield strength in
minum foils caused by localized corrosion along wire-wire and the NaCl and NaCl with H2O2 solutions, failure occurred by
wire-foil diffusion bonds. This form of corrosion is severe intergranular matrix corrosion and separation at diffusion-
because composite plates can be rendered useless even though bonded, fiber-matrix interfaces. Failure times decreased with
corrosion in the bulk of the foils and precursor wires may not be increasing BF content. BORSIC/Al MMCs were stressed to 689
severe. There have been some reports113,114 of preferential corro- MPa along the fiber axis by three-point bending and exposed to
sion of diffusion-bonded regions in marine environments. In synthetic sea-salt spray at 95 C and nearly 100% relative humid-
severe cases of exfoliation, precursor wires are expelled from the ity. The 6061 Al MMCs showed general corrosion attack without
sides of MMC plates.115 preference to tensile regions, whereas the 2024 Al MMCs showed
The cause of exfoliation has been attributed116 to residual about a 2-to-1 depth-of-attack ratio comparing the tensile to the
microstructural chloride95 that is trapped in the diffusion- compressive surfaces, which may have been related to specimen
bonded regions. The residual chloride originates from the Ti-B orientation. Unlike the 6061 Al MMCs, the corrosion resistance
vapor deposit method, which uses titanium tetrachloride (TiCl4) of the 2024 Al MMC was sensitive to heat treatment. In the Nex-
and boron trichloride (BCl3) gases. The chloride is deposited on tel fiber MMC, the prevailing mode of failure was attributed to
the skin of the precursor wires as the wires are extracted from extensive corrosion along the fiber-matrix interface and not to
the aluminum melt. Experiments have shown that in sodium sul- stress-corrosion cracking in a pH 2 NaCl solution.119
fate solutions, in which aluminum should be passive, the chlo- The stress corrosion behavior of particulate Al2O3/2014
ride-contaminated diffusion bonds corrode vigorously116 (see the Al,120 SiCw/6061 Al,120 SiCp/6061 Al,120 and SiCp/2024 Al.100,110
subsection “Determination of Dissolution Behavior Using Polari- MMCs were investigated in NaCl solutions. The Al2O3/2014 Al
zation Techniques”). MMC was susceptible to stress corrosion cracking while sub-
jected to three-point beam bending and alternate exposure and
continuous immersions in an NaCl solution.120 Under the same
conditions, however, the 6061 Al MMCs reinforced with SiCp
FIG. 11 Exfoliation of Gr/6061-T6 Al MMC. MMC exposed to and SiCw were not susceptible to stress corrosion cracking.120
indoor environment. Similarly, SiCp/2024 Al MMCs were not prone to stress-corro-
sion cracking under constant strain in at 75% of ultimate tensile
strength while exposed to an aerated NaCl solution.121 Slow strain
rate tension testing of SiCp/2024 Al MMCs in an NaCl solution
in the open-circuit condition indicated that the MMC lost up to
10% of failure strength compared with exposure in air.122
Effect of Reinforcement Constituents on Corrosion Fatigue

in Al MMCs
Corrosion-fatigue studies have been conducted on Al MMCs
reinforced with graphite fibers,117 SiCW,123–126 and SiCP.124,127 Proc-
essing conditions and the type of reinforcement affect corrosion-
fatigue behavior. Unnotched Gr/6061 Al MMCs were exposed to
natural seawater and stressed parallel to the fiber axis. The cathodic-current densities that were about five times that of
MMCs were processed with either silica (SiO2)-coated or Ti-B- virgin BFs.23 The corrosion rates of actual BF/MA2-1 MMCs in
coated graphite fibers. For a given stress amplitude, the Ti-B type 0.005 N and 0.5 N NaCl solutions were 12.49 g/m2day and
MMC had the longest corrosion-fatigue life, followed by the 81.72 g/m2day, respectively, which were about six times the val-
SiO2 type, and the monolithic matrix alloy. At low stress ampli- ues of the monolithic matrix alloy in respective environments.
tudes corresponding to longer exposure times, the SiO2-type
MMC suffered premature failure because of extensive corrosion. Effect of Graphite
In SiC/Al MMCs, fatigue crack rates of compact tension speci- The general properties of graphite given in the subsection
mens usually are higher in NaCl solutions compared with air123 “Aluminum MMCs: Effect of Graphite Fibers” also apply here.
or argon.127 Loading frequency affects corrosion-fatigue crack Figure 12 shows the cathodic polarization diagrams of pitch-
rates,127 but no consistent trends were observed. Fatigue123 and based graphite (cross-section exposed) in deaerated and aerated
corrosion-fatigue127 crack rates are influenced by loading and 3.15 wt% NaCl with the anodic polarization diagrams of pure
extrusion or rolling direction. The nucleation of a crack was also magnesium and ZE41A magnesium in deaerated 3.15 wt% NaCl.
observed at the bottom of a corrosion pit.105 The shape of the Figure 12 reveals that galvanic-corrosion rates increase in aerated
reinforcement constituent also may have significant effects. solutions. Note that both anodic and cathodic curves of pure
Jones125 developed a model based on crack-tip strain rate that is magnesium and ZE41A magnesium are practically insensitive to
applicable to stress corrosion and corrosion fatigue. The model is solution aeration, indicating that normal corrosion rates are vir-
relatively insensitive to slight variations in reinforcement volume tually unaffected by dissolved oxygen. Figure 12 shows that gal-
fraction. The model predicts that crack rates are reduced by vanic corrosion of magnesium is not anodically controlled,
increasing the reinforcement constituent length-to-diameter and therefore galvanic-corrosion rates should increase with
ratio, implying that MMCs reinforced with whiskers are more increasing area fraction of cathodic reinforcement material.
resistant to stress corrosion and corrosion fatigue than those Trzaskoma130 showed that galvanic-corrosion current densities
reinforced with particles. This is in agreement with results of increased from about 0.3 to 0.6 mA/cm2 (based on magnesium
Hasson et al.124 who found that SiCW/6061 Al MMCs have longer area) as the graphite-to-magnesium area ratio was increased
corrosion-fatigue lives than SiCP/6061 Al MMCs in salt-ladened from 0.25 to 0.44. The galvanic couples consisted of AZ31B mag-
moist air. nesium alloy and pitch-based graphite fiber with fiber ends and
circumferential fiber surface exposed to an aerated, borated-boric
MAGNESIUM MMCs acid solution of 8.4 pH containing 10,00 ppm NaCl. Actual
Very light composites can be fabricated from magnesium, which MMCs immersed in air-exposed 0.001 N NaCl suffered severe
is one of the lightest structural metals. Its density is only 1.7 g/ degradation within five days. Bakkar131 also reported galvanic
cm3. Magnesium, however, is the most active structural metal in currents between Sigrafil C-40 carbon fibers and AS41 Mg alloy
the electromotive series,128 which means that it has a very high and AS41(with 0.5 wt% Ca) exposed to pH 12, 100 ppm NaCl
tendency to corrode. Because magnesium is an active metal, it is solution. The galvanic currents were slightly lower for the
particularly susceptible to galvanic corrosion when in contact AS41(0.5Ca) alloy. Accordingly, Sigrafil C-40/ AS41 Mg MMCs
with noble reinforcement constituents. Corrosion studies have were subjected to severe pitting in the pH 12, 100 ppm NaCl
been conducted on magnesium MMCs reinforced with BF, solution under open-circuit conditions.
graphite fibers, SiCMF, Al2O3 fibers, fly ash particles, and calcium Czyrklis30 showed electrochemical evidence of galvanic cor-
compound particles. Stress-corrosion behavior of an Al2O3/Mg rosion in actual graphite/magnesium (Gr/Mg) MMCs. He mea-
MMC is included in the Al2O3 section. sured open-circuit potentials and calculated corrosion current
Effect of Boron
The general properties of BFs given in the subsection FIG. 12 Anodic polarization diagrams of pure magnesium and
“Aluminum MMCs: Effect of Boron Filaments” also apply here. ZE41A magnesium in deaerated 3.15 wt% NaCl plotted
Pure boron is an insulator and a poor cathode. Galvanic currents with the cathodic polarization diagrams of pitch-based
were unmeasurable between pure boron and magnesium in graphite fiber (cross section exposed) in deaerated and
0.005 N NaCl solutions23,129 (it was not specified if solutions were aerated 3.15 wt% NaCl at 30 C. Scan rate = 0.1 mV/s.
deaerated or aerated). Galvanic currents, however, were measur-
able between virgin tungsten-core BF (cores either shielded or
exposed) coupled to magnesium129 and an MA2-1 magnesium
alloy.23 Galvanic currents were higher when tungsten cores were
exposed.23,129 This is not unexpected because pure tungsten was
shown to be an effective cathode.23 Because galvanic currents
were unmeasurable between magnesium and pure boron, but
measurable between magnesium and virgin BF (with tungsten
cores shielded), it was suspected that the outer layer of BFs
consisted of tungsten boride and not of pure boron.130 It was
also found that BF extracted from the matrix supported
densities (by Tafel extrapolation) of a 40% Gr/Mg MMC and its magnesium and ZE41A magnesium with cathodic polarization
matrix alloy that were exposed to a deaerated 50 ppm chloride diagrams of hot-pressed SiC, SiCMF (with either carbon core or
solution. The open-circuit potential of the composite (-1.127 VSCE) carbon-rich surface exposed) in deaerated and oxygenated 0.5 M
was about 0.3 V noble to that of the matrix alloy, and iCORR of sodium nitrate (NaNO3) solutions, respectively. Galvanic-corro-
the composite (178 lA/cm2) was about 40 times greater than sion rates (as determined by the mixed-potential theory) are
that of the matrix alloy at 25 C. Czyrklis also reported severe greater in oxygenated solutions because of oxygen reduction
degradation of Gr/AZ91C Mg MMCs that were exposed to occurring on the reinforcement materials (compare figs. 13 and
50 ppm chloride solutions and 95% relative humidity atmos- 14). Galvanic-corrosion rates are lowest between magnesium and
pheres. Composite degradation was attributed to galvanic corro- hot-pressed SiC and highest between magnesium and SiCMF
sion and to selective attack of Mg17Al12 precipitates in the (with core exposed).133 The carbon-core and the carbon-rich sur-
magnesium matrix. face appear to have a dominant effect on cathodic behavior of
Interphase formation of Al4C3 was observed in a Gr/Mg the SiCMF. The curves of SiCMF have a stronger resemblance to
(1% aluminum) MMC produced by squeeze casting. The Al4C3 pitch-based graphite fiber (cross-section exposed) than to hot-
formation resulted from heat treatments at 500 C.132 Degrada- pressed SiC (figs. 13 and 14). Similar results were obtained for
tion of these MMCs could be accelerated by both galvanic corro- sodium sulfate (Na2SO4) and NaCl solutions.134 For AZ80A Mg
sion and Al4C3 hydrolysis. and ZK60A Mg reinforced with 20 vol% SiC particles, the corro-
sion rates were significantly increased by the chlorides.135 Corro-
Effect of Silicon Carbide sion rates for both MMCs were over one order of magnitude
The general properties of SiC given in the subsection higher in air-exposed 1 NaCl compared with 1 N Na2SO4.
“Aluminum MMCs” also apply here. Galvanic corrosion between Nunez-Lopez et al.136 conducted studies on particulate ZC71
magnesium and SiC depends to a large degree on the type of SiC magnesium alloy reinforced with 12 vol% SiC particles ranging
reinforcement and on the presence of dissolved oxygen in solu- in size up to approximately 20 lm. Specimens exposed to salt
tion. Figures 13 and 14 show anodic polarization diagrams of pure spray tests did not show signs of galvanic coupling between the
matrix and SiC particles. Preferential attack between SiC par-
ticles and the matrix was not observed. Instead, macroscopic
FIG. 13 Anodic polarization diagrams of pure magnesium and anodic and cathodic regions developed. Corrosion spread over
ZE41A magnesium plotted with cathodic polarization the MMC surface much more rapidly than on the monolithic
diagrams of hot-pressed SiC, SiCMF, and pitch-based alloy, but the local corrosion rates were approximately only three
graphite fibers in deaerated 0.5 M NaNO3 at 30 C. Scan times greater on the MMC. The authors136 speculated that the
rate = 0.1 mV/s. CS = cross section exposed. FS = fiber higher corrosion rates on the MMCs could have been caused by
surface exposed. iron contamination of the magnesium matrix during processing
in a steel crucible. Studies on a model MMC consisting of high-
purity magnesium and well-separated SiC particles exposed to
3.5 wt% NaCl also did not show evidence of galvanic corrosion
between the particles and matrix.137 Studies138 on AZ91 Mg rein-
forced with 0, 5, 10, and 15 vol% alpha-SiC particles showed that
cathodic current densities and corrosion rates increased with
increasing SiC content in 3.5 wt% NaCl (aeration not specified).
The increase in current density was attributed to cathodic activ-
ity on the beta phase that formed in the highly strained matrix
around the SiC particles. Cathodic currents on hot-pressed
alpha-SiC were more than an order of magnitude lower than the
cathodic currents on the MMCs, indicating that galvanic action
with SiC was negligible.
FIG. 14 Specimens and test conditions are similar to figure 13,
except the 0.5 M NaNO3 solution is oxygenated.
Effect of Alumina
The general properties given for Al2O3 in the subsection
“Aluminum MMCs” also apply here. Galvanic corrosion should
not be expected in Al2O3/magnesium (Al2O3/Mg) MMCs since
Al2O3 is an insulator. However, Levy and Czyrklis139 found that
continuous-fiber Al2O3/AZ91C MMCs were much more suscep-
tible to corrosion in chloride-containing solutions compared
with the matrix alloy. They did not specify if the solutions were
deaerated. In a 50 ppm Cl solution at 25 C, the corrosion rate
of the composite was 0.78 mm/y compared with only 0.10 mm/y
for the alloy. When the temperature was increased to 66 C, the
corrosion rate of the composite dramatically increased to about growth.143 Powder metallurgical specimens with 0 wt%, 10% ,
150 mm/y, whereas that of the alloy increased to only 0.13 mm/y. 20%, 30% and 40% CS were sintered. In simulated body fluid
Corrosion rates were highest in 3.5 wt% NaCl at 25 C, where (SBF: solution containing NaCl, NaHCO3, KCl, K2HPO43H2O,
the composite corroded at an astronomical rate of about MgCl26H2O, HCl, CaCl2, Na2SO4, tromethamine) at 37 C
350 mm/y compared with 3.6 mm/y for the alloy. In chloride- (likely air-exposed), the corrosion rates decreased as the CS con-
free environments, the composite showed equivalent or greater tent was increased and reached a minimum corrosion rate at
resistance to corrosion than the alloy. In distilled water at 25 C 20% CS. However, at higher CS content, the corrosion rate began
and 95% relative-humidity environments at 25 C and 66 C, the to increase at 30% CS and reached a maximum corrosion rate at
corrosion rate of the composite and matrix alloy was less than 40% CS. The CS enhanced the formation of a hydroxyapatite
0.25 mm/y. The tremendously higher corrosion rates of the com- (HA: Ca5(PO4)3(OH)) film, which reduced the Mg corrosion
posites in the chloride-containing environments appear to be rate. The higher corrosion rates at 30% and 40% CS were attrib-
caused by the presence of the Al2O3 fibers. It is unlikely that gal- uted to incomplete sintering which lead to the ingress of SBF
vanic corrosion between the matrix and Al2O3 fibers can take into the bulk MMC.143
place since Al2O3 is an insulator. Galvanic corrosion could be Tricalcium phosphate (TCP: Ca3(PO4)2) powder of 99.89%
possible, however, between the matrix and an interphase or pre- purity with sizes ranging from 100 to 150 lm was sintered with
cipitates, which potentially could form because of the presence of pure (99.9%) Mg powder ranging in sizes from 53 to 75 lm to
the Al2O3 fibers. Czyrklis140 reported that ECORR of 35% continu- produce MMCs.145 Specimens were fabricated using no TCP or
ous-fiber Al2O3/AZ91C MMCs was more noble than that of the 5 wt% TCP for corrosion studies in SBF. The pure Mg specimens
matrix alloy in 50 ppm Cl solutions, indicating that galvanic (no TCP) served as a baseline in comparison for corrosion
corrosion is a possibility. It was not specified if the solutions behavior. In immersion studies in the SBF for 72 h at 37 C
were deaerated. (likely air-exposed), the mass loss of the MMC sample was
Evans141 studied the stress-corrosion behavior of continu- 16.1%, whereas that of the pure Mg was and 20.1%. Potentiody-
ous-fiber Al2O3/ZE41A Mg MMC in an NaCl-potassium chro- namic polarization also indicated that the MMC had lower icorr
mate (K2CrO4) solution. Unnotched and notched specimens values compared with the pure Mg. The lower corrosion rates of
stressed parallel to the fiber axis and exposed for approximately the MMC in comparison to the pure Mg was attributed to the
100 to 1,000 h in the NaCl-K2CrO4 solution retained approxi- formation of crystalline HA films, which formed only on the
mately 90% of the strength in air. The matrix alloy and the MMC. Mg(OH)2 films formed on both the MMC and pure Mg
MMC with the stress aligned perpendicular to the fiber axis surfaces. It was suggested the TCP/Mg MMC is promising for
retained only approximately 40% to 60% of the strength in air. enhancing bone growth activity.
Effect of Fly Ash Cordierite LEAD MMCs

Cordierite (Mg2Al4Si5O18) consisting of SiO2 (45–51 wt.%), Lead is a relatively heavy metal with a density of 11.4 g/cm3.
Al2O3 (32–35%), FeO3 (2–12%), and MgO (3–35%) was obtained Lead MMCs, therefore, normally are developed for applications
from fly ash and used in the amount of 2 wt% and 4% to in which a combination of its structural, physical, and chemical
fabricate AM60 Mg matrix MMCs.142 Cordierite is electrically properties are important. The corrosion behavior of pure lead
insulating and should not promote galvanic corrosion. Potentio- MMCs in simulated, lead-acid battery environments has been
dynamic polarization test were conducted in 3.5 wt% NaCl (aera- studied to assess the feasibility of using these composites as posi-
tion not specified, but Mg usually corrodes with proton tive electrode grids in place of conventional lead-based alloy grid
reduction as the cathodic reaction), and icorr values were used to materials. Lead can be alloyed with elements such as arsenic,
determine corrosion rates of the MMCs and base AM60 Mg antimony, or calcium to increase strength and stiffness. These
alloy. The MMCs were examined in the as fabricated and heat- elements, however, reduce corrosion resistance. Monolithic pure
treated conditions with two surface finishes (ground with 600- lead has very good corrosion resistance in lead-acid battery envi-
grit or 2,000-grit grinding paper). No clear trends were observed ronments (which consists of sulfuric acid solutions) but is heavy
in the corrosion rates, which could not be correlated to the pres- and lacks sufficient mechanical strength. Pure lead, therefore,
ence of or amount of cordierite.142 Hence, the cordierite did not has been reinforced with strong, lightweight fibers in hopes of
significantly affect corrosion behavior, as gauged by the polariza- achieving the goals of increasing strength, reducing weight, and
tion tests. retaining the corrosion resistance of pure lead.145–147 More
recently, a study on the corrosion behavior of particulate lead-
Effect of Calcium Compounds
antimony alloy MMCs exposed in sodium chloride solutions has
Calcium silicate (CS: CaSiO3) was used as a reinforcement in
been conducted.148
pure (99.9%) Mg MMC.143 These MMCs were targeted for biode-
gradable orthopedic implant materials as Mg has an elastic mod- Effect of Fibers
ulus relatively close to bone.143 The high corrosion rate of Mg, To simulate corrosion in lead-acid battery environments, Dacres
however, can lead to rapid hydrogen gas generation and prema- et al.145 and others146,147 anodically polarized test materials at
ture loss of mechanical strength before defect bone can be regen- 1.226 V (versus mercury/mercurous sulfate reference electrode)
erated.143 CS is a promising MMC reinforcement for implant in sulfuric acid solutions (of 1.285 specific gravity) at 50 C,
material because it has good bioactivity that can enhance bone 60 C, or 70 C. At 1.226 V, lead and water are oxidized to lead
dioxide (PbO2) and molecular oxygen (O2), respectively.149,150 measured between equal areas of tungsten fibers and the DU
About one-third of the total anodic current is consumed in the alloy was equal to about 4 105 A/cm2. In a 30-day exposure
oxidation of lead under these conditions.147 test in the NaCl solution, the W/DU MMC lost 43.56 mg/cm2,
Al2O3, carbon, SiC, and glass-quartz fibers of various volume which was about 1.3 times that of the DU alloy.
percents have been used in lead MMCs. Fabrication methods as
well as fiber type may have significant effects on corrosion resis- STAINLESS STEEL MMCs
tance. Several types of continuous-fiber Al2O3/lead (Al2O3/Pb) Sintered, particulate composites consisting of ferritic 434L stain-
MMCs.145,147 were examined. MMCs containing 5%147 and 7.5%145 less steel (SS) and Al2O3 particles have been developed for poten-
Al2O3 fibers showed good corrosion resistance. The 5% Al2O3 tial application in chemical processing plants, turbine blades,
fiber MMC had gravimetric and Faradaic corrosion rates of and heat exchanger tubes152,153 Austenitic 316L stainless steels
0.033 mm/y and 0.10 mm/y, respectively. Al2O3/Pb MMCs having reinforced with Al2O3 and Y2O3 also have been investigated for
6%,145 10%,147 15%,147 and 25%145 Al2O3 fibers did not have accept- enhanced strength and wear resistance.154
able corrosion resistance. Poor bonding between Al2O3 fibers and
the matrix allowed the electrolyte to diffuse into fiber-matrix
Effect of Alumina
interfaces, leading to accelerated corrosion145 and swelling of the
The corrosion behavior of sintered Al2O3/434L SS MMCs and
composite because of corrosion-product buildup.147
sintered 434L alloy without Al2O3 particles was examined.152,153,155
Composites reinforced with carbon or graphite fiber were
The volume fraction of Al2O3 particles in these materials ranged
not resistant to corrosion.145,147 Viala, El Morabit, and Bouix146
from 0% to 8%. The effect of small amounts of titanium and nio-
reported that the graphite fibers were oxidized. SiC fiber/Pb
bium alloying elements on corrosion resistance was also investi-
MMCs also did not have good corrosion resistance.146,147 Viala
gated. Galvanic corrosion between 434L stainless steel and Al2O3
et al.146 reported that composites were destroyed by swelling
should not occur because the latter is an insulator. Experiments
because of the formation of PbO2 in the bulk of the composites.
were conducted in 1 N sulfuric acid (H2SO4),152,153 and 5 wt%
The SiC fibers (which do not have carbon cores) were stable. The
NaCl152 solutions at room temperature. It was not mentioned if
corrosion resistance of glass-quartz/Pb MMCs having 9.5% fiber
solutions were deaerated. In 1 N H2SO4, 152,153 there was no strong
was not satisfactory, and gravimetric and Faradaic corrosion
correlation between Al2O3 content and corrosion behavior. The
rates were 0.24 and 0.62 mm/yr, respectively.147 Lead alloys con-
ECORR and iCORR values varied between materials, but clear
taining calcium and tin had gravimetric and Faradaic corrosion
trends relating ECORR and iCORR to Al2O3 content or alloy com-
rates of 0.49 and 1.35 mm/yr, respectively, also showing unsatis-
position were not conspicuous. One of the few generalities that
factory corrosion resistance.145,147 These studies145–147 have indi-
could be made was that passive-like anodic current densities
cated that the penetration of electrolyte into the bulk of the
were high and within an order of magnitude of 1 mA/cm2 for
composites, possibly through poorly bonded fiber-matrix interfa-
almost all materials. Alloying with titanium and niobium tended
ces or by oxidation of fibers, is a major factor governing degrada-
to increase anodic current densities. In the 5 wt% NaCl solutions,
tion properties.
iCORR of the MMCs was less than 10 lA/cm2.152 Upon polariza-
tion, all materials displayed active corrosion behavior in the
Effect of Particles NaCl solutions.
A commercially available lead (80%)-antimony (20%) alloy was Particulate 316L SS MMCs,154 fabricated using powder met-
reinforced with 1, 3, and 5 wt% zircon (ZrSiO4) particles148 and allurgy, were reinforced with 3, 4, and 5 wt% Al2O3 and addi-
exposed to a 1 N NaCl solution. The particles should not induce tions of 2 wt% chromium diboride (B2Cr) or 1 wt% boron
galvanic corrosion. Weight loss measurements, made over a 72-h nitride (BN) for sintering aids. The density of the MMCs ranged
period, showed that weight loss of the lead MMCs increased from 86% to 96% of the theoretical value. Unreinforced 316L
with increasing zircon content. Heat treatment of the ZrSiO4/Pb- specimens were also fabricated using powder metallurgy without
Sn MMC at 200 C also improved resistance to weight loss. sintering aids, resulting in 85% of theoretical density. The test
samples were immersed in 10% sulfuric acid (H2SO4) at room
DEPLETED URANIUM MMCs temperature for 24 h, 1% hydrochloric acid (HCl) at room tem-
Tungsten fiber/depleted uranium (W/DU) MMCs are the antithe- perature for 24 h, and boiling 10% nitric acid (HNO3) for 8 h.
ses of the lightweight MMCs. W/DU MMCs were developed to The pure, unreinforced 316L specimens passivated in the 10%
create high-density materials. Uranium has a density of 18.9 g/cm3. H2SO4 solution, whereas the corrosion rate of the MMC gener-
DU corrodes galvanically when coupled to tungsten fibers ally increased with increasing Al2O3 content to a maximum
in air-exposed 3.5 wt% NaCl solutions at room temperature.151 value of approximately 4 mm/yr. Specimens with the BN sinter-
The open-circuit potential of tungsten fiber (0.25 VSCE) is ing aids corroded at higher rates as compared to those with the
noble to that of the DU alloy (0.80 VSCE). The open-circuit B2Cr sintering aids. The authors correlated this behavior to the
potentials of the W/DU MMC and galvanic couples consisting of local depletion of chromium in the matrix due to matrix reac-
tungsten fiber and DU alloy of equal areas are 0.78 VSCE and tions with BN compared with reactions with chromium-rich
0.77 VSCE, respectively. These potentials fall between those of B2Cr. The MMC performed better than the un-reinforced 316L
tungsten fibers and the DU alloy, which is consistent with the specimen in the 1 wt% HCl solution, but worse than the unrein-
mixed-potential theory. The galvanic-corrosion current density forced specimen in the boiling nitric acid solution. There was no
strong correlation between Al2O3 content in the MMCs and Effect of Graphite
the corrosion rates in 1 wt% HCl and boiling 10 wt% HNO3 Graphite/porous titanium MMCs were processed and heat
solutions. treated to fabricate a graphite/TiC/porous titanium MMC.157
Polarization tests were conducted in 0.9 wt% NaCl and lactated
Effect of Yttria Ringer’s solution for in vitro use. The ECORR values of the graph-
Yttria (Y2O3) is an insulator and galvanic effects are not ite/TiC/porous Ti MMCs were more noble than that of pure Ti,
expected. The 316L stainless steel specimens discussed earlier154 as expected because of the presence of graphite and TiC. The
were also reinforced with 3, 4, and 5 wt% Y2O3 and additions of anodic polarization current densities of the MMCs were signifi-
2 wt% chromium diboride (B2Cr) or 1 wt% BN for sintering cantly higher than that of pure monolithic titanium, which pas-
aids. In all solutions (i.e., sulfuric, hydrochloric, and nitric acid sivated. The authors attributed the higher corrosion rates of the
solutions), the Y2O3-reinforced MMCs exhibited reduced corro- graphite/TiC/Ti MMC to its porosity, which may have prevented
sion resistance compared with the Al2O3-reinforced MMCs. The complete passivation of the titanium matrix. Another possibility
Y2O3 MMCs were sintered to 88–96% of theoretical density, and for the higher current densities could be the oxidation of graph-
the Al2O3 MMCs were sintered to 86–92% of theoretical density. ite particles, and not dissolution of the titanium matrix (see the
The Y2O3 particles also showed better bonding to the matrix, next subsection).
probably forming a complex YCrO3 oxide, compared with the
Al2O3 particles. It is possible that the formation of the reaction Effect of Silicon Carbide
layer around the Y2O3 particles may have depleted chromium Corrosion studies on titanium alloy Ti-15-3-3-3 (15 wt% vana-
from the matrix, resulting in reduced corrosion resistance, com- dium, 3 wt% chromium, 3 wt% tin, 3 wt% aluminum, balance
pared with the Al2O3-reinforced MMCs. titanium)158 and titanium aluminide a2Ti3Al (14 wt% aluminum,
21 wt% niobium, balance titanium)159 reinforced with SiCMF
TITANIUM MMCs have been conducted. The corrosion behavior of SiCMF/Ti-15-3-
Titanium MMCs have been developed for aerospace applications 3-3 MMC was investigated in 3.15 wt% NaCl. There was excel-
as well as potential surgical implant materials. SiC MF/titanium lent agreement in the polarization diagrams of the actual MMC
(SiCMF/Ti) MMCs (fig. 15) have utility in high-temperature and that of a model utilizing the polarization diagrams of the
applications requiring strong, lightweight materials. Titanium individual constituents and the mixed-potential theory (see the
has a density of 4.5 g/cm3. Structural SiCMF/Ti MMCs have been subsection “Determination of Dissolution Behavior Using Polari-
used in prototype drive shafts, turbine-engine discs, compressor zation Techniques”), indicating that the fabrication processing
discs, and hollow fan blades and also are candidate materials for did not affect the dissolution behavior of the MMC constituents.
the skin of the National Aerospace Plane.156 Porous, particulate The matrix passivated and the carbon cores and carbon-rich
Ti MMCs have potential use as surgical implant materials, owing outer surface of the SiCMF oxidized. During anodic polarization,
to the compatibility of titanium and bone growth.157 Porous tita- graphite oxidizes to CO2.116 ZRA studies showed that galvanic
nium is a good surgical implant material because bone growth is currents between the Ti-15-3-3-3 matrix and SiCMF were negligi-
enhanced by the relatively low elastic modulus of titanium, and ble. Based on the polarization diagrams, the galvanic current
bone ingrowth is allowed by the porous structure. Porous tita- density cannot exceed that of the passive current density of Ti-
nium, however, has poor tribological properties and, therefore, 15-3-3-3. The corrosion behavior of the SiCMF/a2Ti3Al159 was
MMCs that incorporate graphite to reduce friction and incorpo- somewhat similar to that of the SiCMF/Ti-15-3-3-3 MMC,158 with
rate TiC to improve wear resistance are of interest.157 the exception that the a2Ti3Al matrix is less resistant to pitting.
During anodic polarization, the a2Ti3Al/SiCMF pitted at approxi-
mately 1 VSCE in 0.5 N NaCl, which was approximately 0.5 V less
FIG. 15 Micrograph of SiCMF/Ti-15-3-3-3 MMC. Monofilament than that of the monolithic matrix alloy. Some matrix pitting
volume fraction is approximately 40%. and crevice corrosion around the SiCMF were also observed after
anodic polarization. The galvanic current density of the a2Ti3Al/
SiCMF MMC was negligible and limited to the passive current
density of the a2Ti3Al matrix.159
COPPER MMCs
Copper MMCs have been investigated for use in marine, elec-
tronic and thermal applications. Copper is relatively heavy, with
a density of 8.96 g/cm3. Reinforcements typically are chosen to
impart strength and stiffness, reduce weight, enhance thermal
and electrical properties, improve machinability, and enhance
wear resistance. Initial studies8 were conducted on a wide variety
of experimental copper and copper alloy MMCs for marine
applications. The MMCs generally showed corrosion behavior
that was similar to that of the monolithic alloys, although
corrosion rates were higher for some of the MMCs. More recent copper interfaces both increased with increasing SiC content.
corrosion studies have also added additional insight to corrosion Hence, the decrease in ECORR with increasing SiC content is
mechanisms of copper MMCs. likely to have been caused by an increase in anodic currents from
voids and SiC-copper interfaces. The SiC particles could also
Effect of Graphite serve as cathodes, but because of their relatively high electrical
Copper MMCs have been reinforced with graphite particles and resistivity, they are not as effective, for example, as graphite.
fibers. The particulate MMCs have been developed for sliding Hence, any increases in cathodic currents with the increase in
electrical contact materials,160 and improved machinability for SiC content may not have been sufficient to shift ECORR to posi-
lead-free copper alloys.161 Fiber reinforced MMCs have been tive values and to overcome the effect of the higher anodic
developed for applications requiring reduced-weight and high currents.
thermal conductivity.162 Highly graphitized fibers have very high
thermal conductivity, exceeding that of silver.3 Effect of Alumina
Sun Orth, and Wheat163 examined the corrosion behavior of A copper MMC reinforced with 2.7 vol% Al2O3 was studied by
pure copper MMCs with 1.2, 5, 15, 25, and 40 vol% graphite par- Sun and Wheat165 in deaerated and aerated 3.5 wt% NaCl. The
ticles and fiber-reinforced pure copper MMCs with 50 vol% corrosion potentials of the MMC were slightly more active (i.e.,
graphite fibers in deaerated and aerated 3.5 wt% NaCl solutions. 0.01 to 0.02 V) than monolithic pure copper. The corrosion rates
The corrosion potential of the particulate reinforced MMCs of the MMCs were comparable to monolithic copper. A galvanic
became more noble with increasing graphite content in both the effect with Al2O3 was not expected because of its insulative
deaerated and aerated solutions, as would be expected by nature.
increasing the content of the noble graphite particles. Polariza-
tion resistance generally decreased, with a few exceptions, with ZINC MMCs
increasing graphite content in both dearated and aerated solu- Zinc MMCs have been developed166 for potential use as bearing
tions. This indicated that corrosion rates generally increased materials. Zinc has a density of 7.14 g/cm3. An MMC with a ZA-
with graphite content, assuming that cathodic and anodic Tafel 27 zinc alloy matrix was cast with 1, 3, and 5 wt% graphite par-
slopes remained relatively constant for the different MMC speci- ticles ranging in sizes from 100–150 lm. Zinc alloys are known
mens (i.e., 1.2 through 40 vol% graphite). The corrosion rate is a to have excellent wear and bearing characteristics.167 Gravimetric
function of both the polarization resistance and Tafel slopes. The corrosion tests were conducted at 23 C in (1) SAE 40-grade
6% porosity of the MMCs may have also been a factor regarding lubricating oil that had been in service for 6 months in an inter-
corrosion behavior. The corrosion potential of the fiber-rein- nal combustion engine and (2) 1 N HCl. The MMCs did not cor-
forced MMC (50 vol% graphite fiber) was approximately as rode in the previously used lubricating oil. Interestingly, in the
noble as the particulate MMC with 40 vol% graphite in the aer- 1 N HCl, corrosion rates decreased with higher content of graph-
ated solution, but was significantly more active than the particu- ite, which is a noble conductor that can induce galvanic corro-
late composite in the deaerated solution. This finding could be sion. Several hypotheses have been made,166 such as the presence
expected if the hydrogen evolution kinetics on the graphite fiber of the graphite network hindering the reaction between HCl and
were significantly different from that of the graphite particles. the matrix. Another possibility is that zinc ions in solution, act-
Rohatgi, Nath, Kim, and Agrawal161 studied C90300 copper ing as a cathodic inhibitor,168 eventually may have precipitated as
alloy reinforced with approximately 1–10 vol% graphite particles zinc hydroxide on the cathodic graphite particles if the local pH
and 1 wt% Ti, added to enhance wettability of the graphite. The resided in the correct range. This would also explain the decreas-
corrosion potentials of the MMCs increased with increasing ing corrosion rates with time that was observed. Similar behavior
graphite content in an aqueous solution containing ferric chlo- was noticed in graphite-aluminum couples in solutions contain-
ride, copper sulfate, and hydrochloric acid. Gravimetric measure- ing zinc chloride.169
ments were made on specimens immersed for one year in an
aqueous solution containing sodium bicarbonate, magnesium
chloride, calcium chloride, sodium sulfate, and sodium chloride. Methods for Evaluating Corrosion
The results showed insignificant weight gain (<0.25%), indicat- Damage
ing that the MMCs were resistant to corrosion in the test
solution. Tests to evaluate corrosion damage of conventional monolithic
alloys are not always applicable to MMCs. Under some circum-
Effect of Silicon Carbide stances, the reinforcement constituents that are left in relief after
Lee, Lee, and Lin164 examined the corrosion behavior of pure matrix corrosion may interfere with measurements. There have
copper MMCs reinforced with 0, 5, 10, and 20 vol% SiC particles been relatively few studies on MMC corrosion in comparison to
in a 5 wt% NaCl solution. The porosity of the materials ranged monolithic metals. Tests that have been more commonly used
from 2.2% to 3.5%, and generally increased with increasing SiC for MMCs are gravimetric and those that assess loss of mechani-
content. Corrosion potentials became more active, and corrosion cal properties. The researcher should be able to use other tests
current densities increased with increasing SiC content. The cor- that have been developed for monolithic alloys; however, data
rosion morphology indicated that there was significant corrosion must be analyzed carefully to ensure that test results are valid
at SiC-copper interfaces. Voids caused by porosity and SiC- because special problems are sometimes associated with MMCs.
Further details regarding corrosion analysis of MMCs are pro- DETERMINATION OF DISSOLUTION BEHAVIOR
vided in the next section. USING POLARIZATION TECHNIQUES
Dissolution behavior of MMCs can be determined by anodic
DEPTH OF ATTACK polarization measurements. To ensure that the polarization setup
Depth of attack can be used to assess corrosion damage in is working properly, it should be checked against ASTM G5,
MMCs. It may be more difficult, however, to assess the penetra- Standard Reference Test Method for Making Potentiostatic and
tion depth in MMCs compared with that in monolithic metals Potentiodynamic Anodic Polarization Measurements. The disso-
because reinforcement constituents that are left in relief can pre- lution behavior of MMCs in specific environments can be deter-
vent a depth gage from contacting the matrix surface and thus mined by generating anodic polarization diagrams of the MMC.
prevent the true depth of penetration from being measured. In To determine the extent of matrix dissolution versus that of rein-
particulate MMCs, the interference may be attenuated because forcement dissolution, polarization diagrams of monolithic
reinforcement particles are free to detach from the matrix as matrix metal and reinforcement constituents should be gener-
they are undercut by corrosion. When reinforcements interfere ated separately. The individual diagrams of the MMC constitu-
with mechanical measurements, depth of penetration can be ents are then used to generate a polarization diagram of the
assessed metallographically. Samples may be mounted and pol- MMC (here called a mixed-electrode diagram) using the mixed-
ished, and penetration measurements can be made with a micro- potential theory. If good correlation exists between the polariza-
scope and a calibrated eye piece. Details for determining tion diagram of the actual MMC and the mixed-electrode dia-
penetration depth are available in ASTM G46, Standard Guide gram, the fraction of dissolution current originating from the
for Examination and Evaluation of Pitting Corrosion. matrix and from the reinforcement constituents can be deter-
mined. The results can be verified by examining the corrosion
GRAVIMETRIC morphology of the MMC. For example, the anodic polarization
Gravimetric evaluation is often used to assess corrosion damage. diagrams of an actual 40 vol% SiCMF/Ti-15-3-3-3 MMC and that
Special problems, however, can be encountered when using gravi- generated using the MMC constituents and the mixed-potential
metric evaluation for MMCs. Results obtained from MMCs can theory corresponding to a 3.15 wt% NaCl solution were in good
be misleading because corrosion is sometimes accompanied by agreement (fig. 16). Corrosion morphology studies have con-
weight gain. MMC samples can experience weight gain when cor- firmed that the high anodic currents measured on the MMC cor-
rosion products and moisture are trapped in composite micro- responded to oxidation of the carbon cores and carbon-rich
structures, resulting in swelling of the MMC. Swelling of MMCs surface of the SiCMF.158
appears to be more troublesome with fiber-reinforced composites, If there is poor correlation between the polarization dia-
as opposed to particulate composites. For details on gravimetric gram of the actual MMC and the mixed-electrode diagram, the
measurements, reference should be made to ASTM G1, Standard discrepancy in dissolution behavior might be caused by forma-
Practice for Preparing, Cleaning, and Evaluating Corrosion Test tion of interphases or contaminants introduced in the MMC
Specimens. This standard addresses metal alloys and references microstructure during processing. For example,116 figure 17 shows
should be followed for the matrix alloy in the MMC. an anodic, mixed-electrode diagram generated from polarization
diagrams of graphite fiber and 6061-T6 aluminum exposed to
LOSS IN MECHANICAL PROPERTIES 0.5 M Na2SO4. The mixed-electrode diagram shows that 6061-T6
Corrosion damage of MMCs is sometimes assessed by measuring
a loss in strength. Changes in strength are measured before and
after exposure to corrosion environments. These tests can be use-
FIG. 16 Anodic polarization diagrams of SiC monofilament
ful for assessing corrosion damage in MMCs when corrosion
(cross section exposed), monolithic Ti-15-3-3-3, and
appears to be mild on the surface but penetrates deep into the
SiCMF (40 vol. %)/Ti-15-3-3-3 MMC exposed to deaerated
bulk along diffusion bonds or reinforcement-matrix interfaces.
3.15 wt% NaCl at 30 C. Scan rate = 0.1 mV/s. A diagram
Test specimens may take on various shapes and sizes, depending
for a composite consisting of 40 vol.% SiC monofilament
on the form of the stock material (e.g., wire, sheet, rod). Refer-
was generated on the basis of the mixed-potential
ence should be made to ASTM G1 (section 7.3.2) and G46 (sec-
theory.
tion 7.5).
Tests for Specific Corrosion Types

Various tests can be performed on MMCs to obtain specific
information on corrosion behavior. Tests used for monolithic
metals can be applied to MMCs with some success. Because
MMCs may have properties significantly different from those of
monolithic metals, conventional tests developed for monolithic
metals may not always produce sought-after results when used
to test MMCs.
current (of the MMC) that has been normalized with respect
FIG. 17 Anodic polarization diagrams of pitch-based graphite matrix area. One difficulty would be to obtain an accurate esti-
fiber (cross section exposed), monolithic 6061-T6 mation of the local-corrosion current density.
aluminum, and Gr(50 vol. %)/6061-T6 Al MMC plate The ZRA technique (ASTM G71, Standard Guide for Con-
exposed to deaerated 0.5 M Na2SO4 at 30 C. Scan ducting and Evaluating Galvanic Corrosion Tests in Electrolytes)
rate = 0.1 mV/s. A diagram for a composite consisting can be used to measure galvanic-corrosion currents between
of 50 vol.% graphite and 6061-T6 aluminum was monolithic pieces of the matrix metal and reinforcement constit-
generated on the basis of the mixed-potential theory. uents. One advantage of this technique is that galvanic-corrosion
currents can be measured over long periods of time. If virgin
MMC constituents are used, changes due to processing cannot be
accounted for. Pohlman24 showed that galvanic-corrosion currents
between aluminum alloys and BFs extracted from an aluminum
MMC were significantly greater than currents between aluminum
alloys and virgin BFs. Aluminum borides that formed on the BFs
during MMC processing were responsible for increasing galvanic-
corrosion currents (see the subsection “Aluminum MMCs: Effect
of Boron”).
These three methods can be used to estimate galvanic-
corrosion behavior. Advantages and disadvantages are associated
with each method. Some comparisons between these methods
aluminum passivates during the anodic scan. The anodic polari- have been made for Gr/Al37 and SiC/Mg MMCs.133
zation diagram of an actual 40 vol% Gr/6061-T6 Al MMC, how-
ever, exposed to the same solution shows that pitting is induced UNIFORM CORROSION
at approximately 0.6 VSCE (fig. 17). The unexpected pitting was Uniform corrosion of MMC matrices can be expected in environ-
found to be caused by residual microstructural chloride116 that ments that attack the matrix metal uniformly. In continuous-fiber
was unintentionally introduced into the microstructure during MMCs, however, fibers will be left in relief as the matrix corrodes,
processing.170 Buonanno171 later verified that the anodic polariza- whereas, in particulate MMCs, reinforcement particles fall free as
tion diagram of chloride-free Gr/Al MMCs traces the mixed- they are undercut. Uniform corrosion rates of MMCs may be
electrode diagram. greater than that of the monolithic matrix alloys because of gal-
vanic action between the matrix and reinforcement constituents.
GALVANIC CORROSION BETWEEN MATRIX AND MMCs should be exposed to environments of interest and
REINFORCEMENT CONSTITUENTS UNDER then inspected. If corrosion is uniform, corrosion rates can be
IMMERSED CONDITIONS assessed using recommendations in ASTM G1. Electrochemical
Galvanic corrosion between the matrix and reinforcement con- measurements also can be used to determine uniform corrosion
stituents can be determined by several methods. The mixed- rates. Refer to ASTM G102, Standard Practice for Calculation of
potential theory can be used with polarization data of the Corrosion Rates and Related Information from Electrochemical
matrix metal and reinforcement constituents to estimate galvanic- Measurements. Note that when determining matrix corrosion
corrosion currents and potentials. The intersection of the anodic rates, the corrosion current should be normalized with respect to
polarization curve of the matrix metal with the cathodic polari- the matrix area if reinforcements are inert.
zation curve of a noble reinforcement constituent gives the
galvanic-corrosion current and potential (refer to appendix of PITTING CORROSION
ASTM G82, Standard Guide for Development and Use of a MMCs are susceptible to pitting in environments that induce pit-
Galvanic Series for Predicting Galvanic Corrosion Performance). ting in the matrix metal. These environments usually contain
When using this method, note that changes in electrochemical halides and are oxidizing. In MMCs that have noble reinforce-
behavior of MMC constituents caused by MMC processing can- ment constituents, galvanic corrosion between reinforcement
not be taken into consideration if virgin MMC constituents are constituent and matrix can accelerate pitting compared with the
used to obtain polarization data. The behavior predicted using monolithic matrix alloy. The presence of the reinforcement con-
virgin MMC constituents could be quite different compared with stituents also may influence pitting by altering MMC microstruc-
that of the actual MMC. Timonova et al.23 showed that BFs tures. In SiCW/Al MMCs, for example, pits were more numerous
extracted from a magnesium matrix supported cathodic-current and much smaller in size compared with pits on monolithic
densities that were about five times that of virgin BFs (see the alloys.71 Apparently, the SiC whiskers enhance the precipitation
subsection “Magnesium MMCs: Effect of Boron”). of the intermetallic particles upon which pits nucleate71 (see sub-
The galvanic-corrosion rate can also be determined from section “Aluminum MMCs: Effect of Silicon Carbide”).
the open-circuit corrosion current of actual MMCs. To obtain MMC specimens should be exposed to environments of
the galvanic-corrosion current density, the local-corrosion cur- interest. The degree of pitting can be assessed using ASTM G46.
rent density172 should be subtracted from the open-circuit Pitting potentials may be obtained by generating anodic
polarization diagrams of the MMCs. Refer to ASTM G5 to ensure matrix. It should be emphasized, however, that ranking by gener-
that the electrochemical setup is working properly. Electrochemi- alities may be misleading because MMC corrosion properties
cal impedance spectroscopy also has been used to detect the can be highly sensitive to the effects of processing conditions.
onset of pitting in some MMCs.173 The formation of interphases, presence of microstructural con-
taminants, and microstructural changes in the matrix metal
STRESS CORROSION caused by reinforcement constituents may significantly deterio-
Studies on stress-corrosion behavior of MMCs have been limited. rate corrosion resistance. Two identical types of MMCs, but fab-
Results for some aluminum and magnesium MMCs are summa- ricated by different methods, may have different corrosion
rized in the subsections on “Aluminum MMCs: Effect of Rein- resistances.
forcement Constituents on Stress Corrosion,” and “Magnesium In the most general terms, titanium MMCs have the best
MMCs: Effect of Al2O3,” respectively. The type of tests that can resistance to corrosion because of the general and localized cor-
be used will depend to some degree on the form in which the rosion resistance of titanium. Al MMCs reinforced with semi-
MMC is produced and whether or not the MMC can be pre- conductors or insulators (i.e., SiC, Al2O3, and mica) were ranked
cracked. Some types of MMCs are produced only in the form of next due to lack of significant galvanic action between reinforce-
relatively thin panels (e.g., less than about 0.25 cm), whereas ment and matrix. Al MMCs reinforced with conductors (i.e.,
other types are available in bars or tubes. It is sometimes impos- graphite, carbon-coated SiCMF) are more susceptible to corrosion
sible to properly precrack unidirectional, continuous-fiber due to galvanic coupling with the reinforcements. Mg MMCs
MMCs because cracks do not always grow perpendicular to the were ranked the least resistant because of the highly reactive
direction of applied stress.174 magnesium matrix. However, Mg MMC reinforced with calcium
A variety of stress-corrosion testing methods, using compounds for biodegradable orthopedic implant materials
unnotched, notched, and precracked specimens have been well show improved corrosion resistance compared to the monolithic
documented.175 The following ASTM standards are also helpful Mg because of the formation of hydroxyapatite films. Lead as
in developing a stress-corrosion testing program: ASTM E399, well as depleted uranium, stainless steel, copper, and zinc MMCs
Standard Test Method for Linear-Elastic Plane-Strain Fracture were not ranked because these MMCs or testing conditions were
Toughness of Metallic Materials; ASTM G30, Standard Practice specialized or limited. This assessment is general and exceptions
for Making and Using U-Bend Stress-Corrosion Test Specimens; are likely.
ASTM G38, Standard Practice for Making and Using C-Ring
Stress-Corrosion Test Specimens; ASTM G39, Standard Practice
for Preparation and Use of Bent-Beam Stress-Corrosion Test ACKNOWLEDGMENTS
Specimens; and ASTM G49, Standard Practice for Preparation The author is grateful to many people and organizations for sup-
and Use of Direct Tension Stress-Corrosion Test Specimens. port and for funding in the area of MMCs over a number of
years. The author acknowledges the following individuals and
CORROSION FATIGUE original affiliations for support: Dr. R. M. Latanision, Massachu-
Relatively few studies on corrosion fatigue of MMCs have been setts Institute of Technology; Dr. A. J. Sedriks of the Office of
conducted. Results for Gr/Al and SiC/Al MMCs are summarized
Naval Research; Dr. S. P. Rawal of Martin Marietta Denver Aero-
in the subsection “Aluminum MMCs: Effect of Reinforcement
space; Dr. B. A. MacDonald of the National Science Foundation;
Constituents on Corrosion Fatigue.” An appropriate testing pro-
Dr. Reynold Kagiwada and Mr. Aaron Oki of TRW, Inc.; Mr. M.
gram will depend on the form of the MMC and the ability to
precrack specimens, which is a problem in some MMCs. The A. Mittnick of Textron Specialty Materials; Mr. Tom Rodjom of
practices for fatigue testing in section 3, “Metals Test Methods Alcoa Inc.; Dr. Herve Deve of 3M Corporation; Mr. Brian
and Analytical Procedures,” vol. 03.01, ASTM Book of Stand- DeForce and Mr. Robert Mason of Concurrent Technologies
ards,176 should be helpful in selecting a testing scheme. Annex Corporation; Dr. Joseph Argento, Mr. John Theis, Mr. Robert
A.1 in ASTM E647, Standard Test Method for Measurement of Zanowicz, and Mr. Donald Skelton of the Army Corrosion
Fatigue Crack Growth Rates, is particularly useful when doing Office; Mr. Lance Miyahara, Hawaiian Electric Company; and
corrosion-fatigue tests in aqueous environments. Mr. Matthew Koch, US Marine Corps, Corrosion Prevention
and Control Program.
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315
Chapter 20 | Water Handling Systems
Walter Young1
Introduction Corrosion monitoring can be used to provide operational

information. If corrosion can be controlled by maintaining a sin-
Corrosion monitoring is an integral part of any water treatment gle variable (e.g., temperature, pH, chemical treatment) within
program. It is used to determine treatment effectiveness and to limits previously determined, then that variable can be used to
establish the optimum level of chemical treatment that is most predict changes in corrosion patterns as the limits are exceeded
cost effective, but not necessarily the cheapest per pound. in both a positive and negative direction. An extension of this
The purpose of corrosion monitoring is to assess or predict technique is to use a monitored variable to control chemical
corrosion behavior of the system. Basically, there are two objec- addition directly through automatic feed systems.
tives to monitoring: (1) to obtain information on the condition The particular corrosion monitoring techniques selected
of the operational equipment, and (2) to relate this information depend on their applicability to the system and the information
to the operating variables (i.e., pH, temperature, water quality, being sought. Some techniques provide information that is effec-
chemical treatment, etc.). Meeting these objectives will provide tively instantaneous. Other techniques provide a measure of cor-
the following results: rosion rate. Others measure total corrosion or the remaining
• Increased life of the plant. metal thickness, while others provide information on the overall
system. Most corrosion monitoring techniques are best suited to
• Improved quality of the plant’s product.
situations in which corrosion is of a general nature, but some
• Prediction of maintenance needs at the plant. techniques provide at least some information on localized attack,
• Reduction in plant’s operating costs. such as pitting.
No one monitoring technique will provide all the necessary
Corrosion monitoring is standard practice in the water data to properly evaluate the efficacy of the treatment program.
treatment industry. The plant engineer can use this information More than one technique may be necessary to monitor a particu-
to predict equipment life. Monitoring helps the engineer identify lar system.
significant factors responsible for corrosion problems and An overview of the various corrosion monitoring techni-
ensures implementation of solutions. ques used in cooling water systems is shown in tables 1–3. The
Corrosion monitoring is a diagnostic tool. It provides infor- essential information is listed in table 1, whereas table 2 lists
mation for the solution of corrosion problems. Knowledge of some of the characteristics of the monitoring techniques. table 3
corrosion trends can be valuable. Frequently, several variables is a summary chart of the various monitoring techniques overall.
might appear to be significant, and the ability to correlate corro-
sion rates with a single variable under specific conditions can be
vital. As a logical extension of its diagnostic capabilities, corro- Corrosion Coupons
sion monitoring is used to assess the effectiveness of a solution The most obvious method of assessing the corrosivity of a cool-
to a specific water treatment problem. ing water system to a specific material is to expose a specimen or
coupon made of that material for a given time in the flowing
1
Corrpro Companies, Inc., 470 Lapp Rd., Malvern, PA 19355, USA water. Coupons are made from specific alloys, which have been
http://orcid.org/0000-0003-4670-8066 cleaned and preweighed with a known surface area. Coupons
The author acknowledges the previous author of this chapter, Bennett P. Boffardi, vary widely in size and shape. Some commonly used coupons are
Boffardi and Associates, Inc., Pittsburgh, PA. This chapter is a revision of 12.5 mm (1/2 in.) wide, 75 mm (3 in.) in length, and 1.6 mm
P. Boffardi, “Water Handling System,” in Corrosion Tests and Standards:
(1/16 in.) thick, having an approximately 2,155 mm2 (3.4 in.2)
Application and Interpretation, MNL20, 2nd ed., ed. R. Baboian, S. W. Dean,
H. P. Hack, E. L. Hibner, and J. R. Scully (West Conshohocken, PA: ASTM surface area. At selected time intervals, the coupons are removed,
International, 2005), 826–833. cleaned, and reweighed to determine the metal loss.
DOI: 10.1520/MNL202NDSUP20190017
TABLE 1 Corrosion Monitoring
Method Measures Applications
Coupon Testing Average corrosion rate expressed as uniform corrosion in mm/y. Most suitable for uniform corrosion under steady conditions. Combined
Weight change over 30- to 90-day duration. with visual observation, can indicate localized attack (i.e., pitting,
underdeposit, galvanic). Coupons made from most engineering alloys.
LPR Instantaneous corrosion rate is measured by electrochemical Suitable for most engineering alloys. Probe must be placed in fluid of
polarization of 6 10 mV between two electrode probes. Pitting sufficient conductivity to provide accurate rate. Alloy multiplier
tendency can be measured. required for materials other than carbon steel.
ER Metal loss is determined from resistance change of a corroding metal Suitable for measurements in low-conductivity environments, either
element. Uniform corrosion rates are calculated from resistance liquid or vapor. Elements made from most engineering alloys. Element
reading. Does not measure localized corrosion. design a function of probe life and sensitivity.
Analytical Concentrations of dissolved or suspended species in fluid systems Determines water quality level of chemical treatment, inhibitory and
including pH and conductivity. Does not measure corrosion. antagonistic species, dissolved and suspended corrosion by-products.
Heat Transfer Units Visual observation of corrosion attack on heat transfer surface. Most suitable in simulating conditions in heat exchanger for corrosive
Unit can determine corrosion rate from weight loss of heated surface. attack. Heat transfer tubes can be made from most engineering alloys.
Test Heat Exchanger Determines the effect of velocity, heat flux, chemical treatment on Most suitable in simulating conditions of critical plant heat exchanger.
corrosion, scale, and fouling. Heat transfer tubes can be made from most engineering alloys.
TABLE 2 Monitoring Technique Characteristics
Time Interval for Response to Plant Ease of

Method Measurement Type of Information Changing Condition Environment Type of Corrosion Interpretation
Coupon Testing Long-term duration, Average uniform corrosion Poor Any Uniform and localized Simple
30 to 90 days rate attack
LPR Instantaneous Corrosion rate, pitting index Fast Conductive Uniform Simple
ER Short duration Integrated corrosion rate Moderate Any Uniform Simple
Analytical Fast Species influencing corrosive Fast Any Not applicable Moderate
attack
Heat Transfer Units Long-term duration, Corrosion rate, scale, and Moderate Any Uniform and localized Difficult
30 to 90 days fouling attack besides deposition
Conversion to English units, mils per year (mpy), requires

TABLE 3 Monitoring Devices that equation (1) be multiplied by 39.4. Corrosion coupons are
highly susceptible to initial corrosion because the metal surface
Test Heat is in an “active” state because of surface preparation. Coupons
Systems Coupon LPR ER Analytical Exchanger
should not be touched during installation and monitoring pro-
Once-through X XX X cesses. Use of plastic gloves when handling the coupons is highly
Cooling recommended. Normally, 30 days is a typical test period for low-
Closed System X X X corrosivity water (under 0.25 mm/y or 10 mpy). Low-corrosivity
Cooling water usually contains chemical treatments to stifle corrosion
Open X X X X attack. Exposure periods less than 30 days can yield misleading
Recirculating Cooling results. Frequently, long-term tests are required, up to 90 days’
exposure. During this time frame, three sets of coupons are nor-
The weight loss is converted to overall thickness loss or mally placed in a test rack and changed in sequence of 30-, 60-,
average corrosion rate expressed in millimeters per year (mm/y) and 90-day intervals. Normally, the longer the exposure period,
as follows: the lower the measured average corrosion rate, and the more
mm=y ¼ 3:65ðDWÞ½ðAÞðdÞðDÞ (1) closely the coupons will approximate conditions in the system.
Figure 1 graphically shows the decrease in corrosion rate with
where exposure time. Steady state is normally achieved in the 60- to
DW ¼ weight change, mg, 90-day time frame.
A ¼ coupon surface area, cm2 Screws and nuts made of nylon or plastic should be used to
d ¼ metal density, g/cm3, and hold the coupons to the coupon holder. Mixed metallurgy should
D ¼ exposure time, (days). be avoided. Copper-base screws and nuts should not be used to
WATER HANDLING SYSTEMS 317
rates between 0.13 to 0.25 mm/y (5 to 10 mpy) are fair, and rates
FIG. 1 Relative carbon steel corrosion rate versus elapsed time. greater than 0.25 mm/y (10 mpy) are poor. Copper-base alloys,
such as admiralty and 90:10 copper nickel, should have rates
under 0.013 mm/y (0.5 mpy). Above this value is considered
excessive. General classification of corrosion rates is shown in
table 4.
Coupon installation should be placed in a coupon test rack
shown in figure 2. Note that the broad face of the coupon is verti-
cal to prevent deposits from settling during periods of low flow.
It is important that the flow rate through the rack corresponds
to the actual service flow rate. Too high a flow rate will keep
debris off of the coupons and may initiate erosion attack on
copper-base alloys. Low flow rates may result in excessive corro-
sion and fouling. Normally, flow rates of 1–2 m/s (3 to 5 ft/s) are
adequate. The coupon rack should be connected to the return
riser to the cooling tower or at the exit of the hottest part of the
system using plastic piping or any other material that will not
hold carbon steel or stainless steel coupons. Galvanized screws TABLE 4 Qualitative Classification of Corrosion Rates
and nuts should never be used.
Coupons having large amounts of deposits or tuberculation Corrosion Rate (mm/y)
may indicate insufficient chemical treatment, unstable water char-
Carbon Steel Copper-Base Alloys Description
acteristics, or highly corrosive conditions. Alternatively, deposits
<0.03 0 to 0.003 Negligible or excellent
may have been transported from elsewhere in the system. Heavy,
0.03 to 0.08 0.003 to 0.006 Mild or very good
uniform deposits will reduce corrosion rates, because they can act
0.08 to 0.13 0.006 to 0.009 Good
as a protective barrier.
0.13 to 0.20 0.009 to 0.0125 Moderate to fair
General guidelines for acceptable uniform corrosion depend
0.20 to 0.25 0.0125 to 0.03 Poor
on the coupon metallurgy. Low-carbon steel (mild steel) corro-
>0.25 >0.03 Very poor to severe
sion rates less than 0.13 mm/y (5 mpy) are considered good,
FIG. 2 Corrosion test rack installation.

influence coupon corrosion rates. For example, do not use galva- Two LPR devices are presently in use, a three-electrode
nized pipe, copper pipe, or brass valves to connect the test loop probe (working, counter, and reference electrodes) and a two-
to the riser. electrode probe. In the author’s opinion, the three-electrode sys-
Note in figure 2 the use of an optional strainer. The strainer tem is a better-designed corrosion monitor; however, it accounts
should be used in water systems known to have high-suspended for a small percentage of LPRs used to monitor corrosion rates
solids or assorted foreign matter, or both. in industrial water treatment systems. The two-electrode LPR
Flow through the coupon rack can be controlled using an device is used by most water treatment vendors and industrial
orifice control valve, but this valve is subject to plugging. A plants. It will be the only LPR device discussed.
plugged orifice control valve will have reduced flow or no flow at The basic operation of the LPR instrument uses two electro-
all, resulting in high coupon corrosion rates. A rotameter valved des made of the material of interest (i.e., carbon steel, Admiralty,
at the end of the coupon rack will give more flexibility and accu- 90:10 copper nickel). One of the electrodes acts as an anode, the
racy in controlling water velocity. A strainer in the system will other as a cathode. During the operation of the instrument, a
prevent plugging of the fluid control valve. Cooling water dis- very small voltage of 20 mV is applied across the electrodes. In
charge from the rack should go to a sump (e.g., drain, tower this region, the polarization curves approach linearity, and hence
basin) and not be plumbed back into the cooling system. The the term LPR. The applied potential divided by the measured
outflow of the rack must be open to the atmosphere. current imeas is a resistance term called polarization resistance, or
In a high-rise building the cooling tower is normally placed Rp. The resistance to current flow between the two electrodes of
on the roof and the corrosion rack is in the mechanical room, the LPR probe is the sum of polarization resistance values at
which are frequently in the basement. In this situation, the corro- each electrode and the resistance of the solution between the
sion rack is plumbed between the down-comer and the riser. electrodes (Rs), as follows:
Materials of construction for the corrosion rack should be made
of stainless steel to provide rigidity and have minimal influence DE ¼ imeas ð2Rp þ Rs Þ: (2)
on the coupons. Use of carbon steel or galvanized steel is not rec-
ommended as construction materials. Coupon placement in the In addition to general or uniform corrosion, localized corro-
rack follows the galvanic series, starting from the active end. sion (pitting) may occur in a system. A pitting index or imbal-
That is, aluminum, carbon steel, stainless steel, and then copper- ance measurement can be obtained from some LPR meters. The
base alloys. electrochemical current generated is a qualitative measurement
Coupon corrosion studies are simple to perform. This is the or index. If the imbalance reading (pitting) is low compared with
most direct method, aside from inspection of the actual plant the corrosion reading, pitting is probably minimal. A high imbal-
equipment, to determine the efficacy of a treatment. Coupon eval- ance reading compared to a general corrosion rate can indicate
uation allows simple comparison between different alloys, which that pitting or crevice corrosion will be the main form of attack.
provides visual examination for localized attack, such as pitting, When a general corrosion rate reading is about the same as the
crevice attack, dealloying, or any other form of nonuniform attack. imbalance index, then some pitting is indicated, but the pits
There are limitations, however, to coupon evaluation. Coupons probably will be broad and shallow. Further information on the
provide weight loss determination of corrosion rates. This consists pitting index can be found in NACE International Publication
of accumulated loss of material over the period of exposure. 3T199.1
Therefore, coupons cannot determine the time or magnitude of The LPR probe should be installed perpendicular to the
corrosion upsets within the exposed time frame. Finally, 30 to 90 water flow in a representative water stream which is part of the
days are needed to allow sufficient weight change to be meaning- piping system or at the end of the coupon test rack, as shown in
ful. This 30- to 90-day exposure can sometimes indicate differ- figure 2. The probe must be installed such that water flows
ences between short-term and long-term corrosion rates. between the two electrodes to avoid fouling of the electrodes. An
aligning pin at the male cable connector of the probe indicates
the electrode position as shown in figure 2. The two electrodes
Linear Polarization-Resistance should project into the flowing water, with the probe lead flush
with the pipe wall, as shown in figure 3.
Meter Serious errors in corrosion rate measurements may occur in
The linear polarization-resistance (LPR) technique is the only low-conductivity water because of solution resistivity effects.
corrosion monitoring method that allows corrosion rates to be This situation tends to occur at moderate to high corrosion rates
measured in real time. Although limited to electrolytically con- and is manifested by indicating lower corrosion rates than actual.
ducting liquids, the response time and data quality of this tech- The operating range for various LPR instruments can be
nique make it superior, where applicable, to all other forms of obtained from the manufacturer.
corrosion monitoring. The LPR probe alloy multiplier should be used when elec-
LPR is particularly useful as a method to rapidly identify trodes are made from materials other than carbon steel. The pur-
corrosion upsets and, thus, evaluate remedial action, reducing pose of the multiplier is to convert the built-in constants that are
and minimizing unscheduled downtime, thereby prolonging specific for carbon steel to other alloys. Corrosion rate multi-
plant life. pliers account for the specific alloy’s anodic reactions, the
corrodes. The metal element or probe is usually in the form of a

FIG. 3 Installation of LPR probe. wire, strip, or tube.
When it corrodes uniformly, the change in electrical resis-
tance is proportional to corrosion
R ¼ K=A, (3)
where:
R ¼ the probe resistance,
A ¼ the cross-sectional area of the metal element, and
K ¼ a constant and a function of probe metallurgy, element
length, and resistivity.
As the probe element corrodes, its cross-sectional area is
reduced, increasing its electrical resistance. Thus, the measure-
ment of electrical resistance is inversely proportional to the
remaining metal in the probe. Therefore, increases in the mea-
sured resistance signal increase the metal loss to corrosion. The
probe is internally temperature compensated for changes in the
valency of the anodic reactions, the alloy equivalent weight, and probe constant, which is temperature dependent.
the alloy density. LPR electrodes should be changed periodically The advantage of the ER meters is their ability to measure
and at least annually. corrosion in liquids, vapor phases, and in inaccessible locations.
Corrosion rates obtained with LPR instruments provide rate The liquid does not have to be conductive or have a minimum
data directly and within a few minutes. This instrument is well conductivity as with the LPR systems. Corrosion rates, however,
suited to applications in which upsets or other accelerated corro- are not instantaneously determined. The time frame required to
sive conditions can be detected quickly so that remedial action determine corrosion rates is a function of probe element and
can be taken. The corrosion rates obtained with the meter metal loss. The ER probes are suitable only for uniform corro-
assume uniform corrosion with a tendency to predict pitting sion. There is no pit index built into the instrument. Any pits
attack. Deposits on the electrodes can bias the pitting index developed on the element will cause rapid penetration and indi-
value. If the index value is high, the probe should be removed cate excessively high corrosion rates.
and the electrode visually examined for debris. Bridging the elec- Typical probe elements are shown in figure 4. Appropriate
trodes with conductive deposits will affect both the general cor- response time information for any given probe can be obtained
rosion value and the pitting index. from the manufacturer. The corrosion rate is calculated from the
The LPR reading may not agree with the coupon corrosion change in dial reading on the instrument.
rate. The LPR data are real time and measure the corrosion rate The corrosion rate is calculated from the change in dial
at the time of measurement. Coupon rates are an accumulated reading on the instrument, as follows:
average mass loss, taking into account all corrosion that has
occurred during its exposure period. Coupon mass losses are a 9:3 103 DD PF
Corrosion rateðmm=yÞ ¼ , (4)
direct measure of corrosion rate, whereas LPR data are gener- T
ated from electrical currents, which are influenced by other fac- where:
tors. The main advantage of LPR devices is the rapid detection AD ¼ the change in the dial reading,
of sudden changes in system operating parameters or chemical PF ¼ the probe factor (supplied with each probe), and
levels. T ¼ the elapsed time in days.
Details on how to calculate corrosion rates from electro-
chemical measurements can be obtained from ASTM G102, Stan- ER probes must be allowed to corrode for a period of time
dard Practice for Calculation of Corrosion Rates and Related before accurate corrosion rate measurements can be made. The
Information from Electrochemical Measurements.2
FIG. 4 Electrical resistance element design.
Electrical Resistance Meter

The electrical resistance (ER) technique is an online method of
monitoring corrosion rates. It is universally applicable to all
types of corrosive environments—that is, conductive to poorly or
nonconductive media (such as deionized or potable waters) and
vapor phase systems (such as steam).
There are many manufacturers of ER instruments. ER
meters measure the change in resistance of a metal element as it
time duration depends on the corrosion rate. The higher the

rate, the shorter the time period and vice versa. TABLE 5 Analytical Parameters
Probe placement in the fluid should be similar to LPR elec-
trode placement—that is, the probe element should protrude Species Impact on Operating System
into the fluid. Flow should pass the element. There is no specific pH Corrosion or scale-forming tendency.
orientation for the probe element. P Reading Monitor buffering capacity, differentiates
Figure 5 shows a plot of dial setting or metal loss from the ER between CO2
3 and HCO3 .
meter versus time, which can give an indication of corrosion rates. M Reading Provides data for calculating CaC03 potential.
A large change in slope represents an increase in corrosion, Includes all hydrogen titratable species (i.e.,
whereas a zero slope indicates no significant increase in corrosion. PO3
4 , SiO2) polymers. If pH/alkalinity relationship
Generally, LPR is the preferred technology for online moni- is outside of norm, then additional alkalinity value
toring of corrosion in highly conductive waters such as those in may be due to other titratable species.
industrial recirculating cooling water systems. The preference is Conductivity Estimates total dissolved solids.
based on two factors: (1) the relative instantaneous nature of the Suspended Solids Monitors general water quality or turbidity.
LPR, and (2) the distortional effect that even a single pit has on Orthophosphate Monitors inhibitor concentration and/or
the ER measurement and reducing the usable life of the ER reversion.
probe. Polyphosphate Monitors inhibitor concentration.

Organic Phosphate Monitors inhibitor concentration.
Total Organic Carbon Monitors overall water quality.
Chemical Analysis Calcium, Total Monitors potential hardness scale deposition.
Calcium, Dissolved Monitors hardness scale deposition if value is
Water parameters relevant to the corrosion process can be pro- different from calcium, total.
vided through chemical analysis. This monitoring technique Magnesium, Total Monitors potential deposition.
does not directly indicate corrosion rate but provides informa- Magnesium, Dissolved Monitors potential silicate or hydroxide
tion on factors that can influence the corrosion process. It deposition if value differs from magnesium, total.
measures parameters that are known to be associated with Aluminum, Total Monitors possible inhibitor adsorption, reducing
acceptable or unacceptable corrosion processes within a system. corrosion protection if concentration >0.1 mg/L.
A thorough water analysis is not required of every water Aluminum, Dissolved Monitors possible inhibitor adsorption, if
sample. Core analyses, however, should be performed to deter- concentration >0.1 mg/L. Loss of 3.5 mg/L of
mine the operating state of the system. It is good practice to peri- phosphate per 1 mg/L of aluminum.
odically obtain complete analyses so that seasonal variations in Copper, Total Monitors potential copper corrosion reducing
water composition can be tracked. steel corrosion protection if concentration
A “well check” analysis is also advisable. This consists of a >0.1 mg/L.
thorough analysis when the plant is operating properly and cor- Copper, Dissolved Monitors potential copper corrosion. Acceptable
level < 0.05 mg/L.
rosion rates are meeting the objectives. The well check can then
Zinc, Total Monitors potential zinc scale deposition and level
be used as base line data when corrosion rates are outside the
of treatment needed to inhibit/disperse solids.
norm and analyses are being performed to determine the cause.
Zinc, Dissolved Monitors background levels and active synergist.
Parameters to be determined for a thorough analysis and
their impact on corrosion/deposit are shown in table 5.
Dissolved Oxygen Monitoring

FIG. 5 Electrical resistance meter dial setting versus time: (A) a Oxygen is the common cathodic reduction species found in water,
medium corrosion rate, (B) essentially no corrosion, and which is responsible for continued corrosive attack on some engi-
(C) high corrosion rate. neering materials, such as low carbon steel. Passive engineering
alloys, however, utilize the oxygen to form thin, tenacious, and
adherent protective oxide films. Some common alloys with protec-
tive films are stainless steels, nickel alloys, copper-base alloys, and
aluminum alloys. The oxygen concentration at ambient tempera-
tures and atmospheric pressure is approximately 6–8 mg/L. An
increase in temperature decreases oxygen solubility, whereas an
increase in pressure increases oxygen solubility.
In open cooling water environments, oxygen cannot be eco-
nomically removed as an antagonistic species. Appropriate
cathodic inhibitors control its impact on corrosion.
In boilers, it is a common practice to remove the oxygen
from the water, because it is a major corrodent. Removal is
through a combination of physical and chemical means.
Deaerators physically remove the oxygen by purging the boiler Quinhydrone is used to calibrate the ORP electrodes. By
feed water with steam, which heats and degases the water. Oxygen placing the quinhydrone in a known pH solution, a standard mV
content can be reduced to 5–7 ug/L by this method. Further reading is achieved. An ORP value of 87 mV is obtained in a
reduction of oxygen is required, and this is achieved through the quinhydrone solution at pH 7, and 240 mV at pH 4. Other cali-
use of chemical oxygen scavenger. The combination of deaeration bration protocol exists for higher ORP readings in the 600 mV
and oxygen scavenger can reduces the oxygen content to zero. range.
Oxygen measurements can be made directly and continu-
ously using online monitors or by wet chemical analysis.
Heat Transfer Systems
Fouling and deposit monitors are used primarily to track the
Oxidation Reduction Potential buildup of scale or deposits on heat transfer surfaces. The heat
Oxygen reduction potential (ORP), or redox potential, is the transfer tube can also be used as a tubular corrosion coupon to
potential of a reversible oxidation-reduction electrode measured monitor corrosion under heat transfer conditions.
with respect to a reference electrode, corrected to the hydrogen These units are designed to simulate heat exchangers under
electrode, in an electrolyte. It is an online, real-time measurement. as near actual operating conditions as possible, taking into
In water treatment, ORP is used to control the addition of oxidiz- account ease of use and simplicity in design. Figure 6 shows a
ing biocides, such as chlorine, chlorine dioxide, bromine, hydro- simplified schematic. An electric resistance heating element is
gen peroxide, and ozone. The presence of these chemicals will used to impose a heat load on the tubular metal surface. The
raise the ORP value. When an ORP probe is placed in the open metal test specimen is inside a glass outer jacket in which water
recirculating cooling water environment in the absence of an oxi- flows in the annular space. The glass tube makes it possible to
dant, its value is taken as an initial set point. The addition of an visually examine the metal surface for deposit buildup or corro-
oxidizing biocide increases the ORP value. The actual ORP read- sion attack.
ing depends on concentration and activity of the oxidant or bio- Heat flux (W/m2), which is the heat transfer rate (W)
cide, temperature of the system, contaminates and nutrients, pH, divided by the exposed metal tube surface area (m2), is constant
and other parameters. Usually, at recommended concentrations of as long as no deposits accumulate on the specimen. Deposits
oxidizing biocides, the ORP value increases hundreds of millivolts coming from hardness salts, corrosion by-products, silt, process
depending on these parameters. Maintaining the recirculating contamination, and biomass, however, can form on the heated
water at the higher oxidizing potential ensures adequate disinfec- surface, raising the surface temperature. If the surface tempera-
tion. ORP measurements are similar to pH measurements. A typi- ture becomes excessive, a temperature cutoff switch can protect
cal ORP cell uses a platinum surface for measuring the ORP the device.
versus a silver-silver chloride reference electrode. Maintenance of It is important to gather as much information about the sys-
an ORP system is similar to that of a pH electrode—that is, the tem using fouling and deposit monitors as possible. Periodic
ORP electrode should remain in the water circuit at all times. visual inspection of the heat transfer tube is necessary to qualify
Electrodes are replaced approximately every two years. The the buildup of deposit. At the termination of the test, the tube
electrodes are cleaned in 5% hydrochloric acid solution to deposit should be collected and chemically analyzed. Photo-
remove any hard-water deposits that may form and interfere graphs of the deposits on the tube can be useful in describing the
with the reference junction. type of buildup. Also, photographs after the tube has been
FIG. 6 Corrosion deposit test unit.

cleaned can be used to document the type of corrosion attack system that is to be duplicated. Once the plant parameters have
that has occurred (e.g., uniform, underdeposit, pitting). After the been determined, they should be duplicated as nearly as possible
tube has been cleaned, the corrosion rate of the heat transfer in the test unit and held constant. Figure 7 is a schematic of a typ-
tube should be determined. This rate should be compared with ical two-tube test heat exchanger. It is used to simulate tube side
nonheat transfer coupons to determine the impact of heat flux. water conditions in a plant exchanger. Heated water or steam on
the shell side is used to heat the tubes.
The flow of cooling water to the tubes must be controlled to
Test Heat Exchanger maintain system velocity. An inlet water strainer is used to elimi-
The test heat exchanger is a monitoring tool that evaluates a heat nate foreign objects, which can restrict flow. A valve ahead of a
transfer surface for corrosion and deposition. The test heat flow indicator controls flow.
exchanger is only as good a monitoring or evaluating piece of The flow of hot liquid on the shell side is pumped through
equipment as its ability to duplicate or represent system condi- the exchanger and the temperature is controlled by a thermostat.
tions. The factors inherent in plant heat exchanger equipment Thermometers on the inlet and outlet waters are used to deter-
that determine the corrosion and deposition of exchanger surfa- mine temperature differential. Once the operating parameters
ces are as follows: have been selected and established, they should be checked and
recorded on a per day or per shift basis.
• Product temperature, which determines metal skin temperature. The two-tube heat exchanger can be used to compare treat-
• Water flow velocity in the tube, which can influence fouling ment, metallurgy, and the impact of heat flux on deposition by
rate. Low velocities of 0–0.6 m/s (0 to < 2 ft/s) can result in varying the flow in one of the tubes. At the end of the monitor-
more severe fouling. Average velocities of 1–2 m/s (3–5 ft/s) ing test period, which is at least 30 days, the heat transfer tubes
would correspond to normal rate of deposition. High veloci- should be evaluated for scale deposition, fouling, and corrosion.
ties of 2–4 m/s (6–12 ft/s) will result in less fouling. Analysis usually includes the following:
• Heat flux, a major influence on scale/deposition rate. Corro-
sion rates will also be influenced but to a lower degree. Heat 1. Cutting the tubes in half for visual inspection on both the
flux of 0–6,300 W/m2 (0–2,000 BTU/ft2-h) are considered heat transfer and nonheat transfer surfaces (tube exten-
low. Heat flux of 6,300–15,800 W/m2 (2,000–5,000 BTU/tf-h) sion outside the shell).
are average. Heat flux of 15,800–31,500 W/m2 (5,000–10,000 2. Scraping the deposits from the tube for analysis.
BTU/ft2-h) are considered high. 3. Brushing and chemically cleaning the tube to examine
tube surface for general and localized corrosion.
• Cooling water temperature, which accepts heat from the plant
exchanger.
These heat exchanger devices require considerable time and
To obtain reliable results from a test heat exchanger, these expertise to properly operate. They are not commonly used
factors must be determined from the plant exchanger in the because of manpower commitment and ancillary expenses.
FIG. 7 Field evaluation test heat exchanger.

Conclusion 2. Standard Practice for Calculation of Corrosion Rates and Related

Information from Electrochemical Measurements, ASTM G102
A wide range of corrosion monitoring techniques is used in (West Conshohocken, PA: ASTM International, approved
water treatment to systematically measure the corrosion or deg- November 1, 2015), http://doi.org/10.1520/G0102-89R15E01
radation of equipment and distribution piping. Corrosion moni- 3. W. H. Ailor, Handbook on Corrosion Testing and Evaluation (New
toring is a viable tool to assess the performance of any chemical York: Wiley, 1971).
treatment program. No one technique is universally applicable.
The wide variety of corrosion monitoring tools can be used in 4. Standard Test Methods for Corrosivity of Water in the Absence of
Heat Transfer (Electrical Methods), ASTM D2776 (West
any industry, and, although each technique has limitations, they
Conshohocken, PA: ASTM International [historical version]).
provide a practical means to monitor corrosion behavior. More
details on the various monitoring techniques can be found in the 5. Standard Practice for Online Monitoring of Corrosion in Plant
technical literature.3–7 Equipment (Electrical and Electrochemical Methods), ASTM G96
(West Conshohocken, PA: ASTM International, approved May 1,
2018), http://doi.org/10.1520/G0096-90R18
References 6. Cooling Water Test Units Incorporating Heat Transfer Services,

NACE TM0286 (Houston, TX: NACE International, 2001).
1. Techniques for Monitoring Corrosion and Related Parameters in
Field Applications, Item No. 24203-SG, NACE Publication 3T199- 7. Recommended Practice On-line Monitoring of Cooling Waters,
2012 (Houston, TX: AMPP, 2012). NACE RP0189 (Houston, TX: NACE International, 1989).
325
Chapter 21 | Pipeline
Abdelmounam M. El-Sherik1
Introduction ASM Metals Handbook provides a summary of the different

specifications used for pipelines.1
In the oil and gas industry, pipelines are the primary economical Steels such as API 5L X52 and X65 remain the most widely
and safest method for the transportation of high volumes of used grades in oil and gas pipelines.2 In many cases the mechani-
hydrocarbon fluids at high flow rates over short and long distan- cal properties of these grades are insufficient to meet the increas-
ces (thousands of kilometers). To transport a greater volume of ing demands to transport higher volumes of fluids at higher
fluids in pipelines, higher operating pressures are required, while operating pressures and at lower costs. To meet these industry
also maintaining pipeline network integrity and reliability. This demands, line pipe steel development has focused on improving
can be achieved through proper corrosion testing strategies that the strength and mechanical properties, without reducing tough-
include inspection, in situ testing, and monitoring as well as pre- ness and weldability, of pipeline steels. This is achieved through
dicting the likelihood of corrosion occurring along the pipe. thermo-mechanical treatments and the addition of small
Corrosion testing of pipelines is conducted for several rea- amounts (typically less than 1 wt%) of alloying elements (Nb, V,
sons. One is to evaluate the pipeline condition to determine Mo, Ni, Cr, and Zr) in various combinations to achieve the
whether or not it is safe to operate. If repairs are needed, testing desired properties.2,3 These efforts led to the development of
is performed to determine if repair is feasible or if replacement is high-strength low-alloy (HSLA) steels, or microalloyed steels,
needed. Testing is performed to track the pipe condition so that namely, API 5L 70X, X80, X100, and X120 grades. With increas-
repair or replacement can be budgeted. Another reason for testing tensile strength, the pipe wall thickness required for pressure
ing pipes is to evaluate the effectiveness of corrosion control containment is reduced, leading to lower pipe laying and welding
measures, such as inhibitors for internal pipe surfaces or costs.3 These remarkable improvements in mechanical properties
cathodic protection (CP) and coatings for external pipe surfaces. and lower pipeline-laying costs, however, do not come without
The intent of this chapter is to provide an overview of the adverse side effects. HSLA steels are more susceptible to hydro-
primary testing techniques and methods most commonly uti- gen damage and embrittlement than the lower-strength API
lized in the field for testing and monitoring of corrosion in bur- grades in sour service environments.
ied oil and gas pipelines. Before discussing test techniques, the
chapter will discuss briefly pipeline materials, relevant corrosion
threats, and corrosion control methods and strategies. This chap- CORROSION-RESISTANT ALLOYS
ter is by no means a detailed text on corrosion and corrosion Under extreme operating conditions (high pressures and temper-
testing of pipelines, and the reader is encouraged to consult the atures) and more aggressive environments, such as unprocessed
references for further detail. production fluids containing high chloride, hydrogen sulfide
(H2S), and carbon dioxide (CO2) contents, carbon and low-alloy
steels are susceptible to rapid corrosion attacks, such as pitting,
crevice, or underdeposit corrosion. This rapid corrosion occurs
Pipeline Materials even when corrosion inhibitors are factored into the design life
of the carbon and low-alloy steel pipe. In such extreme service
CARBON AND LOW-ALLOY STEELS
environments, corrosion-resistant alloys (CRAs) are the pre-
Carbon and low-alloy steels are probably the most commonly
ferred material design option.4 CRAs are typically classified into
used materials for pipelines transporting hydrocarbon fluids.
four main material classes: martensitic stainless steels, duplex
1
stainless steels, super-austenitic stainless steels, and nickel-based
Saudi Aramco, P.O. Box 62, Dhahran 31 311, Saudi Arabia http://orcid.org/
0000-0002-0863-9576
alloys. Each of these four CRA classes consists of several grades
The author acknowledges the previous author of this chapter, Paul S. Rothman, that are compositionally fine-tuned for specific service environ-
The Port Authority of New York and New Jersey, New York, NY. ment. For several tables showing chemical compositions and
DOI: 10.1520/MNL202NDSUP20190039
applications for each of the CRA class material, see Hill and The 10 to 2 o’clock and 4 to 8 o’clock orientations in pipe-
Perez.4 lines are typically more prone to internal corrosion attacks as a
CRAs can be employed as solid pipe or as clad product.5 result of water condensation and precipitation at these locations,
The first reported application of CRAs dates back to 1975 in flow respectively. Internal corrosion occurring at the 10 to 2 o’clock
lines internally clad with 316L stainless steel and also as solid orientation is typically termed top-of-the-line corrosion (TLC),
duplex stainless steel lines.4 Because of the prohibitive cost of whereas corrosion taking place at the 4 to 8 o’clock position
CRAs, their application is limited to short distances, such as flow termed bottom-of-the-line corrosion (BLC). Internal corrosion
lines carrying aggressive production fluids. The decision whether in these locations is primarily affected by the composition (e.g.,
to use CRA instead of carbon and HSLA steels typically is made CO2, H2S, water cut, salts) of the transported fluids and pipeline
during the design phase of a pipeline through the use of corro- operation conditions (temperature, pressure, flow regime, and
sion prediction software packages that can predict uniform and velocity). CO2 and H2S gases in combination with liquid water
pitting corrosion rates in the intended service environment. (condensed or produced) are the main causes of corrosion in oil
Although CRAs show superior resistance to localized and uni- and gas pipelines. The corrosivity of the water phase is normally
form corrosion compared with carbon and HSLA steels, even enhanced by the presence of dissolved salts naturally occurring
with inhibition, they remain susceptible to environmental crack- in the production fluids. The concentrations of H2S and CO2
ing corrosion attacks particularly in sour and chloride containing gases determine the corrosion mechanism (sour, sweet, or
environments. mixed), composition of corrosion products, corrosion damage
mechanisms (CDM), and the appropriate mitigation strategies.
THERMOPLASTIC LINERS According to Kermani, Martin, and Esaklul,14 there are three cor-
Thermoplastic liners such as high-density polyethylene and poly- rosion domains for mixed CO2/H2S systems, which can be repre-
amides (PA11 and PA12) are used to internally line carbon steel sented by the ratios of their partial pressures in the system:
pipes.5–10 The final product (a lined steel pipe) is made by the
insertion of a solid thermoplastic pipe into a carbon steel host CO2/H2S < 20 Sour corrosion dominates with iron sulfide as the
pipe. The thermoplastic liner provides protection to the under- main corrosion product
neath carbon steel pipe by acting as a barrier between the corro- 20 < CO2/H2S < 500 Mixed regime with both iron sulfide and
sive production fluids and the steel surface. Lined products are iron carbonate corrosion products
almost always significantly cheaper than CRA clad pipes and CO2/H2S > 500 Sweet corrosion dominates with iron carbonate
therefore provide a cost-effective alternative to clad pipes. Ther- as the main corrosion product
moplastic liners have been used successfully for the past several
decades in a range of onshore and offshore pipeline applications. These ratios are used by corrosion engineers as a general
For example, a 2013 report issued by Alberta Energy Regulator,11 rule of thumb to predict the corrosion mechanism expected to
indicated that in Alberta, there are approximately 7,900 km of occur. The ratios are based on the original work by Dunlop, Has-
lined steel pipelines. More than 90% of this inventory is in water sell, and Rhodes,15 published in 1983. More recently, Smith16,17
and multiphase services and the remainder is in gas service. investigated the origins of these ratios and reported that these
Some of the drawbacks of using thermoplastic liners are ratios were developed for low-ionic-strength solutions at a tem-
their temperature limitations and permeation by water, H2S, and perature of 25 C and are extremely sensitive to the quality of the
CO2 molecules leading to corrosion of the host carbon steel pipe input thermodynamic data. These key assumptions cover a nar-
and pressure buildup at the liner–steel interface (annulus). If the row range of oilfield environments. Smith recalculated these
lined pipe is not operated as per standard operating procedures, ratios using higher quality thermodynamic input data and a
this pressure buildup in the annulus can cause buckling of the wider temperature range. He proposed that a CO2/H2S ratio val-
liner. ues of below 1 and above 5,000 are more accurate as cutoff values
The following standards provide guidelines for the use of for sour and sweet corrosion, respectively. Smith continued to
thermoplastic liners in oilfield applications: state that laboratory testing or thermodynamic modeling is
required to determine the corrosion mechanism for ratio values
• NACE Recommended Practice SP-0304 (latest revision), between 1 and 5,000.
Design, Installation, and Operation of Thermoplastic Liners for Mahajanam18,19 and Gunaltun20 provide more information
Oilfield Pipelines on these types of corrosion.
Internal corrosion protection can be achieved through cor-
• Canadian Standards Association (CSA) Z-662, Oil and Gas rosion inhibitors and biocides, frequent internal cleaning of pipe-
Pipeline Systems, Clause 13 lines, coatings, linings, claddings, design process control, and
materials selection.21
External corrosion of pipelines can take on different forms
Corrosion Threats depending on whether the pipeline is buried or above ground.
Steel pipes in oil and gas environment tend to corrode by various Atmospheric corrosion of aboveground pipelines is visible and
internal and external corrosion mechanisms.12,13 Table 1 presents typically not a serious problem. Corrosion control requirements,
the most common corrosion threats to pipelines and provides a however, are still needed. The pipeline must still be protected from
brief synopsis of each threat.12,13 atmospheric corrosion through the application and continual
PIPELINE 327
maintenance of corrosion-resistant coatings. A continuing pro- Soil properties are strongly interdependent and show
gram of visual inspection and maintenance of the coatings must variability with time (rainy versus dry seasons) and location
be conducted to prevent the deterioration of the coating and (horizontal versus vertical), which further complicate examin-
the pipe.21 ing the effect of one factor (e.g., resistivity) on the corrosion of
In contrast, external corrosion of buried pipelines can pose a buried pipeline.22–24 Because of this complexity, soil corrosiv-
a serious integrity risk because of the invisibility of the corrosion ity is difficult to quantify for any given soil type (e.g., clay
attack and the corrosivity of the soil environment. Soils are a versus silt). No single property (e.g., soil resistivity, redox
complex environment with different chemical-physico-hydro- potential, or soil pH) can be used alone to determine the soil
bio properties that may affect soil corrosivity, the corrosion rate, corrosivity of a soil. For this reason, multivariate point scale
and the CDM of a buried pipeline.22–24 Soil properties such as methods, such as the American Water Works Association
soil resistivity, redox potential, concentrations of soluble salts, (AWWA) C-105 method25 or Dechema Soil Corrosivity Work-
pH, bacterial activity, and soil type (rocky, silt, clay, sandy, or a sheet,26 that incorporate many of the key soil parameters are
mixture of all or some), as well as particle size, moisture content, better methods to classify soil corrosivity. As a rule of thumb,
aeration, compaction, and organic content, influence soil corro- however, soil corrosivity increases with increasing moisture,
sivity.22–24 Laboratory and field standard test methods can test increasing acidity, soluble salts, dissolved oxygen contents in
these soil properties. Table 2 summarizes the main test methods the soil, decreasing redox potential, and presence of sulfate-
used to test soil properties affecting corrosion. reducing bacteria (SRB).
TABLE 1 Most Common Pipeline Corrosion Threats, Influencing Factors, and Management Strategies
Corrosion Threat Internal External Description Influencing Factors Management Strategies References
AC Corrosion A buried pipeline that runs parallel to – AC density – DC decoupling 27–30

high-voltage powerlines, develops an – CP potential level – Connection to natural
induced alternating current (AC) in – Coating type and drains (e.g., steel casings)
the pipe as a result of the alternating condition – Providing additional
magnetic field associated with the – Coating defect size grounding
powerlines. The induced AC escapes – Soil type and resistivity – Insertion of isolating
the pipe steel surface through holidays – Distance from high-power joints between pipeline
in the external coating. These sites then voltage towers and power sections
become the sites where AC corrosion loads – Monitoring of AC
initiates and progresses. AC can induce – Electrical grounding of potentials and AC
corrosion in coated buried pipelines the pipeline densities
despite adequate CP protection levels. – Number of pipelines
running parallel to the
high-voltage lines
Stray DC Corrosion Stray DC currents are electrical currents – Soil type and resistivity – Removal of the stray cur- 31–33
flowing in the soil from external sources, – Coating type and rent source or reduction
not directly associated with the CP condition in its output current
system. A buried pipeline represents a – Depth of buried pipeline – establishment of an elec-
low-resistance current path and therefore – Applied CP potential level trical connection between
is prone to the effects of stray currents. – Presence of undesirable the interfering and
Stray DC currents tend to enter and stray currents sources interfered-with structure
escape a buried pipeline through defects – Cathodic shielding
in the coating. It is where the current – Use of sacrificial anodes
escapes the pipeline surface into the soil – Application of coatings
that severe corrosion can be expected. to current pickup areas
Top of the Line Corrosion TLC occurs primarily in subsea pipelines – Temperature gradient – Providing corrosion allow- 34–37
(TLC) carrying unprocessed multiphase fluids between the carried ance to the carbon steel
(sweet or sour) with stratified and strati- production fluid and the pipe wall thickness during
fied-wavy flow regimes. TLC occurs pipeline surface the design phase
because of water condensation at the – Flow regime (TLC occurs – Insulation (thermal or
10 to 2 o’clock orientation. The condensed only in stratified and concrete) of the pipe to
water phase is highly corrosive because stratified-wavy flow reduce temperature
of the presence of dissolved acid gases regimes) gradient
(H2S and CO2) and organic acids. – Pipe material
(continued)
TABLE 1 (continued)
Sour TLC primarily exists as uniform – Applying corrosion inhibi-

corrosion attack with low corrosion rates. tors (batch or slug treat-
In contrast, sweet TLC leads to localized ment) or vapor phase
corrosion attacks with high penetration inhibitors
rates. – Using CRA solid pipe or
CRA clad material
– Using thermoplastics
lined pipes
Hydrogen Damage Hydrogen damage causes loss of ductility – Exposure time – Materials selection via 38–40
– Hydrogen embrittlement (HE only) and reduction in strength and fracture – Fluid composition laboratory testing
or loss in ductility (HE) toughness of the pipe steel to a degree – Operating conditions remains the principal
– Hydrogen-assisted that could result in catastrophic failures (temperature and approach for qualifying
cracking (HAC) of the pipe. Hydrogen damage is more pressure) and selecting line pipe
– Hydrogen-induced dominant in high-strength low-alloy steels – Stress level and state steels in applications
blistering (HIB) (X70, X80, X100, and X120) and CRAs and (applied or residual) where hydrogen damage
– Hydrogen-induced is most severe in the presence of H2S – Hardness, strength, and can be a potential
cracking (HIC) because of the inhibition of hydrogen microstructure of the damage mechanism.
– Sulfide stress recombination reaction. pipe steel – Use of internal coatings
cracking (SSC) – CP level (in case of HE) – Fitness-for-Service (FFS)
– Pipe manufacturing assessment using API 579
process
Microbiologically Microbiologically influenced corrosion – Nutrients (must be – Use of high-performance 41–44
Influenced (MIC) infers to the effect of specific present) corrosion inhibitors and
Corrosion (MIC) microorganisms on the corrosion pro- – Water (must be present) biocides coupled with
cesses that take place at the metal – Temperature (<90 C) frequent pipeline pigging
surface. MIC typically takes on the form – Salinity to remove biofilms and
of localized attack. Although sulfate- – Fluid velocity and flow solid deposits
reducing bacteria (SRB) is the most fre- regime – Fluid velocity control
quently reported bacteria type causing (avoid stagnant flow
MIC, other types of bacteria have also conditions during design
been reported to cause MIC. stage)
– Control fluid quality
Stress Corrosion Cracking Two types of SCC in buried pipelines have – Coating type and condi- Adherence to common 45–49
(SCC) been identified: high-pH SCC (occurs at tion (e.g., disbondment) industry guidelines stated
pH range of 9.6 to 12.3 and is primarily – Local environment in ASME Code for pressure
49
intergranular) and near-neutral pH SCC – CP potential piping
(occurs at pH 7.5 and is primary trans- – Operating stresses
granular). Both types are associated with – Temperature
colonies of microcracks near disbonded – Pipeline age
coatings. High-pH SCC is more predomi- – Distance from pump sta-
nant on coal tar or tape coated pipelines, tion or compressor
whereas near-neutral pH SCC is more likely
to occur on tape or asphalt coated pipe-
lines. SCC has not been report on Fusion
bonded epoxy (FBE)-coated pipelines and
this is believed to be due to the nonshield-
ing properties of FBE.
Black Powder Black powder refers to the blackish mate- – Gas not meeting Strict adherence to gas 50–55
rial that forms inside internally uncoated moisture specification moisture content specifica-
cross-country pipelines carrying “dry” is the primary factor tion coupled with in-pipeline
sales gas. Black powder is composed – Presence or absence of removal methods, such as
mainly of corrosion products mechanically internal coating filtration and pigging, are
or chemically mixed with impurities, such – Commissioning practice the primary strategies to
as sand, metal debris, elementals sulfur, mitigate black powder for-
and hydrocarbon liquids. The primary rea- mation and its impacts.
son for the corrosion in otherwise-“dry”
(continued)
PIPELINE 329
TABLE 1 (continued)
sales gas lines is water condensation on

the internal surfaces of these lines as a
result of deficiencies in gas dehydration
process (i.e., process upsets or under
design of the dehydration units). Black
powder adversely affects pipeline opera-
tions and sales gas customers alike.
Underdeposit Corrosion UDC is most prevalent in dead legs and – Type and concentration – Improved design of pipe- 56–58
(UDC) low-flow/intermittent-flow pipelines. UDC of solids in the fluid lines to avoid locations
typically takes on the form of localized – Pipe geometry and prone to solids and water
attack that occurs beneath or around elevation accumulation
deposits/solids that accumulate and – Fluid velocity – Improved quality of the
settle at the bottom of the pipeline. The – Pigging frequency fluid (solids management)
corrosion mechanism and severity of the – Optimization of flow
UDC is influenced by the type of deposit, velocity to keep solids
and therefore an effective mitigation entrained
strategy relies on understanding the – Use of high-performance
nature of the deposit that is present. corrosion inhibitors and
biocides coupled with fre-
quent pipeline (pigging).
Pitting Corrosion Internal pitting attack is more likely to – Operating conditions Chemical inhibitors coupled 35, 59
occur at the 10 to 2 o’clock (sweet TLC) (flow, temperature) and with periodic pigging, FBE
and 4 to 8 o’clock (BLC) orientations as fluid composition coating, monitoring of coat-
result of water condensation and pre- – Soil type, properties ing condition and CP levels
cipitation at these locations, respectively. and resistivity using aboveground inspec-
Locations along the external surface of – Coating type and tion techniques (to be
buried pipelines that experience coating condition discussed)
damage or disbondment are more prone – CP level at coating
to pitting corrosion. defect areas
Erosion-Corrosion (EC) EC is typically reported in multiphase – Type, concentration, and – Enhanced design by 60–62
pipelines where one of the phases is geometry of solid changing flow geometry
solids (e.g., sand) and high-fluid velocity. particles – Materials selection
It is believed that the erosion action – Fluid velocity – Corrosion inhibitors
removes the corrosion protective scale – Flow regime – Solids management
(e.g., FeCO3 and FeS scales on carbon – Geometry and diameter – Flow velocity control
steels pipes and oxide layers on CRAs) of pipe – Erosion and corrosion
exposing the bare metal for corrosion to Monitoring
occur. Typically, the damage caused by – Monitoring of eroding
EC is higher than the damage incurred by particles
either erosion or corrosion alone. The
damage caused by EC is typically
localized in locations where high changes
in flow are experienced, such as pipeline
bends, tees, and pressure control valves.
Flow-Induced Localized FILC is typically associated with high flow – Fluid velocity and – Improved pipeline design 63–65
Corrosion (FILC) and high turbulence fluids creating hydro- composition to avoid high-turbulence
dynamic conditions that cause the – Flow regime hydrodynamic conditions
destruction of the protective corrosion – Temperature and – High-shear-resistant
product films and hinder their reformation pressure corrosion inhibitors
leading to increased localized corrosion – Geometry and diameter
rates. Also, the high shear accelerates the of pipe
transfer of the corrosive elements (e.g.,
corrosive gases, salts) to the bare steel
pipe surfaces
(continued)
TABLE 1 (continued)
leading to increased corrosion at these

sites. FILC is different than EC in that
fluids causing FILC are solid free or do
not contain solid particles in sufficient
concentrations or sizes to cause erosion.
Preferential Weld Corrosion Weldments can experience accelerated Welding Factors – Improved welding proce- 2, 66–70
(PWC) preferential corrosion attacks compared – Welding procedure dures and filler metal
with the adjacent parent metal even – Choice of filler metal selection
though both areas are exposed to the – Weld quality – Corrosion inhibitors
same environment. This is mainly due to Environmental Factors – Quality of girth weld
the fact that weldments are not exactly of – Fluid composition and coating
the same metallurgy and have higher hydrodynamic condition
stresses than the rest of the pipe. PWC – Soil type and properties
can exist in various forms, such as pitting, – External coating type
crevice, galvanic, SCC, and different types and condition
of hydrogen damage. PWC can initiate – CP level
and progress from inside (fluid side) or – Stress (applied or
outside (soil side) of the pipe. residual)
TABLE 2 Test Methods for Testing Soil Properties Affecting Corrosion of Buried Metal Structures
Property Test Method F/L
Resistivity ASTM G57, Standard Test Method for Measurement of Soil Resistivity Using the Wenner Four-Electrode Method F
ASTM G187, Standard Test Method for Measurement of Soil Resistivity Using the Two-Electrode Soil Box Method L
Moisture Content ASTM D4959, Standard Test Method for Determination of Water Content of Soil by Direct Heating L
Chloride Content ASSHTO T291-94, Standard Method for Test for Determining Water-Soluble Chloride Ion Content in Soil L
Sulfate Content ASSHTO T290-95, Standard Method for Test for Determining Water-Soluble Sulfate Ion Content in Soil L
pH ASTM G51, Standard Test Method for Measuring pH of Soil for Use in Corrosion Testing F/L
MIC Accepted laboratory test methods (e.g., quantitative polymerase chain reaction [qPCR] technique) L
Redox Potential ASTM G200, Standard Test Method for Measurement of Oxidation-Reduction Potential (ORP) of Soil F/L
Note: F, Field test method; L, Laboratory test method.
The susceptibility of buried pipelines to different external

CDM, such as pitting, stress corrosion cracking (SCC), alternat- FIG. 1 A schematic representation of the key factors influencing
ing current (AC), and direct current (DC) corrosion, is further soil corrosivity and external corrosion of pipelines buried
complicated by other non-soil-related factors, such as external in soils.
coating type and condition, CP levels, distance from compressors
or pump stations, and distance from high-power voltage towers.
Figure 1 illustrates the complexity of factors affecting external
corrosion of buried pipelines in soils.
External corrosion protection of buried pipelines can be
achieved through materials selection, selective backfill, barrier
coatings, AC and stray DC control, and CP.21
In some cases, however, external corrosion of buried pipe-
lines can be eliminated by installing these pipes above grade,
rather than burying them. To further safeguard against soil cor-
rosion of the bottom side of the pipe (if the pipe were to be
placed immediately on the soil), flow lines typically are raised off
the ground on “sleepers,” which are typically concrete blocks.
This has become a common practice with oil and gas companies
operating in the Middle East.
PIPELINE 331
Corrosion Testing It is often difficult to evaluate the condition of a pipe by

simple examination in the ditch because of the presence of corro-
Pipeline operators and owners resort to different testing strate- sion products, deposits, and coatings. Cleaning and measuring
gies to ensure the integrity of their pipelines. These strategies can corrosion on a section of pipe in the ditch provides the most
be categorized into three main time domains: (1) Reactive, which accurate information, and the collected data are used in the sta-
utilizes nondestructive testing (NDT) technologies that reveal tistical analysis. Extending the data from a single pipe section to
corrosion defects that existed in the pipeline before the com- the entire pipe is not recommended beyond 1,000 ft (305 m) or
mencement of NDT (i.e., reveal past conditions); (2) present, where the environment is known to vary significantly from that
which uses testing and monitoring methods and techniques to in the excavated section.21
assess the “current” corrosion performance of the pipeline; and Uncoated pipeline should be thoroughly cleaned to remove
(3) proactive, which employs indirect inspection techniques, all corrosion product and foreign matter (as in the evaluation
modeling, and direct assessment (DA) methods to predict the of any corrosion, samples of the corrosion product should be
likelihood of corrosion occurring along the length of a buried retained for further analysis if the cause of the corrosion is
pipeline. unknown). Irregular surfaces and hard brownish deposits on
Table 3 lists the primary testing techniques and methods the pipe are indicators that corrosion has occurred. Black or
that most commonly are used in the field for testing and moni- whitish deposits are indicators of possible anaerobic SRB.
toring corrosion in a pipeline along its life span. The following Visual inspection of an uncoated pipe in the ditch before
sections provide a brief overview of each of these testing pipe preparation includes the following steps:21,76
strategies.
For the entire range of testing, inspection, and corrosion
1. Take macro shots of the excavated pipeline section and
monitoring methods available to oil and gas pipelines operators,
close-up photos of the defect areas.
see NACE International publications and paper presentations.71–75
2. Clean the pipe surface to remove loose soil and debris
and expose the defect areas.
Reactive Testing Strategies 3. Describe locations of corroded areas (near spiral or
seam weld, near girth weld, under heat shrink sleeve
VISUAL [HSS], at bends, clock position).
Field evaluations consist of documenting both visual observa- 4. Photograph and describe corrosion product properties
tions and measurements of corrosion on pipeline sections. Evalu- (color, smell, dry/wet).
ation of the environment also provides valuable information in 5. Collect corrosion product in well-sealed and clean con-
the analysis of pipe corrosion. Visual methods are difficult to use tainers for further laboratory analyses.
on underground pipes because the pipeline must be excavated to 6. Take soil samples from the location near the corroded
be examined; however, this is often the best way to evaluate the area for further lab analysis.
condition of a pipe. Carefully obtained corrosion measurements 7. On site, evaluate black or whitish deposits for SRB. A
can be analyzed using normal probability and extreme value quick qualitative determination can be made using a
statistics.21 There are no standards for performing this type of 10% hydrochloric acid solution in water. Place a drop of
test. It is suggested that the locations for visual evaluations be the solution on the deposit. An aroma of H2S (rotten
carefully selected from leak and inspection records, excavation eggs) indicates that SRB are present. Significant corro-
reports, close-interval potential (CIP), alternating current attenu- sion of the pipe might have occurred and further inves-
ation (ACA), direct current voltage gradient (DCVG), and alter- tigation is warranted. Wear safety glasses and gloves
nating current voltage gradient (ACVG) surveys results (to be when handling the acid and observe all necessary safety
discussed), and soil resistivity. The visual examination and corro- precautions. Commercial test kits are available that can
sion measurement sites can also be selected through the use of provide a quantitative determination of the type and
DA methodologies (to be discussed). quantity of bacteria present.
TABLE 3 Commonly Used Field Techniques and Methods for Testing and Monitoring of Pipeline Corrosion
Reactive Present Condition Proactive
– Visual – Corrosion Coupons – Close-Interval Potential (CIP) Survey

– Liquid Penetrant Testing – ER Probes – Alternating Current Attenuation (ACA) Survey
– Magnetic Particle Testing – LPR Probes – Direct Current Voltage Gradient (DCVG) Survey
– In-Line Inspection (ILI) – Alternating Current Voltage Gradient (ACVG) Survey
– Handheld Ultrasonic Testing – Direct Assessment (DA) Methods
– Guided Wave Testing – Modeling and Prediction
8. Photograph the steel surface beneath the corrosion

TABLE 4 Key Field Test Methods Used for External Coated
product (after removal of all corrosion using grit blast)
Buried Pipelines
and describe the appearance of exposed steel surface.
9. Describe the steel surface defect (size, spacing, shallow-
ness, elongation) and measure wall thickness loss (e.g., Test Method Purpose
pit depths). Bresle Test ISO 8502-9, Preparation of Used to determine
10. Document all observations on data sheets and with (surface salt) steel substrates before preexisting contamination.
photographs. application of paints and Surface salt on the steel
related products—Tests for draws in moisture through
Coated pipes are somewhat more difficult to evaluate, the assessment of surface the film through osmosis,
because corrosion occurs only at coating defects and sometimes cleanliness; Part 9: Field leading to blistering.
under disbonded coating. Visual inspection of coated buried method for the conducto-
pipelines includes the following steps:76 metric determination of
water-soluble salts
1. Take macro shots of the dugout pipeline section and Glass Slide Test ASTM A380 (7.3.1), Grease and oil on steel
damaged coating areas. Standard Practice for surface are dissolved with a
2. Describe damaged coating locations (near spiral or Cleaning, Descaling, and nonpolar solvent, and then
Passivation of Stainless evaporated away from a
seam weld, near girth weld, under HSS, at bend, clock
Steel Parts, Equipment, and glass slide. The oily film
position).
Systems retained is indicative of
3. Extract liquid from any intact coating blisters, measure
hydrocarbon contamination.
pH (using litmus paper) and send extracted liquid sample
Tape Test ISO 8502, Part 3, Tape applied to the steel
to laboratory for further analysis (CNS, pH). Use safety Assessment of dust on steel surface will collect any dust
gloves and glasses when extracting these liquids (pH val- surfaces prepared for and this can be rated to
ues as high as 12 of the liquids have been measured). painting (pressure-sensitive comment on plant
4. Document color of coating and describe coating proper- tape method) cleanliness. Dust affects film
ties (brittle, fragments, flexible, tough). adhesion.
5. Describe any pipe markings/stencils on the underside of Surface Profile ASTM D4417, Standard Test Coatings bond to steel
coating. Methods for Field mechanically, so a minimum
6. Describe any scratches, gouges, or impact marks on the Measurement of Surface profile is needed.
coating. Profile of Blast Cleaned
Steel
7. Describe any contamination or adherent corrosion visi-
ble on underside of the coating.
8. Measure dry film thickness of damaged coating and examined. The advantages of both techniques are their maturity
adjacent areas. and reliability, low cost, speed of the tests, and simplicity of
9. Remove the damaged coating by prying. application and interpretation. By their nature, these techniques
10. Describe appearance (rusted, pristine) of exposed steel are limited to examining the external surfaces of pipelines for
surface underneath the removed coating and take macro surface-breaking and shallow near-surface (in case of MP only)
and close up photos. flaws.
11. Measure blast profile and identify contamination, if any, When performing LP testing, a liquid penetrant(normally a
on steel surface (abrasive, grease, oil, dust). colored dye or a fluorescent material) is applied to a clean pipe
12. Determine salt levels using a Bresle patch. surface. The liquid is allowed time to soak the cleaned pipe sur-
face area and some of this liquid penetrates into any existing
Table 4 shows some of the key field test methods used for cracks that are open to the surface. The excess liquid is then
external coated buried pipelines. For more information on how removed (wiped off) from the pipe surface and a developer (nor-
to conduct in-ditch examination of uncoated and coated buried mally white in color) is applied to the area. The developer draws
pipelines, see El-Sherik, Dakwar, and Byrnes76 and Zinter.77 out the liquid penetrant from the surface cracks and onto the
steel surface to form visible indications. These indications can be
observed easily by the naked eye under visible light or, if neces-
LIQUID PENETRANT AND MAGNETIC PARTICLE sary, using ultraviolet light in case fluorescent penetrant was
TESTING applied. LP is effective for detection of open-to-surface hairline
Liquid penetrant (LP) and magnetic particle (MP) testing techni- cracks, such as SCC.
ques are visual methods employed by inspectors to aid in the When carrying out MP testing, the surface to be examined
visual inspection of the external surfaces of pipelines. Removal of is magnetized, inducing a magnetic field in the pipe. Surface or
external coating as well as cleaning of the pipe steel surface of shallow subsurface flaws distort the magnetic field, leading to
any corrosion product, rust, dirt, and soil are essential steps flux leakage at these distortion sites. To visually identify these
before carrying out these testing methods. In the case of a buried flux leakage sites, fine magnetic particles, either dry or in a wet
pipeline, this also implies excavation of the pipe section to be suspension, are applied to the magnetized surface. The fine
PIPELINE 333
particles (normally white or yellow in color) become attracted to must be fully immersed in a homogenous fluid. This makes pipe-
the flux leakage sites and take on the shape and size of the imper- lines carrying crude oils and refined products suitable for ILI-UT
fections. MP testing is effective in detecting open to surface or inspection, whereas gas and multiphase pipelines unsuitable.
shallow subsurface flaws such as SCC and hydrogen-induced A recent advancement in ILI testing is the use of an EMAT
cracking (HIC) cracks, respectively. The application of MP tech- tool to detect tight cracks (e.g., SCCs, step-wise cracks), coating
nique is limited to ferromagnetic materials, such as iron, nickel, damage and disbondment that exist on the inside and outside of
and cobalt, and some of their alloys. the pipe.83,84 ILI-EMAT uses guided wave acoustics sensors that
The following standards provide guidelines for conducting do not require liquid coupling; therefore, this technology is
LP and MP techniques: widely used to test gas pipelines.
ILI instruments also can be equipped with more than one
• ASTM E1444/E1444M (latest revision), Standard Practice for tool to increase their effectiveness of detection and sizing of
Magnetic Particle Testing for Aerospace different defects at a lower cost (one instrument run instead
• ASTM E1417 (latest revision), Standard Practice for Liquid of multiple runs each using a specific ILI tool). For example,
Penetrant Testing ILI-MFL-UT can detect and size various defects more effectively
and at a lower cost than running a separate ILI-MFL and follow-
ing it with an ILI-UT run.
IN-LINE INSPECTION
ILI testing of the same pipeline segment is typically repeated
In-line inspection (ILI) of pipelines is carried out using instru-
every several years (three- to five-year cycles is typical). This
mented or "smart pigs" that travel inside the pipeline from one
repeat test cycles provide corrosion growth rate information of
end of the pipe to the other. Only pipelines that are designed
the same reported defects.
with an ILI instrument launcher and receiver ports and have no
The following standards provide general guidelines for per-
obstructions, such as sharp bends or changes in diameter, can be
forming ILI of pipelines:
tested using ILI technique.78 These pipelines are normally desig-
nated as “piggable” pipelines. “Unpiggable" pipelines can be
• NACE Standard Practice SP0102 (latest revision), In-Line
inspected employing different methods and techniques other
Inspection of Pipelines
than ILI. For several techniques used for inspection of unpig-
gable pipelines, see Steinvoorte.79 • NACE Publication 35100, Inline Non-destructive Inspection of
ILI instruments are equipped with nondestructive testing Pipelines
tools (probes), such as magnetic flux leakage (MFL), ultrasonic,
eddy current, and electromagnetic acoustic transducer (EMAT). HANDHELD ULTRASONIC NONDESTRUCTIVE
These probes can detect and measure different types of defects TESTING
and anomalies, including pitting, cracks, coating disbondment, Ultrasonic testing (UT) is a nonintrusive NDT technique that
dents, and gouges, that exist on the inside and outside surfaces of uses high-frequency sound waves to detect and measure flaws
the pipe wall. and dimensional changes. UT operates on the principal of mea-
Ultrasonic devices work by measuring the time that it takes suring the time that it takes a high-frequency sound waves to
a high-frequency sound wave to travel across the pipe thickness travel across the pipe thickness and back to the transducer. The
and back to the transducer. The instrument is calibrated to mea- instrument is calibrated to measure this time as thickness of the
sure this time as thickness of the pipe wall. A change in wall pipe wall. A change in wall thickness or the presence of a crack
thickness or the presence of a crack perpendicular to the UT perpendicular to the UT wave will cause a change in the height
wave will cause a change in the height of reflected UT echo. of reflected UT echo. Conventional UT probes use single-
Magnetic or eddy current devices work by sensing deviations in element transducer or paired-element transducers, one for trans-
a magnetic flux field caused by corrosion pits or other defects mission of the sound waves and the other for receiving. Phased
that distort the flux field. For more information, consult Holm,80 arrays UT (PAUT) is the latest advancement in handheld UT
Schmidt,81 and NACE International.82 testing and uses transducers that contain a large number (16 to
The choice of ILI tool is largely dictated by the purpose of 256) of elements. The main advantage of PAUT is that it pro-
the inspection (e.g., what the pipeline operator/owner is looking vides improved flaw detection and flaw visualization.85
for). For example, ILI-MFL, an ILI instrument equipped with In principle, UT techniques can measure wall thickness
MFL probe, is primarily used to detect metal loss caused by gen- losses of 0.025 mm given that the transducer is accurately posi-
eral corrosion, pitting, erosion, or mechanically induced metal tioned in contact with the pipe surface.74 The detection accuracy
loss (e.g., gouges).78 ILI-MFL can be used in gas and crude lines is strongly affected by several factors, such as variations of sound
and the MFL sensor comes with different resolutions depending velocity in different metals, temperature variations in the metal
on the required level of detection. ILI-UT is employed primarily substrate, improper surface preparation, and the ability of the
for the detection and measurement of cracks along the major transducer to resolve the different acoustic reflections. Under
access of the pipeline such as HIC and blisters.78 This method realistic field conditions, UT can detect wall losses larger than
requires that the UT sensors be fully coupled to the pipe wall for 0.1 mm.74 Ultrasonic measurements can be used to verify and
the ultra–sound wave to travel through the wall thickness. This validate ILI results and to supplement mechanical pit depth
implies that the UT sensors and by extension the instrument measurements and also can be used in areas where the internal
condition of the pipe must be determined.21 Ultrasonic measure- difficult-to-inspect pipes (e.g., overhead pipes and pipelines
ments can be analyzed using the same statistical approach as inside casings).
mechanical measurements. The following standard provides general guidelines for the
There are several important considerations relative to ultra- application of GWT in pipeline inspection:
sonic measurements. One is the doubling effect of some digital
gages when the thickness limitation of the transducer is reached. • NACE Standard Practice SP0313 (latest revision), Guided
Another is the effect of coatings on the readings. Most pulse- Wave Technology for Piping Applications
echo instruments will provide inaccurate information when the
tester tries to read through an organic coating on the pipe. Coat-
ings must be removed unless the equipment used compensates
Present Condition Testing Strategies
for the presence of the coating. The surface roughness of the CORROSION COUPONS
pipe, both internal and external, plays an important role in the Coupons are relatively small pieces of metal, with the same met-
accuracy of the data. The surface must be relatively smooth. allurgy as the pipeline being evaluated, that are inserted into the
Roughness can make it either difficult or impossible to obtain environment to which the pipeline is exposed. Coupons can be
accurate thickness data. It is sometimes necessary to grind the buried in the soil next to the pipeline to measure soil corrosivity
surface just enough to allow the transducer a flat surface. An and CP protection level and to reveal the CDM.21,86,87 For existing
important consideration is the nature of the internal corrosion. pipelines, coupons should be connected to the pipe to expose
Internal pitting that consists of narrow or widely scattered pits them to galvanic and stray currents and to the surrounding soil
might be difficult to find with handheld UT devices, because the environment. Coupons can be inserted inside the pipeline and
probability of the transducer being immediately above a pit can into the carried fluid to measure fluid corrosivity and determine
be low.21 In that case, a scanning approach should be used to the effectiveness of the inhibition program. Coupons should be
cover the widest area possible. A visual inspection of the pipe is a inserted at locations where corrosion is expected to be the high-
good idea if at all possible to determine the type of corrosion est (e.g., 4 to 8 o’clock position) and not at the most convenient
present. location (e.g., 10 to 2 o’clock). Coupons can be evaluated, after
The following standards provide general guidelines for immersion in the environment, at predetermined periods of time
using UT inspection: (typically 90 or 180 days) using mass loss following ASTM G112,
Standard Guide for Conducting Corrosion Tests in Aluminum
• ASME (4) Boiler and Pressure Vessel Code, Section V, Non- Alloys.88 This method provides general corrosion rate informa-
destructive Examination tion in terms of thickness loss (in millimeters per year). All cou-
• ANST Recommended Practice No. SNT-TC-1A, Personnel pons should be large enough for pitting to develop and should be
Qualification and Certification in Non-destructive Testing evaluated visually after exposure for the presence of corrosion
• NACE 3T199, Techniques for Monitoring Corrosion and pits. If present, pit depths should be measured after cleaning of
Related Parameters in Field Applications coupons surface as per ASTM G112. Simple methods, such as
handheld pin micrometer, or more sophisticated automated
methods, such as surface profilometry (mechanical or chromatic
GUIDED WAVE TESTING light) or high-powered digital microscopy, can be used to mea-
Another technique that is increasingly gaining acceptance with sure pit depths. Another method for measuring pit depth is to
pipeline operators is guided wave testing (GWT). GWT employs use nondestructive X-ray radiography technique. The latter three
ultrasonic waves that propagate through the pipe wall for long methods quantify pitting corrosion both in terms of pit depths
distances along the pipe and, as such, GWT has the potential to and percentage of affected areas. Regardless of which method is
achieve many meters of inspection using one probe location. used to evaluate pitting, the pitting corrosion rate should be cal-
GWT sensors are made into a ring that can be installed around culated based on the deepest pit.
the pipe circumference. This ring configuration provides 360 More information on this topic can be found in the follow-
inspection coverage of the inspected pipe length. GWT provides ing standards:
only qualitative information and therefore is used as a rapid
screening tool for corrosion detection. Once defect areas are • ASTM G46, Standard Guide for Examination and Evaluation
identified by GWT, other corrosion mapping technologies, such of Pitting Corrosion
as handheld UT, are used to examine these specific areas and col-
• ASTM G4, Standard Guide for Conducting Corrosion Tests in
lect more in-depth information, such as the size, depth, and type
Field Applications
of corrosion defects.
GWT is not suitable for the detection of pits, cracks, and • NACE Technical Committee Report 3T199, Techniques
pinholes but is most effective in detecting general internal or for Monitoring Corrosion and Related Parameters in Field
external metal loss (normally above 5% wall loss). GWT cannot Applications
distinguish whether the wall loss is on the internal or external • NACE Standard Recommended Practice SP0775 (latest revi-
surface of the pipe. GWT is ideal to inspect inaccessible pipes sion), Preparation, Installation, Analysis, and Interpretation of
(under road crossings where excavation is not possible) or Corrosion Coupons in Oilfield Operations
PIPELINE 335
ELECTRICAL RESISTANCE PROBES pipelines operators and owners to react quickly to acquired
Similar to coupons, electrical resistance (ER) probes can be information (e.g., adjusting inhibitor dosage). To work properly,
installed inside the pipeline and into the transported fluid to deter- LPR probes require high-conductivity solutions such as disposal
mine the internal corrosion rate and evaluate the effectiveness of water pipelines but they have poor performance in low conduc-
the inhibition program. They can also be installed in the soil next tivity fluids such as crude oil, hydrocarbons etc.
to the pipe to measure soil corrosivity and determine potential More information on LPR technique can be found in the
CDM. For soil side applications, ER probes are also referred to as following NACE and ASTM publications:
soil corrosion probes (SCP).87 SCP also can be used to evaluate the
effectiveness of the CP particularly in high resistivity soils. • NACE Technical Committee Report 3T199, Techniques for
All ER probes consist of sensing wires of the same metal- Monitoring Corrosion and Related Parameters in Field
lurgy as the pipe of interest. The change (increase) in the ER of Applications
these sensing wires is due to the reduction in the cross-sectional • NACE Publication 31014, Field Monitoring of Corrosion Rates
area as a result of corrosion. This is the basis by which the corro- in Oil and Gas Production Environments Using Electrochemi-
sion rate is calculated,86,89 per the following formula: cal Techniques
R ¼ rmetal L=A; (1) • ASTM G96, Standard Guide for Online Monitoring of Corrosion
in Plan Equipment (Electrical and Electrochemical Methods)
where:
R ¼ measured resistance, ohm, Proactive Testing Strategies
rmetal ¼ resistivity of the metal, ohm-m,
L ¼ length of the sensing wire, m, and POTENTIAL MEASUREMENTS
A ¼ cross-sectional area of the sensing wires, m2. Corrosion testing often involves determining the relative level of
It is assumed that the reduction in the cross-sectional area electrical activity of various structures, such as pipelines in the
of the sensing wire is uniform and therefore ER probes can pro- environment in which they are installed. These environments
vide only general corrosion rates. ER probes cannot be used to may be soil or water. The environment in which the structure is
measure pitting corrosion rates.86,89 Another important applica- installed is the electrolyte that can and will support corrosion
tion of ER probes is in the monitor of corrosion under insula- activity. Pipeline-to-electrolyte potential measurements may be
tion. This is achieved by direct detection of the early corrosion used at various stages in the corrosion evaluation to determine
taking place under the insulation.90 the existence of corrosion activity. This is accomplished by mea-
ER probes do not measure the instantaneous corrosion rate suring the “native” or “natural” potential of the pipeline. This
as it takes place but until a certain detectable amount of thinning involves using the circuit shown in figure 2.
of the sensing wire occurs over a period of time (this is the reason The measurements taken will indicate the electrical charac-
ER probes are considered near-real-time probes). The response teristics exhibited by the pipeline in its natural state. For exam-
time of ER probes is a function of the corrosion rate and the start- ple, for a pipeline installed in soil, the potential with respect to
ing thickness of the sensing wire and can be in the range of hours the soil by means of a standard reference electrode, taken at reg-
or days. For example, in one ER probe configuration, response ular intervals along the pipeline, will indicate the corrosion pat-
times of 7 h and 30 h for a corrosion rates of 10 mpy and 5 mpy, terns affecting the pipeline (described in the next section).
respectively, were reported.91 Corrosion rate measurement may be Once the potential pattern has been measured for a struc-
taken periodically using a portable data logger or on a continuous ture, potential measurements can be used to evaluate the effects
basis using a permanently installed unit. of the application of CP current. While a measured quantity of
ER probes can be used in low- or high-conductivity fluids current is applied to a structure, potential measurements are
but should be used with caution in sour fluids because of the taken at locations at which the native potential measurements
potential of forming conductive corrosion deposits (FeS) cover-
ing the sensing elements leading to short circuiting.86 Short cir- FIG. 2 Pipe-to-soil potential measurement.
cuiting can be reduced through the selection of the appropriate
wire design configuration (ring, cylinders, flat shaped, flush).
For more information on this topic, see NACE International
publications and paper presentations.71–74
LINEAR POLARIZATION RESISTANCE PROBES

Linear polarization resistance (LPR) probes also intrusive devices
that can be inserted into the pipeline and into the carried fluid to
measure fluid corrosivity (and determine the internal corrosion
rate) and provide information about the effectiveness of the inhi-
bition treatment.86–89 Their chief merit is that they provide
instantaneous corrosion rates (real-time devices) permitting
had been taken. The shift in potential as well as polarization

effects due to the application of the current can be measured. FIG. 3 A representation of on-potential and instant off-potential
These data can be used to determine the quantity of current profiles obtained by CIPS on buried pipeline. Locations of
required to achieve CP of the structure. inadequate CP are marked as (ICP) on the pipe.
Potential measurements also are used to gauge the effective-
ness of a CP system, after it has been installed and is operating,
in mitigating the corrosion activity detected by the native poten-
tial profile. The pipe-to-soil potential measurement has been
established by corrosion engineers as a standard for determining
the degree of CP on buried pipelines. Various criteria have been
promulgated; the three currently in use for steel structures are as
follows:21 (1) the achievement of a pipe-to-soil potential of 850
mV referenced to a copper-copper sulfate (CSE) electrode with
CP current applied considering IR drop, (2) the achievement of
a polarized potential of 850 mV (instant-off) versus CSE, and
(3) the achievement of a 100 mV shift in potential because of
cathodic polarization. Although these are the generally accepted
CP criteria, different criteria also can be used to address unique
environments (soil types). For example, one company in the
Middle East uses 1,000 mV ON versus CSE for pipelines buried
in Sabkha areas (Sabkha is a low-resistivity soil found near the
pipeline in figure 3. These locations of inadequate CP protection
sea shores; Sabkha is quite corrosive because it is high in mois-
can further be examined during the direct examination step in
ture and salt content) and 1,100 mV ON versus CSE for non-
the external corrosion direct assessment (ECDA) method (dis-
Sabkha areas (dry soils).
cussed in the following sections).
These potential measurements can be taken at set locations
Sophisticated computerized data loggers to record the large
(test station surveys) along a pipeline, or continuously, as in the
numbers of potential readings that can be collected during the
case of a close interval potential survey (CIPS). Test station sur-
course of CIPS have been developed and are commercially avail-
veys do not guarantee that the pipeline segments between these
able. These data loggers along with personal computers can pro-
test stations are adequately protected against corrosion. For this
vide a continuous profile of the potential along miles of pipeline
reason, CIPSs are more reliable in determining the effectiveness
traversing all types of terrain. Some instrumentation can be
of CP in providing corrosion protection along the entire length
linked to global positioning systems synchronization software.
of a buried pipeline.
The following standards provide general guidelines for per-
forming a CIPS for pipelines:
CLOSE-INTERVAL POTENTIAL SURVEY
The CIPS technique measures pipe-to-soil potential to assess the • NACE Recommended Standard Practice SP0207, Performing
performance of the CP system. CIPS provide both the on- Close Interval Potential Surveys and DC Surface Potential Gra-
potential and the instant off-potential profiles along the length of dient Surveys on Buried or Submerged metallic Pipelines
the pipeline at the ground surface.21,92–97 The CIPS is achieved by • NACE Standard Practice SP0502, External Corrosion Direct
connecting an insulated electrical wire (typically few kilometers Assessment Methodology (ECDA)
long) to the buried pipeline with the other end of the wire con-
nected to the positive port of a high impedance (107 ohms or
higher) data logger-voltammeter or multimeter.92 The positive ALTERNATING CURRENT ATTENUATION SURVEY
port of the voltmeter is connected to a reference electrode (typi- ACA technique provides the average coating quality over a pipe-
cally a CSE electrode). The center line of the pipeline must be line segment typically of 50 to 300 ft in length.75,92 The ACA sur-
located accurately before performing the survey. The surveyor vey does not locate coating flaws but instead provides a macro
walks over the centerline of the pipeline, unwinds the insulated assessment of the coating condition over a given length of buried
electrical wire, and places the reference electrode directly above pipeline.75,92 It is normally performed to prioritize pipeline seg-
the pipeline at intervals of 1 to 2 m. Both the on- and instant off- ments for subsequent closer indirect inspection using the ACVG
potentials between the buried pipeline and the reference elec- technique (discussed in the next section).75
trode are measured. Locations where both potentials are more The ACA survey is conducted by placing an AC current-
positive than the established CP protection criteria (see previous transmitter at one end and a receiver (detector) at the other
section) are sites of inadequate CP protection and therefore are end of the pipe segment to be surveyed. Both transmitter and
the most probable sites for external corrosion to occur.21,92–97 receiver are placed above the ground surface over the centerline
Figure 3 is a schematic representation of on-potential and instant of the pipe section to be surveyed. The transmitter has to be in
off-potential profiles obtained by a CIPS on a buried pipeline. physical contact with the ground surface and in conductive
Sites of inadequate CP protection are marked as ICP on the contact with the pipe, but the detector can be located some
PIPELINE 337
distance off the ground.92 In carrying out this survey, an AC soil from the anode bed to the pipeline polarizing the pipe with
current signal of low frequency is applied by the transmitter to respect to the surrounding soil.92–96 As such a potential gradient
the buried coated metallic pipe. The AC current flows away exists between the pipe and the surrounding soil where the
from the injection point (transmitter) down the length of the potential is highest (most negative) at the pipe surface and drop-
pipe inducing an electromagnetic (EM) field around the pipe. ping off rapidly to zero value at a certain distance away from the
The EM field attenuates (i.e., becomes weaker) as a function of pipe. In the case of a perfect coating (no holidays), the potential
distance from its source (AC transmitter). The principal of the in the vicinity of the pipe at the ground surface over the pipe will
ACA technique is the measurement of the attenuation in the be close zero and no potential gradient exists. In the presence of
strength of EM field between the transmitter and receiver loca- a coating defect, however, the DC current flows primarily into
tions. Figure 4 is a schematic representation depicting the prin- the defect site polarizing the pipe with respect to the surrounding
cipals of ACA survey. soil and, as such, a voltage gradient is developed.92–96 This volt-
EM field attenuation is measured in milibells per unit length age gradient can be measured using two CSE reference electrodes
of pipe (mB/m or mB/ft) allowing comparison of coating quality positioned at the bottom of walking cane probes. The two cane
of different pipeline segments. The rate of attenuation is affected probes are connected to a standard voltmeter measuring voltage
by pipe diameter, wall thickness and depth, AC current fre- in mV.
quency, soil resistivity, and coating dielectric constant.92 For a DCVG survey can be performed in two different ways: per-
given set of these parameters, EM field attenuation is affected by pendicular mode and in-line (or parallel) mode.97 In both modes,
the coating quality. For a perfectly coated pipe, the magnitude of no direct electrical connection is made to the pipeline, and the
the EM field decreases gradually as it flows from the transmitter center line of the pipeline must accurately be located before per-
to the receiver. When a coating contains flaws, however, EM forming the survey. In the perpendicular mode, the two probes
attenuates more rapidly. Comparison of the rate of current atten- (while electrically connected to the voltmeter) are placed perpen-
uation of several pipe segments allows for the ranking of the dicular to the pipeline direction. One probe is positioned over
coating condition on these pipe sections. the centerline of the pipe and the other probe is placed typically
The following standard provides guidelines for performing 5 ft away from the first probe. With this probe spacing main-
ACA survey: tained, the surveyor walks down the length of the pipeline plac-
ing the probe pair at intervals (typically 5 ft) and measures the
• NACE Standard TM0109, Above-ground Survey Techniques potential difference between the two probes at the ground
for the Evaluation of Underground Pipeline Coating Condition surface.
In the in-line (or parallel) mode, a surveyor walks over the
pipe placing the two probes at different locations directly over
DIRECT CURRENT VOLTAGE GRADIENT SURVEY the centerline of the pipe measuring the potential gradient
DCVG surveys typically are performed on well-coated pipelines between the two probes.
with the goal of locating coating flaws and assess the relative In both DCVG survey modes, the voltage gradient increases
severity of these flaws once found. Locations of coating defects as the surveyor approaches the defect and decreases moving
are expected to be the most likely sites for external corrosion to away from the defect. The maximum voltage gradient measured
occur.75,92–97 between the two probes indicates the location of the center of a
DCVG surveys involve soil-to-soil potential difference (volt- coating defect.92 Factors such as soil resistivity, pipe depth and
age gradient) measurements at the ground surface over the pipe- diameter, coating type, clock position of the coating defect (e.g.,
line. In CP-protected buried pipelines, DC current flows in the 12 o’clock versus 6 o’clock), probe contact to the ground surface,
and density of coating defects affect the magnitude of the mea-
sured voltage gradient. For a given set of these factors, the mag-
FIG. 4 A schematic representation depicting the principals of nitude of the voltage gradient is directly related to the size of the
ACA survey. EM field lines attenuate as the current flows coating defect.92,95
away from the transmitter. Once a coating defect is located (as discussed previously),
the severity of the defect is determined through % IR drop calcu-
lation.96,97 Table 5 provides general guidelines for interpretation
of % IR values and recommended actions.
Taking the % IR measurement involves successive lateral
measurements of the soil-to-soil potential difference in the per-
pendicular direction moving away from the defect. Figure 5 is a
schematic representation of % IR measurements. The potential
measurements are made using a CSE electrode placed on the
ground surface at intervals of approximately 5 ft. The measure-
ments are stopped when the potential gradient is equal or less
than 1.0 mV. To calculate % IR, the potential gradient of the suc-
cessive measurements are added and then divided by the IR drop
poles is at its maximum. McKinney97 provides the detailed pro-

TABLE 5 % IR Values, Defect Severity, and Recommended cedure for carrying out ACVG survey.
Actions Factors such as soil resistivity, pipe depth and diameter,
coating type, clock position of the coating defect (e.g., 12 o’clock
% IR Defect Severity Recommended Action versus 6 o’clock), probe contact to the ground surface, and den-
1–15 Very minor No action; existing CP is assumed to provide
sity of coating defects affect the magnitude of the dBlV indica-
adequate protection tion.95 For a given set of these factors, the magnitude of the
16–35 Minor Monitor; schedule another DCVG in near future severity of the coating defect is related to the magnitude of the
36–60 Moderate Excavate and examine OR monitor using DCVG dBlV indication. In general, the larger the dBlV indication,
61–100 Severe Immediate action; excavate and repair coating the more sever the coating defect. Normally, a voltage gradient
above 30 dBlV indicates the presence of a coating defect.92
ACVG, in most instances, is a more sensitive survey tech-
nique than DCVG and will provide more information about the
FIG. 5 A representation illustrating lateral measurements of % IR. overall coating condition. For example, the ACVG technique can
identify extremely small areas of coating damage (smaller than
0.01 square inch).75
Many operators perform a CIPS simultaneously with
DCVG and ACVG or both to obtain the combined benefit of
these techniques in identifying high-corrosion-risk areas.93,95
The following NACE standards provide guidelines for con-
ducting ACVG and DCVG surveys:
• NACE Standard TM0109, Above-ground Survey Techniques

for the Evaluation of Underground Pipeline Coating Condition
• NACE Standard Practice SP0502, External Corrosion Direct
Assessment Methodology (ECDA)
• NACE Standard Practice SP0207, Performing Close Interval
Potential Surveys and DC Surface Potential Gradient Surveys
on Buried or Submerged metallic Pipelines
at the ground surface directly above the coating defect. Details
on how to calculate % IR can be found in McKinney.97
DIRECT ASSESSMENT METHODS
ALTERNATING CURRENT VOLTAGE GRADIENT DA methods are structured processes and procedures that iden-
SURVEY tify areas where corrosion (internal or external) is most likely or
ACVG is similar to DCVG in that it is an indirect inspection unlikely to occur along the length of a buried pipeline as well as
technique capable of pinpointing coating defects and evaluating detect existing corroded areas. In this way, DA methods are con-
their severity.77,92–97 The ACVG technique utilizes very low AC sidered proactive techniques in predicting the most probable
frequency (typically 3 Hz and 6 Hz or 4 Hz and 8 Hz) to induce locations for corrosion on underground pipelines. These meth-
an electric current in the pipeline.95,97 The AC current creates a odologies require the presence of qualified personnel who can
voltage gradient around coating defects. The produced voltage conduct and interpret the results of these methods.
gradient is measured by a paired reference electrode connected NACE has developed several DA standard practices for
to a monitoring device. pipelines:
The hardware required to carrying out ACVG has three
main components: (1) a transmitter capable of generating low- • NACE Standard Practice SP0110 (latest revision), Wet Gas
frequency AC current that is electrically connected to the pipe, Internal Corrosion Direct Assessment Methodology (WG-
(2) a specialized voltmeter that is tuned to the generated AC fre- ICDA)
quencies and capable of measuring low voltages in decibel lV • NACE Standard Practice SP0206 (latest revision), Internal
(dBlV) range, and (3) a paired reference electrode positioned at Corrosion Direct Assessment Methodology for Pipelines Carry-
the bottom of a structure (called A-frame with fixed distance ing Normally Dry Natural Gas (DG-ICDA)
metal poles) connected to the voltmeter.
• NACE Standard Practice SP0288 (latest revision), Internal
The ACVG survey is conducted in a similar fashion as the
Corrosion Direct Assessment Methodology for Liquid Petro-
DCVG survey. The voltammeter connected to the A-frame mea-
leum Pipelines (LP-ICDA)
sures the voltage difference, in decibel lV (dBlV) between the
two poles.92 When one of the poles is placed directly above the • NACE Standard Practice SP0116 (latest revision), Multiphase
center of a coating defect (the other pole being remote from Flow Internal Corrosion Direct Assessment Methodology for
the defect), the measured voltage difference between the two Pipelines (MP-ICDA)
PIPELINE 339
• NACE Standard Practice SP0502 (latest revision), External are valid only for situations with identical conditions as those in
Corrosion Direct Assessment Methodology (ECDA) which the relationships were originally developed.
Papavinasam102,103 presents excellent reviews of internal cor-
• NACE Standard Practice SP0204 (latest revision), Stress Cor-
rosion models and external corrosion models, respectively.
rosion Cracking Direct Assessment Methodology (SCCDA)
The reader is also encouraged to consult with the following
NACE publications for the selection and use of the various flow
All of these DA methods have four common steps: (1) pre-
and internal corrosion models.
assessment, (2) indirect inspection, (3) direct examination, and
(4) post-assessment. • NACE Technical Committee Report 21413-SG, Prediction of
The objectives of pre-assessment (step 1) is data collection, Internal Corrosion in Oilfield Systems from System Conditions
selection of DA regions, and selection of appropriate indirect • NACE publication 21410-SG, Selection of Pipeline Flow and
examination tools. In case of ICDA projects, the appropriate Internal Corrosion Models
pipeline flow and internal corrosion models are selected. NACE
Publication 21410-SG, Selection of Pipeline Flow and Internal STATISTICAL EVALUATION
Corrosion Models,98 is required for selection of models for all Corrosion, particularly pitting corrosion, tends to be distributed
ICDA methodologies. For ECDA, the appropriate aboveground in a nonuniform manner. The depth of pits on a surface can be
inspection techniques, such as CIP, ACA, DCVG, or ACVG sur- described by a normal probability curve. This can be used to
veys, or combinations thereof, are identified for indirect inspec- advantage when evaluating a pipeline, because it is necessary
tion (step 2). In this step, at least two of these techniques are to measure only a few representative areas and to use statistics to
applied to gather critical information required to select excava- determine the condition of the entire pipe. There are no standard
tion locations and perform the direct examination (step 3). Gath- test methods, but ASTM G16, Standard Guide for Applying
ered data from the direct examination step is then used to Statistics to Analysis of Corrosion Data,104 describes statistical
predict remaining life and reassessment intervals (step 4). approaches to laboratory data, and applicable references can be
More information on this topic can be found in Beavers, found in Gumbel,105 Hawn,106 and Bushman and Mehalick.107
Bensman, and Kowalski99 as well as in NACE publications and The reader is also encouraged to consult the following
paper presentations.98,100–101 standards:
MODELING AND PREDICTION • ISO 11463 (latest revision), Corrosion of Metals and alloys -
The primary function of corrosion models is to predict whether Evaluation of Pitting Corrosion
a given material is susceptible to a particular CDM in a given • ASTM G46 (latest revision), Standard Guide for Examination
environment and to estimate the corrosion rate at which the and Evaluation of Pitting Corrosion
material would corrode in that environment. Modeling helps
the corrosion professionals establish corrosion allowance (i.e., The corrosion data collected in ASTM G16 provide informa-
material wall thickness) and decide if additional corrosion tion about the samples tested, but not necessarily about the pipe
control strategies (e.g., chemical treatment, coatings, CP) are as a whole. Thus, it is important not only to select sampling loca-
required. tions that represent the condition of the pipe run as a whole but
Existing corrosion models can be classified as mechanistic also to include the worst-case conditions. Whatever areas are
(or theoretical), semi-empirical, and empirical (or statistical) selected, it is possible that more severe corrosion exists. Statistical
models. Mechanistic models are first principal models that are analysis is a method that uses known data to predict the range of
developed from the equations that govern the corrosion phe- corrosion.
nomenon of interest. The appealing aspect of these models is For a statistical analysis to provide useful results, the data
that a wide range of parameters and conditions can be used as must be taken in a systematic fashion. The corrosion measure-
inputs into these types of models; however, they often are ments for both the field and laboratory evaluation, as described
extremely difficult to validate especially when modeling complex earlier, provide corrosion data at known and consistent intervals
CDM, such as localized corrosion. along the pipe sample. This provides usable data for the statisti-
Semi-empirical models are developed from a combination cal analysis.
of empirical relationships and mechanistic equations that govern The statistical analysis procedure most useful in evaluating
the corrosion phenomenon of interest. These types of models are corrosion on pipes is the extreme value statistical method. The
applicable in situations with similar conditions to that of the referenced publications provide details on extreme value statis-
experiments used to develop them, but they are more limited tics and their application to pipeline corrosion. The extreme
than purely mechanistic models. There are also some issues with value statistical approach analyzes the maximum pit depth (or
the validation of semi-empirical models but not as many as minimum wall thickness) per unit length to estimate the range of
mechanistic models. corrosion data for the pipe. The results, of course, assume that
Empirical or statistical models are based on statistical rela- the pipe run is in the same condition as the sample tested. The
tionships, which are developed purely from actual data (field or more samples tested, the greater the accuracy of the result.
laboratory or both). The strength of these models is that they can Normal probability and extreme value statistics have already
easily and reliably be validated, but their weakness is that they been discussed as means of evaluating corrosion and soil
resistivity. Statistical methods have been applied to determine (Cambridge, MA: Elsevier, 2017), 613–626, https://doi.org/
when steel tanks will fail.107 Individual soil characteristics, such 10.1016/b978-0-08-101105-8.00026-7
as resistivity, pH, and soluble salt ion content, are unsatisfactory 5. S. J. Hall, D. J. Hill, and P. Dang, “Plastic Liners for Hydrocarbon
methods of predicting the corrosion behavior of a structure in a Transport: A Qualified and Cost Efficient Alternative to CRAs”
particular soil. The statistical method is based on a regression (paper presentation, Offshore Technology Conference 2009,
analysis of all of the soil characteristics that affect corrosion as paper no. 19937, Houston, TX, 2009).
compared with actual corrosion of structures found in those 6. K. A. Esaklul and J. Mason, “Nonmetallic Applications in Oil and
soils. This method yields a mean time to corrosion failure as Gas Production (Pipes, Liners, Rehabilitations)” in Trends in Oil
opposed to an actual corrosion rate. Its validity for structures and Gas Corrosion Research and Technologies: Production and
other than steel tanks has not been demonstrated. Transmission, ed. A. M. El-Sherik (Cambridge, MA: Elsevier, 2017),
627–657, https://doi.org/10.1016/b978-0-08-101105-8.00027-9
7. J. Mason, “Thermoplastic Liners for Oilfield Pipelines,” in Oil and

Conclusion Gas Pipelines Integrity and Safety Handbook, ed. Winston Revie
(New York: Wiley, 2015), 447–455, https://doi.org/10.1002/
Buried oil and gas pipelines can experience a variety of corrosion
9781119019213.ch31
damages that may impact the integrity and reliability of these
lines. Corrosion monitoring, inspection and testing of pipelines 8. J. Mason, A. Ponda, M. Stanley, and D. Demicoli, “Case Study:
is conducted for several reasons to ensure the integrity of the Engineered Polyamide 12 (PA12) Pipeline Liner for Management
of Sour Gas Corrosion at Elevated Temperatures” (paper
pipeline network. One reason is to evaluate the pipeline condi-
presentation, Corrosion/2017, paper no. 9592, NACE
tion to determine whether or not it is safe to operate. If repairs
International, New Orleans, LA, March 26–30, 2017).
are needed, inspection and testing are performed to determine if
repair is feasible or if replacement is needed. Monitoring and 9. J. Mason, “Pipe Liners for Corrosive High Temperature Oil and
inspection are performed to track the pipe condition so that Gas Production Application” (paper presentation, Corrosion/
1997, paper no. 80, NACE International, New Orleans, LA, March
repairs or replacements can be budgeted. Another reason for
1997).
monitoring and inspection of pipes is to evaluate the effective-
ness of corrosion control measures, such as inhibitors for inter- 10. B. Bulleri, A. Ticci, M. Genoni, and J. Sutherland, “Engineering
nal pipe surfaces or cathodic protection (CP) and coatings for Thermoplastic-Liners” (paper presentation, Corrosion/2004,
paper no. 04705, NACE International, New Orleans, LA, March
external pipe surfaces.
28–April 1, 2004).
To ensure the integrity of their pipelines, pipeline operators,
inspectors and corrosion engineers need to employ a variety of 11. Alberta Energy Regulator, “Report 2013-B: Pipeline Performance
testing strategies coupled with industry standards and best prac- in Alberta, 1990–2012” (2013), http://web.archive.org/web/
tices in developing and implementing their pipeline integrity 20210430140207/https://static.aer.ca/prd/documents/reports/
R2013-B.pdf
management programs.
12. S. Papavinasam, “Inspection, Monitoring, Model: Past, Present
ACKNOWLEDGMENT and Future” (paper presentation, Corrosion/2018, paper no.
The author would like to thank Saudi Aramco management for 10607, NACE International, Phoenix, AZ, April 16–19, 2018).
their support. Also, I would like to thank the reviewers for their 13. B. Kermani and T. Chevrot, “Pipeline Corrosion Management;
comments and suggestions that improved the chapter. A Compendium” (paper presentation, Corrosion/2014, paper
no. 3723, NACE International, San Antonio, TX, March 9–13,
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345
Chapter 22 | Highways, Tunnels, and Bridges
Stephen R. Sharp1 and Jason T. Provines1
Introduction Environmental Exposure

To counter the effects and high maintenance costs of corrosion Because of the nature of transportation structures, many differ-
on highways, tunnels, and bridges, improvements in materials ent exposure conditions can be encountered. This section focuses
and testing have been made and many have been implemented. on five commonly encountered conditions that can have an
Furthermore, member organizations like American Association effect on corrosion performance. These conditions include atmo-
of State Highway and Transportation Officials (AASHTO), spheric, concrete (alkaline encasement), saltwater, soil, and
ASTM, American Welding Society (AWS), Concrete Reinforcing water. It is also important to highlight that some transportation
Steel Institute (CRSI), NACE International, National Steel Bridge structures are subjected to a combination, if not all, of these
Alliance (NSBA), American Institute of Steel Construction environments.
(AISC), The Society for Protective Coatings (SSPC), and many
others have continued to improve specifications, standards, and ATMOSPHERIC EXPOSURE
guidelines that support the effort to mitigating corrosion issues Because highways, bridges, and tunnels are designed for transport-
in these vital resources. In addition, some organizations like the ing people and goods along the highway network, most structures
Transportation Research Board (TRB) sponsor meetings and are subjected to atmospheric exposure. The atmospheric exposure,
research activities, such as the National Cooperative Highway however, can be quite different for different types of transporta-
Research Program (NCHRP), so practitioners can pursue issues, tion structures. For example, a complex tunnel might use an
discuss challenges, and learn about new transportation-related exhaust system to remove what otherwise would be trapped
advancements in corrosion. exhaust gases, whereas this is not necessary for a bridge. More-
One of the challenges in dealing with corrosion of the high- over, the bridge in a bridge-to-tunnel system might also be
way network is that the materials used are exposed to a variety of exposed to small microclimates as it starts on dry land, and then
environments. Some of these environments aide in reducing the moves over saltwater, before ending on a natural or humanmade
corrosion rate, like placing steel in alkaline concrete, whereas island, where it connects to the tunnel structure. This difference in
others accelerate corrosion, such as steel exposed to salt water. the atmospheric environment between transportation structures,
To reduce the chance of unexpected corrosion related mainte- or even between different locations on the same structure, can
nance, the design of a transportation structure should incorpo- vary for several factors, including the following:
rate durable materials to ensure that it reaches its expected
design life. Although some of these materials have inherent cor- • time of wetness, with variability because of highway structures
rosion resistance, like carbon fiber–reinforced polymer (CFRP) having different distances to the water;
strands, for example, other structural materials rely on a second • sulfur dioxide, with variability because of the structure’s ori-
material to mitigate corrosion, for instance, a coating on a mild entation in the vicinity of a source burning fossil fuels; and
steel beam. Therefore, it is important to understand how these
materials will perform in their environments when specified dur- • chloride exposure, with variability because of the seasonal use
ing the design stage of a project. of deicing salts.
All of these factors can strongly alter the corrosiveness of a

highway structures environment.
1
Virginia Transportation Research Council, 530 Edgemont Rd., Charlottesville, VA
22903, USA S. R. S. http://orcid.org/0000-0003-1850-6280
CONCRETE (ALKALINE) EXPOSURE
The author acknowledges the previous author of this chapter, James B. Bushman, Reinforced concrete (RC), a system consisting of concrete with
Bushman and Associates, Inc., Medina, OH. embedded steel reinforcement (rebar), is commonly used for
DOI: 10.1520/MNL202NDSUP20190020
transportation structures. In this case, the concrete mitigates important to minimize the possibility of corrosion development
steel corrosion by creating a protective barrier and beneficial in the structural elements as well.
alkaline environment around the embedded rebar. The protec-
tive barrier is created by using concrete mix designs that restrict WATER EXPOSURE
the movement of ions, especially salts that contain chlorides, Many structures are commonly exposed to sources of water, like
through the pore system within the concrete. The barrier is fur- rivers, rain, groundwater, and even flooding. Furthermore, the
ther enhanced by increasing the concrete thickness over the amount of time the water remains in contact with a surface can
rebar, which is called cover. In Portland cement concrete mix- be influential. When carbon steel is directly exposed to water, it
tures, the alkaline environment is a natural outcome of the reac- will corrode, although at a slower rate than when in contact with
tion between the cement and water, which results in an elevated saltwater. Moreover, water can provide a mechanism for trans-
pH value adjacent to the rebar in the hardened concrete. porting abrasive materials, for example, through a culvert, which
When uncracked, RC can provide a durable structural sys- can damage a protective coating and expose the underlying car-
tem that is highly resistant to rebar corrosion; however, it is bon steel, initiating corrosion.
important to note that if the concrete mix is not designed prop-
erly, cracks in the concrete can form, creating a pathway for
moisture and chlorides to reach the rebar and cause corrosion.1 Corrosion Design and Mitigation
Concrete cracking can depend on design restraint, weather con-
Techniques
ditions during placement, concrete mix proportions, cement
types, and even cement paste and aggregate content.2–4 Factors The materials commonly used to construct the highway network
like these can significantly influence the tendency of the concrete include both metallic and nonmetallic materials. Asphalt, aggre-
to crack, with some of these factors being difficult to control out- gate, concrete, steel, cast iron, aluminum, wood, and various
doors or when larger RC elements are being cast. Therefore, it is polymeric materials are commonly found throughout the net-
important to consider the effects of concrete cracking when eval- work. In addition, composite materials like CFRP and glass
uating materials for corrosion resistance. Furthermore, when the fiber–reinforced polymers (GFRP) are also finding use. Although
cracks occur in bridge decks or tunnel liners, other metal compo- all of these materials are used in highways, tunnels, and bridges,
nents, whether embedded in concrete or not, then can be sub- the two primary materials that are most prevalent and suscepti-
jected to direct contact with water or saltwater that can lead to ble to corrosion damage are steel and concrete. The following
corrosion. sections present some general corrosion design and mitigation
techniques for both steel and RC.
SALT EXPOSURE STEEL

A transportation structure’s exposure to salt typically comes There are some typical methods for providing corrosion pro-
from either saltwater or de-icing salts. The location of a structure tection to steel plate within the highway system. This section
often dictates if routine exposure to saltwater will occur. This is provides background information on each of these corrosion
most obvious when a structure is located close to a body that protection systems.
contains brackish water or saltwater. In certain regions where
snow and ice are a concern, however, salt or brine are used to Coatings
prevent ice forming on the roadway and improve traction for Zinc-rich primer paint systems are the most common form of
traveling vehicles. The application of de-icing salts can be corrosion protection for steel plate used on bridges and generally
observed as spreading dry salt, pretreating the road surface consist of three coats of paint: primer, intermediate coat, and
before an ice event using a brine solution, or spreading a salt and topcoat. Before being coated, the steel substrate must be blast-
sand mixture on the road. All of these de-icing treatments gener- cleaned to a surface level of “near white” (SSPC-SP 10) to allow
ally contain sodium chloride, but other chloride containing salts for good bonding with the primer, which is essential for good
can be used too. paint performance.5 The primers used for bridges are made using
either inorganic or organic zinc.6 Once the primer has been
applied, it is typically followed by an intermediate coat, which
SOIL EXPOSURE provides additional barrier protection. After the intermediate
Other chapters of this book discuss the factors that can influence coat, the topcoat is applied and provides a first layer of corrosion
corrosion in soil. It is important to understand the characteristics protection against the environment. The topcoat can have aes-
of the soil for transportation structures because contact with soil thetic requirements depending on the requirements of the bridge
is inevitable. The soils in contact with these structures can owner. For best performance, paint coats must be used as a sys-
exhibit a wide range of characteristics as these structures can tem, designed by a single manufacturer and used together
have substantial lengths, with some elements also going deeply according to the manufacturer’s recommendations. When select-
into the ground. In addition, the structures might not only con- ing a zinc-rich primer paint system, other non-corrosion-related
tact native soils but also fill materials that commonly are used items to consider include the drying times, curing times, and slip
during construction. Ensuring that the fill materials exhibit resistance of the primers being applied to faying surfaces of
favorable characteristics to promote corrosion resistance is bolted connections.
HIGHWAYS, TUNNELS, AND BRIDGES 347
Coating Removal and Recoating with a TSC. The process, however, does require specialized
Once coated steel has been in service for years, the paint coating equipment and expertise and can be time-consuming. TSC has
can eventually fail and flake off. When this occurs, a decision extensive use in Europe and is slowly continuing to gain traction
must be made to either over-coat or recoat the member. If over- within the United States.
coating is performed, it temporarily extends the time before a A duplex coating system, as referred to as in the steel bridge
full coating removal and recoating operation must be applied. If community, is a corrosion protection systems consisting of multi-
recoating is selected, the failed coating must be removed ple layers, such as either HDG or TSC acting as the base layer and
completely, down to the bare steel, before recoating. The coating then a topcoat paint layer to provide enhanced corrosion resis-
removal process is typically done using a metallic blast media. In tance and aesthetics.10 Conventional thinking suggests that when
some regions, depending on agency requirements, all of the predicting the corrosion resistance of a duplex coating system, the
removed coating and discarded blast media must be collected predictive life of both coatings can be added together to get the life
and properly disposed of due to environmental concerns. of the complete system. Observational data suggest that the life of
Worker safety also must be considered during this process, espe- a duplex coating system performs better than the sum of its indi-
cially if the coating being removed contains lead. Once the failed vidual coatings, depending on the severity of the environment.11
coating has been removed, a new coating can be applied in the Bridge owners, however, have had mixed results using these sys-
field to provide corrosion protection to the steel substrate. The tems. Some past issues include HDG or TSC quality, adhesion of
new coating must be applied in the field to the manufacturer’s the topcoat layer, or insufficient performance leading to required
recommendations. It is generally believed that field-applied coat- maintenance sooner than expected. There are current research
ings do not possess the service life that shop-applied coatings do. projects within the United States to develop guidelines for the
Coating removal and recoating is an especially common repair improved usage of duplex coating systems on steel bridges. The
technique for steel bridges. use of these systems has had increased success in Europe.
Metallic Coatings Alloyed Steel

Hot-dip galvanizing (HDG) is another common corrosion pro- Corrosion-resistant steels have become increasingly common for
tection method for steel. This process begins with dipping steel steel bridges. Within the United States, all bridge steel plates fall
into a series of surface preparation solutions, including degreas- under ASTM A709, Standard Specification for Structural Steel for
ing, pickling, and fluxing. Once the steel is properly cleaned, it is Bridges.12 One corrosion-resistant steel within this specification is
dipped into a bath of molten zinc.7 Typically these baths are Grade 50W, which is essentially identical to ASTM A588, Stan-
approximately 40 ft long in the United States, but longer baths dard Specification for High-Strength Low-Alloy Structural Steel,
do exist. When dipped into the molten bath, a chemical bond is up to 50 ksi [345 MPa] Minimum Yield Point, with Atmospheric
formed between the steel and zinc to form a sacrificial zinc Corrosion Resistance, and commonly is referred to as
layer.7 The thickness and composition of this zinc layer depends “weathering steel.”13 The high-performance steels within ASTM
on the steel chemistry. When the silicon content in the steel is A709, such as grades HPS 50W, HPS 70W, and HPS 100W, are
either between 0.04 and 0.15 or more than 0.22 percent, the steel also considered weathering grades. Weathering steel provides
is considered “reactive.” When reactive steels are hot-dip galva- inherent corrosion resistance by forming a stable oxide layer,
nized, the zinc can grow to excessively thick levels and become which is tightly adherent to the steel substrate. This oxide layer,
brittle, increasing the potential for the zinc to flake off.8 Nonreac- sometimes referred to as a “patina,” forms after many wet and
tive steels have much more consistent zinc thicknesses after dry cycles. The historical performance of weathering steels
being hot-dipped galvanized. When selecting an HDG protection within the United States has been successful in some environ-
system, it is important to be cognizant of the length limitations ments, but poor in others. Much of the poor performance of
of galvanizing baths for the steel, which can lead to additional weathering steel was in areas, such as marine coastal environ-
splices within structural members. ments, areas of prolonged wetness, or industrial areas. This led
Thermal spray coating (TSC), also known as metalizing, is to a Federal Highway Administration (FHWA) technical advi-
the process of heating a metallic feedstock and then spraying it sory in 1989 detailing areas in which uncoated weathering steel
onto a steel plate substrate. The wire or powder feedstock typi- is not recommended.14 The use of weathering steel has continued
cally used for steel bridges are pure zinc, pure aluminum, or an in the United States because of its inherent corrosion resistance
85 percent zinc/15 percent aluminum alloy.9 The feedstock is and minimal cost increase when compared with non-weathering
heated using a flame or an electric arc, and then compressed air bridge steels. In many cases, weathering steel is also painted for
is used to spray the molten metal onto the steel. Once the metal use in steel bridges. In some cases, weathering steel beam ends
hits the steel, it instantly solidifies to form a sacrificial protective are painted for increased corrosion protection.
coating. Multiple passes are required to achieve the specified Another corrosion-resistant steel plate within ASTM A709 is
thickness for the TSC to perform as intended. Similar to other Grade 50CR, which is nearly identical to ASTM A1010, Standard
systems, TSC has both advantages and disadvantages. It is a Specification for Higher-Strength Martensitic Stainless Steel Plate,
mobile process that can be performed in the field where HDP Sheet, and Strip.12,15 Grade 50CR steel is a dual-phase stainless steel
would be nearly impossible. There are also no length restrictions made up of fine-grained ferrite and tempered martensite. It con-
like for HDP baths, so longer steel plate members can be coated tains 10.5 wt% chromium and 1.5 wt% nickel to provide much
more inherent corrosion resistance than weathering steel. Accord- ponding of water. Snipes on stiffeners at the stiffener to web and
ing to accelerated corrosion testing, Grade 50CR can provide bottom flange connection should be made large enough to allow
approximately 10 times more corrosion resistance compared with water to flow and prevent clogging.8 Drip bars can also be added
weathering steel when placed in the vertical direction and approxi- to redirect the flow of water off of the bottom flange.11 Welded
mately four times more in the horizontal direction, with the differ- drip bars should be placed in areas of low stress to prevent unin-
ence being attributed to time of wetness.16 An FHWA-funded tended fatigue issues related to the resultant welds. Horizontal or
research study used lifecycle cost analysis to show that Grade built-up members should be limited, but when necessary, they
50CR could be more cost-effective than painted carbon steel after should employ a corrosion protection system, such as painting,
one or two repainting cycles.17 As of 2019, Grade 50CR has been HDG, TSC, or alloyed steel. In other cases, the thickness of a
used in six bridges in the United States and two in Canada.18 It is member can be increased to allow for some section loss without
expected that provisions for welding Grade 50CR steel are compromising the structural performance of the member. When
expected to appear in interim editions of the 2020 edition of the existing steel bridge connections experience corrosion damage,
AASHTO/AWS D1.5 Bridge Welding Code. Numerous research the existing corrosion should be thoroughly removed before
studies are being conducted on Grade 50CR to increase the knowl- installing welded or bolted repairs. Once in place, repairs should
edge on welding consumables, bolted connections, galvanic corro- have a corrosion protection system in place to increase the
sion when in contact with other metals, and cost analysis. remaining service life of the susceptible location.
A third type of corrosion-resistant steel available for use on Closed box members should be used sparingly because they
steel plate girder bridges is duplex stainless steel. Duplex stainless can trap moisture and are difficult to inspect. Open members,
steels have a two-phase microstructure made up of ferrite and such as wide flange beams can serve as an alternative, if they are
austenite. The most prominent grades of duplex stainless steel designed with corrosion in mind. If box members must be used,
for bridge use are likely UNS S32205 (2205), UNS S32304 weep holes should be placed at the lowest point practically possi-
(2304), and UNS S32101 (2101), although many other types do ble on the member to allow for drainage of water. The inside of
exist. Duplex stainless steels have excellent inherent corrosion box members often are painted with a high-contrast white coat-
resistance, likely multiple orders of magnitude better than weath- ing to facilitate easier inspection. Other corrosion protection sys-
ering steel or Grade 50CR.19 Much of this is due to their high tems, such as HDG or alloyed steel, also can be used in these
chromium, nickel, and molybdenum contents. They also are instances.
attractive for steel bridge use because of their high strength and
good toughness when compared with austenitic or ferritic stain- Washing
less steels. Duplex stainless steels have been used on more than In some cases, it may be beneficial to wash steel bridges made of
30 vehicular, pedestrian, and rail bridges in Europe and around weathering steel. Multiple studies have shown that washing can
the world. Within the United States, they have been used either remove debris, loose rust flakes, and surface chlorides that can
as primary members or specific components on five vehicular cause extended periods of wetness; these extended periods of
and pedestrian bridges. Fabrication and design guides are both wetness are detrimental to weathering steel because the protec-
available for duplex stainless steels, which is important since tive patina cannot form without alternating wet and dry cycles.22
guidance on items like the welding parameters need to be sound Some items to consider when washing weathering steel bridges
to ensure corrosion resistance is maintained.20,21 These steels are include the water pressure and nozzle spray angle.23 Location
expected to cost more than traditional steels, although their use specific agency requirements also must be considered for envi-
may be warranted when considering a lifecycle cost analysis. ronmental concerns. In some cases, all water and debris washed
off the bridge must be collected and properly disposed of after
washing. In some cases, this requirement can significantly
Detailing increase the cost of bridge washing.
In many instances, the corrosion resistance of steel bridges can
be improved through detailing during the design stage. One of Isolation
the ways this can be done is to increase the vertical clearance In steel bridges where dissimilar metals, such as carbon steel and
between an overpass structure and the roadway below. In this stainless steel, are used, electrical isolation can be implemented
example, de-icing salt applied to the roadway below can be to alleviate galvanic corrosion. Isolation is a common galvanic
splashed up on to the overpass bridge, causing accelerated corro- corrosion mitigation technique in which another material, such
sion of the overpass. There is no current guidance on the mini- as nylon or plastic, is placed in between the two dissimilar metals
mum clearance that would eliminate this effect; however, the to prevent the formation of a galvanic cell The concept of using
minimum vertical clearance on the United States interstate sys- isolation is to prevent the use of a small anode to protect a large
tem has been 16 ft, and this type of corrosion has continued to cathode from preferentially corroding. Isolation can be challeng-
occur.13 If increasing the minimum clearance is neither possible ing to use on large structures such as bridges, because isolation
nor desirable, another strategy is to apply a corrosion protection materials typically do not offer adequate structural characteristics
system, such as painting, HDG, or the use of corrosion-resistant for bridge use. For example, using a nylon washer for isolation is
steel, to the inbound fascia girder of the overpass bridge. not recommended in structural bolted applications because
Steel bridge connections should be designed with corrosion nylon is a compressible material compared with steel, and it use
in mind. Members should be sloped when possible to prevent can lead to lower levels of pretension or relaxation in the bolt,
unless additional testing and bolt tightening procedures are many years with increased success when compared with carbon
developed. As new corrosion-resistant and more noble materials steel rebar, at only a slight cost increase.
are used for bridges, isolation will need to be considered. Similar to steel plate, there are also alloyed solutions for
rebar. One such option is ASTM A1035, Standard Specification
CONCRETE for Deformed and Plain, Low-Carbon, Chromium, Steel Bars for
Similar to steel plate, a few common corrosion protection meth- Concrete Reinforcement, Grade CS.24,25 Rebar meeting these
ods can be employed for concrete structures in the transporta- requirements contains 8–10.9 wt% chromium, making it slightly
tion system. These methods can provide corrosion protection to below the minimum level of chromium to qualify as a stainless
the concrete, reinforcing steel, or both. This section provides steel. Nevertheless, it still provides an increased amount of corro-
information on each of these systems. sion resistance compared with traditional-grade rebar.26 Duplex
stainless steel rebar also exists and can be specified according to
Concrete Mix Design ASTM A955, Standard Specification for Deformed and Plain
Stainless Steel Bars for Concrete Reinforcement,25,27 For example,
The concrete mix design is vital for ensuring a long service life of
a UNS S3108 rebar has 21–23 wt% chromium and 4.5–6.5 wt%
the concrete. Service life extension is achieved through low-
nickel. Other lower-nickel-containing rebar, including UNS
permeable and low-cracking concrete mix designs. Concretes
S32304 and UNS S32101, also have become more common for
routinely now use supplementary cementious materials (SCM)
use in bridges. The increased alloy content contained in these
to improve durability and make the concrete less permeable to
duplex stainless steels allows it to provide a much higher corro-
chlorides. SCMs typically used include ground granulated blast
sion resistance than either traditional-grade or ASTM A1035
furnace slag, fly ash, and silica fume. Low cracking concrete
Grade CS rebar. Overall, alloyed rebar carries an increased cost,
mixes are also now possible by selecting proper admixtures or
but it has excellent corrosion resistance and is capable of provid-
lightweight aggregates within the concrete mix design.
ing a long service life.
During the design stage of a concrete element, it should be
As a replacement for mild steel reinforcement, composite
considered that the cover of concrete over the embedded steel,
materials are also available for RC structures. GFRP and CFRP
also called cover depth, could delay the movement of chloride
provide a corrosion-free option for bridges. Prestressed and
ions and increase the time before corrosion initiation of the steel
post-tensioned concrete elements also have reinforcement mate-
reinforcement. It is common for designers to increase the cover
rials available with improved corrosion resistance. The steel used
depth to extend the service life of steel reinforcement within a
in these elements traditionally has been seven-wire strands with
concrete section.
a minimum tensile strength of 250 ksi or 270 ksi. Historically,
Consolidation of the concrete also plays a significant role in
these strands have been encased in grout with the hope of pro-
its durability. Properly consolidated concrete provides a barrier
viding corrosion resistance, but they have experienced increased
between environmental and salt exposure. When consolidation
corrosion damage because of poor grout consolidation from
is inadequate, voids can form in the concrete that can reduce the
improper construction practices and chloride contamination
cover over the steel or, even worse, provide incomplete embed-
within grout mixes. Coated steel strands are available, but ten-
ment of the steel. Concrete consolidation is achieved through
sioning them can be more challenging compared with conven-
vibration of fresh concrete at the worksite or fabrication shop. It
tional steel strands.
also can be improved by using a self-consolidating concrete mix
Corrosion-resistant and corrosion-free solutions are also
design that provides good flow. Improper curing can cause
available for seven-wire, high-strength strand, including stainless
cracks to form that can create voids and nullify the benefit of
steel and CFRP. Duplex stainless steel grade 2205 strand has a
cover depth.
minimum tensile strength of 250 ksi and has been used by U.S.
agencies for prestressed concrete piles. Corrosion-free CFRP
Concrete Reinforcement
seven-wire prestressing strand with a minimum tensile strength
RC members commonly are used in highway network applica-
of 338 ksi also has been used by several U.S. agencies for both
tions to simultaneously use the beneficial properties of both con-
prestressed concrete piles and beams. CFRP also has been used
crete and steel. The reinforcement can be in the form of rebar,
in post-tensioned concrete girder bridge systems.
strand, rods, welded wire fabric, or fibers. In addition to provid-
Fiber RC is another option for increasing corrosion resis-
ing strength, reinforcement is routinely used to overcome con-
tance. Research into fibers and how to incorporate them in the
crete’s tendency to crack in a brittle manner or minimize the
concrete mix continues to advance. Metallic and nonmetallic
width of the cracks once they form.
fiber materials have found use in making concrete elements
One mechanism for improving the corrosion resistance of
stronger, more ductile, or with tighter crack widths. Fieldwork
an RC element is the use of a corrosion-resistant reinforcing
on bridges has demonstrated the benefits of using fibers to
material compared with the conventional carbon steel reinforce-
improve strength or reduce crack widths in concrete.28–30
ment. When rebar is used, coatings or corrosion-resistant steel
grades can be used. Two of the commonly used coating systems
include epoxy- and metallic-coated, such as galvanized, rebar. Overlays, Sealants, and Coatings
Combinations of epoxy and zinc have been used to create dual- The addition of a barrier, in the form of an overlay, sealant, or
coated rebar. These types of reinforcement have been used for coating, can aid in restricting the movement of aggressive species
through the concrete to improve the service life of an RC struc- the surrounding infrastructure. This includes the guardrails, cul-
ture; these barriers are especially helpful where de-icing salt or verts, and ancillary structures. Corrosion vulnerabilities for each
saltwater are present. Overlays can provide additional protection of these three elements are discussed in the following sections.
to a bridge deck, for example, by providing a riding surface that
is more impermeable to chloride ions than a standard bare deck. Guardrail
Crack sealants can be used to seal existing cracks to restrict the Roadside safety barriers are located relatively close to moving
movement of aggressive ions through the cracks. Concrete seal- traffic; therefore, these devices can experience high levels of
ants and coatings can be used on uncracked concrete to provide water spray and de-icing salts. Within the United States, the
increased corrosion protection. FHWA advises against the use of weathering steel guardrails.14,31
The concern is that the barrier could experience significant sec-
Electrochemical Techniques tion loss because the patina fails to form as a result of frequent
Cathodic Protection wet cycles and salt exposure. Galvanized steel is acceptable, how-
Cathodic protection increases the corrosion resistance of an RC ever, and if aesthetics are important, then powder coated galva-
structure by incorporating a second metal into the system; the nized guardrails are allowed.31
existing reinforcement within the structure then becomes the In 2008, FHWA sponsored a report, “W-Beam Guardrail
cathode, and the second metal becomes the anode. Two common Repair: A Guide for Highway and Street Maintenance.” This
types of cathodic protection include galvanic anode cathodic report discusses maintenance of commonly used W-shape beam
protection (GACP) and impressed current cathodic protection guardrails and indicates that corrosion-related maintenance is
(ICCP). When using GACP, sometimes termed sacrificial anode important to ensure the safety barrier perform as expected.32
cathodic protection, the second metal incorporated into the Because these types of guardrails are routinely galvanized, W-
structure is less noble than the reinforcing steel, thus making the beam guardrail sections were also evaluated in 2014 to determine
second metal sacrificial. Zinc is one of the commonly used sacri- whether galvanizing using either a hot-dip batch or a hot-dip
ficial metals in GACP. ICCP systems use a rectifier that polarizes continuous process altered the corrosion protection.32,33 This
the reinforcing steel with a negative rectifier pole; once the sec- work concluded that increasing the coating thickness provided a
ond metal is incorporated into the structure, it becomes polar- greater corrosion resistance and that its benefit was not sensitive
ized positively, and thus it becomes the anode. Although ICCP to the type of galvanizing method.33 It also highlighted that mat-
systems require monitoring to ensure the applied current and ing metal surfaces could exhibit crevice corrosion.33
voltage are within tolerances, this has been made easier by the Although corrosion of guardrails can occur, these structures
use of remote monitoring systems. NACE International and often are replaced because of vehicular crashes, rather than because
other similar organizations have standards that cover cathodic of significant corrosion damage. Guardrails are described as
protection of RC structures. “critical safety devices” that reduce the chance of a motorist experi-
encing a “more severe crash when leaving the roadway.”32 When
Electrochemical Chloride Extraction impacts occur on guardrails, many agencies may require that the
Electrochemical chloride extraction (ECE) systems are similar to guardrail be replaced or upgraded, meaning that the service life of
ICCP in how they are connected to the structure. The systems guardrail could be relatively short compared with other steel ele-
are different, however, in that they are not a permanent part of ments, so replacement because of corrosion is less common.
the structure, but instead are installed temporarily for a much
Culverts
shorter duration of time. ECE systems are operated at a higher
It is important to understand the properties of the soil and water
voltage difference and current density than ICCP. NACE Inter-
that will be in contact with the culvert. These properties and how
national and other organizations have standards that cover the
they interact with the culvert, possibly because of flow or abra-
use of ECE systems for RC structures.
sion, will influence material selection.
Electrochemical Realkalisation In 1986, FHWA published the “Culvert Inspection Manual”
supplement to the “Bridge Inspector’s Training Manual.” It states
Electrochemical realkalisation (ER) is similar to cathodic protec-
that damage to the culvert materials used at that time could be
tion, but its purpose is to increase the alkalinity around the steel
the result of corrosion and abrasion.34 Bushman and Chaker
of the carbonated concrete.
highlight this issue with culverts in the 2005 version of this man-
ual, indicating that commonly used hot-dipped galvanized steel
Vulnerable Areas and Repair corrugated pipe exhibited higher corrosion rates on the invert
section of the pipes. This was attributed to harsh water condi-
Strategies tions and higher flow rates.35
The following sections highlight areas that are most vulnerable More recently, the NCHRP sponsored a study to update the
to corrosion on typical highways, tunnels, and bridges. 1986 FHWA culvert manual. A more recent study was needed
because different materials, such as plastic pipe, now are com-
HIGHWAYS monly used but were not addressed in the 1986 FHWA manual.
On a highway system, some of the elements that are most sus- These changes were incorporated in the 2019 manual released by
ceptible to corrosion are not the highways themselves, but rather AASHTO.36
Ancillary Structures and Luminaires bridge population in the United States. Aging bridges require sig-
Ancillary structures, such as signs and luminaires, are subject to nificant maintenance to extend their service lives, and because
corrosion because of the atmosphere and through de-icing salt bridges and tunnels of the same era were built with the same
when they are located close to the roadway. Corrosive soils can steel and concrete materials, it is likely that tunnels will require
affect these structures if they are not encased in concrete at the significant maintenance as well.41
level of the soil; accelerated corrosion also can occur if the encas-
Tunnel Liners
ing concrete cracks and allows the soil to penetrate to the anchor
rods or other connecting elements from the structure to the Bushman and Chaker highlighted that, over time, tunnel linings
foundation. Weathering steel has shown poor performance as a have been constructed using segmental cast iron, steel ribs and
light pole material, as noted by a 1989 FHWA Technical Advi- wood lagging, fabricated steel, pressed steel plates, and precast
sory.14 The FHWA cited section loss or localized structural fail- concrete.35 The TOMIE manual suggests that, in recent years, the
ure as potential failure modes, likely because of the increased three most common tunnel lining materials are RC (prefabri-
time of wetness associated with these low-lying structures. In a cated or cast-in-place), cast iron, and steel.39 One typical corro-
similar fashion, anchor rods can experience accelerated corrosion sion mechanism of tunnel linings is from groundwater, which
when encased in grout in between the structure base and founda- can deteriorate and corrode the lining from sources of salt, gal-
tion. In many instances, common practice has been to encase vanic interactions, and stray currents aggravating the problem.39
them in grout to prevent corrosion, but when cracks in the grout Corrosion damage of linings includes metal section loss, concrete
do occur, they can retain moisture and salt to cause corrosion spalling, and damage to electrical systems. If any corrosion dam-
damage at an accelerated rate. Similar to the discussion in the age is observed, repairs should be made to mitigate the damage,
section “Concrete,” it is important to minimize cracking of the and actions should be taken to protect the liner from ongoing
encasing grout. corrosion.39
Many ancillary structures and luminaires are designed with Ceiling Panels
either HDG steel or aluminum to provide increased resistance to In many instances, the ceiling panels, supporting hardware, or
corrosion. In many cases, the hardware, including the anchor hardware for attachments have experienced failures because of
rods, nuts, and washers, are also HDG. It is recommended to
corrosion. Many of these cases were due to the materials irregu-
leave a space between the bottom of the structure and the top of larities resulting from poor fabrication or construction. For
the foundation, rather than filling this void with grout. If a gap is example, if corrosion-inducing materials are found within a con-
left here, it can allow moisture to dry and de-icing salts to be
crete mix design, they could cause the corrosion-resistant sup-
washed away, rather than potentially being encased in grout. porting hardware in contact to be more susceptible to stress
Generally, when sign structures and luminaires have significant corrosion cracking. Attachment hardware can be susceptible to
corrosion, it is recommended that the damaged areas, or the
corrosion damage if it is not manufactured properly, such as
entire structure, be replaced because of the high maintenance during the casting or sintering process.
cost relative to the cost of the structure. Corrosion damage of ceiling panels and adjacent hardware
can largely be prevented in the design process by having specifi-
TUNNELS cations that ensure that all of the materials are properly manu-
The impediment a tunnel must pass through to create a passage- factured and fabricated. If corrosion damage is discovered on
way can also vary widely. For example, in the western part of the any hardware, it is recommended that the damaged hardware be
Commonwealth of Virginia, travelers pass through a mountain replaced before reaching a critical state.
using the Big Walker Mountain Tunnel.37 In the eastern part of
the state, however, several tunnels pass under the waterways Flood Gates
leading to the Atlantic Ocean.38 Although the environments Flood gates are an important element of a tunnel for mitigating
through which these tunnels must pass are different, the meth- corrosion. When tunnels are located in regions where storm
ods of construction also are different, which can affect the corro- surges can occur, flood gates can seal a tunnel and protect the
sion resistance of the structure. interior of the tunnel from exposure to water. Although the dis-
The FHWA “Tunnel Operations, Maintenance, Inspection, cussion on tunnels has focused mainly on the structural elements
and Evaluation (TOMIE) Manual” discusses some of the com- and materials, tunnels also can contain other systems sensitive to
mon tunnel construction methods and how the method is often corrosion, like electrical or mechanical components.42
selected by the project conditions.39 As with other civil struc-
tures, the amount of damage associated with corrosion is sensi- BRIDGES
tive to exposure time. Time is needed for chlorides to move Bridges often are broken up into three components: deck, super-
through concrete or coatings on steel to degrade, which then structure, and substructure. In general, the deck carries the wheel
mitigates the benefit from the original corrosion protection sys- loads from the traffic above and transfers them to the superstruc-
tem. In the United States, nearly 70% of the tunnels were built ture. The superstructure, typically made from either steel or con-
over a 50-year span, between 1922 and 1972, which means this crete girders, then transfers the loads to the substructure. Each of
group of tunnels is quickly approaching 50 years old.40 This these three main components will be discussed in terms of their
trend for the aging tunnel population is similar to the aging corrosion vulnerability.
Deck penetrate to the superstructure below, causing accelerated corro-

Steel Decks sion. To mitigate salt movement through the cracks, bridge own-
Although not extremely common, steel decks, such as open grid ers must decide on the appropriate maintenance operation that
or orthotropic decks, can be used in long span bridges, where might include using a crack sealant.
dead load needs to be minimized. This puts the steel in direct Bridge decks often contain joints to allow for thermal
contact with de-icing salts applied to the deck from above. expansion and contraction of the bridge. These joints typically
Corrosion-resistant steels can be used in these instances to pre- have expected service lives that are much shorter than the decks
vent accelerated corrosion. Improved detailing of the steel deck themselves. Once a joint fails, it can cause leakage of water and
also can be used to prevent de-icing salt and moisture from col- de-icing salts onto the bridge girders below; after several years,
lecting in specific areas. this leakage can cause significant corrosion because water and
de-icing salts can become trapped on the girders. It is important
Concrete Decks to repair leaking joints in the early stages of failure to prevent
A properly designed concrete bridge deck can protect the super- future, expensive repairs on the bridge girders. Although more
structure below from salt exposure, acting as a first line of expensive, eliminating a deck joint can lead to significantly better
defense against corrosion damage. Figure 1A shows a photograph corrosion performance for the deck and the superstructure.
of a bridge under construction; figure 1B provides a closer view of Superstructure
the deck reinforcement, which is alloyed for corrosion resistance; The majority of bridge superstructures are made of either steel
and figure 1C shows the finished concrete surface with cracks. or concrete girders. The corrosion deterioration of each type of
Because the deck typically acts as the primary riding surface, it superstructure is different, so the two types of superstructures
can be subject to large amounts of de-icing salts in regions that will be discussed separately.
receive snowfall and ice. Concrete decks typically have a mini-
mum cover between the top layer of reinforcing steel and the top Steel Superstructure
of the riding surface; this cover assists in preventing corrosion of The continuous application of chlorides and moisture onto a steel
the reinforcing steel. If, however, the concrete cracks, the de- girder under a leaking joint, and subsequent ponding on the bot-
icing salt can penetrate through the concrete to the reinforcing tom flange, can lead to accelerated corrosion and section loss in
steel. If the reinforcement corrodes enough, it can lead to spal- the web and bottom flange of the steel beam. An example of this is
ling or larger cracks, which can allow water and de-icing salts to shown in figure 2. Ultimately, the best strategy for repairing
FIG. 1 A bridge deck that is (A) under construction with the corrosion-resistant reinforcing steel being placed, (B) close-up of the
corrosion-resistant reinforcing steel that will be encased in concrete, and (C) cracks (yellow arrows) in the concrete bridge deck.
trucks kicking up de-icing salts from the roadway, similar to the

FIG. 2 Corroded steel beam end. tunnel effect described previously. In this case, the de-icing salts
are sprayed both upwards and sideways, affecting the diagonals,
vertical members, and horizontal members that cross over the
roadway. Another case in which trusses can experience increased
corrosion is due to the presence of closed box-members. Many
trusses have closed members that, if not detailed properly, can
prevent drainage. Because it is nearly impossible to completely
prevent water and other debris from entering these closed mem-
bers, the lack of drainage will certainly lead to accelerated corro-
sion from the inside out. Due to the closed nature of these types
of members, inspecting them for the presence of corrosion is
also difficult.
Concrete Superstructure
Similar to a concrete bridge deck, concrete used for the super-
corrosion damage to steel beam ends is to replace the deck joint
structure can crack, especially when restrained. These cracks can
above the areas of corrosion. Once the section loss in the steel
provide a direct path for corrosive exposure to penetrate to the
beam reaches a critical state, however, repairs will need to be made
reinforcing steel and quickly nullify the benefit of mitigation
to restore the structural capacity of the beam. If the corrosion
techniques such as SCMs in the mix design and additional con-
damage is severe enough, portions of the beam web and bottom
crete cover. Overall, using a good quality concrete, including low
flange may need to be cut out and a new beam portion will need
permeability and low cracking additives, in conjunction with a
to be welded in its place. Field welding, however, historically has
corrosion-resistant reinforcement can provide a cost-effective,
had many challenges and can lead to further complications if not
long-term method of preventing corrosion in a structure. The
done properly. Another repair strategy is to bolt repair plates to
benefit of this combination is more evident in locations where
the existing beam to restore the beam’s structural capacity. This
aggressive environmental conditions increase the probability of
process is started by cleaning and removing all of the existing cor-
corrosion in a structure.
rosion damage. Steel repair plates then can be bolted into place
On example of when a concrete superstructure would be
over the once-corroded area. It is important that these repair plates
more likely to experience accelerated corrosion is if the bridge is
extend into unaffected portions of the steel beam and provide ade-
located in an area where de-icing salts are applied. This could
quate structural capacity. The repair plates should have some form
occur if the concrete deck is a part of the concrete girders, such as
of corrosion protection system, such as painted, TSC, or alloyed
in a decked bulb tee or adjacent box girder. In this type of system,
steel. Care also should be taken to close the gaps between the exist-
the post-tensioning rods between the box girders can corrode,
ing beam and repair plates using some form of sealant.
leading to a loss of transverse post-tensioning between the girders.
Steel bridges also can experience increased corrosion when
Using a good quality grouting material between the girders and
used as a grade separation between two intersecting traffic
corrosion-resistant steel like Type 2304 is expected to provide a
routes. This scenario is referred to as a “tunnel effect” in the
longer service life than conventional carbon steel rebar.43
FHWA Technical Advisory regarding the use of uncoated weath-
In both examples, salt exposure over time will result in chlo-
ering steel because the bridge acts as the ceiling of the tunnel
ride ions diffusing through the concrete, and cracks in the con-
over the roadway below. In this case, de-icing salts are applied to
crete will increase the rate of chloride movement, until a
the roadway below the bridge. As trucks travel on the roadway
sufficient quantity of chlorides reach the steel, which then causes
below, they splash the de-icing salts up onto the bridge above.
cracking and spalling of the concrete.
Many of these de-icing salts come into contact with and stick to
Corrosion related repairs in RC can include starting with
the inbound fascia girder to cause accelerated corrosion.
trying to minimize the structural damage. Early corrosion pre-
Steel bridge connections, especially those that are oriented
vention methods could include using a barrier method to keep
horizontally, are susceptible to increased corrosion because they
corrosive electrolytes from reaching the steel.
form a natural ponding area for de-icing salt, water, bird guano,
and other debris to accumulate. If this corrosion-inducing debris
is stagnant and is not able to drain off of the surface naturally, it Substructure
can lead to localized accelerated corrosion. Many older bridges The bridge substructure transfers the load from the bridge deck
also contain built-up members, which are made up of individual and superstructure to the foundation. In bridges, the superstruc-
plates and angles and then are bolted or riveted together to form ture elements are typically referred to as abutments and piers,
a structural member. Built-up members are susceptible to crevice and can be made out of either steel or concrete.
corrosion because of the presence of multiple plates for which
water or chlorides to penetrate. Steel Substructure
Trusses can experience accelerated corrosion because of a H-piles are a common form of steel substructure used to support
multitude of factors. Deck trusses are subject to corrosion from pier caps. Because these support the rest of the bridge above, it is
critical they have sufficient durability to match the design life of FLEXIBLE FILLER ALTERNATIVES FOR GROUT IN
the structure. These H-piles can be subject to corrosion through POST-TENSIONED CONCRETE APPLICATIONS
aggressive soil or water conditions. One example of H-pile corro- As mentioned in a previous section, post-tensioning strands
sion occurred in 2013, when the piles supporting a bridge in the encased in grout have experienced increased corrosion because of
United States experienced a local failure that caused approxi- chloride-infused grout and poor grout consolidation. In the past,
mately 2 ft of vertical displacement at the pier.44 When steel segregation of grouts and the formation of soft grout has been a
H-piles are used as substructure elements, it is advised that a cor- concern that is compounded by the difficulty in detecting these
rosion protection system be applied to them, such as metallic issues using nondestructive methods. One potential solution to
coatings or alloyed steel. this problem is to use a flexible filler, such as wax or grease, in
place of the grout. Flexible fillers have been used in the past, but
Concrete Substructure this approach is relatively new to many agencies so it could usher
Piles, drilled shafts, or spread footings are all examples of RC in a new type of corrosion that will have to be addressed when
substructure elements. Depending on the bridge location, these designing and maintaining post-tensioned structures. One of the
elements can be subject to corrosion because of being exposed unique concerns with switching to flexible fillers is that the fill
to aggressive soil conditions or through direct contact with salt- material could support microbiologically influenced corrosion.48
water or brackish water. Using a good quality concrete and Fortunately, if this is the case, post-tensioned structures can be
corrosion-resistant or corrosion free, like UNS Type 2205 or designed so that the strands can be replaced if needed.
CFRP, prestressing strands can greatly improve the service
life.45,46 Concerns also have been raised that as utility and light SEA-LEVEL CHANGE
rail share more of the right-of-way with existing bridges, the In the coming years, the sea level is expected to rise along the
bridges could be exposed to stray currents that could damage coastlines and lower elevation inland areas. A large portion of the
the foundations. world’s population lives in these areas, which means there is a
large amount of transportation infrastructure in these locations.
As sea-level rise continues, the risk is greater for corrosion on
these highways, tunnels, and bridges because of the influx of salt-
Future Corrosion Related Ventures
water. These systems likely will require maintenance to address
LASER ABLATION COATING REMOVAL corrosion that occurred earlier in their service lives, and new struc-
Laser ablation coating removal (LACR) is a coating removal tures in these areas will require more corrosion-resistant designs.
technique that uses high-energy light pulses that are directed at
the coated surface to vaporize the coating. Then, a vacuum and
filtration system is used to collect the coating as it is being Corrosion-Related Standards for
removed; in doing this, LACR is expected to reduce the total Highways, Tunnels, and Bridges
coating removal time, personnel exposure to hazardous waste,
Although individual transportation departments can use docu-
and the amount of hazardous waste generated during the
ments that provide corrosion-related guidance when doing work
removal process. The process can be used on both steel and
for them, the following documents have been generated for
concrete coated bridge components. Although this technology
broader use. Some of these documents are referenced in the
is newer to the bridge community, LACR has been used in
guidance provided by the individual transportation departments.
other industries with positive results. LACR is slower than con-
ventional coating removal methods, but this technique could
ATMOSPHERIC TEST METHODS
provide a means for removing coatings from corroded sections
• ASTM G33, Standard Practice for Recording Data from Atmo-
while improving capture efficiency of environmental con-
spheric Corrosion Tests of Metallic-Coated Steel Specimens
taminants, and reducing the amount of material requiring
disposal.47 • ASTM G50, Standard Practice for Conducting Atmospheric
DISSIMILAR METAL STEEL BRIDGES • ASTM G84, Standard Practice for Measurement of Time-of-
Corrosion-resistant steel bridges can be built more cost effec- Wetness on Surfaces Exposed to Wetting Conditions as in
tively when dissimilar metals are used. This can be done by Atmospheric Corrosion Testing
using corrosion-resistant alloyed steels in targeted, highly cor- • ASTM G87, Standard Practice for Conducting Moist SO2 Tests
rosive areas, such as beam ends and areas close to water, and • ASTM G91, Standard Practice for Monitoring Atmospheric SO2
lesser corrosion-resistant or coated steels would be used in Deposition Rate for Atmospheric Corrosivity Evaluation
benign locations. By doing this, the more durable, but higher
• ASTM G101, Standard Guide for Estimating the Atmospheric
cost steels would be used only where truly needed, and the
Corrosion Resistance of Low-Alloy Steels
more common, lower cost steels would be used elsewhere. Gal-
vanic corrosion of the dissimilar metal connections, either • ASTM G116 (replaced ASTM G104), Standard Practice for
bolted or welded, would need to be considered before employ- Conducting Wire-on-Blot Test for Atmospheric Galvanic
ing such designs.19 Corrosion
SALTWATER TEST METHODS • FHWA, “Underground Transportation Systems in Europe:

• ASTM G52, Standard Practice for Exposing and Evaluating Safety, Operations, and Emergency Response,” International
Metals and Alloys in Surface Seawater Technology Scanning Program, June 2006
• ASTM G78, Standard Guide for Crevice Corrosion Testing of • NCHRP, “Best Practices for Implementing Quality Control
Iron-Base and Nickel-Base Stainless Alloys in Seawater and and Quality Assurance for Tunnel Inspection,” NCHRP Pro-
Other Chloride-Containing Aqueous Environments ject 20-07/Task 261, Transportation Research Board, October
2009
SOIL TEST METHODS • NCHRP, “Best Practices for Roadway Tunnel Design, Con-
• ASTM G51, Standard Test Method for Measuring pH of Soil struction, Maintenance, Inspection, and Operations,” Domes-
for Use in Corrosion Testing tic Scan 09-05, NCHRP Project 20-68A, Transportation
• ASTM G57, Standard Reference Test Method for Measurement Research Board, April 2011
of Soil Resistivity Using the Wenner Four-Electrode Method • NCHRP, “Development of Guidelines for Rehabilitation of
Existing Highway and Rail Transit Tunnels,” NCHRP Project
STEEL TEST METHODS 20-07/Task 276, Transportation Research Board, July 2010
• ASTM G46, Standard Guide for Examination and Evaluation
of Pitting Corrosion BRIDGE GUIDANCE
• ASTM G61, Standard Test Method for Conducting Cyclic General
Potentiodynamic Polarization Measurements for Localized • AASHTO, Manual for Bridge Evaluation, 2011
Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-Based • AASHTO, Guide Manual for Bridge Element Inspection, 2011
Alloys
• ACI 301, Specifications for Structural Concrete
REINFORCED CONCRETE TEST METHODS Structural Steel Plate

• ASTM C876, Standard Test Method for Corrosion Potentials in • ASTM A709, Standard Specification for Structural Steel for
Uncoated Reinforced Steel in Concrete Bridges
• ASTM G109, Standard Test Method for Determining Effects of • ASTM A588, Standard Specification for High-Strength Low-
Chemical Admixtures on Corrosion of Embedded Steel Rein- Alloy Structural Steel, up to 50 ksi [345 MPa] Minimum Yield
forcement in Concrete Exposed to Chloride Environments Point, with Atmospheric Corrosion Resistance
• ASTM G180, Standard Test Method for Corrosion Inhibiting • ASTM A780, Standard Practice for Repair of Damaged and
Admixtures for Steel in Concrete by Polarization Resistance in Uncoated Areas of Hot-Dip Galvanized Coatings
Cementitious Slurries
• ASTM A1010, Standard Specification for Higher-Strength Mar-
• AASHTO T 373, Linear Polarization Resistance and Potentio- tensitic Stainless Steel Plate, Sheet, and Strip
dynamic Polarization Test
• ASTM A123, Standard Specification for Zinc (Hot-Dip Galva-
• AASHTO T 374, Tombstone Test nized) Coatings on Iron and Steel Products
• AASHTO T 376, Macrocell Slab Chloride Threshold • ASTM A153, Standard Specification for Zinc Coating (Hot-
• Bureau of Reclamation M-82, Time-to-Corrosion Slabs Dip) on Iron and Steel Hardware
• FHWA-RD-98-153, Southern Exposure Time-to-Corrosion • ASTM A385, Standard Practice for Providing High-Quality
Slabs Zinc Coatings (Hot-Dip)
• ASTM B6, Standard Specification for Zinc
HIGHWAY GUIDANCE • ASTM D6386, Standard Practice for Preparation of Zinc (Hot-
Guardrail, Culverts, and Ancillary Structures and Luminaires Dip Galvanized) Coated Iron and Steel Product and Hardware
• See the “Structural Steel” section for ASTM Standards on Surfaces for Painting
Galvanizing. • AASHTO/SSPC-PA 18/NSBA S 8.2, Specification for the
Application of Thermal Spray Coatings to Steel Bridges
TUNNEL GUIDANCE
• FHWA, “Tunnel Operations Maintenance, Inspection, and Grade 60 to Grade 100 Reinforcing Bars
Evaluation (TOMIE) Manual” • ASTM A615, Standard Specification for Deformed and Plain
• FHWA and Federal Transit Administration, “Highway and Carbon-Steel Bars for Concrete Reinforcement
Rail Transit Tunnel Maintenance and Rehabilitation Manual”, • ASTM A706, Standard Specification for Deformed and Plain
2005 Low-Alloy Steel Bars for Concrete Reinforcement
• FHWA and Federal Transit Administration, “Highway and • ASTM A767, Standard Specification for Zinc-Coated (Galva-
Rail Transit Tunnel Inspection Manual”, 2005 nized) Steel Bars for Concrete Reinforcement
• ASTM A775, Standard Specification for Epoxy-Coated Steel • NACE RP0281-2004, Standard Recommended Practice,
Reinforcing Bars Method for Conducting Coating (Paint) Panel Evaluation Test-
• ASTM A934, Standard Specification for Epoxy-Coated Prefab- ing in Atmospheric Exposures
ricated Steel Reinforcing Bars • NACE RP0287-2002, Field Measurement of Surface Profile of
• ASTM A955, Standard Specification for Deformed and Plain Abrasive Blast-Cleaned Steel Surfaces Using a Replica Tape
Stainless Steel Bars for Concrete Reinforcement • NACE RP0290-2000, Impressed Current Cathodic Protection of
• ASTM A1035, Standard Specification for Deformed and Plain, Reinforcing Steel in Atmospherically Exposed Concrete Structures
Low-carbon, Chromium, Steel Bars for Concrete Reinforcement • NACE SP21427-2019, Detection and Mitigation of Stray-Current
• AASHTO M284, Standard Specification for Epoxy-Coated Corrosion of Reinforced and Prestressed Concrete Structures
Reinforcing Bars: Materials and Coating Requirements
• AASHTO M 334M/M 334-17, Specification for Uncoated
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vulnerability-of-citys-tunnels.html D. R. Becker, R. Liu, and A. Runion, Innovative Coating Removal
Techniques for Coated Bridge Steel, VTRC 20-R2, (Charlottes-
43. “Instructional and Informational Memorandum: Corrosion ville, VA: Virginia Transportation Research Council, August 2019),
Resistant Reinforcing Steels (CRR),” Virginia Department of https://web.archive.org/web/20210616155506/http://www.
Transportation, October 15, 2018, https://web.archive.org/web/ virginiadot.org/vtrc/main/online_reports/pdf/20-R1.pdf
20220119042335/https://www.virginiadot.org/business/
resources/bridge/Manuals/IIM/SBIIM81.8.pdf 48. F. J. Presuel-Moreno, C. F. Castaneda, I. Santillan, A. Kaxemi, and
F. Tang, Corrosion Prevention of Bridge Tendons Using Flexible
44. Wisconsin DOT (WisDOT), I-43 Leo Frigo Memorial Bridge Filler Materials, FDOT Report No. BDV27-977-10 (Tallahassee, FL:
Investigation Report, Executive Summary, Report Florida Department of Transportation Research, November
No. ID 1220-15-01 (Wisconsin Rapids, WI: Wisconsin DOT 2018).
359
Chapter 23 | Automotive
Niamh Hosking1
Introduction in corrosion resistance have led to extended warranties, which

are typically 6–12 years for perforation and 3–5 years for cos-
The automotive industry is one of the key sectors of the economy metic corrosion. Corrosion testing, of both components in the
throughout the world. It drives a significant percentage of laboratory and full vehicles at the test track, has played a major
research in engineering and science, totaling $125 billion globally role in the development of corrosion-resistant vehicles. The cost
in 2018, and supports around 5% of private-sector employment of conducting a corrosion test track study depends primarily on
in the United States, contributing at least 3% of America’s total the duration and complexity of the test, which varies consider-
gross domestic product.1 The automotive industry is a prime sec- ably from manufacturer to manufacturer as described by Ström.3
tor for the deployment of emerging technologies in robotics, Estimates for the test range between $100,000 and $200,000 per
connectivity and data analytics, and artificial intelligence, which vehicle, excluding the vehicle cost. Therefore, there is strong
are pillars of the newest industrial revolution, known as Industry interest in the industry to use alternative (i.e., quicker and
4.0.2 Despite the transformation and disruption of much of the cheaper) assessment methods to determine performance charac-
industry’s traditional manufacturing methods and materials, teristics of vehicles and components in service environments.
high- and medium-volume passenger car production continues This chapter addresses the testing technology used in the devel-
to rely on the use of metallic construction materials. Corrosion opment of corrosion-resistant vehicles and highlights some
management, including testing, of those metallic structures emerging trends for future corrosion testing.
remains a priority for the automotive engineer and across the
industry generally.
Vehicle production starts with the input of sheet metal, typ- Automotive Materials
ically steel or aluminum in coil form. The metal is cut and
formed into 300–500 pieces, which are joined together to form The automobile has evolved into a complex, multi-material sys-
the vehicle body in the bodyshop of the automotive factory. tem that is exposed to a highly aggressive and variable environ-
Castings, extrusions, and rolled frames also may be incorporated ment. Its design includes highly finished external body panels
into the body structure. The assembled vehicle body passes to and structural materials; hardware, such as trim, bumpers, and
the paint line where corrosion protection coatings, sealants, and brackets; engine and batteries; drive train; exhaust systems; elec-
paint are applied. The final trim, chassis, and powertrain compo- trical systems; systems incorporating liquid passages and reser-
nents (e.g., seats, carpets glass, engines, transmissions, suspen- voirs, such as heat exchangers, hydraulic brake lines, fuel lines,
sions, electrics, wheels, tires, and brakes) are fitted in the final and tanks; and oil and transmission fluid reservoirs. Nontradi-
assembly line to produce the finished vehicle. tional powertrains, such as hybrid electric, battery electric, and
Since the early 1980s, strategies to improve fuel economy fuel cell–powered vehicles, present novel corrosion challenges.
and environmental impact, as well as vehicle quality and reliabil- Thus, the variety of materials used is extremely large. Some of
ity, while also reducing manufacturing costs and increasing the metallic materials used in various automotive systems are
profit margins, have brought about considerable change in the listed in table 1. The most significant change in automotive mate-
industry. New designs and powertrains, improved processing, rials in the 1980–2000 period was the transition from bare steel
and new or improved materials and components have been to precoated sheet steels, such as galvanized steel, which enabled
developed to meet these challenges. The resulting improvements gage reductions of the sheet steel. More recent material changes
include the increased use of high-strength and ultra-high-
1
strength steels, aluminum and magnesium alloys, plastics, and
Ford Motor Company, Research and Advanced Engineering, 2101 Village Rd.,
Dearborn, MI 48124, USA https://orcid.org/0000-0002-7774-3967
plastic composites. High-strength steels have found several
The author acknowledges the previous author of this chapter, Robert Baboian, RB applications in the vehicle body structure, particularly for load-
Corrosion Service, Greenville, RI. bearing and energy-absorbing features (i.e., the crash structure)
DOI: 10.1520/MNL202NDSUP20190022
TABLE 1 Metallic Materials Used in Automotive Vehicle Systems TABLE 2 Coatings Used in the Automotive Industry
System/Component Materials Precoated Steels
Body panels and Steel, high-strength-low-alloy (HSLA) steel, coated Hot Dip Zinc, zinc-iron, aluminum, aluminum (55%)-zinc,
structure steel (zinc, zinc-iron, zinc-nickel, zinc-aluminum, zinc-aluminum (5%), zinc-aluminum-magnesium, terne
zinc-aluminum-magnesium, aluminum), high- and (lead-tin), nickel terne (nickel/lead-tin)
ultra-high strength steels, aluminum alloys, Electroplated Zinc, zinc-iron, zinc-nickel, tin plate, tin free (chrome)
magnesium alloys Organic/Precoat Zinc-rich organic primer, magnesium-rich organic primer
Chassis Steel, HSLA steel, coated steel (zinc, zinc-aluminum, Post-Applied (Protective and Decorative)
aluminum), aluminum alloys, magnesium alloys Metallic Cadmium, zinc, lead, copper, copper/nickel/chromium,
Trim and hardware Chrome-plated steel, stainless steel, aluminum, nickel/chromium, chromium (micro-discontinuous),
chrome plated zinc, stainless steel, clad aluminum chrome flash, hard chromium, nickel-iron
(bimetal), magnesium Chemical Conversion Coatings
Exhaust system Steel, coated steel (zinc, zinc-aluminum, aluminum), Inorganic Zinc phosphate, manganese phosphate, iron phosphate,
stainless steel, Monel zirconium oxide, silanes, black oxide, anodic oxide
Engine and Iron, steel, aluminum, magnesium (aluminum), oxide/chromate, magnesium oxide, zirconium
components oxide, organophosphate
Transmission Steel, stainless steels, copper and alloys, nickel and Organic Primers and Topcoats
alloys, aluminum
Organic Base Epoxies, epoxy esters, polyesters, alkyds, vinyls, acrylics,
Fasteners Steel, coated steel (wide range of metallic and oils, urethanes, cellulosics
nonmetallic coatings), aluminum
Pigments Molybdates, lead, zinc, coloring
Cooling system Copper and alloys, aluminum alloys, cast iron, steel,
Other Organics
stainless steel, solder (lead-tin, tin, zinc) braze alloy
Sealers Asphaltic, rubber, vinyl, hot melts
(aluminum, copper), brass
Fuel system Steel, coated steel (zinc, zinc-aluminum, zinc-nickel,
aluminum, lead-tin, tin) resistance for the next generation of galvanized steel was
Brake system Steel, coated steel (zinc, zinc-aluminum, zinc-nickel, highlighted in a 2016 study by Prosek et al.,13 which reported cor-
lead-tin, tin), stainless steel, cupro-nickel alloy rosion benefits through the addition of a fourth alloying element
Electrical and Aluminum, copper and alloys, coated steel (cadmium, to Zn-Al-Mg coatings on steel.
electronics chromium, nickel, copper, tin, lead), solder, beryllium, Some coatings are applied on individual components or
gold, silver stainless steels, magnesium raw materials before assembly. For example, metallic precoat-
ings for steels and organophosphate treatments for aluminum
of the vehicle body.4–6 The use of aluminum has expanded from alloys are applied to coils of sheet materials at the rolling mills,
hang-on parts, such as hoods and decklids dating back to the or are batch applied to components or preformed parts before
1970s and earlier in some models,7 to a much broader range of delivery to the original equipment manufacturer or bodyshop.
applications and structures in almost every system of the Chemical conversion coatings develop a controlled surface suit-
vehicle.8 able for subsequent painting, and the conversion coating along
Magnesium alloys, typically in cast form, also have found with the organic primer form the basis of the corrosion protec-
applications in vehicles, with different alloys developed depend- tion of the substrate by the paint system.14 These processes may
ing on their mechanical properties and service conditions.9 Their be applied both at the component level, before vehicle assem-
unfavorable and fluctuating material cost, among other factors, bly, and to the assembled vehicle body, as described in the fol-
however, has limited their application compared with aluminum lowing section.
alloys. Joost and Krajewski6 reported in 2017 that magnesium The selection of a specific material and the appropriate
makes up less than 0.5% of the weight of the average vehicle. coatings from the wide range available is made through consider-
Carbon fiber–reinforced plastics (CFRP) also suffer from unfa- ation of the mechanical, processing, cost, weight, and service
vorable material costs compared with aluminum and steel alter- environment of the target component within the overall vehicle
natives; nonetheless, some components for lower-volume system. In all cases, consideration also must be given to the cor-
vehicles have been produced from CFRP,6,10–12 allowing for sig- rosion prevention strategies required. Corrosion management of
nificant weight reductions compared with steel components. the vehicle system is particularly important when the vehicle
Metallic and nonmetallic coatings used in the automotive design includes combinations of dissimilar materials.
industry are listed in table 2. Improvements in the corrosion
resistance of galvanized steel continue with the development of
alloyed coatings of zinc-aluminum, zinc-magnesium, and zinc-
Processing
aluminum-magnesium, variants of which are commercially Automotive manufacturing processes evolve continuously, and
available at large volumes, suitable for the mass production of significant changes and new processes have been introduced to
automobiles. The quest for further enhancements in corrosion vehicle factories in recent years. Quality and efficiency are two of
AUTOMOTIVE 361
the prime drivers of innovation in automotive manufacturing. In separation strategies have been implemented to reduce galvanic
addition, the increasing use of mixed materials in contemporary corrosion at mixed-material interfaces.
vehicles has required the development of new joining methods
and approaches, with, for example, an increased use of adhesives,
rivets and novel welding techniques, at high rates, in body con- Automotive Environment
struction. Environmental legislation has stimulated innovation
The automotive environment can be categorized as (1) external
in automotive processing, particularly in the paintshop processes
exposure, (2) internal combustion exposure, and (3) internal
that traditionally consumed significant amounts of water and
functional liquids. Of these, the most complicated and the most
electricity and previously may have involved the use of restricted
highly investigated environment is external exposure.
or controlled materials. The paintshop processes that contribute
to the final vehicle corrosion resistance include the pre-treatment
EXTERNAL EXPOSURE
system, electrocoat primer (E-coat) application, sealing, painting,
The severity of external automotive corrosion varies considerably
and wax augmentation coating of the body structure.
around the world, because of differences in the chemistry of the
The vehicle manufacturer’s pretreatment system of the
environment. The most severe corrosion environments are in the
assembled body includes three main steps: (1) a cleaning stage
snowbelt areas where deicing salts are used, and along coastal
to remove oils and contamination from the assembled body,
areas where warm, humid, salty atmospheres exist. To design
(2) deposition of a pretreatment layer through a chemical con-
automobiles for corrosion resistance, it is necessary to under-
version process, and (3) rinsing the vehicle body of the pretreat-
stand the nature of the environment and how materials react in
ment chemicals.14,15 The pretreatment imparts a relatively inert,
that environment. Rain and snow are important to provide mois-
chemically resistant finish to the metal substrates and delivers a
ture to the environment. Atmospheric moisture and the condi-
consistent surface, enhancing the adhesion of the E-coat and
tions that produce fog and dew are also important. Extensive
providing the foundation for visually appealing paint finish.
studies and historic data, however, have shown that moisture
Strong adhesion of the E-coat is required to establish and main-
alone does not cause serious corrosion problems on automobiles.
tain an effective barrier to corrosion upon exposure of the vehicle
Aggressive corrosive constituents include chlorides and pollu-
to the corrosive environment.
tants. Marine environments are corrosive because of dissolved
Pretreatment and paint suppliers, in partnership with vehi-
chlorides. A typical seawater composition has a sodium chloride
cle manufacturers, continuously enhance established processes
(NaCl) content of about 3.5 wt%, although this content will vary
and materials to deliver improvements in quality, efficiency,
depending on location, such as that near tidal rivers or oceans.
effectiveness, and robustness, leading to many variants of these
Splash and spray, which cause the atmospheric redistribution of
processes and chemical systems across the industry. In addition,
seawater, are extremely important in marine environments.
an entirely new conversion coating system, based on zirconium
Larger seawater droplets fall out rapidly closer to the source.
oxide chemistry, has been introduced to the automotive industry
Smaller droplets distribute over a wide area while evaporating to
in recent years, such that vehicle manufacturers currently have
an equilibrium size and deposit according to local weather condi-
more options in their selection of a pretreatment type and vari-
tions. Slamova et al.18 mapped the global corrosivity of coastal
ant.14,16,17 The zirconium-based pretreatments are thin films,
regions using models for airborne salinity, relative humidity
about 100 times thinner than the traditional zinc phosphate sys-
(RH) levels, and atmospheric sulfur dioxide (SO2) levels and a
tems, and they are more compatible with aluminum-intensive
Geographical Information System (see fig. 1). Florida was identi-
than ferrous-dominant body structures. The zirconium thin film
fied as having the most severe coastal corrosion in the United
pretreatment process offers advantages in water consumption,
States.
energy costs, and waste generation compared with the zinc phos-
Salts applied to roadways for winter weather treatments are
phate process.
the other major source of corrosive chlorides encountered by
vehicles in service. The use of NaCl as a deicing agent for U.S.
roadways was first trialed in New Hampshire in 1938,19 with an
Design application of approximately 5,000 tons of rock salt. A concept
Design improvements have played a major role in the develop- termed “bare pavement,” under which motorists could expect
ment of corrosion-resistant vehicles. Areas of entrapment, where snow- and ice-free pavements shortly after storms, became a pol-
salt, poultice, or liquids may accumulate and generate a corrosive icy in most cities and suburbs starting from the 1950s, resulting
environment, have been eliminated to enhance corrosion resis- in a marked increase in salt use, from around 1 million tons in
tance in vehicles. For example, wheel wells are designed to have 1955 to approximately 8 million tons by 1975.20–22 The applica-
a sloping configuration so that corrosives can be washed or will tion of salt remains the primary mechanism for clearing ice- and
drain out. Drain holes have been incorporated in the lowest snow-covered roads today, and the amount of salt applied each
points of cavities that might become wet and sealers and baffles winter has continued to increase, with on average 2.5-times
are used to exclude contaminants and moisture from cavities more salt used on roads annually in the 2010–2019 decade com-
that are designed to be dry in vehicle service. Adhesives and seal- pared with 1980–1989,19,21,23 as illustrated in figure 2.
ers between and outside joints effectively eliminate crevices and Year-to-year changes in the amount of salt applied are due to
joints, thereby preventing corrosion within flanges. Isolation or variations in the severity and number of winter weather events.26
FIG. 1 Distribution of atmospheric corrosivity on the global map. Source: Reproduced from Slamova et al.18 with permission.
21,23 24,25
FIG. 2 Road salt usage and average annual emissions in the United States, 1980–2019.
AUTOMOTIVE 363
For example, the 2011–2012 winter was relatively mild nation- deicing salts as a prewetting process. Equally, dry agents can be
wide, leading to a decrease in the use of road salt in 2012,27 applied to the roads before or after a winter storm. Many brines
whereas much colder temperatures and a greater number of fro- are a blend of different chlorides and the quantities shown in
zen precipitation and winter weather events in the 2013–2014 figure 3B are based on the primary agent in the brine—that is,
winter, even in some southern U.S. states, led to a peak in road NaCl brine also may contain some amount of magnesium or cal-
salt usage of 30 million tons in calendar year 2014.28 cium chloride and vice versa. Composition of the enhanced brines
The number of types, as well as the total amount, of road shown in figure 3B was not given in the Clear Roads report,20 but
salts has increased significantly.20 Different agents may be it is likely a blend of salts—for example, the data sheet for one par-
required depending on the road condition: the use of NaCl is not ticular enhanced brine deicer reported 13% NaCl, 8% calcium
effective if the pavement temperature is below -10 C. In such chloride, and 2% magnesium chloride content.30
cases, a more expensive chloride or acetate treatment is required A 2007 study by Prosek et al.33 found that the type of chlo-
to prevent or remove ice formation on the road. Some general ride used affected the corrosion rates for steel and zinc sub-
properties of the deicing agents summarized by the Western strates. The effect of the cations (Naþ, Mg2þ or Ca2þ) was
Transportation Institute29 and with cost data taken from Kelting stronger for the zinc substrate under the test conditions used and
and Laxson30 are shown in table 3. the corrosivity effects of the chlorides on zinc increased in the
The various treatment agents may be applied to roadways in order of MgCl2 < CaCl2 < NaCl. This finding was later corrobo-
dry or wet form, as indicated in figure 3. Salt brines may be used rated by a study at the Swedish Corrosion Institute,34 which
as anti-icing agents when sprayed to the roadways before a winter reported a similar effect of chloride cations on zinc corrosion
storm, or used as a deicing agent when they are sprayed onto rates in both a laboratory cyclic corrosion test and an outdoor
exposure with weekly spray by pollutants. The order of corrosiv-
ity was different for steel substrates compared to zinc substrates
TABLE 3 Summary of Road Treatment Agent Properties in both studies, with NaCl < CaCl2 < MgCl2. The reversal of the
trend of chloride corrosivity between zinc and steel was attrib-
uted to the hydrolyzation of the bivalent cations Mg2þ and Ca2þ,
Lower Functional
Agent Type Formula Temperature Cost per Tona leading to an overall reduction in pH in the surface electrolyte,
Sodium chloride NaCl 9 C (15 F) $42
which tends to promote steel corrosion but inhibit zinc corrosion
Magnesium chloride MgCl2 21 C (-5 F) $111
under atmospheric conditions. These findings highlight the
Calcium chloride CaCl2 26 C (-15 F) $140
importance of the interactions of the chloride cations with the
Potassium acetate KAc 32 C (-26 F) $1,166
electrolyte and, subsequently, with the substrate material.
Calcium magnesium CMA 18 C (0 F) $1,492
The various chlorides also have different characteristics in
acetate terms of their capacity to absorb water vapor at different atmo-
a
spheric conditions (e.g., RH and temperature). Magnesium and
Costs reported in 2010, relevant for comparison purposes only.
29
Source: Adapted from Western Transportation Institute, and with cost informa- calcium chloride absorb water and form a liquid over a much
30
tion from Kelting and Laxson. broader range of RH conditions (RH > 30%) than NaCl
FIG. 3 Types and amounts of (A) dry, and (B) liquid, treatment agents used on U.S. roadways over the 2018–2019 winter season. Source:
20,32
Data taken from Clear Roads and New Jersey Department of Transportation.
(RH > 75%), leading to greater opportunity for electrolyte film both the level of industrialization and the impact of air-pollution
formation and corrosion reactions to occur under different controls. The data in figure 2 show the marked decrease in the
atmospheric exposures.33–35 In the experiments performed by average SO2 concentration measured at 37 sites across the
Prosek et al.,33 water absorption was not found to be higher for United States, as reported by the Environmental Protection
zinc samples dosed with MgCl2 and CaCl2 compared with NaCl, Agency.25 The presence of SO2 in the atmosphere and its effect
and the authors concluded that an important interaction of the on corrosion has been studied extensively. The complex reaction
cations with the substrates controlled the corrosion dynamics. involves the SO2 molecule striking a metal surface and convert-
The influence of sugars, as found in agricultural byproducts, ing to sulfuric acid as a result of oxidation and hydrolysis. This
mixed with salts was also investigated by Jönsson.34 The influ- introduces reactive ions, increased conductivity, and a lower pH.
ence of the sugar additives in laboratory cyclic corrosion test was The presence of hygroscopic sulfate corrosion products also low-
not observed, but reduced corrosion rates (50% and 25%, respec- ers the critical humidity for corrosion reaction.
tively) were observed for steel and zinc with sugar-salt blends Nitrous oxides, NO and NO2 (collectively known as NOx),
exposed in the outdoor corrosion test. The benefit of the sugar are produced by fossil fuel consumption and their concentration
additive on the corrosion performance was attributed to the abil- in the atmosphere reflects the level of industrialization, as well as
ity of the sugar to block the metal surface from the corrosive the density of gasoline and diesel-fueled vehicles, in a given
environment. This blocking was not effective in the laboratory region. NO from tailpipe emissions is rapidly converted to NO2
cyclic corrosion test because the sugar-dosing of the surface in the air37 and measurements of NO2 in the atmosphere are
occurred only once at the start of the test and was not replen- chiefly influenced by vehicle emissions. Significant progress has
ished during the exposure. The importance of the exposure con- been made in reducing the levels of NOx emissions from
ditions, and indeed the duration of the exposure for the slow vehicles, with a 25-factor reduction in median NOx emissions
kinetics that can be associated with corrosion processes and cor- measured for newer (around 2 years in service) versus older (up
rosion product formation and transformation, is highlighted by to 28 years in service) gasoline-fueled vehicles in a 2014 study by
these observations. May et al.38 Reduction of NOx emissions from diesel-fueled
A 2006 study by Blücher, Svensson, and Johansson35 investi- vehicles is more challenging,39,40 although a 50% reduction mea-
gated the effects of aluminum, magnesium, and sodium chlorides sured by May et al. for newer versus older heavy-duty diesel
on high-purity aluminum under controlled atmospheres with and vehicles38 indicated some progress toward that aim. Technical
without carbon dioxide. In the carbon dioxide–free (<1 ppm) challenges, possibly compounded by older vehicle fleets, heavy
atmosphere, the corrosivity of the chloride salts increased in the congestion, and greater numbers of vehicles on the roads, have
order MgCl2.6H2O < AlCl3.6H2O < NaCl. When the experiment resulted in a more modest reduction in NO2 pollution compared
was repeated with approximately ambient levels of carbon dioxide with SO2 over the past few decades (see fig. 2). This has led to an
(350 ppm), strong inhibition of corrosion by NaCl was observed, increase in the relative NO2/SO2 molar ratio over time.41 Labora-
and similar aluminum corrosion rates were found for all three tory tests have shown a synergistic effect of the corrosiveness of
chloride types. The authors concluded that the availability of car- SO2 to steel,41 zinc,42,43 and nickel,44 but not aluminum,45 in the
bon dioxide to form carbonates on the corroding aluminum sur- presence of NO2 and high RH. The marked influence of NO2 on
face tended to inhibit corrosion activity at high pH sites and SO2 corrosivity to those metals measured in controlled laboratory
attenuate overall corrosion rates. This important effect of carbon exposures has not been observed in outdoor exposures,36,44,46 pre-
dioxide also has been reported for zinc and magnesium, and labo- sumably because of the more complicated and varying chemistry,
ratory tests that do not account for these atmospheric influences temperature, and RH of the outdoor environment.
may lead to false predictions of corrosion rates in the field. At the The combined effect of chloride (a film disruptor on metals)
same time, the lack of access to atmospheric carbon dioxide, oxy- and acids formed from atmospheric pollutants (which provide
gen, and drying cycles can occur on a vehicle in service—for reducible hydrogen ions) can be much worse than the added sep-
example, underpaint corrosion of a galvanized steel or aluminum arate effects. Thus, geographic areas that are subjected to both
body panel or crevice corrosion within a weld flange or under an road or marine salts and acid deposition are likely to be the most
adhesive bead. The general studies published in the literature corrosive to automobiles. The external environment in which
highlight a need for further specific research on the effects of dif- vehicles operate has become increasingly complex and varies
ferent road treatment agents, including acetates, on automotive considerably from region to region. The general corrosivity cate-
vehicle construction materials, joint configurations, and painted gories of rural, industrial, and marine considered in atmospheric
substrates. corrosion studies and defined by ISO standard 922347 may not
Atmospheric pollutants, including sulfur dioxide, nitrogen consider the very high seasonal chloride contamination of
oxides, hydrogen sulfide, ammonia, ozone (SO2, NOx, H2S, NH3, vehicles driving on salt-treated roads. Therefore, the automotive
O3 respectively), and particulate matter, are known to influence engineer must pay attention to this significant and automotive-
the corrosion of metals. Leygraf and Graedel36 reported that steel specific corrosive environment. Another important factor in the
and zinc have high sensitivity, and aluminum has moderate sen- external environment that is specific to vehicles is the highly
sitivity, to corrosion because of the presence of SO2 and SO4. localized and corrosive environment produced by the accumula-
Fossil fuel consumption is a major source of atmospheric SO236 tion of dirt, vegetation, and other debris in metallic entrapment
and the levels of SO2 pollution in a given region tend to reflect areas.48 These areas remain wet almost continuously because of
AUTOMOTIVE 365
the presence of this poultice and produce a stationary electrolyte glycol are required to impart corrosion inhibition, pH buffering
environment. The result is a concentrating effect of the corrosive or neutralizer, foam suppression, and identification color to the
species, similar to the phenomena observed in crevices. When coolant. The selection of the coolant package depends on the
metals are exposed to this poultice environment, the corrosion materials and operating conditions of the cooling system. Cool-
process may become autocatalytic, leading to rapid deterioration. ant systems up to around 1995 typically were of dilute ethylene
glycol with corrosion inhibitors based on inorganic compounds,
INTERNAL COMBUSTION EXPOSURE such as silicates, phosphates, and nitrites.55 These inhibitors
Internal combustion produces water vapor and exhaust gases, operate effectively for vehicles with cast iron engine blocks and
which can condense in internal areas such as the exhaust system heads, and copper or brass in the heat exchangers. Their mode
of automobiles.49–51 This condensate chemistry includes sulfate, of corrosion protection, however, depletes the inhibitor content
sulfite, nitrate, ammonium, carbonate, bicarbonate, and chloride at a rate that requires their replenishment, or replacement of the
ions. The acidity of the condensate is high because of the pres- coolant, within 2–3 years of operation.55 A testing and replenish-
ence of nitric, hydrochloric, sulfuric, and sulfurous acids. Nitric ment strategy may be feasible within heavy truck fleets but a bet-
acid is formed from atmospheric nitrogen, which is converted to ter solution for light-duty vehicles emerged in 1995, when
oxides in the engine and then to the acid. Sulfuric and sulfurous General Motors introduced a long-life coolant, which used
acids are formed because fuels and lubricating oils contain sulfur, organic acid technology (OAT) or hybrid organic acid technol-
which converts to SO2 and then reacts with water vapor to form ogy (HOAT) corrosion inhibition systems.55 instead of inorganic
these acids. In addition, catalytic converters are designed to con- inhibitors. OAT- or HOAT-inhibitor coolants have a 5-year or
vert SO2 to SO3 yielding acids. Chloride additives to fuels yield 150,000-mile projected service life, because of their slower inhibi-
hydrochloric acid. tor-depletion rate compared to inorganic inhibitors. Coolants for
The temperature of the system has a great impact on the vehicles with aluminum blocks and heads also may be configured
environment within the exhaust system. If the system does not with lower pH control than coolants for vehicles with cast iron
become hot enough (above the dew point), the condensate blocks and heads to enhance the corrosion protection of the for-
remains and concentrates. Thus, vehicles that are driven for mer. Further developments in coolant technology have targeted
short distances are more susceptible to corrosion by exhaust gas longer service life, or greater tolerance to nonideal operating
condensates, sometimes referred to as cold-condensate corro- conditions, such as coolant makeup with chloride-containing
sion.49 The inclusion of drain holes at strategic locations in the water or excessive temperatures or pressures within the cooling
exhaust system helps to avoid the accumulation of these corro- system.
dents.51 Deterioration is also accelerated by stress (both cyclic The functions of engine oil are manifold, including the dis-
and static) and by design configurations (such as at joints and sipation of heat, reduction of friction and wear, detergency, seal-
welds). ing of critical areas, and separation of water.56 The composition
Direct exhaust-gas impingement (erosion corrosion) can of the oil is about 75–90% base stock (such as mineral oil) and
occur because of the high-velocity exhaust gas stream on the 10–25% chemical additives, such as viscosity index (VI)
internal surfaces of the exhaust system. This effect is important improvers, antioxidants, corrosion inhibitors, detergents, disper-
at sharp bends and surfaces normal to the gas flow. The combi- sants, and antifoam agents. The performance of engine oil
nation of particulate matter with hot corrosive gas produces this depends on the blend of these chemically active and chemically
type of attack. inert additives. The aging of engine oil, as determined by the
High-temperature oxidation of exhaust system components type of driving and exposure to contaminants,57 can result in an
is governed mainly by the temperature encountered, as well as aggressive liquid. Examples include oxidized oil resulting from
the exhaust gas composition. Temperatures measured near the exposure to heat and oxygen, loss of buffer when it is used up in
exhaust-manifold typically range up to 800 C and the skin tem- neutralizing acids, and contamination by coolant, gasoline, and
perature of metal components in this area can reach 600 C. engine exhaust gases. Prolonged use of aged engine oil can lead
to general corrosion, pitting, fretting, and erosion corrosion.
INTERNAL FUNCTIONAL LIQUIDS Automatic transmission fluid (ATF) performs many func-
The vehicle includes many internal functional liquids, such as tions, including cooling and lubrication, and it also must main-
engine coolants, engine oil, transmission fluid, hydraulic brake tain the friction-speed characteristics that prevent shudder.58
line fluid, and fuels. The function of engine coolants is to transfer ATF consists of a base mineral (paraffinic, naphthenic, and aro-
heat from the engine to the radiator where it is dissipated and matic hydrocarbons) or synthetic base oils and an additive pack-
used to provide heat to the passenger compartment. Properties age. The additives prevent fluid oxidation, corrosion, loss of
must include high specific heat, good thermal conductivity, low lubricity, and foaming. Even though antioxidants, inhibitors, and
freezing point, high boiling point, chemical stability, and noncor- stabilizers are added to the ATF, the base oil can react with oxy-
rosivity. The coolant system includes many different metals, as gen to form organic acids. The acidity is quantitatively measured
noted in table 1. Glycols remain the principal component of as the total acid number (TAN). In addition, some additives,
modern coolants,52,53 and ethylene glycol diluted to a 50 vol% such as organothiophosphates, are reactive to some metals.
solution with water provides boiling point protection to 130 C Hydraulic brake line fluids are usually glycols, and commer-
and freezing point protection to -37 C.54 Additives to the dilute cial brake fluids are hygroscopic and absorb moisture when
exposed to humid atmosphere. Water contamination also can Corrosion degradation generally is classified into structural
occur from atmospheric condensation. The result of this water (inside-out) and cosmetic (outside-in) corrosion. Structural corro-
contamination is a liquid with various degrees of corrosivity sion in the auto-body may lead to perforation of the panel, gener-
toward brake cylinders, the master cylinder, hydraulic brake line ally from the inside out, as shown in figure 4. Cosmetic corrosion
tubing, and other brake system components.59 eventually may lead to perforation, from outside to inside, if repair
or remedial actions are not implemented. Structural corrosion is
most likely to occur at crevices, such as weld flanges, hem flanges,
and other entrapment areas where poultice can build up and
Corrosion Mechanisms moisture can accumulate. The most visible part of the automobile
The occurrences and modes of corrosion on automobiles depend is the exterior body panel structure and cosmetic corrosion usually
on such factors as physical and chemical properties of the envi- is associated with these high-visibility, painted, outer-body panels.
ronment, vehicle construction materials, and the specific applica- The quality and nature of the paint–metal interface is important
tion. A summary of corrosion mechanisms according to different to avoid premature cosmetic corrosion. Paint coating failure can
applications is given in table 4. Although they have many modes initiate at thin, missing, or damaged paint associated with the cut
in common, different forms of corrosion may occur for ferrous edges of panels, fretting effects, abrasion from sand, or chips from
versus nonferrous metals, particularly for painted body panels, as gravel impingement. Propagation of corrosion under the paint
noted in table 4. can be stimulated by a wide range of mechanisms, including
TABLE 4 Corrosion Mechanisms in Automobile Applications
System/Component Ferrous Nonferrous
Body Panels, Structural Uniform, pitting, crevice, fretting, poultice, coating failure, stress Pitting, intergranular, galvanic, exfoliation, crevice, stress cracking,
cracking, galvanic galvanic
Body Panels, Cosmetic Paint blistering, paint delamination, perforation, galvanic, fretting Filiform, paint blistering, paint delamination, perforation,
galvanic, fretting
Chassis Uniform, pitting, crevice, fretting, stress cracking, coating failure, Pitting, intergranular, crevice, fretting, stress cracking, coating
poultice, galvanic failure, poultice, galvanic
Trim and Hardware Uniform, pitting, intergranular, crevice, galvanic, dealloying, fretting, stress cracking, coating failure, poultice
Engine and Components Uniform, pitting, crevice, galvanic, dealloying, fretting, intergranular, stress cracking, high temperature oxidation
Transmission Uniform, crevice, galvanic, fretting
Fasteners Uniform, pitting, crevice, galvanic, fretting, stress cracking, coating failure
Cooling System Uniform, pitting, crevice, galvanic, dealloying, erosion, cavitation, intergranular
Fuel System Pitting, crevice, coating failure
Brake System Pitting, crevice, galvanic, fretting, coating failure
Electrical and Electronics Fretting, uniform, pitting, crevice, galvanic, dealloying, stress cracking, coating failure, corrosion product creep
Exhaust System Uniform, pitting, crevice, dealloying, erosion, fretting, intergranular, stress cracking, coating failure, high-temperature oxidation
FIG. 4 Ferrous corrosion examples, with (A) structural corrosion (inside-out perforation) at the leading edge of the steel hood and
(B) cosmetic corrosion (outside-in) on a roof panel where the paint was damaged by stone impingement.
AUTOMOTIVE 367
differential cells, cathodic disbondment, anodic undermining, fili- zinc coating has previously corroded) and the aluminum.60 Pit-
form corrosion, galvanic (bimetallic) effects, and fretting. Exam- ting corrosion of an aluminum heat shield because of the instal-
ples of these corrosion modes are shown in figures 4–6. lation of a steel fastener and the exposure of both to the road
Galvanic corrosion can occur if two dissimilar materials are environment, can lead to the perforation of the thin sheet com-
joined and exposed to the corrosive environment; the more ponent, as shown in figure 6.
anodic of the two materials will corrode at a high rate, which The chassis and vehicle underbody are susceptible to
may lead to perforation within the lifetime of the vehicle. Gal- mechanical damage of coatings due to dirt, sand, and stone
vanic corrosion is avoided by careful management of dissimilar impingements and seasonal dousing in salty water because of
material interfaces, including the use of isolation or separation their proximity to external road conditions. Coatings failure can
components and robust barrier coatings and moisture exclusion enhance deterioration, as can poultice that is built up in entrap-
strategies. CFRP and stainless steel are two of the most noble ment areas. The vehicle underbody may be considered to be “low
materials used in automotive construction, and any materials visibility” and therefore not subject to stringent requirements for
joined to these materials are prone to galvanic corrosion attack.12 cosmetic corrosion resistance, depending on the customer usage
Aluminum is frequently joined to galvanized steel in vehicle profile in a given market; however, the safety-critical chassis and
structures with optimized strength-to-weight designs, and alumi- structural components in the underbody must have adequate cor-
num alloys may suffer increased pitting attack when a galvanic rosion resistance to avoid functional degradation for the entire
cell is established between steel (e.g., at a cut edge or where the life of the vehicle, typically considered to be at least 15 years.
FIG. 5 Cosmetic corrosion on painted aluminum panels: (A) paint blistering and delamination and (B) paint blistering and filiform
corrosion.
FIG. 6 Corrosion associated with (A) fretting action between rear bumper panel and bodyside panel and (B) galvanic corrosion of
aluminum heat shield with ferrous fastener.
FIG. 7 Assessments of underbody corrosion resistance showing: (A) superficial rust of uncoated chassis components, and (B) coated
components showing no corrosion attack. Source: Photos courtesy of Ford Motor Company.
Trim and hardware are used for several reasons, including it necessary for the industry to improve corrosion protection
styling, hiding of joints and welds, and protection from mechani- through (1) proper design, (2) choice of corrosion-resistant
cal damage. Underbody shields may offer dual-functionality with materials, (3) use of coatings and sealants, and (4) proper con-
both aerodynamic and corrosion resistance benefits through sumer maintenance.63–66
air flow control and protection of the underlying vehicle struc- Proper design has been recognized as an important aspect
tures from stones, sand, and water splashed up by the tires. of automobile corrosion resistance.65,66 Thus, elimination of
Trim materials, such as stainless steel and anodized aluminum, entrapment areas where moisture and poultice can collect, mini-
are susceptible to pitting, crevice corrosion, and discoloration. mization of crevice configurations, elimination of unnecessary
Stainless steel and chromed trim materials can cause galvanic holes in body panels, provision of drainage holes, access for com-
corrosion of painted auto-body steel and aluminum panels. Con- plete pretreatment and primer coverage, and elimination of dis-
versely, some trim materials such as aluminum and zinc die cast similar metal crevices are common practices in the design of
are anodic to auto-body steel and corrode sacrificially. automobiles.
The exhaust system and engine are exposed to a dual (exter- The development of automotive construction materials with
nal and exhaust gas) environment. Therefore, the materials must enhanced corrosion resistance (compared with bare steel) is one
be chosen to perform in more complex service conditions. High of the most important factors in the development of corrosion-
temperatures are important along with the chemistry of the resistant automobiles. The use of precoated steel is typical for all
exhaust gas condensate. Corrosion mechanisms include those automobile body and chassis parts exposed to the external envi-
normal in the external environment with the additional tempera- ronment. A wide range of materials is used as coatings, including
ture factor.49,61 hot dip and electrodeposited zinc, zinc-iron, zinc-aluminum,
Electrical and electronic systems are extremely susceptible zinc-aluminum-magnesium, zinc-nickel, and zinc-nickel/organic
to corrosion caused by the aggressive automobile environment. composite-coated steel. Other materials include aluminum- and
This susceptibility has only increased with the development of aluminum-zinc-coated steels, stainless steels for exhaust systems,
much smaller electronic units in recent times.62 Fretting, pitting, terne- (tin-lead) coated steel for fuel tanks, and tin-coated steel.67
crevice, and galvanic corrosion, and corrosion product creep are New alloys have been introduced for specific automobile
all important mechanisms. In many cases, these mechanisms are applications, including type 434 stainless steel for exterior trim,
accelerated by leakage currents, which impose a potential bias on type 409 and 430 stainless steels for exhaust systems, and alumi-
the materials. num alloys from the 5XXX, 6XXX with and without post-form
heat treatment (PFHT), and 7XXX series for auto-body and
structural parts. The use of aluminum for body panels such as
Controlling Automotive Corrosion hoods and decklids has prompted the development of new proc-
This section discusses strategies to avoid, manage, and control essing and corrosion protection techniques for this material.
automotive corrosion for vehicle systems exposed to the exterior Today, many vehicle bodies are almost completely constructed
and internal combustion environments. It also presents consider- from aluminum alloys, pioneered by the Audi A8 and imple-
ations for liquid passages and reservoirs, and electrical and elec- mented on the Tesla Model S, Jaguar XJ and Honda NSZ, among
tronic systems. others. The highest-volume enterprise in the use of aluminum-
intensive body structures is the Ford F150 truck body (see the
EXTERIOR EXPOSURE material details in fig. 8).68 Many other advanced body structures
The severe corrosivity of the automobile environment resulting utilize a mixed-material strategy, with targeted applications of
from road salts, atmospheric salts, and acid deposition has made aluminum alloys in sheet, extrusion, and cast form, along with
AUTOMOTIVE 369
adhesion of the paint to the assembled body. Then, an epoxy

68
FIG. 8 Materials used in the Ford F150 truck body. primer is applied by cathodic electrocoating, whereby the assem-
bled body is negatively charged and is immersed in an aqueous
bath where it is coated with a positively charged organic primer
under the influence of an electric field. The advantages of this pro-
cess, known as E-coating, include uniform coverage, edge protec-
tion, penetration into enclosed areas, and full automation. The
next step is a primer surfacer, which offers protection against
stone-chipping, provides adhesion to the topcoat and prevents
ultraviolet (UV) light from reaching the UV-sensitive E-coat
layer.64 Finally, the topcoat is applied, usually in two or more
steps, including a base coat and a clear coat. These are generally
advanced and ultra-high-strength steels, exemplified in the Cad- enamels and urethanes. The performance of these complex
illac CT6 and Chevrolet Malibu.69 painted auto-body materials in the aggressive automobile environ-
A wide range of inorganic and organic coatings and sealants ment is understandably dependent on a number of factors. Photo-
is used to provide supplemental corrosion protection to automo- graphs of the paint stages are shown in figure 9 and typical
biles.64,70 Conversion coatings formed by the interaction of the thicknesses and functions of the paint layers are noted in figure 10.
metal surface with constituents in solution to form an inert inor- Sealers play an important role in automobile corrosion pro-
ganic film may be used for components supplied to the automo- tection by preventing water and contaminants from entering
tive manufacturer. Examples of pretreatments used in the crevices and joints. Examples of the different types of additional
automotive industry are phosphate, zirconium, chromate, and coatings and sealers that may be applied to vehicles and their
various anodized and oxide coatings. Organic coatings also are functions are shown in figure 11. These protective materials may
used extensively, and they function as a barrier between the be applied to the E-coated body (and under topcoat) and to the
metal surface and the environment. These include primers, underbody. The choice depends on the specific application, such
waxes, seam sealers, shields to mechanical damage, and petro- as at door hem flanges, brackets, fasteners, and body joints.
leum-based rust preventives. Structural adhesives also are used to bond assemblies, such as
The automobile paint system involves several different pro- doors, decklids, and hoods, thereby sealing crevices and eliminat-
cess steps and coating layers.64,70 The first stage of the paintshop ing welds.
line includes cleaning and a conversion coating, such as phosphate Consumer maintenance is an important part of automobile
or zirconium, to improve corrosion protection and ensure good corrosion protection. Automobile manufacturers have provided
FIG. 9 Photographs of a car body in different stages of the paintshop: (A) E-coat, (B) primer, (C) basecoat, and (D) clearcoat applications.
Source: Photos courtesy of Ford Motor Company.
70
FIG. 10 Automotive paint layers, including typical thicknesses and functions. Source: Reproduced from Akafuah et al.,
with permission.
FIG. 11 Coatings and sealers that may be applied to the vehicle body, and their functions. Source: Figure reproduced from Akafuah et al.,70
with permission.
recommendations for maintenance to prevent deterioration from acidity buildup due to the decomposition of base organics can
corrosion. The first defense is regular washing to remove road occur, however, depending on the nature of vehicle use and
salts and other corrosive agents, and poultice. The procedure maintenance practice. For example, engine coolant formulations
should ensure that mud and dirt is removed from entrapment contain a complex inhibitor package providing protection to
areas underneath the vehicle. Drain holes should be cleaned out. component metals, such as copper, steel, aluminum, and sol-
The second defense includes repair of paint damage to avoid der.54 When inhibitor depletion occurs, failure of an aluminum
propagation of corrosion in these areas. Precautions should be water pump due to corrosion can result, but this component is
taken to exclude corrosive agents from the interior, such as driv- easily replaced. When a transmission component fails due to cor-
ing in or splashing seawater or road deicing salt puddles on the rosion, replacement is more costly and therefore more corro-
vehicle, although many customers may choose to use their sion-resistant materials generally are used. For example, copper
vehicles in such off-road scenarios. The corrosion engineer and brass may corrode in used ATF, whereas steels and stainless
should consider the customer usage profile for any new vehicle steels are generally resistant in that environment. The develop-
design. ment of long-life coolant systems and a proper maintenance
schedule of replacement of these fluids are very important in
INTERNAL COMBUSTION maintaining corrosion protection within liquid passages and
The service life of exhaust systems has been greatly extended reservoirs.55
through the use of more corrosion-resistant materials, most
notable ferritic 400-series stainless alloys.51 The use of catalytic ELECTRICAL AND ELECTRONIC SYSTEMS
converters presents some special problems because of the cata- The use of electrical and electronic components on automobiles
lyzed oxidation reactions that take place in the exhaust gas has increased dramatically in recent years, such that electronic
stream. The converter itself must be highly corrosion resistant systems are now an integral part of all types of vehicles with
because of its location near the exhaust manifold and the reac- more than 400 connectors and 3,000 electrical contacts on board
tion to form acids such as sulfuric acid. Therefore, stainless steel a single vehicle.71 Electronic sensors are primed for deployment
is used widely for the catalytic converter canister. More corro- in self-driving cars, and it has been predicted that electronic
sion-resistant materials also are being used downstream from the devices will constitute 50% of total vehicle cost by 2030.72 These
converter. devices and systems enable new functions and capability for the
automotive engineer, and offer enhanced safety, convenience,
LIQUID PASSAGES AND RESERVOIRS and comfort to the vehicle driver. The primary method for cor-
Internal functional liquids generally have inhibitors in the for- rosion protection of these systems is to minimize exposure to the
mulation to minimize degradation caused by corrosion. These environment by locating wiring and other components within
inhibitors provide the necessary protection as long as they are the passenger compartment, by shielding or providing good
present in the required concentration. Inhibitor depletion and drainage, and by sealing and coating.73 Proper design,
AUTOMOTIVE 371
manufacturing, and quality are a precursor. Electrical connectors and exposure periods must be chosen carefully so that under- or
allow electronic devices and components to be installed and over-exposure is avoided, and the degree of corrosion developed
maintained individually, or in chunks, within the full vehicle gives a reasonable prediction of the real, in-service scenario.
electrical system. Such an architecture enables efficiency and Some methods and guidelines that are used in the automobile
flexibility in individual vehicle configurations, as well as lower- industry for design and interpretation of corrosion tests are listed
cost part replacement, upgrades and service.74 The use of noble in table 5.
metals, notably gold, for electrical contacts provides corrosion
resistance, but their cost prohibits their use in the automotive
industry with the exception of high-performance race cars.71
Copper alloys generally are used for automotive electrical
TABLE 5 Test Methods and Guidelines for the Design and Inter-
contacts and contact failure can occur through a fretting corro-
pretation of Corrosion Tests
sion mechanism. The damage to the contacts’ surfaces from the
vibrational fretting action leads to wear particles, which are oxi-
dized in air. The presence of the resultant corrosion products Test Method or Guideline Organization
increases the electrical resistance between two parts of electrical Standard Practice for Rating of Electroplated Panels ASTM B537
contact, resulting in contact failure.72 Automobile printed circuit Subjected to Atmospheric Exposure
boards (PCBs) are sensitive to a specific corrosion mechanism Standard Practice for Preparation of Cold-Rolled Steel ASTM D609
known as corrosion product creep, whereby moisture adsorbed Panels for Testing Paint, Varnish, Conversion Coatings,
on the surface of the PCB and exposed to atmospheric pollutants and Related Coating Products
leads to the growth of copper- or tin-containing corrosion prod- Standard Practice for Evaluating Degree of Rusting on ASTM D610
ucts.71 Various organic and inorganic coatings are used to Painted Steel Surfaces
exclude air, moisture, and chemical contaminants and to Standard Test Method for Evaluation of Painted or ASTM D1654
Coated Specimens Subjected to Corrosive Environments
increase lubricity and reduce thermal degradation within the
Standard Guide for Testing Filiform Corrosion Resistance ASTM D2803
electrical system. These include paint, primer, varnish, resin, sili-
of Organic Coatings on Metal
cone compounds, oil, and greases. A wide range of sealed con-
Standard Practice for Preparing, Cleaning, and ASTM G1/
nectors has been developed for use on automobiles because even
Evaluating Corrosion Test Specimens ISO 8407
the best selection of base materials and plating cannot provide
Standard Practice for Conventions Applicable to ASTM G3
the necessary termination protection in the severe automotive
Electrochemical Measurements in Corrosion Testing
environment. The problems associated with leakage currents
Standard Guide for Applying Statistics to Analysis of ASTM G16
(bias) have been addressed by ensuring that proper barrier coat- Corrosion Data
ings, sealing, and design are used. Standard Guide for Laboratory Immersion Corrosion ASTM G31
Testing of Metals
Standard Practice for Recording Data from Atmospheric ASTM G33
Test Methods Corrosion Tests of Metallic-Coated Steel Specimens
Standard Guide for Examination and Evaluation of ASTM G46
Corrosion testing has played a major role in the development of
Pitting Corrosion
corrosion-resistant automobiles. These tests generally are classi-
Standard Guide for Conducting and Evaluating Galvanic ASTM G71
fied as laboratory tests or field tests. The difference involves the
Corrosion Tests in Electrolytes
nature of the environment and the duration of the test. Labora-
Standard Guide for Development and Use of a Galvanic ASTM G82
tory tests simulate the environment and accelerate corrosion
Series for Predicting Galvanic Corrosion Performance
processes, whereas field tests are conducted in the natural envi-
Standard Practice for Calculation of Corrosion Rates ASTM G102
ronment usually without additional acceleration factors. Some and Related Information from Electrochemical
tests combine a simulated environment and the natural environ- Measurements
ment. Although laboratory test results are obtained in shorter Standard Guide for Conducting Exfoliation Corrosion ASTM G112
times, field test results are more reliable because they are con- Tests in Aluminum Alloys
ducted in the actual environment. The design and interpretation Standard Terminology and Acronyms Relating to ASTM G193/
of laboratory tests are important to obtain data for material Corrosion ISO 8044
selection, process approval, and joint designs for corrosion-resis- Corrosion Tests in Artificial Atmosphere—General ISO 7384
tant vehicles. Requirements
Test parameters are categorized according to their chemical Methods for Corrosion Testing of Metallic and Other ISO 10289
and physical effects. Chemical parameters involve the composi- Inorganic Coatings on Metallic Substrates—Rating of
tion of the environment, such as the concentration of constitu- Test Specimens and Manufactured Articles Subjected to
ents, pH, and dissolved gases. The complexity of the automobile Corrosion Tests
environment was described earlier in this chapter. The physical Guidelines for the Introduction of Scribe Marks through ISO/DIS 17872
Coatings on Metallic Panels for Corrosion Testing
conditions include temperature, static or flowing solution or
Direct Calculations of Economic Appraisals of Corrosion NACE RP0272
vapor, liquid or atmospheric volume, and mechanical factors
Control Measures
such as stress and impingement. Finally, the duration of the test
LABORATORY TESTS: EXTERNAL EXPOSURE

Categories of laboratory tests are as follows: electrochemical, TABLE 7 Standard Immersion Tests Used on Automotive
immersion, chamber, cyclic, and proving grounds. These acceler- Materials
ated tests require (1) selection of environmental and physical
conditions representative of service exposure, (2) accelerated cor- Test Method Organization
rosion rates without a change in the mechanism, (3) reproduc- Standard Test Methods for Evaluating the Corrosion ASTM B895
ibility of results, and (4) acceleration factors which relate to Resistance of Stainless Steel Powder Metallurgy (PM)
service performance. Parts/Specimens by Immersion in a Sodium Chloride
Electrochemical tests are rapid techniques to determine Solution
mechanisms, determine the effect of various parameters on cor- Standard Test Method for Exfoliation Corrosion ASTM G34
rosion rate, and screen out a large number of materials.75 They Susceptibility in 2XXX and 7XXX Series Aluminum Alloys
usually involve measurement of corrosion potentials, corrosion (EXCO Test)
currents, polarization curves, and electrochemical impedance. Standard Practice for Exposure of Metals and Alloys by ASTM G44
They are used to evaluate metals and alloys and the behavior of Alternate Immersion in Neutral 3.5% Sodium Chloride
metallic, inorganic, and organic coatings. The simplest test Solution
involves the measurement of the corrosion potential and its use Standard Test Method for Pitting and Crevice Corrosion ASTM G48
Resistance of Stainless Steels and Related Alloys by the
in conjunction with other measurements. A zero-resistance
Use of Ferric Chloride Solution
ammeter (ZRA) is used to measure corrosion currents between
Standard Test Method for Visual Assessment of Exfoliation ASTM G66
dissimilar metals and alloys. Controlled potential tests and
Corrosion Susceptibility of 5XXX Series Aluminum Alloys
anodic and cathodic polarization curves using potentiostats are (ASSET Test)
the most commonly used electrochemical tests. These are power- Standard Test Method for Determining the Susceptibility ASTM G67
ful tools for investigating the effect of various parameters on cor- to Intergranular Corrosion of 5XXX Series Aluminum Alloys
rosion behavior. Cyclic polarization and polarization resistance by Mass Loss after Exposure to Nitric Acid (NAMLT Test)
tests are used to probe localized corrosion and the corrosion rate Standard Practice for Evaluating Intergranular Corrosion ASTM G110/
of material surfaces. Electrochemical tests used for corrosion Resistance of Heat Treatable Aluminum Alloys by ISO 11846
tests in the automobile industry are listed in table 6. Immersion in Sodium ChlorideþHydrogen Peroxide
Immersion tests, whereby specimens are immersed in a Solution
fluid of interest, that might be used in the automotive industry
are listed in table 7. Variations of the test can be used to enhance produce wetting and drying effects. The latter test, along with
certain types of exposure such as partial immersion to create the ferric chloride spot test, is used to determine the behavior of
oxygen concentration cells, and alternate (cyclic) immersion to exterior stainless steel trim materials.
Environmental or corrosion test chambers enable the corro-
sion engineer to approximate a desired environment under
TABLE 6 Common Electrochemical Tests Used on Automotive controlled conditions. A list of tests that typically require such
Materials chambers is given in table 8. The simplest of these tests is the
humidity test, whereby the temperature and RH within a cham-
Test Method Organization
ber are controlled. A condensing humidity chamber, which oper-
ates at 100% RH and 38 C, provides an environment whereby
Standard Reference Test Method for Making ASTM G5
condensation occurs continuously on the specimens. The moist
Potentiodynamic Anodic Polarization Measurements
SO2 test (the Kesternich test; ASTM G87, Standard Practice for
Standard Test Method for Conducting Potentiodynamic ASTM G59
Polarization Resistance Measurements
Conducting Moist SO2 Tests) is a modification of the humidity
Standard Test Method for Conducting Cyclic ASTM G61
test but is much more aggressive because of the presence of SO2,
Potentiodynamic Polarization Measurements for which converts to sulfuric acid. Another modification commonly
Localized Corrosion Susceptibility of Iron, Nickel, or referred to as the mixed flowing gas test (ASTM B827, Standard
Cobalt-Based Alloys Practice for Conducting Mixed Flowing Gas (MFG) Environmen-
Standard Test Method for Measurement of Corrosion ASTM G69 tal Tests) uses extremely low quantities of pollutants, such as
Potentials of Aluminum Alloys H2S, SO2, NOx, Cl2, and HCl, with humidity to duplicate envi-
Standard Test Method for Conducting Cyclic ASTM G100 ronments within the passenger compartment. This test is espe-
Galvanostaircase Polarization cially useful for electrical and electronic systems.76
Standard Practice for Verification of Algorithm and ASTM G106 The automotive industry has a long history and deep expe-
Equipment for Electrochemical Impedance Measurements rience of using steel for automotive body construction. Neutral
Standard Test Method for Electrochemical Reactivation ASTM G108 salt spray (NSS) testing according to ASTM B117, Standard Prac-
(EPR) for Detecting Sensitization of AISI Type 304 and tice for Operating Salt Spray (Fog) Apparatus, was first released
304L Stainless Steels
in 1939 and was the traditional and preferred method of assess-
Standard Test Method for Electrochemical Critical Pitting ASTM G150
ing material and vehicle corrosion resistance for many decades.
Temperature of Stainless Steels and Related Alloys
The increased use of galvanized steel in the automotive industry
AUTOMOTIVE 373
construction materials.79–81 Cyclic corrosion tests are by nature

TABLE 8 Standard Chamber Corrosion Tests Used for Automo- more challenging to run in a controlled manner than static tests,
tive Materials and expensive test chambers and rigorous maintenance may be
required to ensure the test protocol is followed with integrity. This
Test Method Organization may be one of the reasons for the persistence of the relatively sim-
Standard Practice for Operating Salt Spray (Fog) ASTM B117/
ple and cheap salt spray test in the industry. Modifications to the
Apparatus ISO 9227/ salt spray test have emerged as ASTM G85, Standard Practice for
JIS Z2371 Modified Salt Spray (Fog) Testing, which now includes five varia-
Standard Test Method for Copper-Accelerated Acetic ASTM B368/ tions: acetic acid-salt spray test; cyclic acidified salt spray test;
Acid-Salt Spray (Fog) Testing (CASS Test) JISH8681-2 cyclic seawater acidified test (SWAAT); cyclic SO2 salt spray; and
Standard Test Method for Corrosion Testing of Decorative ASTM B380 dilute electrolyte cyclic fog dry test (see ASTM G85, Annex 1–5,
Electrodeposited Coatings by the Corrodkote Procedure respectively). The ISO standard for cyclic corrosion testing (ISO
Standard Practice for Conducting Mixed Flowing Gas ASTM B827 11997-1) also includes different variations based on alternative
(MFG) Environmental Tests methods; for example, Annex A is based on Japanese Automobile
Standard Practice for Testing Water Resistance of ASTM D1735 Standards (JASO) M609 and M610, and Annex B is a test cycle
Coatings Using Water Fog Apparatus based on the German Automobile Association method VDA
Standard Test Method for Rust Protection by Metal ASTM D1748 621-415. Some of the standard methods for static and cyclic corro-
Preservatives in the Humidity Cabinet sion tests that are used for automotive materials, and typically
Standard Practice for Testing Water Resistance of ASTM D2247 require a test chamber, are listed in table 8.
Coatings in 100% Relative Humidity
In addition to the standard methods listed in table 8, many
Standard Practice for Testing Water Resistance of ASTM D4585
automotive manufacturers have developed their unique and cus-
Coatings Using Controlled Condensation
tom corrosion test procedures independently,79,82 despite the
Standard Practice for Conducting Cyclic Humidity ASTM G60
efforts of cross-functional team to develop standard methods,
Exposures
such as SAE J2334 and VDA 233. This in-house development by
Standard Practice for Modified Salt Spray (Fog) Testing ASTM G85
the automakers has led to a proliferation of cyclic corrosion test
Standard Practice for Conducting Moist SO2 Tests ASTM G87/
procedures across the industry,79 with each vehicle manufacturer
DIN 50018
typically preferring their own test method. Examples of automo-
Corrosion Tests in Artificial Atmosphere at Very Low ISO 10062
Concentrations of Polluting Gases
tive manufacturers’ cyclic corrosion test methods and some of
Determination of Resistance to Cyclic Corrosion ISO 11997
the principal test parameters are given in table 9. Note that Volvo
Conditions test method ACT-2 is the same as Ford test method L-467.
Chip Resistance of Surface Coatings SAE J400 Automotive manufacturers typically use standard or custom
Accelerated Exposure of Automotive Exterior Materials SAE J2020 cyclic corrosion tests (see table 8 and table 9, respectively) for the
Using a Fluorescent UV and Condensation Apparatus assessment of construction materials, components, and smaller
Laboratory Cyclic Corrosion Test SAE J2334 subassemblies that are exposed to the external environment. The
Cyclic Corrosion Testing of Materials and Components in VDA 233-102/ lack of a single, standard test procedure for corrosion assessment
Automotive Construction DIN 55635 of automotive materials and designs means that research scien-
tists and suppliers to the industry may be required to assess their
products and technologies using a different corrosion test for
highlighted the shortcomings of ASTM B117, and the equivalent each automotive customer. Even accelerated laboratory tests typ-
ISO standard ISO 9227, in predicting the corrosion behavior and ically run for 6–12 weeks, and with several replicates usually
rates of these materials in their actual service environment.77,78 required, a full corrosion qualification test plan for several auto-
The automotive manufacturers, suppliers, test standard, and makers can easily become costly and time consuming,79,83,84 with
research institutions have invested significant effort to develop the possibility of conflicting outcomes in terms of corrosion per-
cyclic corrosion tests that correlate better to vehicle service con- formance. It is obvious that the adoption of a single standard
ditions and that give realistic corrosion rates for nonferrous corrosion test method would be beneficial to the automotive
TABLE 9 Example Cyclic Corrosion Test Methods Developed by Automakers, Including Some Test Parameters for Each79,82
Manufacturer Test Method Corrodent (wt%) T Set Points (8C) RH Set Points (%)
Daimler-Chrysler KWT-DC 1% NaCl, pH 6.5–7.2 15 & 50 50 & 100

Ford / Volvo CETP L-467 / VCS 1027,1449 (ACT-2) 0.5% NaCl, pH unadjusted 25 & 50 70 & 95
General Motors GMW 14872 0.9% NaCl þ 0.1% CaCl2 þ 0.075% NaHCO3 25, 49 & 60 30, 45, 100
Renault D172028 (ECC 1) 1% NaCl, pH 4 35 20, 55 & 90
Volvo STD423-0014 (ACT-1) 1% NaCl 35 & 45 50 & 95
Volkswagen PV1210 1% NaCl, pH 6.5–7.2 23 & 40 50 & 100
industry generally; however, there may be resistance from the

automakers to abandon a test approach with which they have FIG. 13 Example design of an overlapping coupon that also
developed numerous data and mechanistic understanding, with could be used as a mixed-material coupon for galvanic
reasonable correlation to field experience, and to “start over” corrosion studies.
with a new test. Even among the standard bodies, several differ-
ent corrosion test methods have been proposed, as discussed pre-
viously and indicated by the number of tests (excluding annexes)
listed in table 8.
In addition to making a judicious choice of test method, the
corrosion engineer must also select or design a suitable test
object. The corrosion resistance of bare panels of steel or galva-
nized steel can be assessed by recording the time or number of
corrosion cycles until the formation of red rust is observed.85
Painted panels, with a deliberate scribe cut in through the paint,
commonly are used to assess the resistance of the panel substrate
(which may be ferrous or nonferrous), and the paint system, to
corrosion propagation from a controlled defect.3,86–88 Photo-
graphs of diagonally scribed painted steel and aluminum panels
following corrosion exposure are shown in figures 12A and 12B,
and digital images for analysis of creep-back and paint blistering
are shown in figures 12C and 12D.
Acceptance criteria, based on the extent of creep-back or The proving ground (PG) test allows the entire vehicle to be
length of filaments after a certain corrosion exposure, are set by exposed, with materials, processes, and geometries representative
the automotive manufacturer and typically are benchmarked of fully assembled vehicles.55 Much like the laboratory tests listed
versus a well-tested system of known corrosion performance. in table 9, the PG test procedure varies between automakers. It is
Scribe creep panels are one of the simplest test objects used in desirable that the automaker’s laboratory test correlates with the
automotive corrosion testing, and yet there is no standard agree- automaker’s PG test. PG tests generally include a driving sched-
ment among automakers on panel size or panel orientation in ule over various roads, including highway travel, salt highway,
the test chamber; scribe location, orientation, cutting method, gravel road, mud trough, and salt trough (see fig. 14), and signifi-
shape, or width; or scribe creep-back measurement procedure.89 cant time under controlled temperature and relative humidity
Overlapping coupons that simulate a hem flange, weld flange or conditions in large environmental chambers. Exposure to rain,
crevice configuration,3,90 and mixed-material coupons with dif- snow, drying, elevated temperature, freezing temperatures, and
ferent joining elements60,91 are frequently custom-designed for a UV also may be included. The period required to complete one
given joint and material configuration of interest. Reference cou- set of exposure is termed a cycle and usually a number of cycles
pons with known corrosion rates (e.g., mass loss) in laboratory is related to a set number of years of automotive service. SAE
and outdoor exposures frequently are used to give context to test standard J1950 describes PG vehicle corrosion testing with
objects of unknown performance. details of the cycles at four U.S. proving grounds. Note, however,
FIG. 12 Scribe creep panels after corrosion exposure: diagonally scribed paint on (A) steel, and (B) aluminum alloy; digital images of creep-
back from (C) steel and (D) aluminum alloy, with scribes cut perpendicularly to the rolling direction.
AUTOMOTIVE 375
FIG. 14 Environmental loading on test vehicle at the proving ground: (A) mud splash, (B) salt highway, and (C) gravel road. Source: Photos
courtesy of Ford Motor Company.
that the tests described are not recent—for example, the current specimens, such as coupons, parts, and components, on racks at
Ford PG test method does not match the cycles presented in stationary test sites. The nature of the site varies depending on
SAE J1950.92 geographic area and specific location within an area. Factors
One method to provide comparison to previous and future such as environmental chemistry (e.g., chlorides, pollutants),
tests, as well as to service performance is by the use of coupons time of wetness, temperature, humidity, hours of sunlight, and
with known field behavior mounted on the test vehicle, as illus- seasonal changes have an important effect on the corrosion rate
trated in figure 15. Reference coupons are routinely used in auto- and mechanism. The most useful field tests include measure-
motive corrosion testing to ensure that the corrosion exposure is ments of these important parameters so that corrosion rates can
running as expected and, in some methods, to adjust the expo- be understood within the context of the environment, and simi-
sure period accordingly. Typically, these reference coupons are larities and differences between different exposure sites and
of mild steel, such as that shown in figure 15B, and corrosion rates accelerated test methods can be clarified.93,96
are checked by mass loss or gage loss measurements. As noted Mobile test racks or plates are mounted on vehicles or trailers
by Ström,3 however, open steel faces corrode at a rather stable that are subjected to normal driving conditions. They are mounted
and consistent rate over a rather broad range of corrosive condi- on various locations on vehicles, such as the underbody, as
tions, and zinc is a more sensitive indicator of corrosion rates. described in SAE J1293.97 These racks or plates, however, also may
Because these tests simulate service exposure but still represent be mounted on bumpers, grilles, and truck trailers. Panels, cou-
accelerated conditions, considerable expertise is required for pons, parts, and components are attached to these racks and are
evaluation and interpretation of results. Fuller discussion of the exposed to driving conditions in the natural environment. Direct
advantages and limitations of automotive proving ground corro- comparisons therefore can be made on the corrosion behavior of
sion testing can be found in Ström.3 these materials. As with static atmospheric exposures, measure-
ments of the relevant environmental conditions and the inclusion
FIELD TESTS—EXTERNAL EXPOSURE of reference materials yield a richer dataset than exposure of test
When products or materials are exposed to the natural environ- panels alone. A truck used for mobile exposure of a variety of cor-
ment, they are considered field or service tests. Included in this rosion test coupons is shown in figure 16. Sensors for time of wet-
category are atmospheric exposure, mobile test racks, fleet tests, ness, temperature, and relative humidity were co-located with the
and field surveys. Atmospheric exposure consists of placing test panels.
FIG. 15 Proving ground test preparations showing: (A) test vehicle with coupons attached to the door lowers, (B) close-up of a reference
coupon, and (C) close-up of a mixed-material test coupon showing E-coat blistering on the base panel. The reference and test
coupons are carried through the corrosion test by the vehicle. Source: Photos courtesy of Ford Motor Company.
laboratory tests are valuable for evaluating internal exhaust sys-

FIG. 16 Test coupons and sensors mounted on racks, fixed to the tem deterioration. These tests are conducted with actual engines
underbody of a truck driving in the Montreal region of to produce the exhaust gas, which is directed through the appro-
Canada. Source: Photo courtesy of Dr. Danick Gallant, priate materials to be tested. This can be a coupon exposed to
National Research Council Canada. the exhaust stream or an actual exhaust system, depending on
the test design. The dew point temperature can be controlled
such that condensation occurs within a temperature range. This
control provides an acceleration factor for the test. Each of these
approaches has advantages and disadvantages, as discussed by
Garcia,100 but it is difficult to find an optimum balance of corro-
sion stimulation and the simulation of realistic in-service scenar-
ios. Although corrosion vehicles tested at the proving ground do
include driving cycles, it has been observed that the relatively
short driving times are not sufficient to stimulate long-term
exhaust system corrosion mechanisms. Therefore, various labo-
ratory bench and dynamometer tests are required to ensure cor-
rosion performance. In general, the widespread use of stainless
Fleet tests are extremely valuable in providing direct infor- steels together with sound design principles, as discussed by
mation on corrosion behavior in specific geographic locations. Douthett,51 ensures adequate corrosion resistance.
Groups of cars that typically are used for these tests are taxi-
cabs, rental cars, municipally owned cars, and sales fleet cars.
Because the operating parameters can be recorded through fleet TESTING—LIQUID PASSAGES AND RESERVOIRS
recordkeeping, this type of test is probably the most reliable of Laboratory tests to determine the behavior of materials and cor-
all for automobile corrosion performance. rosivity of automotive fluids, such as engine coolants, engine oils,
Field surveys are valuable because of the large number of and ATFs, and fuels involve exposure to the actual fluid as close
vehicles that can be inspected visually over a short period of to operating conditions as possible. In most cases, aging of the
time. In general, a location and time of year is chosen and a team fluids due to their functional use produces a more corrosive liq-
of evaluators inspect vehicles in parking lots, on streets, and at uid; therefore, it is important that the test be conducted on used
dealerships with survey sheets. Therefore, corrosion performance or pre-aged liquids or that the aging of the fluid occurs in situ.
is based on inspection and evaluation of actual standard produc- Simple immersion tests can be used if chemical and physical
tion vehicles exposed to natural environments and normal oper- environmental effects are introduced. This is not always possible
ating conditions. Some drawbacks to field surveys are that actual and therefore simulated service tests have been developed. These
driving conditions and history (e.g., crashes and repairs) for each laboratory bench tests simulate more closely actual service condi-
vehicle cannot be determined unless each owner is interrogated, tions by using a model of a particular automobile function. Field
and the survey typically is restricted to visible body panel corro- service tests are the most reliable but also the most time consum-
sion.98,99 More in-depth analysis of the entire vehicle’s long-term ing and costly.
corrosion performance can be undertaken by the purchase of a Corrosion testing of engine coolants is the most advanced
vehicle, ideally with known driving history, that has been in use in this group. These are divided into three categories, including
for a useful period, typically several years. Such studies are infor- (1) laboratory tests, (2) engine tests, and (3) field service tests.
mative to the automaker, particularly for corroboration of accel- Tests under these categories are listed in table 10. Laboratory
erated laboratory and PG tests. Besides the long waiting period tests have been the primary means for evaluating the corrosive
for such data, another disadvantage of this approach is the effects of engine coolants and the effectiveness of the coolant
uncertainty of how representative the selected vehicle might be inhibitor formulation. The most important of these is ASTM
of the fleet in general. D1384, Standard Test Method for Corrosion Test for Engine
Coolants in Glassware. A wide range of other tests is used,
including electrochemical techniques. ASTM D2570, Standard
TESTING—INTERNAL COMBUSTION Test Method for Simulated Service Corrosion Testing of Engine
The complex exhaust system environment including internal Coolants, is also used quite widely and includes the use of a
condensate corrosion, high-temperature oxidation, and exhaust- pump, radiator, thermostat housing, and a large pot to house test
gas impingement makes it difficult to obtain meaningful acceler- coupons. An extension of this test includes an actual operating
ated corrosion test results. Laboratory tests generally are based engine, which is referred to as a no-load engine test (ASTM
on exposure to exhaust gas condensate. The condensate may be D2758, Standard Test Method for Engine Coolants by Engine
delivered to the test parts as gas flow through alternate immer- Dynamometer). Field service tests evaluate materials and inhibi-
sion, or through liquid condensate injection through the system tor systems under actual vehicle operating conditions and are the
with air flow.100,101 Various test temperatures, immersion times, most reliable. The test is described in ASTM D2847, Standard
and condensate chemistries are used, depending on the specific Practice for Testing Engine Coolants in Car and Light Truck Ser-
component and manufacturers’ requirements. Controlled engine vice. The ASTM specifications for engine coolants (e.g., ASTM
AUTOMOTIVE 377
TABLE 10 Standard Tests and Specifications for Engine Coolants TABLE 11 Tests and Specifications for ATF
Test Method or Specification Organization Test Method or Specification Organization
Standard Test Method for Boiling Point of Engine Coolants ASTM D1120 Standard Test Method for Corrosiveness to Copper from ASTM D130/
Standard Test Method for Reserve Alkalinity of Engine ASTM D1121 Petroleum Products by Copper Strip Test ISO 2160
Coolants and Antirusts Standard Test Method for Rust-Preventing Characteristics ASTM D665
Standard Test Methods for Water in Engine Coolant ASTM D1123 of Inhibited Mineral Oil in the Presence of Water
Concentrate by the Karl Fischer Reagent Method Ford Aluminum Beaker Oxidation Test (ABOT) FLTM BJ110-04
Standard Test Method for Corrosion Test for Engine ASTM D1384 R -III Automatic Transmission
General Motors DEXRONV GM-6297M
Coolants in Glassware Fluid Specification
Standard Test Method for Simulated Service Corrosion ASTM D2570 Testing Methods for Oxidation Stability of Lubricating Oils JIS K2514
Testing of Engine Coolants Oxidation Stability of Lubricating Oils Used in Automotive CEC L-48-00
Standard Test Method for Engine Coolants by Engine ASTM D2758 Transmissions by Artificial Ageing
Dynamometer
Standard Test Methods for Cavitation Corrosion and ASTM D2809
content and in-depth surface analysis of deposits on tested parts58
Erosion-Corrosion Characteristics of Aluminum Pumps
are methods used for evaluation of ATF performance.
with Engine Coolants
A laboratory immersion test for corrosion in hydraulic
Standard Practice for Testing Engine Coolants in Car and ASTM D2847
Light Truck Service
brake line fluid is described in Motor Vehicle Brake Fluid Stan-
Standard Specification for Glycol Base Engine Coolant for ASTM D3306
dard SAE J1703. This test includes the use of standard metal cou-
Automobile and Light-Duty Service pons for mass change and visual examination after immersion at
Standard Specification for ASTM Reference Coolant for ASTM D3585 100 C in the brake fluid. Other tests are used to evaluate specific
Coolant Tests components in the braking system, such as that described in SAE
Standard Test Method for Corrosion of Cast Aluminum ASTM D4340 J1047 for hydraulic brake line tubing. Internal corrosion is not
Alloys in Engine Coolants Under Heat-Rejecting considered to be as important as external corrosion of the brak-
Conditions ing system and therefore only simple tests are used outside of
Coolants for Internal Combustion Engines SAE J814 on-vehicle service tests.
Automotive and Light Truck Engine Coolant Concentrate SAE J1034 Corrosion tests for hydraulic brake line fluid, as well as for
Principles of Engine Cooling Systems and Maintenance SAE HS-40 motor oil, grease, and lubricants are listed in table 12. In addition,
the interactions of various fuels on materials have been important
because of the effect of small amounts of water, which can become
D3306, Standard Specification for Glycol Base Engine Coolant for trapped in areas, such as the fuel tank. Various additives to fuels
Automobile and Light-Duty Service) include performance can prevent corrosion effects and include inhibitor packages and
requirements on corrosion resistance according to the test meth- small amounts of alcohol and aromatics. Corrosion of metals
ods. Additional specifications not listed in table 10 are available within the fuel system can occur if the fuel is contaminated with
specifically for heavy-duty engines, which may require pre- water and chlorides. Corrosion testing of bio-based fuels and mix-
charging and re-charging with inhibitors during vehicle service. tures, such as ethanol blended with gasoline, has been of interest
The behavior of ATF and its effect on materials has also because ethanol has both higher affinity for water and significantly
been investigated through several different test approaches, as higher conductance than gasoline,103 increasing the likelihood of
listed in table 11. The most commonly used are bench tests, labo- biofuel-system corrosion issues compared with gasoline alone.
ratory motor-driven transmission tests, and field service tests. Corrosion resistance of steel and aluminum alloys in the fuel sys-
Laboratory tests for ATF include the copper corrosion test tem depends on fuel contamination, conductance, and tempera-
(ASTM D130, Standard Test Method for Corrosiveness to Copper ture; ferrous materials have been reported to have higher corrosion
from Petroleum Products by Copper Strip Test), rust test (ASTM rates in water-contaminated fuel blends than in water-free or dry
D665, Standard Test Method for Rust-Preventing Characteristics fuel, whereas the opposite trend was observed for aluminum
of Inhibited Mineral Oil in the Presence of Water), and a variety alloy.104,105 Tests for fuels include electrochemical polarization, elec-
of glassware oxidation tests. Various bench tests, such as Ford’s trochemical impedance spectroscopy, and immersion tests.
Aluminum Beaker Oxidation Test and Japanese Industrial Stan-
dard JIS K2514, are used by manufacturers to determine ATF TESTING—ELECTRICAL AND ELECTRONIC SYSTEMS
oxidation stability.102 General Motor’s ATF fluid specification Corrosion testing of electrical and electronic systems has gener-
includes oxidation testing with the use of transmissions mounted ally followed the guidelines used for testing in external environ-
on test beds. These tests are designed to deliberately oxidize the ments. A large degree of evaluation is performed in the standard
ATF under controlled conditions so that the extent of oxidation tests used for external exposure (tables 5–8). Proving grounds
and the effects on materials can be measured. The behavior of and field tests are the most reliable, but these are lengthy and
copper wire, strip, or components frequently is used as a standard costly procedures and are not practical for rapid innovation. At
for corrosion resistance in the tests. Visual examination of copper the same time, microelectronics perform critical vehicle
TABLE 12 Standard Tests for Automotive Fluids TABLE 13 Tests for Automotive Electrical and Electronic Systems
Brake Fluid Organization Test Method Organization
Motor Vehicle Brake Fluid SAE J1703 Environmental Conditions and Testing for Electrical and ISO 16750
Motor Vehicle Brake Fluid Based Upon Glycols, Glycol SAE J1704 Electronic Equipment
Ethers, and the Corresponding Borates Corrosion Preventive Compound for Connectors MIL-C-81309
Low Water Tolerant Brake Fluids SAE J1705 and 16173
Specification of Non-Petroleum Based Brake Fluids for ISO DIS 4925 Environmental Testing of Electronic and Associated MIL-T-5422
Hydraulic Systems Equipment
Standard Test Method for Detection of Copper Corrosion ASTM D130 Environmental Conditions & Testing for Electrical & ISO 19453
from Petroleum Products by the Copper Strip Test Electronic Equipment for Drive System of Electric
Standard Test Method for Corrosiveness and Oxidation ASTM D4636 Propulsion vehicles
Stability of Hydraulic Oils, Aircraft Turbine Engine Electric and Hybrid Electric Vehicle Rechargeable Energy SAE J2464
Lubricants, and Other Highly Refined Oils Storage System (RESS) Safety & Abuse Testing
Motor Oil, Grease, Lubricants
Standard Test Method for Evaluation of Rust Preventive ASTM D6557
Characteristics of Automotive Engine Oils Test Standards
Standard Test Method for Corrosiveness to Copper from ASTM D130/
Automobiles consist of a wide range of materials fabricated into
Petroleum Products by Copper Strip Test/Standard Test ASTM D849
Method for Copper Strip Corrosion by Industrial Aromatic
various components and exposed to complex environments,
Hydrocarbons including external driving conditions, functional internal fluids,
Standard Test Method for Determining Corrosion ASTM D1743 and exhaust gas. Therefore, a wide range of corrosion tests is
Preventive Properties of Lubricating Greases required to ensure corrosion resistance of the vehicles in service.
Standard Test Method for Corrosion Characteristics of ASTM D2649 Corrosion standards are developed to ensure that results are
Solid Film Lubricants reproducible and consistent. The wide range of standards used in
Fuels the automobile industry is demonstrated by the long lists for cor-
Standard Test Method for Rust-Preventing Characteristics ASTM D665 rosion testing of body, chassis, trim, and hardware materials
of Inhibited Mineral Oil in the Presence of Water given in the previous sections. In addition to the ASTM, SAE,
Standard Test Method for Detection of Copper Corrosion ASTM D130 ISO, VDA, and JISO (and others globally) standard methods,
from Petroleum Products by the Copper Strip Test automakers have developed further corrosion test methods. In
some cases, these methods have been considered proprietary.
operational and safety functions, such as the deployment of air- The long service life expected for today’s vehicles; the emergence
bags during traffic accidents,62 and so corrosion avoidance for of innovative materials, technologies, and powertrains; and the
these systems is essential. The emergence of the battery electric increasing corrosivity of the road environment because of high
vehicle (BEV), which does not require a traditional internal com- levels or road salts (see fig. 1) highlight the need for consistent
bustion engine (ICE) or transmission system, offers the opportu- approaches in corrosion standards across the automakers to
nity to reconfigure the vehicle architecture.69 Battery packs for innovate safely at a rapid pace. Opportunities to rationalize test
BEV are rather large and heavy, and their mounting location has methods, where appropriate, should be considered.
a significant impact on weight distribution and crash perfor-
mance. In the case of the Tesla Model S, the battery pack is inte-
grated with the chassis; this underbody location is more exposed Automotive Corrosion Testing:
to a severe external environment than the ICE underhood loca-
tion. As noted by Liu et al.,69 future designs for BEVs are likely
Outlook
to include electric motors at or integrated into the vehicle wheels, The scientific research that underpins corrosion testing for auto-
where they would be exposed to the most corrosion-severe envi- motive vehicles has led to much greater corrosion resistance of
ronment. These comments highlight the systems engineering vehicles and has enabled the automotive sector to embrace new
approach required for the development of robust corrosion strat- materials, technologies, and processes; to extend vehicle life and
egies for electrical and electronic systems. The type and duration service intervals; and to enhance the customer experience.
of the corrosion test most appropriate for the system under test Despite the establishment of many standard tests that claim to
depends on the installation condition, mounting location, and have good correlation to in-service conditions, challenges in
in-service environmental exposure. The ISO standards listed in repeatability and reproducibility of corrosion tests persist.106,107
table 13 distinguish between electrical and electronic equipment Round-robin tests have highlighted differences in interpretations
that are installed within the vehicle from equipment that is of a test method, idiosyncratic behaviors of test chambers or lab-
exposed to the external environment. Judicious choice of testing oratories, and varying approaches to test object preparations and
approach and the generation of field data are required to ensure corrosion measurements. Variations in materials and processes
safety in these novel systems. that might be unknown to the corrosion test engineer—for
AUTOMOTIVE 379
example, the rolling direction and thermal history of a heat- 4. K. Olsson and J.-O. Sperle, “New Advanced Ultra-High Strength
treatable aluminum alloy, or the presence of micro-defects in a Steels for the Automotive Industry,” AutoTechnology 6, (2006):
coating sublayer—can influence and even control corrosion rates 46–49.
for a painted scribed panel. 5. O. Bouaziz, H. Zurob, and M. Huang, “Driving Force and Logic of
An approach with controlled test objects and known envi- Development of Advanced High Strength Steels for Automotive
ronments offers a path toward the establishment of the funda- Applications,” Steel Research International 84, no. 10 (2013):
mental interactions of the test material and that environment. 937–947.
For painted or adhesive-covered panels, the substrate micro- 6. W. J. Joost and P. E. Krajewski, “Towards Magnesium Alloys for
structure, pretreatment chemistry and morphology, and coating High-Volume Automotive Applications,” Scripta Materialia 128
or adhesive performance must be treated as an interacting sys- (2017): 107–112, https://doi.org/10.1016/j.scriptamat.2016.07.035
tem. The establishment of a known environment in the labora-
7. K. R. Brown, R. A. Woods, W. Springer, C. Fujikura, M. Nabae,
tory is more complex than temperature and RH control within a Y. Bekki, R. Macé, J. C. Ehrstrom, and T. Warner, The Corrosion
test chamber; the real environment of interest is the electrolyte Performance of Aluminum Automotive Body Panels in Service,
formed on the test material’s surface. The use of corrosion rate Technical Paper Series No. 980460 (Warrendale, PA: SAE
sensors, along with localized temperature, RH, time of wetness, International, 1998).
and electrolyte impedance sensors, and in test chamber with 8. J. Hirsch, “Recent Development in Aluminium for Automotive
high levels of control, gives in situ, quasi-instantaneous data on Applications,” Transactions of Nonferrous Metals Society of China
material-environment interactions.67,108–110 Such data are neces- 24, no. 7 (2014): 1995–2002.
sary to clarify corrosion mechanisms and rates under the differ-
9. M. K. Kulekci, “Magnesium and Its Alloys Applications in
ent conditions likely to be encountered in service.
Automotive Industry,” International Journal of Advanced
Corrosion is one of the few vehicle attributes that is not Manufacturing Technology 39, nos. 9–10 (2008): 851–865.
simulated with computer-aided engineering. There is a strong
desire for accurate prediction of the corrosion rates of vehicles in 10. M. Wayland, “Carbon Fiber Truck Bed Just a Beginning,”
Automotive News, April 29, 2019, http://web.archive.org/web/
service, as well as structures generally, to avoid failure modes,
20210509191523/https://www.autonews.com/manufacturing/
implement timely service, and reduce the amount of physical carbon-fiber-truck-bed-just-beginning
testing required to achieve these ends. Much research is focused
on providing numerical solutions to these problems.111–113 Simula- 11. R. Miel, “Toyota Says Carbon Fiber Goes beyond
Lightweighting,” Automotive News, July 31, 2017,
tion of atmospheric corrosion is a complex problem and the
http://web.archive.org/web/20210509193815/https://
development of models is currently in its early stages, with many www.autonews.com/article/20170731/OEM01/170739914/
researchers focused on simplified test samples under controlled toyota-says-carbon-fiber-goes-beyond-lightweighting
laboratory electrolyte films. Simple setups, such as galvanic cou-
ples of two well-characterized materials, turn out to be compli- 12. B. Reinhold, D. Blücher, and M. Korte, “Herausforderungen
an Füge- und Oberflächentechnik für Zukünftige
cated systems because of the dynamic nature of atmospheric
Leichtbaukonstruktionen im Automobilbau,”
corrosion and the complex interactions occurring for today’s Materialwissenschaft und Werkstofftechnik 44,
highly engineered construction materials.113 Even if reliable pre- no. 1 (2013): 58–69.
dictive models for atmospheric corrosion are a long-term pros-
13. T. Prosek, A. Nazarov, F. Goodwin, J. Šerák, and D. Thierry,
pect, the value offered by such models, and the insight to be
“Improving Corrosion Stability of ZnAlMg by Alloying for
gained from the research into these questions, ensure that this Protection of Car Bodies,” Surface and Coatings Technology
corrosion research area will be pursued actively over many years 306 (2016): 439–447.
to come.
14. S. J. Simko, B. Schneider, J. L. Tardiff, M. Jagner, and A. Drews,
Characterization of Zirconium Oxide-Based Pretreatment
Coatings, Part 1: Variability in Coating Deposition on Different
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385
Chapter 24 | Commercial Aircraft
Edward L. Colvin1
Introduction TABLE 1 Contributing Causes of Corrosion—Manufacturer

Corrosion of aircraft structures has plagued the airline industry Related
since the first use of metals in aircraft manufacture. It is costly
both in unscheduled downtime and maintenance. The Interna- Causes Factors
tional Air Transport Association (IATA) reported in 1983 that
Basic Design • Anticipated operating environments
corrosion costs the airlines between $8 and $20 per flight hour.1
• Materials selection
These numbers did not reflect the unscheduled downtime, both
• Dissimilar metals
at the main bases and route stations, nor the additional corrosion
• Finish system
inspections of aging airplanes recently mandated by the regula-
• Drainage
tory agencies. In fact, unlike fatigue damage, corrosion is
• Crevices
extremely difficult to predict (i.e., when and where it will start,
• Pockets and cavities
how fast it will progress, or how much damage it will cause).
• Access to structure
Because of this unpredictability, corrosion inspections are an
• Process selection
integral part of an airline’s maintenance program and make up a
• Maintenance schedules and protocols
significant part of its cost.
Manufacturing • Assembly and residual stresses
Corrosion problems on commercial aircraft are the result of
• Metal finishing process control
combinations of factors whose causes can be found in the basic
• Bonding process control
design, manufacturing, materials interactions and operations of
• Inspection
the aircraft. Some of these factors are summarized in table 1
Processing • Assembly quality and misfits
(manufacturer) and table 2 (operator and service environment).
• Handling of parts and structures
These present unique problems to the manufacturer who must
• Storage of parts and structures
make the best design, materials, and process choices that are
compatible with structural requirements and the economics of
building and operating an airplane. To achieve these ends, delib- important to recognize that no one accelerated, laboratory corro-
erate and comprehensive corrosion evaluations and risk assess- sion test can possibly simulate all situations that a fleet of air-
ments must be conducted before establishing requirements for planes may experience during service. With over 60 years of
design, structural materials and compatible finish systems, as service history on commercial jet aircraft, corrosion problems
well as the numerous manufacturing protocols, interior materi- continue to be addressed systematically and evaluated with
als, and operational maintenance fluids that will ensure the deliberate processes and intent around the world and in many
structural integrity of the aircraft during its useful life. adjacent applications.2 Many improvements that are being incor-
In addition, anticipation and consideration of factors whose porated into today’s new aircraft would not have been possible
presence may at times be accidental in the operation of the without laboratory and outdoor corrosion tests.
airplane is necessary to the selection of the appropriate standard-
ized corrosion tests. Sometimes test modifications, which Service Environments
account for these factors, are necessary, and it is especially
Environmental conditions inside and outside an airplane vary
considerably from one operator to another. Factors that influence
1
HELM Technology, LLC , 1423 Simmonsville Rd., Newport, VA 24128, USA
environments include airplane interior configuration, an airline’s
The author acknowledges the previous authors of this chapter, A. A. Adjorlolo and geographic location, route structure, and world climatic conditions.
J. A. Marceau, The Boeing Company, Seattle, WA. The commercial jet airplane is designed to be a self-contained
DOI: 10.1520/MNL202NDSUP20190033
The rest of the fuselage interior is regularly exposed to con-

TABLE 2 Contributing Causes of Corrosion—Service Related densing humidity caused by colder temperatures that result from
the ground-air-ground flight cycle. Although this condensate is
Causes Factors initially fairly benign compared with the fluids encountered
Finish Deterioration • Chipping
under galleys and lavatories, it can absorb other chemical species
• Scratches
and accelerate corrosion and structural damage processes, such
• Breaks around fasteners
as fatigue and fatigue crack growth.
• Abrasion
The exterior surfaces of airplanes are always exposed to the
• Deposits
elements, and hence, are affected by world and local climatic
• Age
conditions, including rain, humidity, airborne industrial pollu-
Environmental Conditions • Skydrol (hydraulic fluid)
tants, hot and/or cold temperatures, dust, runway dirt, and spray
within Airplane • Condensation
from the oceans and seas. Corrosive contaminants trapped in
• Animals (cargo)
exterior cavities and cove areas (e.g., wheel wells, wing front and
• Fish (cargo)
rear spar cove areas, and fairing areas) are not washed off by rain
• Microbial growth
in contrast to aerodynamic surfaces, thereby compounding
Accidental Contamination • Lavatory spills
potential corrosion problems.
• Galley spills
• Cargo spills
• Chemical spills
Techniques Used to Control
• Mercury
• Fire smoke and extinguisher residues
Corrosion
Operational Environment • Seacoast The primary defenses for corrosion control of the airplane struc-
• Tropical environment ture are proper design, material selection, finishing systems, and
• Humidity maintenance protocols. For the first three, which are built into
• Industrial environment the airplane, intelligent corrosion evaluation of metals, assem-
• Ground-air ground cycle blies, and compatible finish systems must inform their selection.
Maintenance Problem Areas • Neglect The tests for evaluating these materials, assemblies, and finishes
• Improper repairs depend on the function and the anticipated environmental expo-
• Inadequate corrosion control program sure of the component parts. Finishes that will be used during
or lack of implementation
repairs must have been demonstrated that they can be applied
• Inadequate training
locally over surface preparations accomplished in the field under
• Ignorance of corrosion
less-than-optimum conditions. Techniques available to the airlines
• Plugged drain systems
for controlling corrosion involve (1) maintaining drain holes open
for proper drainage of condensed moisture, (2) restoring the fin-
ish, and (3) using corrosion inhibiting compounds to protect the
pressurized vessel that creates a comfortable living environment paint in problem areas and to drive trapped moisture from joints
for flight durations of less than 0.5 min to longer than 12 h. Inside and crevices.
the fuselage, the air is conditioned for the comfort of passengers. Many of the corrosion tests described in the section “Use of
Galleys (food stations) are provided for food and drink, and lava- Test Methods to Evaluate Corrosion” are used routinely in the
tories are provided for the needs of passengers. materials and aircraft industries to evaluate materials, compo-
Creating these passenger comforts directly results in local- nents, and finish systems. The tests specifically aim to assess
ized environments that are unique, and if the structural compo- expected performance during long-term service, usually relative
nents are not properly protected, these environments can be to an incumbent material, finish, or process with well-established
aggressive to structural components. Aqueous solutions form the in-service capability. It is essential that interactions among the
essential basis for corrosion of many metallic materials, such as material, finish, and processing be considered in the testing pro-
aluminum alloys, steels, and bimetallic structures. For instance, tocol, including specimen design. Because laboratory tests repre-
fluids from food and drink spillage drain under floor panels. sent relatively short-term exposures compared with the lives of
Trapped in crevices between the floor panels and the underlying airplanes, and cannot always simulate the inherent variability in-
structure, these fluids fester and become a corrosive solution for service airplanes experience, the rationale used to establish test
the structural components. The same is true for lavatory fluids, duration and protocols must be relevant. It may be necessary to
which can leak and become trapped between the flooring and use multiple predictive tests to account for these various service
floor structure; excess fluids from galleys and lavatories will flow conditions. To provide context for the accelerated tests, various
to the bilge; and entryways (e.g., passenger, service, and cargo) organizations, industry, government, and independent laborato-
are exposed to the weather and occasional spills, which all com- ries have devoted extensive resources to long-term testing in nat-
bine to generate a corrosive environment that also flows beneath ural and service environments, such as seacoast and industrial
the floor structure to the bilge. sites.3,4
COMMERCIAL AIRCRAFT 387
IN-SERVICE MONITORING resistance to intergranular forms of corrosion such as intergran-

Despite the obvious economic advantage of allowing airlines the ular, exfoliation, and stress-corrosion cracking,6 for which spe-
ability to disassemble a structure for repairs only when corrosion cific ratings are listed in ASTM G64, Standard Classification of
is known to exist in certain areas, in situ monitoring of corrosion Resistance to Stress-Corrosion Cracking of Heat-Treatable Alumi-
is not practiced in the industry. The resulting monitoring sys- num Alloys. To varying degrees, all of the high-strength alloys
tem’s complexity, added weight, and future certification issues used are susceptible to corrosion and must be protected appro-
are certainly negative factors. The authors are aware of only one priately; protection systems have become especially important in
instance of experimentation with sensors in U.S. commercial avi- multimaterial structures that utilize increasing amounts of
ation to detect the presence of moisture in certain areas prone to carbon-fiber reinforced composites and titanium, both of which
corrosion, such as floor support structure. A system using an are galvanically cathodic to aluminum alloys requiring appropri-
optical fiber-based sensor and data acquisition system is being ate protection systems for the aluminum, especially systems that
field-tested. This system was described at an Aging Aircraft 2000 will electrically isolate aluminum from the other materials.
Conference.5 Corrosion protection of the aluminum alloys relies primar-
Currently, in-service monitoring of corrosion on commer- ily on alloy-temper selection and the protection systems used.
cial airplanes is accomplished by inspection during routine Anodic, or sacrificial, protection can be used in specific situa-
maintenance checks. Although most airlines have corrosion con- tions. The largest use is aluminum cladding applied to aluminum
trol programs implemented in their maintenance programs, the sheet used for fuselage skins; the Alclad layer consists of a rela-
regulatory agencies recently have required mandatory corrosion tively pure aluminum alloy that protects the high strength core.
inspections based on calendar time rather than airplanes’ cumu- Plated, thermal, and vapor-deposed coatings also have been
lative flight hours, as well as defining the specific areas to be used, especially for fasteners that often have metallic coatings
inspected and at what frequency. For instance, a known problem that provide sacrificial protection. Barrier protection systems,
area, such as the fuselage bilge, is inspected much more fre- including anodizing, conversion coatings, primers, sealants, etc.,
quently than the crown (ceiling) area. These directed inspections, typically fail at joints, faying surfaces, or crevices where water
such as FAA-mandated Corrosion Prevention and Control Pro- and aggressive electrolytes can become trapped for long periods
gram (CPCP), assign levels of 1, 2, and 3 to corrosion findings. of time. Crevices can be created by many conditions, (e.g., joints,
These levels relate to the amount of material blend-out required poorly adhering paint, insulation blankets against structure in
to remove the corrosion occurring between repeat inspections wet areas, etc.). Although coatings are helpful, control of certain
(level 1 or 2) and identify whether airworthiness concerns exist forms of corrosion, such as stress corrosion cracking (SCC) and
(level 3) with specific corrosion findings. exfoliation, should focus on material selection, because once a
barrier coating has been breached, the environment will propa-
INSPECTION gate with the corrosion to the interior of the metal.7
Inspection for corrosion is conducted primarily by visual meth- When corrosion problems exist in the highly susceptible
ods, requiring very good access to the structure and the ability to areas described in the previous section, they are greatly com-
recognize various forms of corrosion, their early signs in differ- pounded. Other potentially corrosive conditions would include
ent metallic structures, or conditions leading to corrosion, such dissimilar metal couples—for example, an aluminum-nickel-
as finish damage and blocked drains. Other difficult-to-access bronze bushing in an aluminum alloy housing or an aluminum
areas may require borescope inspection. In some cases of hidden hinge fitting attached to a carbon fiber–reinforced plastic control
structure, such as lap joints, nondestructive inspection (NDI) surface (e.g., elevator, aileron, etc.). Some of these conditions are
techniques, such as eddy current or X-ray (radiography), may be unavoidable; therefore, it is extremely important that the proper
used. Ultrasonic inspection has the advantage of detecting small finish protection schemes be incorporated.
cracks that may appear in corroded locations. Because some of
these techniques may require significant amounts of material
loss for detection, are complex, and require high technician skills,
visual observation of a partially opened lap joint is necessary to Use of Test Methods to Evaluate
determine the full extent of the corrosion. Corrosion
The foregoing discussions on airplane corrosion problems, service
environments, techniques for corrosion control, and problem
Specific Problem Areas areas underscore the need for comprehensive corrosion testing,
Most corrosion problems on commercial aircraft are associated including sound rationale and methods. Table 3 summarizes the
with aluminum alloys in part because material selection has corrosion tests used in the commercial airplane industry, includ-
focused on maximizing mechanical and damage-tolerant proper- ing names of the tests, how they are used, the type of information
ties, such as fracture toughness, thus sacrificing the better corro- sought, and the type of comparative control used. These tests pri-
sion resistance of lower strength alloy systems used in marine, marily address alloys, coatings, manufacturing aids or process
building, industrial, and transportation applications. For these evaluation, and also service conditions. The tests, particularly
high-strength alloy systems used in aerospace, tempers such as those from ASTM, lend themselves to multiple applications (e.g.,
2xxx-T8X and 7xxx-T7X have been developed to improve there are many uses of the salt spray test—ASTM B117, Standard
TABLE 3 Corrosion Tests Conducted in the Commercial Airplane Industry
Where Used
General Test Name (Alternate Test Name) Information Sought Control
EXCO Test (ASTM G34, Standard Test Method for Alloy evaluation Resistance to exfoliation corrosion after 48 to Conventional alloy and/or
Exfoliation Corrosion Susceptibility in 2XXX and 96 h immersion in test solution thermomechanical treatment
7XXX Series Aluminum Alloys (EXCO Test))
Modified ASTM Acetic Acid Salt Intermittent Alloy evaluation Resistance to exfoliation corrosion after 14 to Conventional alloy and Al-Li
Spray-MASTMAASIS (ASTM G85, Standard 28 days exposure treatment
Practice for Modified Salt Spray (Fog) Testing)
3.5% NaCl Alternate Immersion (ASTM G44, Alloy evaluation SCC resistance per ASTM G47 Resistance to Conventional alloy
Standard Practice for Exposure of Metals and pitting of unstressed specimens
Alloys by Alternate Immersion in Neutral 3.5%
Sodium Chloride Solution)
Double Cantilever Beam (ASTM G168, Standard Alloy evaluation SCC growth rate, threshold K1scc Conventional alloy
Practice for Making and Using Precracked Double
Bean Stress Corrosion Specimens)
Electrochemical Tests Alloy evaluation. Paint/coating Passivation characteristics (ASTM G5) Corrosion Conventional alloy
evaluation rates Pitting/protection potentials (ASTM G61, Conventional paint/coating
Standard Test Method for Conducting Cyclic
Potentiodynamic Polarization Measurements
for Localized Corrosion Susceptibility of Iron-,
Nickel-, or Cobalt-Based Alloys) Corrosion
potential (ASTM G69, Standard Test Method
for Measurement of Corrosion Potentials of
Aluminum Alloys) Polarization resistance
Galvanic corrosion Impedance spectrum
(ASTM G106, Standard Practice for Verification
of Algorithm and Equipment for Electrochemical
Impedance Measurements)
Notched Tension Test (ASTM F519, Standard Test Alloy evaluation Resistance to hydrogen embrittlement Conventional alloy
Method for Mechanical Hydrogen Embrittlement Maintenance fluid evaluation Potential to cause hydrogen embrittlement on Conventional fluid
Testing of Plating/Coating Processes and Service AISI4340 steel per ASTM F519, Standard Test
Environments) Method for Mechanical Hydrogen Embrittlement
Evaluation of Plating/Coating Processes and
Service Environments, Section 7.2
Plating process evaluation Resistance to hydrogen embrittlement of plated Specification requirement per
AISI 4340 per ASTM F519, Section 7.3 ASTM F519, Section 7.3
Intergranular Attack/End Grain Pitting (IGA/ Process assessment and quality Potential to cause end grain pitting or Aluminum alloys 2x24-T3,
EGP) (ASTM G110, Standard Practice for control evaluation (deoxidizer/ intergranular attack in excess of recommended 7178-T6X, 7075-T65X
Evaluating Intergranular Corrosion Resistance of cleaner) limits
Heat Treatable Aluminum Alloys by Immersion in
Sodium Chloride þ Hydrogen Peroxide Solution)
Filiform Corrosion Test (ASTM D2803, Standard Metal surface preparation Resistance to filiform corrosion Vi in. (3.2 mm) Conventional organic coatings
Guide for Testing Filiform Corrosion Resistance processes and paint evaluation beyond line scribed on a painted panel specimen
of Organic Coatings on Metal) pre-exposed to HC1 vapor and held at 104 F at
80 % RH for 1,000 h
Salt (Fog) Spray (ASTM B117, Standard Practice Alloy evaluation General corrosion, pitting resistance after Conventional alloy
for Operating Salt Spray (Fog) Apparatus) 30 days, 90 days, or one-year exposure
Modified Salt Spray (Fog) Test (ASTM G85, Chemical conversion coating/ Resistance to pitting after 168 h exposure period Conventional chemical coating/
Standard Practice for Modified Salt Spray (Fog) process evaluation (ASTM G117 only per specification) qualified process
Testing)
Outdoor Environmental Exposures Anodizing/process evaluation Resistance to pitting after 336 h exposure period Conventional chemical coating/
(ASTM B117 only per specification) qualified process
Paint/alloy evaluation (scribed Resistance of scribed line to corrosion after Paint over conventional alloys
line test) predetermined exposure period; loss of or conventional paint over alloy
adhesion; blistering
(continued)
TABLE 3 (continued)
Where Used
General Test Name (Alternate Test Name) Information Sought Control
Paint/alloy evaluation (fastener Resistance to corrosion around fastener heads; Paint over conventional alloys
insulation test) rating per ASTM D1654, Standard Test Method or conventional paint over alloy
for Evaluation of Painted or Coated Specimens
Subjected to Corrosive Environments
Paint/alloy evaluation (Al/ Resistance to corrosion aided by galvanic Paint over conventional alloys
CRES or CFRP coupling) coupling; rating per ASTM D1654 or conventional paint over alloy
All adhesive bonding process Reduction in lap shear strength after exposure Qualified adhesive/primer over
evaluation (metal/metal) (Lap for predetermined period recommended surface
Shear Corrosion Test) preparation
All adhesive bonding process Crack growth rate after exposure to salt spray Same as above
evaluation (metal/metal) for 30, 60, and 90 days, or longer
(Wedge Corrosion Test)
All adhesive bonding process evaluation (metal/ Crack growth after exposure to Same as above
metal) (Double Cantilever Test) neutral salt spray for one year
or longer; resistance to galvanic
corrosion
Titanium Compatibility Test Manufacturing aids evaluation Potential of fluid considered to cause pitting, Currently qualified material
(lubricants/coolant) cracking, or rough etching on titanium
Evaporation Corrosion Test Manufacturing aids evaluation Potential for pitting caused by fluid left to Currently qualified fluid
(lubricants/coolant) evaporate on machined alloy after 7 days
Interior materials (silicone Assessment of the corrosivity of water-leachable Deionized or distilled water
rubber-coated fabric, floor cov- species from tested materials left to evaporate
ering, carpet and underlay, on 2024-T3 aluminum after 7 days
thermal/ acoustical insulation,
flame-resistant polymer-
coated fabric, Nomex felt, etc.)
R&D (evaluation of corrosion General corrosivity and pitting caused by water Deionized, 3.5% NaCl, or
inhibitors; maintenance fluids, soluble extract from material of interest left to distilled water
and various extracts) evaporate on 2024-T3 aluminum after 7 days
Manufacturing aids evaluation Resistance to general corrosion or staining Deionized, distilled water, or
(lubricants and coolants) caused by fluid entrapment on 7075-T6, 2024- conventional fluid
T3 bare or clad Al alloys
Maintenance fluids evaluation Resistance to general corrosion or staining Deionized, distilled water, or
caused by fluid entrapment on 7075-T6, 2024- conventional fluid
T3 bare or clad Al alloys
Immersion Test (ASTM F483, Standard Practice Manufacturing aids (lubricants Resistance to weight loss of AISI 4130 and 2024- None—Allowable weight loss
for Total Immersion Corrosion Test for Aircraft and coolants) evaluation T3, 7075-T6 Al alloys in fluid of interest table
Maintenance Chemicals)
Maintenance fluids evaluation Resistance of selected aerospace aluminum, None—Allowable weight loss
steel, titanium, and magnesium alloys, cadmium table
plate, to weight loss in fluid of interest;
Resistance to galvanic corrosion
Galvanic Entrapment Manufacturing aids (cuttings Resistance to crevice corrosion caused by test Deionized water, conventional
fluids and greases) evaluation fluid entrapment between drilled and fastened fluid
Al/Cad plated steel/Ti stackup
Stress Corrosion Test Manufacturing aids evaluation Resistance to corrosion crack growth, pitting on Conventional fluid
(lubricants and coolants) precracked, 50 ksiHin prestressed specimens
immersed for 24 h in test fluid, and in ambient
environment for 76 h minimum
Drip Test Titanium/coating evaluation Resistance to hydraulic fluid of coating and Bare 6A1-4V titanium specimen
substrate at various temperatures (usually
450 F)
Practicing for Operating Salt Spray (Fog) Apparatus). Alternately, Standard Practice for Making and Using Precracked Double Bean
multiple tests are available to evaluate a particular corrosion issue Stress Corrosion Specimens,5 and the breaking load test per
(e.g., pitting can be evaluated using many different tests). ASTM G139, Standard Test Method for Determining Stress-
The following detailed discussion explains why some of Corrosion Cracking Resistance of Heat-Treatable Aluminum
these tests are used in the selection of materials and processes. Alloy Products Using Breaking Load Method, also have been used
Importantly, no single laboratory test method, or even natural to that effect. The contrasting performance of SCC-resistant
environmental exposure, can simulate all possible environments 7075-T73X and 7075-T74X aluminum products, against that of
that the materials and structures of an in-service aircraft may see 7079-T6, replaced by the more SCC-resistant alloys in the 1960s
over 20 to 50 years of service. To the extent possible, designers and 1970s, is a reflection of the implementation of these two test
and those making material selections must anticipate the service methods.
conditions and evaluate design choices using a menu of tests for Note that for certain tempers, with somewhat improved
various corrosion morphologies, such as exfoliation, SCC, pit- exfoliation or SCC resistance, the material may take longer to
ting, intergranular, etc., as well as assembly conditions, such as exhibit attack and the performance of the material may be more
galvanic cells, sealants, and coatings. variable. The precision and bias statement in ASTM G47
describes just such a situation for a laboratory temper with inter-
MATERIALS SELECTION mediate SCC resistance.
The desirability of light structures for increasing payloads in
commercial aircraft design dictates the use of materials with high TESTING OF HIGH-STRENGTH STEELS
strength-to-weight ratios. High-strength aluminum alloys, 7xxx- Because most high-strength steels have requirements for chro-
and 2xxx-series, and their tempers, are evaluated for their integ- mium, low-embrittlement cadmium, or cadmium-titanium plat-
rity in environments likely to cause exfoliation and SCC. Steels ing, their selection is dictated by their ability to be processed in a
must demonstrate that they are no more susceptible to hydrogen way that avoids the hydrogen-embrittling effects of these pro-
embrittlement and SCC than conventional high-strength, low- cesses. Requirements for avoiding hydrogen embrittlement in
alloy (HSLA) steels. These represent the most commonly used AISI 4340 steel establish a baseline that must be met by any new
ferous alloys and also are the most susceptible to hydrogen alloy. A notch tensile test generally is performed using AISI 4340
embrittlement. as control material and evaluated according to ASTM F519, Stan-
dard Test Method for Mechanical Hydrogen Embrittlement Eval-
ALUMINUM ALLOY/HEAT-TREAT EVALUATION uation of Plating/Coating Processes and Service Environments.
Exfoliation corrosion is the flake-like degradation of high-
strength aluminum alloys caused by corrosion product forming PAINT EVALUATION
along the elongated grain boundaries of sheet, plate, forgings, or Paints are used on a wide variety of materials and parts as a
extrusions, which act as propagation paths for corrosion pro- means to protect the underlying metal and generally are the first
cesses. Susceptibility to exfoliation corrosion is predicted by test- line of defense. The paint itself must adhere to the substrate
ing in accordance with ASTM G34, Standard Test Method for under dry, humid, or wet conditions, a requirement that under-
Exfoliation Corrosion Susceptibility in 2XXX and 7XXX Series scores the critical nature of a base surface preparation. The abil-
Aluminum Alloys (EXCO Test), and ASTM G85, Standard Prac- ity of the paint to protect against corrosion is evaluated using
tice for Modified Salt Spray (Fog) Testing, Annex A2. Proper ASTM G85 and ASTM B117 for a test duration of 1,000–3,000 h
choice of exfoliation corrosion test varies by alloy type; a very on scribed surfaces, with fasteners installed, or on specimens gal-
good discussion of the proper test environment by alloy forms vanically coupled to a more noble metal. These tests are designed
the core of ASTM G112, Standard Guide for Conducting Exfolia- to simulate accidental scratch marks, corrosion-prone areas, or
tion Corrosion Tests in Aluminum Alloys. For example, ASTM conditions that accelerate corrosion.
G85 (i.e., the MASTMAASIS test with Dry Bottom conditions)
has been demonstrated to more accurately predict seacoast per- SURFACE FINISHES EVALUATION
formance of aluminum-lithium (Al-Li) alloys and certain 2xxx ASTM B117 is the standard test typically used for evaluating
alloy-tempers than EXCO. This and other environmental factors the corrosion resistance of unpainted aluminum alloy surfaces
responsible for exfoliation are difficult to integrate into one labo- when treated by anodizing, conversion coating, and plating pro-
ratory test, and ideally, one would like to expose the materials in cesses aluminum surfaces, which are anodized and then sealed
outdoors for two or more years depending on severity of the for corrosion protection. These surfaces must be able to resist
local environment. the salt spray environment for at least 336 h without pitting.
Several test methods currently are used for the testing of Conversion-coated surfaces must resist the salt spray environ-
SCC in aluminum alloys, including ASTM G47, Standard Test ment for at least 168 h. Cadmium plate on ferrous or copper
Method for Determining Susceptibility to Stress-Corrosion Crack- alloys must also resist this environment for 96 h without showing
ing of 2XXX and 7XXX Aluminum Alloy Products, in conjunc- base metal or cadmium corrosion. Although it is generally agreed
tion with ASTM G44, Standard Practice for Exposure of Metals in industry that the salt spray test is used too broadly, individual
and Alloys by Alternate Immersion in Neutral Sodium Chloride pass/fail criteria developed for each process have helped detect
Solution. The double-cantilever beam test per ASTM G168, and monitor process problems. For example, ASTM G85 has
been shown to be useful for coated aluminum.8 Alternate testing References

methods (e.g., electrochemical tests) are under development and
1. International Air Transport Association (IATA), Guidance Material
have found limited use to aid in the evaluation of alloys and
on Design and Maintenance against Corrosion of Aircraft
finishes. Structures, DOC GEN/2637A, Issue 2 (Montreal, Canada: IATA,
November 1983).
Conclusion 2. R. Wanhill and M. Wisndisch, Corrosion and Stress Corrosion

Testing of Aerospace Vehicle Structural Alloys, Briefs in Applied
The multiplicity of external environments, the unpredictability Sciences and Technology (Cham, Switzerland: Springer, 2018).
of various spillage inside an airplane, the influence of environ-
3. J. J. Thompson, “Exfoliation Corrosion Testing of Aluminum
mental and loading cycles on material and finishes, and the long
Lithium Alloys,” in New Methods for Corrosion Testing of
design life of an airplane account for the main difficulties Aluminum Alloys, ed. V. S. Agarwala and G. M. Ugiansky
encountered in selecting and conducting the most appropriate (Philadelphia, PA: ASTM International, 1992), 70–81.
laboratory corrosion tests to evaluate commercial airplane. As a
large amount of data from the commercial airplane fleet has 4. S. Dean and W. Anthony, “Atmospheric Corrosion of Wrought
Aluminum Alloys during a Ten-Year Period,” in Degradation
become available, service history has emerged as the most impor-
of Metals in the Atmosphere, ed. S. Dean and T. Lee
tant criterion in validating design choices, modifying the corro- (West Conshohocken, PA: ASTM International, 1987), 191–205.
sion tests, and developing better test acceptance criteria.
Materials with improved corrosion resistance, such as Al-Li 5. J. L. Elster, A. Trego, M. Jones, P. Tulou, B. Fitzpatrick, and I.
alloys, which have been demonstrated to perform well in severe Perez, “Corrosion Monitoring in Aging Aircraft Using Optical
Fiber-Based Chemical Sensors” (paper presentation, DOD/
environments, can improve durability.9
NASA/AFRL Aging Aircraft 2000 Conference, St. Louis, KS, May
The history of airplane corrosion testing includes many 15–18, 2000).
successful tests that are now performed routinely (e.g., ASTM
G85 Annex A2, and ASTM G44). Some other successful tests, 6. J. E. Hatch, ed., Aluminum Properties and Physical Metallurgy
such as the wedge test (ASTM D3762, Standard Test Method for (Metals Park, OH: ASM International, 1984).
Adhesive-Bonded Surface Durability of Aluminum [Wedge Test] 7. D. O. Sprowls and R. H. Brown, “What Every Engineer Should
[Withdrawn 2019]), discovered as a result of bond line corro- Know about Stress-Corrosion Cracking of Aluminum Alloys,”
sion problems on airplanes, are not described here because they Metal Progress 81, no. 4 (1962): 77–83, 118–122.
are not strictly corrosion tests. Many of the tests described here
8. E. L. Colvin, L. F. Vega, T. Nakayama, K. Ikeda, H. Shige, T. Ueda,
are current ASTM standards. As discussed previously in this M. W. Egbert, and M. Inman, Filiform Corrosion of Aluminum
chapter, addressing specific circumstances, including environ- Auto Body Sheet in Accelerated and Outdoor Environments,
ment, structure, and dissimilar metals, may require refinements Technical Paper Series No. 970735, (Warrendale, PA: SAE
to these standard tests and even may require completely differ- International, 1997).
ent, dedicated test protocols designed to address specific appli-
9. J. P. Moran, F. S. Bovard, J. D. Chrzan, R. J. Rioja, and E. L. Colvin,
cations. As the industry progresses, improved understanding of “Improvements in Corrosion Resistance Offered by Newer
the fundamental interaction between environmental factors Generation 2x99 Aluminum-Lithium Alloys for Aerospace
and dynamic loads will take the airplane industry closer to the Applications,” in Proceedings of the 12th International Confer-
ultimate goal of minimizing corrosion costs and failures in ence on Aluminum Alloys (Yokohama, Japan: Japan Institute of
aircraft. Light Metals, 2010), 1492–1497.
393
Chapter 25 | Military Aircraft and Associated Equipment
Diane Buhrmaster1 and Nicholas Wilson1
Introduction Storage, Transportation, and

This chapter discusses the typical corrosion tests used to verify Deployment of Equipment
the performance of military equipment, from basic components During these phases of the military equipment life cycle, it gener-
to fully mission-capable ordinance, aircraft, space vehicles, and ally is assumed that the asset is packaged as carefully as possible,
supporting equipment. For military operations, corrosion is perhaps even partially disassembled, and then transported by
defined as the deterioration of a material or its properties truck, rail, airplane, or ship. In some cases, however, the military
because of a reaction of that material with its chemical environ- equipment is flown to the operating location. With each method
ment. Military aircraft, ordinance, space equipment, and sup- of transportation, the equipment is exposed to some temperature
porting equipment must be designed to operate for long periods and humidity fluctuation, and sometimes to pressure changes.
of time in extreme environments. This includes from the Arctic These fluctuations and exposures can still occur even when using
Circle to the equator, desert to the coast, urban to remote areas, packaging that attempts to provide environmental control or
and ground units to space assets. This chapter defines ground protection. Mechanical wear (i.e., rubbing or abrasion) can occur
temperatures from very cold ( 70 F [ 57 C]) to very hot on equipment transported in shipping containers. Equipment
(136 F [58 C]) and relative humidity from near zero to near sat- might be stored in environmentally controlled warehouses when
urated. Extreme environments also can have high levels of ozone possible (i.e., office and computer equipment) or in unimproved
(O3), sodium chloride (NaCl), sodium carbonates (Na2CO3), sul- temporary storage locations at forward operating bases (i.e., tem-
fur oxides (e.g., SO, SO2, SO3), sodium sulfates (Na2SO4), and porary buildings or mobile operating structures). In these vari-
sodium bicarbonate (NaHCO3), in addition to reactive dust or able environments, military equipment may experience diurnal
sand particles and volcanic ash dust (as small as 140 lm in cycling with both high and low humidity, high and low tempera-
diameter). ture, and often direct sunlight. These environments may be expe-
Military equipment must be designed to operate in these rienced for days, weeks, or months. Operational environments
various exposure conditions, because these conditions could be also may experience chemical attack, which requires potentially
experienced during the life cycle of the item. This includes corrosive decontamination processes. Transportation and stor-
manufacturing, transportation, storage, mission theater, forward age limitations must be part of the corrosion prevention and mit-
operating base deployment, and depot refurbishment. Military igation planning, because there is wide variability in military
aircraft can spend time at ground bases outside, under tents, in equipment size, use, and expected life cycle. Appropriate testing
hangars, packaged for transportation, shipped on cargo vehicles, and references covering these phases are described later.
and of course flying. With these many environments, test pro-
grams must be designed around the corrosion resistance of the
base materials (traditional aluminum and newer polymeric com-
posites) as well as the assembled component systems (avionics, The Military Mission
propulsion, hydraulics, and ordinance). Careful planning is
required to ensure that the final product, whether it is a small During its mission, military equipment will be exposed to vari-
drone, ordinance, large aircraft, or mobile communications unit, ous weather conditions, including fully wet conditions in rain
has the ability to perform as intended in extreme environments. and condensing humidity from dew; blowing and settling sand
or dust and debris; and salt spray in coastal areas. Additionally,
1
mission threats will expose military equipment to chemical and
Materials and Manufacturing Directorate, Air Force Research Laboratory, 2179 12th
St., Building 652, Wright-Patterson AFB, OH 45433, USA
biological attack agents, explosive ordinance, and live fire. Vari-
The authors acknowledge the previous author of this chapter, Harvey S. Rosenberg, ous military specifications and standards provide guidance for
Guild Associates, Hilliard, OH. these latter military-specific exposures, but planning for future
DOI: 10.1520/MNL202NDSUP20190028
corrosion protection of equipment can have a beneficial impact than 18 F (10 C) per minute. In the context of MIL-STD-810,
on protection from other mission-related exposures. this method is designed around tracked and wheeled vehicles,
such as ground support equipment, in a mission environment.
This method focuses on surface changes following air delivery or
Environmental Testing air drop from high altitude/low temperature to ground level, or
transfer of an item from very high temperature areas in a desert
Testing involves basic materials testing to ensure that the equip-
to a cold air-conditioned enclosure. Several variations are listed
ment or military article will withstand the mission environment.
in MIL-STD-810, but the most frequently cited procedure has
This includes testing the components that are made from those
three cycles between low- and high-temperature extremes. When
materials and testing the final product that contains the individual
testing a component or subsystem, the test article starts at ambi-
components. These tests do not have the same rigidity, and a
ent temperature and is placed at the extreme low (e.g., for a mili-
materials test may be more focused on lifetime and endurance,
tary application, 70 F [ 57 C]) and held there for a long
whereas a component test may focus on operational functionality.
enough period of time for the article to equilibrate to that tem-
Many of the general military corrosion test standards from
perature. This could be 1 h or several hours, depending on the
MIL-STD-810, Environmental Engineering Considerations and
thermal capacitance and heat transfer rate of the component or
Laboratory Tests,1 now include the phrase “tailoring is essential.”
subsystem in test. Once the test article has equilibrated, it is
The majority of the test methods should not be called out in a
transferred to a different test chamber set to very hot (e.g., for a
blanket fashion nor applied as unalterable routines, but rather
military application, 136 F [58 C]) and again left to equilibrate
should be selected and tailored to generate the most relevant test
for 1 h or several hours. This represents one cycle. After three
data possible. Many military equipment requirements docu-
cycles, the test article is visually evaluated for damage. Further
ments for new acquisition now cite MIL-STD-1568, Department
postexposure testing may be warranted if the test article shows
of Defense Design Criteria Standard, Materials and Processes for
cracks or failure of the corrosion protection system. Typically,
Corrosion Prevention and Control in Aerospace Weapons Sys-
this would evaluate that the component or subsystem operates as
tems.2 This military standard is specifically designed for aero-
intended after testing.
space weapon systems, whereas MIL-STD-810 is generic and
provides guidance on hundreds of test areas. The corrosion sci-
entist or engineer must evaluate the appropriate testing guidance MICROBIAL-INFLUENCED CORROSION
and design protocols that ensure that the data provides confi- Microbial-influenced corrosion (MIC) is a potentially major con-
dence in the longevity of the military equipment. tributor to corrosion that affects aircraft structures and fuel sys-
tems. Over time, mold, mildew, fungi, bacteria, and other
HUMIDITY TESTING organic contaminants can build up on aircraft structures. Some
Military aerospace equipment require verification that the corro- produce acids and enzymes that contribute to corrosion on air-
sion control design is sufficient for components and subsystems. craft surfaces. Other microbes can cause illness and become a
Testing from MIL-STD-1568 includes ASTM D2247-15(2020), health hazard for military personnel. Still others simply have an
Standard Practice for Testing Water Resistance of Coatings in unsightly appearance and need to be removed before new com-
100% Relative Humidity.3 This is a 30-day humidity test to verify ponents can be installed on an aircraft or before new coating
that the sealants, coatings, and other protective layers on the test materials can be applied.
article will prevent moisture ingress. Test articles must have no One area of high interest is fuel systems. Biofuels are particu-
blistering, softening, loss of adhesion, or other notable damage to larly conducive to microbial growth because they serve as a nutri-
the corrosion protection layers. ent source for the microbes.4 Some biofuels are from processed
General testing for other military hardware, such as ground vegetable oils and animal fats, substances in which microbes can
vehicles, may include one or more of the MIL-STD-810 humidity thrive. Few predictive measures are in place that allow for the sys-
tests. These vary between simulating diurnal solar radiation tematic evaluation of the susceptibility of emerging fuels to micro-
and high humidity of tropical environments, severe dew point bial contamination or evaluation of their ability to contribute to
changes in the Persian Gulf and Red Sea area, and induced stor- corrosion. Fuel components are investigated for compatibility
age and transit cycles. The appropriate testing is dictated by the with an aircraft fuel system, and additives are investigated for
materials, components, subsystems, and final equipment or interactions with materials in those fuel systems. Because of the
hardware. As stated previously, these test methods must be tai- risk of biocontamination, similar evaluations need to be per-
lored to capture the suitable life-cycle expectations for the test formed in which biologically derived fuels are used or could be
article. There is no one-size-fits-all test for components and sub- used. Once identified, the impact of that contamination must be
systems. The corrosion scientist or engineer must select appro- understood and mitigated. General guidance is available in MIL-
priate testing to reduce risk. STD-810 to determine the susceptibility of materials to fungal
growth. Additional guidance can be found in MIL-STD-1568.
THERMAL SHOCK
In the context of corrosion testing, thermal degradation evaluates SALT SPRAY
physical damage or deterioration in performance of the compo- Multiple ASTM standard practices can be employed to evaluate
nent, or subsystem with a sudden air temperature change greater the corrosion protection system against salt sprays, sea water
MILITARY AIRCRAFT AND ASSOCIATED EQUIPMENT 395
mist, and industrial pollutants in salt mist. For many decades, Operating Xenon Arc Light Apparatus for Exposure of Non-
the baseline has been ASTM B117-19, Standard Practice for Oper- Metallic Materials,7 Cycle 1, which is 102 min of irradiance at
ating Salt Spray (Fog) Apparatus.5 Salt spray testing in a continu- 0.35 W/(m2nm) at 340 nm and a black panel temperature of
ous fog of 5 wt% NaCl at 95 F (35 C) has been used to evaluate 145.4 F (63 C), followed by 18 min of irradiance only and water
basic barrier properties. It often is used to extrapolate corrosion spray (air temperature not controlled). This method often is run
inhibition performance in a marine or coastal environment but continuously, and the test article may be exposed for a few days
cannot be directly correlated to field exposure results. Some mili- to many weeks, depending on the intended mission require-
tary operations require resistance to industrial chemicals in salt ments. Post-test materials evaluation determines whether the
spray, and ASTM G85-19, Standard Practice for Modified Salt corrosion protection system has degraded by loss of color, adhe-
Spray (Fog) Testing,6 Annex 4 salt spray with SO2 is used for that sion, or visual deformation, such as cracking, crazing, peeling, or
verification. Additionally, in ASTM G85, Annex 5, the dilute other damage. Post-test component or subsystem evaluation also
electrolyte cyclic fog/dry test is used to rapidly evaluate both the requires that the test article be verified for performance.
barrier and the inhibitor performance of aerospace aluminum
corrosion protection systems. To date, there is no accelerated RAIN
test that correlates with field exposure, and this topic continues There are two scenarios for rain exposure testing. One is for mili-
to be of high interest in the Department of Defense (DoD) and tary equipment that will be outside, either at a runway or in a
commercial aviation world. storage area. The other scenario is for the military equipment
that will be flying or be on-wing of an aircraft. After either of
LOW-PRESSURE DEGRADATION these scenarios, the materials, components, or subsystems are
Low-pressure degradation occurs when an aerospace component, evaluated for loss of key properties or reduced functionality.
subcomponent, or system is transported or operated in unpres- In the first scenario, the test article is exposed to simulated
surized areas of an aircraft. This includes scenarios of “on-wing” wind and blowing rainfall as if it were stored outside or sitting
ordinance that is rapidly taken from ground to operational alti- on the runway. If the test article has already been tested for resis-
tude attached to the wing of the aircraft. MIL-STD-810 provides tance to water immersion, there is no need to perform the blow-
a baseline test for aircraft and missiles that will operate below ing rain test. The test article is exposed to droplets that
70,000 feet. With rapid loss of pressure, test articles can experi- predominantly are 500 lm with some up to 4,500 lm, and with
ence deformation of sealed areas and leakage of gases or fluids, rain rates of 4 in./h (1.7 mm/min). Simulated wind velocity is
which may cause components to fail. A typical test is MIL-STD- 40 mph (18 m/s). The test duration can be as short as an hour to
810, Method 500, which requires altitude changes at 32.8 ft/s as long as several hours, simulating continual rain and storms.
(10 m/s) or lower. In full military power takeoff, military trans- In the second scenario, the test article is exposed to simu-
port aircraft have an average altitude change of 25 ft/s (7.6 m/s), lated rain particle damage during flight. Typical areas of degra-
so using the 32.8 ft/s change rate provides sufficient information dation are optical windows, radomes, leading edges on wings,
to determine whether sealed areas or corrosion protection sys- flaps, and rudders, as well as damage to the protective coatings
tems on test articles will be deformed, allowing for moisture, and sealants. Liquid impingement erosion and cavitation is well-
chemicals, or other contaminants to damage the component. described in ASTM G73-17, Standard test Method for Liquid
Typically, after a low-pressure test cycle, an operational check on Impingement Erosion Using Rotating Apparatus,8 along with
the military component or subsystem will be performed to verify methods for testing certain situations. Military applications also
that the item still performs as intended. There is no blanket per- will use the description from AMS-C-83231, Coatings, Polyure-
formance test for all components or subsystems, so the corrosion thane, Rain Erosion Resistant for Exterior Aircraft and Missile
scientist or engineer must collaborate with other materials and Parts.9 This method uses airfoils, coupon testing, or other sample
process engineers to determine the best test cycle for the item in configurations that are coated with a rain erosion–resistant
question. material and placed on a double-blade whirling arm. The test
article is accelerated to 500 mph and exposed to simulated natu-
SOLAR RADIATION ral rainfall with an average droplet size of 0.08 inches (2 mm)
Military equipment will be exposed to solar radiation during its and a rainfall rate of 1 in./h. Test duration can be a few minutes
life cycle. As with any accelerated test method, there are limita- to more than 2 h, depending on the intended use of the material.
tions to solar radiation tests because they do not correlate to the After either of these test scenarios, the materials, compo-
effects of a natural environment. For this reason, test method tai- nents, or subsystems are evaluated for loss of key properties or
loring is essential to determine the best procedures that reduce reduced functionality.
risk and provide confidence in the life cycle of the test article. At
high elevations, solar radiation contains more ultraviolet-B radi- SAND AND DUST PARTICLES
ation than at sea level. Solar radiation also can be absorbed by Sand or dust particles exist in nearly every military operational
some military corrosion protection systems, causing oxidation environment. Not all sand and dust particles are created equal.
and degradation of those systems. Particles collected from southwestern United States have differ-
A common test procedure for worldwide deployment of ent mineral chemistry, angularity, and size distribution than
military equipment utilizes ASTM G155-13, Standard Practice for those collected from the United Arab Emirates. Particles
collected from soil in Hawaii have substantial volcanic ash, but select materials across all engineering disciplines. Advanced mate-
particles in the Iraq Peninsula are course and glassy with clay rials degradation tests will require new innovative protocols for
grains. The damage expected by sand and dust is directly related better prediction of materials performance and service life. Once
to aerospace vehicle velocity and altitude. Larger particles are developed, these methods will provide materials developers with
closer to ground level altitude below 10,000 ft, whereas lighter realistic and reliable data that correlate to real-world operation for
dust particles reach higher altitudes. materials selection, with an eye toward corrosion prevention in
Sand particles cause erosive corrosion damage because they the military equipment design.
impinge on surfaces and ablate corrosion protection systems.
The damaged, unprotected surfaces collect ambient chemicals,
such as industrial pollutants and salts, which can cause corrosion Standards and Specifications
when dew or other moisture comes into contact with those surfa- Military specifications have undergone many changes over the
ces. Sand and dust particles will enter air intakes on engines, past decade. In the early- to mid-20th century, when aerospace
erode at the protective high-temperature resistant coatings on was largely the purview of militaries and governments, military
blades and stators, and cause premature failure of the engine specifications existed for materials formulas, properties, fluids,
(hot corrosion damage) in extreme cases. fuels, test methods, and complete design criteria. In the mid-1990s,
Effective methods to design for hot corrosion are still in the DoD revised numerous military specifications with the goal to
development, but methods for evaluating sand or dust impinge- replace them with existing industrial specifications such as ASTM
ment of leading edges has been developed in MIL-STD-3033, International, the International Organization for Standardization
Particle/Sand Erosion Testing of Rotor Blade Protective Materi- (ISO), the Society for Automatic Engineers (now SAE Interna-
als.10 This military standard uses the apparatus in ASTM F1864, tional), and others. This led to reliance on the industrial base to
Standard Test Method for Dust Erosion Resistance of Optical and provide specifications that would meet both commercial and mili-
Infrared Transparent Materials and Coatings,11 and focuses on tary needs. In many cases, these dual-purpose standards were
evaluating exterior surfaces of rotor blades for helicopters and appropriate. In other cases, it became clear that the industry and
other rotary-driven aircraft that could be located in hot arid commercial use of aircraft was not always close enough to that of
regions. Particles are sieved to between 240 lm and 550 lm, the military. In the early 21st century, there has been a greater
which is comparable to the particles that have been found on air- push for reapproval of military standards and the development of
craft in desert hover or low-level flight testing. Particle velocity new standards and specifications that focus on military needs.
is controlled to 730 ft/s with a mass loading between 30 and MIL-STD-1530, Aircraft Structural Integrity Program
50 g/cm2 for the test. The impingement angle is between 20 and (ASIP),12 requires materials, components, and subsystems to be
90 depending on the life cycle and use of the military equip- tested for durability in operational environments. Design analy-
ment. This method has been used for the design and sustainment sis and development testing requirements in that standard pro-
of various helicopters and low-altitude hover vehicles. Post-test vide guidance on how corrosion tests should be conducted. The
evaluation requires mass loss, visual examination, and metallo- standard emphasizes that corrosion protection systems should
graphic analysis to determine if the material has sufficient dura- be tested on representative structures in relevant and operational
bility. Testing can be tailored for components and smaller environments.
subsystems, particularly when sand or dust encroachment may There are several ways to locate military standards and
cause electrical or hydraulic failure of a military component. specifications related to corrosion prevention and control. One
As with all accelerated or simulation testing, corrosion scientists website is the Acquisition Streamlining and Standardization
and engineers must plan select and design testing that reduces Information System (ASSIST) operated by the Defense Standard-
improves likelihood that the military equipment will function ization Program (DSP) and managed by the Defense Logistics
as intended in extreme environments. Agency (DLA) Document Service.13 Additional standardization
information can be found at the Defense Standardization Pro-
ACCELERATED AND COMBINED EFFECTS gram website.14
CORROSION TESTS
The DoD corrosion community has long recognized the need to
expose materials to a simultaneous mix of two or more environ-
Conclusion
mental variables during development and to consider the interac- Military aircraft and equipment are exposed to all climates and
tion of autonomous materials during validation, verification, and conditions. Unlike commercial aviation, there are cases where
ultimately operation. Such environmental factors include, but are the military equipment is required to perform a mission that
not limited to, electrolytes (salt spray), temperature and humidity could expose that equipment to chemicals or environmental
cycles, insolation, background gases, solar exposure, acoustic load- stresses that have an unknown effect on service life. Various mili-
ing, sand or rain exposure, and dynamic loading. The DoD has tary and industry standards attempt to address the underlying
been taking aggressive steps toward the development of advanced failure mechanisms and to reduce the risk that the equipment
accelerated test methodologies that will allow testing for true could be damaged. The extensive DoD systems engineering pro-
material performance in relevant service environments. Such an cess exists to design, integrate, test, validate, and verify new mili-
approach has clear potential to change the way engineers test and tary capabilities. The DoD Corrosion Policy and Oversight
MILITARY AIRCRAFT AND ASSOCIATED EQUIPMENT 397
Office published the Corrosion Prevention and Mitigation Stra- 7. Standard Practice for Operating Xenon Arc Light Apparatus
tegic Plan in 2011, providing policy, strategy, objectives, and for Exposure of Non-Metallic Materials, ASTM G155-13
plans to address corrosion prevention in the planning and devel- (West Conshohocken, PA: ASTM International, approved June 1,
2013), http://doi.org/10.1520/G0155-13
opment phase of acquisition. Instead of looking at corrosion
control as a “find and fix” approach many years after military 8. Standard Test Method for Liquid Impingement Erosion Using
equipment has been deployed, corrosion design strategy now Rotating Apparatus, ASTM G73-10(2017) (West Conshohocken,
focuses on “prevent, predict, detect, and manage.” Specific mili- PA: ASTM International, approved July 15, 2017), http://doi.org/
tary corrosion policy and strategies can be found at either the 10.1520/G0073-10R17
Defense Acquisition University website,15 or the DoD Corrosion 9. Coatings, Polyurethane, Rain Erosion Resistant for Exterior
Policy and Oversight Office website.16 Aircraft and Missile Parts, AMS-C-83231 (Warrendale, PA:
Aerospace Material Specifications, SAE International, 2001).
10. Particle/Sand Erosion Testing of Rotor Blade Protective

References Materials, MIL-STD-3033 (Arlington, VA: Department
of Defense, 2010).
1. Environmental Engineering Considerations and Laboratory Tests,
MIL-STD-810 (Arlington, VA: Department of Defense, January 11. Standard Test Method for Dust Erosion Resistance of Optical and
2019). Infrared Transparent Materials and Coatings, ASTM F1864-16
(West Conshohocken, PA: ASTM International, approved April 1,
2. Department of Defense Design Criteria Standard, Materials and
2016), http://doi.org/10.1520/F1864-16
Processes for Corrosion Prevention and Control in Aerospace
Weapons Systems, MIL-STD-1568 (Arlington, VA: Department of 12. Department of Defense Standard Practice, Aircraft Structural
Defense, August 2015). Integrity Program (ASIP), MIL-STD-1530 (Arlington, VA:
Department of Defense, October 2016).
3. Standard Practice for Testing Water Resistance of Coatings in
100% Relative Humidity, ASTM D2247-15(2020) (West Consho- 13. Acquisition Streamlining and Standardization Information
hocken, PA: ASTM International, approved June 1, 2020), http:// System (ASSIST), Defense Standardization Program (DSP),
doi.org/10.1520/D2247-15R20 Defense Logistics Agency (DLA) Document Service,
4. E. Mansfield, J. Sowards, W. Crookes-Goodson, “Findings and
assist.dla.mil/
Recommendations from the NIST Workshop on Alternative Fuels
and Materials: Biocorrosion,” Journal of Research NIST 120 14. Defense Standardization Program, http://web.archive.org/web/
(March 2015): 28–36, http://doi.org/10.6028/jres.120.003 20210505142139/https://www.dsp.dla.mil/
5. Standard Practice for Operating Salt Spray (Fog) Apparatus, 15. Defense Acquisition University, http://web.archive.org/web/
ASTM B117-19 (West Conshohocken, PA: ASTM International, 20210505144319/https://www.dau.edu/
approved November 1, 2019), http://doi.org/10.1520/B0117-19
16. DoD Corrosion Policy and Oversight Office, http://web.
6. Standard Practice for Modified Salt Spray (Fog) Testing, ASTM archive.org/web/20210505153437/https://www.dau.edu/cop/
G85-19 (West Conshohocken, PA: ASTM International, approved cpc/Pages/Default.aspx
November 1, 2019), http://doi.org/10.1520/G0085-19
399
Chapter 26 | Industrial Chemicals: Manufacture and Usage
Sheldon W. Dean, Jr.1
Introduction TABLE 1 Organizations That Write Standards Used by the CPI

Industrial chemicals are usually relatively pure chemical com-
pounds that are manufactured for use in a variety of applica- Organization Types of Standards
tions.1 In some cases, they are mixtures of compounds. In other ASTM International Tests, practices, guides,
cases, they are blended with other materials to make products. specifications, nomenclature,
They constitute a major class of industrial products that are used classifications
in commerce. These materials are produced in large volumes NACE International Tests, practices, guides,
and, in many cases, are corrosive, toxic, or flammable. As a nomenclature
result, the manufacture, storage, and transportation of these International Organization for Tests, practices, nomenclature
materials must be handled with care. Leaks or other releases to Standardization (ISO)
the environment can result in substantial damage and present American Society of Mechanical Practices, specifications
hazards to both workers and others in the vicinity.2 Engineers (ASME)
Standards are used in the design, production, transportation, American Petroleum Institute (API) Practices
and storage of industrial chemicals and in the inspection of equip- American Society for Non-Destructive Certification
ment exposed to these materials to ensure safe operation, contain- Testing (ASNT)
ment, and protection of the environment. Corrosion damage can
result in leaks and other releases to the environment. Corrosion
equipment, maintenance of the facility, and inspection and
also can cause contamination of chemical products. Corrosion
repair of the facility. Storage and shipment of the chemical prod-
standards are a significant source of information that is used to
ucts are also covered. Corrosion of the materials of construction
prevent, minimize, or manage issues resulting from corrosion pro-
is a significant damage mechanism that can lead to release of the
cesses. A number of different organizations write standards that
chemical products with all of the issues that can result. Corrosion
are used in the chemical process industries to deal with corrosion
testing is used to establish the suitability of the materials for con-
issues. Several of these organizations are listed in table 1. ASTM
struction and to determine inspection intervals.
International, NACE International, and the International Organi-
Corrosion damage occurs in several characteristic forms.
zation for Standardization (ISO) produce standards directly
Many of the most common forms are listed in table 2. It is
relating to corrosion testing and best practices associated with cor-
important to recognize that these forms can occur, and each one
rosion issues. The other organizations shown in table 1 address
has specific characteristics. Understanding these characteristics
specific issues that result from corrosion damage.
can aid in planning a corrosion test program and will be impor-
tant in analyzing the results of the program. For example, a test
program that is solely designed to determine general corrosion
Corrosion Testing for Industrial rates may not detect stress corrosion cracking, thereby missing a
Chemicals Manufacturing critical failure mechanism.
When designing a test program, a review the existing refer-
The subject of manufacturing industrial chemicals covers the ences on the possible materials of construction and the environ-
design of the process, construction of the facility, operating the ments that may be encountered can be helpful. Such information
1
may be available from material suppliers, academic sources, pro-
Dean Corrosion Technology, Inc., 306 Marshall Landing, Glen Mills, PA 19342, USA
fessional society papers, and publications from organizations
The author acknowledges the previous author of this chapter, Robert B. Puyear, such as NACE International, the Materials Technology Institute
Chesterfield, MO. (MTI), and ASTM International.
DOI: 10.1520/MNL202NDSUP20190019
PROCESS DESIGN
TABLE 2 Forms of Corrosion Damage The selection of materials of construction for a process is an
important issue in the design phase of the project. In cases in
Type Characteristics which the process has been used previously, the selection usually
General Uniform attack, constant rate retains the materials from the previous design if the performance
Pitting Local areas of accelerated attack of those materials was satisfactory. In some cases, newer alloys
Under Deposit Pitting under solid deposits may be available that offer benefits in terms of cost, ability to be
Crevice Accelerated attack in occluded areas fabricated, or performance. In such cases, it might be important
Stress Corrosion Cracking Cracking from corrosion in areas under to run laboratory tests to obtain actual data on the performance
tensile stress of the newer material as compared with the material previously
Liquid Metal Embrittlement Cracking in areas under tensile stress from used. Table 3 shows a number of ASTM standard laboratory tests
liquid metal methods and procedures for metals and alloys. These different
Hydrogen Embrittlement Cracking in tensile stressed areas from standards are used to test for the various forms of corrosion
hydrogen permeation damage that might occur.
Corrosion Fatigue Cracking resulting from corrosion and cyclic
tensile stressing LABORATORY TESTING
Galvanic Corrosion Accelerated attack from electrical contact The most widely used laboratory test procedure for immersion
with a more noble material
testing is the NACE TM01-69/ASTM G31-12A, Standard Guide
Fluid Flow Accelerated Accelerated attack from flowing liquid or
for Laboratory Immersion Corrosion Testing of Metals (Historical
turbulence
Version).3 This guide was developed independently by both
Intergranular Localized corrosion at grain boundaries
ASTM Committee G01 and NACE International. Subsequently,
TABLE 3 ASTM Laboratory Corrosion Test Procedures
Type ASTM No. Title Metal
General Corrosion G31 Standard Guide for Laboratory Immersion Corrosion Testing of Metals All
Pitting G46 Standard Guide for Examination and Evaluation of Pitting Corrosion All
G48 Standard Test Method for Pitting and Crevice Corrosion of Stainless Steels and Related Alloys by Use of Ferric SS
Chloride Solution
G61 Standard Test Method for Conducting Cyclic Potentiodynamic Polarization Measurements for Localized Corrosion SS
Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys
G150 Standard Test Method for Electrochemical Critical Pitting Temperature Testing of Stainless Steels and Related Alloys SS
Crevice Corrosion G48 Standard Test Method for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys Solution by SS
Use of Ferric Chloride Solution
G78 Standard Guide for Crevice Corrosion Testing of Iron-Base and Nickel-Base Stainless Alloys in Seawater and Other SS
Chloride Containing Aqueous Environments
Galvanic Corrosion G71 Standard Guide for Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes All
G82 Standard Guide for Development and Use of a Galvanic Series for Predicting Corrosion Performance All
High-Temperature, G111 Standard Guide for Corrosion Tests in High Temperature or High Pressure Environment, or Both All
High-Pressure Testing G142 Standard Test Method for Determination of Susceptibility of Metals to Embrittlement in Hydrogen Containing All
Environments at High Pressure, High Temperature, or Both
Flow Accelerated G184 Standard Practice for Evaluating and Qualifying Oil Field and Refinery Corrosion Inhibitors Using Rotating Cage CS
Corrosion G185 Standard Practice for Evaluating and Qualifying Oil Field and Refinery Corrosion Inhibitors Using the Rotating CS
Cylinder Electrode
G202 Standard Test Method for Using Atmospheric Pressure Rotating Cage CS
G208 Standard Practice for Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors Using Jet Impingement CS
Apparatus
Intergranular Corrosion A262 Standard Practices for Detecting Susceptibility to Intergranular Attack in Austenitic Stainless Steels SS
G28 Standard Test Methods for Detecting Susceptibility to Intergranular Corrosion in Wrought, Nickel-Rich, Chromium- SS
Bearing Alloys
G108 Standard Test Method for Electrochemical Reactivation (EPR) for Detecting Sensitization of AISI Type 304 and 304L 304
Stainless Steels
(continued)
INDUSTRIAL CHEMICALS: MANUFACTURE AND USAGE 401
TABLE 3 (continued)
Type ASTM No. Title Metal
Stress-Corrosion Cracking G30 Standard Practice for Making and Using U-Bend Stress-Corrosion Test Specimens All
and Hydrogen G35 Standard Practice for Determining Susceptibility of Stainless Steels and Related Nickel-Chromium-Iron Alloys to SS
Embrittlement from Stress-Corrosion Cracking in Polythionic Acids
Corrosion G36 Standard Practice for Evaluating Stress-Corrosion-Cracking Resistance of Metals and Alloys in Boiling Magnesium SS
Chloride Solution
G37 Standard Practice for Use of Mattsson’s Solution of pH 7.2 to Evaluate the Stress-Corrosion Cracking Susceptibility Brass
of Copper-Zinc Alloys
G38 Standard Practice for Making and Using C-Ring Stress-Corrosion Test Specimens All
G39 Standard Practice for Preparation and Use of Bent-Beam Stress-Corrosion Test Specimens All
G41 Standard Practice for Determining Cracking Susceptibility of Metals Exposed under Stress to a Hot Salt Environment All
G44 Standard Practice for Exposure of Metals and Alloys by Alternate Immersion in Neutral 3.5% Sodium Chloride All
Solution
G49 Standard Practice for Preparation and Use of Direct Tension Stress-Corrosion Test Specimens All
G58 Standard Practice for Preparation of Stress-Corrosion Test Specimens for Weldments All
G123 Standard Test Method for Evaluating Stress-Corrosion Cracking of Stainless Alloys with Different Nickel Content in SS
Boiling Acidified Sodium Chloride Solution
G129 Standard Practice for Slow Strain Rate Testing to Evaluate Susceptibility of Metallic Materials to Environmentally All
Assisted Cracking
G168 Standard Practice for Making and Using Precracked Double Beam Stress Corrosion Specimens All
the two documents were merged into a joint standard. The test
vessel used to hold the specimens is shown in figure 1. This FIG. 1 Typical resin reaction flask used for laboratory immersion
approach is most often used for mass loss rate determinations, testing (see NACE TM0169/G31).
but it also has been used to study other forms of corrosion dam-
age, depending on the specimen design. A modification of this
approach is shown in figure 2. In this case, the setup can simulta-
neously expose specimens to boiling liquid, vapor, and hot
condensate.
One laboratory mass loss corrosion study determined the
corrosion mechanism on the top tray of a vacuum distillation
column used to purify toluene diamine (TDA).1 This column had
an internal condenser at the top of the column to minimize the
pressure drop. The column used valve trays and was constructed
of carbon steel. There was no reason to expect corrosion of the
carbon steel in this case. It was noted that the gas exiting the col-
umn through the vacuum system was a mixture of water vapor
and carbon dioxide.
A test was set up using the ASTM G31 flask assembly with
TDA liquid held at the temperature at the top of the column. A
nitrogen gas stream was sparged through the liquid to maintain
an oxygen-free environment and to provide a flow of condensate
that contacted the specimens. Carbon steel coupons showed no
corrosion after one week of exposure. Then the test was repeated
with a gas mixture containing 10% by volume carbon dioxide.
Again, no corrosion was found after a one week of exposure.
This test was repeated again after saturating the gas with water
vapor at ambient temperature, and again no corrosion was
noted. Finally, an addition was made to the TDA of cyclohexyl
amine at about 0.1%, and the test was repeated using the gas
mixture. In this case, the carbon steel coupons showed a corro-
sion rate of about 20 mpy. This was believed to have resulted
from the formation of cyclohexyl amine carbamic acid, which is
FIG. 2 Modified flask system for multiple exposure of coupons to FIG. 3 Spool corrosion rack for use in vessels (see ASTM G4).
1
boiling liquid, vapor, and condensate.
FIG. 4 Pipe insertion rack (see ASTM G4).
about as acidic as an acetic acid. Although this compound will

decompose spontaneously in hot TDA, its presence is sufficient
to cause the corrosion damage noted. A similar amine can be
generated during the hydrogenation of dinitro-toluene if the
hydrogenation catalyst is too active. A test with coupons of type
304L stainless steel showed no corrosion, so it was decided to
line the column top with this alloy and use it for the top tray. In
this case, ASTM G31 provided guidance that enabled the success-
ful completion of this test program. Thereafter, no corrosion
problems have been noted with this column.
PILOT PLANT TESTING

In the case of a new process in which a pilot plant test program
has been set up, the inclusion of corrosion specimens of various
candidate materials is usually a desirable procedure.4 The pilot
plant operation can create conditions that are difficult or impos-
sible to simulate in a laboratory test. In such situations, ASTM
G4, Standard Guide for Conducting Corrosion Tests in Field
Applications, provides several designs of coupon holders that
may be appropriate for a pilot plant situation. Three different
types of specimen holders are shown in figures 3, 4 and 5. In
these cases, the coupons are used for corrosion rate determina-
tion by means of mass loss measurement. Stressed coupons,
bimetallic specimens, welded coupons, or crevice assemblies also
can be included, if desired.
FIG. 5 Retractable “slip-in” specimen holder (see ASTM G4).
Electrical resistance probes or electrochemical probes pro- to its cross-sectional area. Corrosion reduces this cross section,
vide the possibility of obtaining corrosion rate information with- so the measurement of the resistance of the rod provides a way
out the necessity of removing and analyzing specimens. ASTM to monitor the extent of any corrosion that is occurring.
G96, Standard Guide for Online Monitoring of Corrosion in Plant Electrochemical probes are based on the concept that the
Equipment (Electrical and Electrochemical Methods), provides polarization resistance of an electrode is inversely proportional
guidance on the design and use of both electrical resistance and to the corrosion rate that is occurring. Polarization resistance is
electrochemical probes. These approaches are particularly helpful the slope of the electrode potential versus current density curve
in cases in which the same apparatus is being used to produce a at the corrosion potential.5 The electrochemical probes consist of
number of different chemicals in a campaign mode, or in cases two or three identical electrodes that are placed into the environ-
in which the process conditions are being varied, and it is desired ment. The measurement process consists of applying either
to understand how the changing conditions affect the corrosion 20 mV for the two electrode system or 10 mV relative to the ref-
behavior of the metal being tested. Figure 6 shows a typical elec- erence electrode for the three-electrode system. In either case,
trical resistance probe assembly. This concept is based on the the resulting current that flows between the working electrodes is
fact that the electrical resistance of a rod is inversely proportional measured and converted to a corrosion rate by the apparatus.
Figure 7 shows a typical three-electrode system.
FIG. 6 Typical electrical resistance probe (see ASTM G96). TESTING IN OPERATING PLANTS
In operating plants corrosion, testing is carried out from time to
time for a variety of reasons. Such testing can be helpful in inves-
tigating the performance of new materials. In cases in which a
significant change in the process is being evaluated, it is impor-
tant to include corrosion testing as part of the evaluation. In
plants that operate in a campaign mode where different products
are manufactured using the same equipment, running corrosion
tests during each campaign can help pinpoint which campaigns
are responsible for the problems that are occurring. In cases in
which impurities are observed in the product, corrosion testing
can assist in determining if corrosion of the metals in the system
is the source of the contamination. In these cases, ASTM G4 cou-
pon holders and procedures are used if mass loss measurements
are carried out. The decisions regarding specimen size and shape
are based on the type of holder used and the space available.
FIG. 7 Three electrode polarization resistance probe design and installation (see ASTM G96).
Special designs are required if the specimens are to be inserted it is necessary to use robust designs that are not as susceptible to
and removed while the plant is operating. In addition, a safety contamination or mechanical damage. In the case of a system
evaluation is necessary in this case to ensure that the procedures that is showing marginal passivity, it may be important to
will not result in a hazardous situation. If the procedure results increase the inhibitor addition or investigate why the change has
in removing some of the process stream along with the coupon occurred.
rack, this material must be recovered and discarded appropri-
ately. Figure 5 shows a slip-in rack assembly that allows the speci-
mens to be withdrawn without shutting the operation down. Specialized Testing
High-pressure systems pose particular risks because of the force
they exert on the withdrawal devices. CORROSION UNDER THERMAL INSULATION
Electrical resistance and electrochemical probes are also Thermal insulation is widely used in chemical manufacturing
used in operating plants. They offer the possibility of obtaining facilities. Traditionally, thermal insulation is applied after the
data without the need to remove the probe from service. They facility construction is completed, usually without any protective
have been used in cooling water service to monitor the perfor- coatings applied to the metal surfaces. Thermal insulation is
mance of corrosion inhibitors in these systems. This was espe- used to minimize heat loss from the item, and to protect workers
cially important when the use of chromates was ended, and new from exposure to hot metal surfaces. A variety of different types
inhibitor systems were instituted. ASTM G96 provides important of insulation is used depending on the temperature of the sur-
operating information on these devices. face, the degree of insulation required, and other factors. In most
Electrode potential measurements have also been used to cases, a metallic covering is added after the insulation is installed.
monitor passivity in process systems. ASTM G215, Standard The covering is intended to protect the insulation from rain or
Guide for Electrode Potential Measurement, provides information other water exposure. In many cases, however, the covers are
in this type of measurement. This approach is helpful when an damaged or breached during normal operation, or when modifi-
inhibitor is added to the system to maintain the surfaces in a pas- cations are made to the facility, and repairs usually are post-
sive condition. It is necessary to install a reference electrode to poned or not carried out. As a result, water penetrates through
obtain the electrode potential measurement. Reference electrodes the insulation and causes corrosion of the metal. Carbon steel is
are widely used in laboratory testing, but in plant environments the most widely used construction material in chemical plants,
and it is most susceptible to corrosion damage from being exposed A test procedure was also developed to simulate the corro-
to water permeating through insulation. Generally, soluble electro- sion process that occurs under thermal insulation. This proce-
lytes in the insulation are extracted during the water permeation, dure, ASTM G189, Standard Guide for Laboratory Simulation of
and they accelerate the corrosion of the steel.6 Such damage can Corrosion under Insulation, uses carbon steel ring specimens
be discovered only by removing the insulation, but that step is sel- that are heated internally using a heat transfer fluid, while an
dom carried out unless there is evidence of damage.7,8 aqueous solution flows over them under the insulation being
In a related situation, insulation with soluble chloride– tested. Figure 8 shows the specimen design and the nonconduc-
containing compounds was discovered to be responsible for stress tive spacer design, figure 9 shows the insulation orientation, and
corrosion cracking of stainless steel components. In this case, the figure 10 shows the dimensions of insulation pieces. Figure 11
insulation could be checked to verify that it did not contain dam- shows the assembly. This approach can be used to evaluate
aging chloride levels by exposing stressed stainless steel to the inhibitor systems for insulation or to evaluate coatings.
wet insulation while heating the stainless steel above the boiling
point for an extended period. If the stainless steel item was LEAK DETECTION FLUIDS
cracked at the end of the exposure the insulation would not be Industrial gas suppliers and users regularly employ a number of
used (see ASTM C795, Standard Specification for Thermal Insula- devices manufactured from brass. Brass components have given
tion for Use in Contact with Austenitic Stainless Steel). excellent service because they provide leak tight connections, and
Note that this problem occurs in many industries other they are resistant to degradation both from the atmospheres
than in chemical processing. For example, problems have been where they are used and the gases that are flowing through them.
noted in power plants. Because of the breadth of this problem, It is usually necessary, however, to verify that a connection is
many standards have been developed to deal with it by several leak tight after the system is pressurized by applying a leak detec-
organizations, including ASTM International, NACE Interna- tion fluid (LDF) to the joint. If a leak is present, bubbles will
tional, American Petroleum Institute (API), and others. This is form to reveal the leak. The problem that has been observed is
covered in more detail elsewhere in this manual. that occasionally the LDF has caused the brass components to
FIG. 8 Ring specimen and nonconductive spacer for corrosion under insulation (CUI) cells (see ASTM G189).
FIG. 9 Cross section of CUI cell showing orientation of thermal FIG. 10 Dimensions of thermal insulation for CUI cell (see ASTM
insulation (see ASTM G189). G189).
C-ring specimens exposed to the LDF for 15 wet-dry cycles.

Figure 12 shows the C-ring design for this test method. If no
cracks are found at the end of this exposure the LDF is judged to
develop cracks resulting from a stress corrosion cracking process. be acceptable. ASTM G188, Standard Specification for Leak Detec-
Test method ASTM G186, Standard Test Method for Determining tor Solutions Intended for Use on Brasses and Other Copper
Whether Gas-Leak-Detector Fluid Solutions Can Cause Stress Alloys, is a standard specification requiring the ASTM G186 test
Corrosion Cracking of Brass Alloys, was developed to demon- method be carried out on LDFs. Purchasers can use this specifi-
strate that an LDF was not capable of causing brass to stress cor- cation to obtain products that will not cause brass components
rosion crack. This method uses hard drawn brass (UNS C27200) to crack from stress corrosion cracking.
FIG. 11 Schematic diagram of the CUI cell.

FIG. 12 C-ring specimen for LDF test (see ASTM G186). TABLE 4 Fourteen Environments for Evaluating General
Corrosion Resistance of Alloys for Use in Chemical
Manufacturing Facilities
Test Environment Formula Concentrations, mass %a
Hydrochloric acid HCl 0.2, 1.0, 5.0

Sulfuric acid H2SO4 10, 60, 96b
Nitric acid HNO3 10, 70b
Phosphoric acid H3PO4 85
Formic acid HCOOH 50
Acetic acid CH3COOH 80
Sodium hydroxide NaOH 50
Hydrochloric acidþ HClþFeCl3 1.0 HClþ0.3 FeCl3c
ferric chloride
Acetic acidþacetic CH3COOHþ(CH3CO)2 50/50
anhydride
STANDARDIZED CORROSION TESTS FOR ALLOYS a

All aqueous solutions are to be prepared with purified water.
b
FOR CHEMICAL MANUFACTURERS Undiluted reagent grade acids may be used.
c
Ferric chloride concentration based on anhydrous reagent.
Alloy producers have developed newer products that could offer
significant improvements over the traditional corrosion-resistant
Alloys with Different Nickel Content in Boiling Acidified Sodium
alloys. The problem for corrosion engineers is to determine if
Chloride Solution, and is run for 1,000 h. If an alloy does not
these alloys are improvements for the processes that they are
crack in the ASTM G123 environment, a second round of testing
evaluating. Ultimately, specific corrosion tests would be neces-
is conducted for 30 days in boiling magnesium chloride solution,
sary for each process for such an evaluation to be made, but it is
as proposed in ASTM G36, Standard Practice for Evaluating
helpful if the performance of new alloys in a range of typical
Stress-Corrosion-Cracking Resistance of Metals and Alloys in a
environments could be available. The problem is determining
Boiling Magnesium Chloride Solution.
which environments should be tested. MTI instituted a project to
The results of this program provide a reasonable selection
create a list of tests that alloy producers could use to evaluate
of environments that can be used to determine if an alloy might
their alloys. The advantage to this approach is that because the
have application in a new process. Additional testing can be car-
tests are standardized, it is possible to compare the results from
ried out if an alloy looks promising, but this group of results
different laboratories on different alloys without having to
should provide a good basis for determining which alloys would
include all of the alloys in a single program.
be candidates for that testing.
The MTI program was developed by Treseder and Degnan,
and their report became the basis for ASTM G157, Standard
Guide for Evaluating Corrosion Properties of Wrought Iron- and
Nickel-Based Corrosion Resistant Alloys for Chemical Process References
Industries.9–11 The various test environments are shown in table 4. 1. S. W. Dean, Jr., Laboratory Corrosion Testing of Metals and Alloys
ASTM G157 also recommends that welded specimens be (St. Louis, MO: Materials Technology Institute, 2014).
included. Crevice coupons and ASTM G30, Standard Practice for 2. S. W. Dean, Jr., Field Testing of Metals and Alloys (St. Louis, MO:
Making and Using U-Bend Stress-Corrosion Test Specimens, U- Materials Technology Institute, 2018).
bend stressed specimens also are included. The concept for mass
loss corrosion rate evaluations is to determine the lowest temper- 3. B. S. Covino, Jr., “Introduction to Corrosion Testing and
Evaluation,” in ASM Handbook, vol. 13A, Corrosion:
ature at which the corrosion rate exceeds 0.13 mm/yr. Tests are
Fundamentals, Testing, and Protection, ed. S. D. Cramer and
carried out at 30 C, 50 C, 70 C, 90 C, 110 C, and 130 C, or if B. S. Covino, Jr. (Metals Park, OH: ASM International, 2003), 419.
the normal boiling temperature is lower than 130 C, at the boil-
ing point. The tests are run for 96 h. If a specimen shows a corro- 4. R. B. Puyear, “Industrial Chemicals,” in Corrosion Tests and
sion rate in excess of 0.13 mm/yr, tests at higher temperatures Standards: Application and Interpretation, 2nd ed., ed.
R. Baboian (West Conshohocken, PA: ASTM International,
are not necessary. The crevice corrosion test uses the acidified
2005), 418-424.
ferric chloride solution specified in ASTM G48, Standard Test
Methods for Pitting and Crevice Corrosion Resistance of Stainless 5. F. Mansfeld, “Electrochemical Methods of Corrosion Testing,” in
Steels and Related Alloys by Use of Ferric Chloride Solution, to ASM Handbook, vol. 13A, Corrosion: Fundamentals, Testing, and
determine the critical crevice corrosion temperature. The chlo- Protection, ed. S. D. Cramer and B. S. Covino, Jr. (Metals Park,
OH: 2003), 446–462.
ride stress corrosion cracking testing is done according to the
acidified sodium chloride solution in ASTM G123, Standard Test 6. P. Elliot, “Designing to Minimize Corrosion,” in ASM Handbook,
Method for Evaluating Stress-Corrosion Cracking of Stainless vol. 13A, Corrosion: Fundamentals, Testing, and Protection,
ed. S. D. Cramer and B. S. Covino, Jr. (Metals Park, OH: ASM 9. R. S. Treseder and E. A. Kachik, “MTI Corrosion Tests for Iron- and
International, 2003), 929–939. Nickel-Base Corrosion Resistant Alloys,” in Laboratory Tests and
Standards, ed. G. S. Haynes and R. Baboian (West Consho-
7. W. G. Ashbaugh and T. F. Laundrie, “A Study of Corrosion of hocken, PA: ASTM International, 1985), 373–399.
Steel under A Variety of Thermal Insulations,” in Corrosion of
Metals under Thermal Insulation, ed. B. J. Moniz and W. I. Pollock 10. R. S. Treseder and T. F. Degnan, Corrosion Testing of Iron- and
(West Conshohocken, PA: ASTM International, 1985), 121–131. Nickel-Base Alloys, Part I: Test Methods (Revised), MTI vol. 46
(St. Louis, MO: Materials Technology Institute, 1995).
8. P. Elliot, “Materials Selection for Corrosion Control,” in ASM
Handbook, vol. 13A, Corrosion: Fundamentals, Testing, and 11. T. F. Degnan, Corrosion Testing of Iron- and Nickel-Base Alloys,
Protection, ed. S. D. Cramer and B. S. Covino, Jr. (Metals Park, Part II: Test Data, MTI vol. 46 (St. Louis, MO: Materials
OH: ASM International, 2003), 909–928. Technology Institute, 1995).
409
Chapter 27 | Flue Gas Desulfurization
James R. Crum1 and Ralph W. Ross 2
Description of Materials of stack liners. Clad plate can be manufactured by hot rolling,
explosive bonding, or welding the cladding and base plate
Construction Used and Selection together.1,2 However, these methods are generally applicable only
Criteria to new or replacement FGD components, because existing sys-
tems already have the substrate (e.g., carbon steel) in place. A
A variety of construction materials has been used in flue gas
method that is applicable to both new and retrofit construction
desulfurization (FGD) systems on utility boilers. They can all be
is called “wallpapering” (NACE SP-0292, Installation of Thin
classified into three major categories: metals, organics, and non-
Metallic Wallpaper Lining in Air Pollution Control Equipment
metallic inorganics.
and Other Process Equipment).3,4 This method, which has been
used in the chemical industry for many years, involves welding
METALS thin sheets, usually 1.6 mm (1/16 in.) thick, of an alloy, such as
Metals ranging from carbon steel to stainless steels and nickel- C-276, C-22, 622, 686, or 59 to the carbon steel substrate. The
based alloys have been used in most components of FGD sys- clad plate method is discussed in NACE SP-0199, Installation of
tems. Unlined carbon steel is used in cases in which the flue gas Stainless Chromium-Nickel Steel and Nickel-Alloy Roll-Bonded
is above the acid dewpoint or in which alkaline conditions are and Explosion-Bonded Clad Plate in Air Pollution Control Equip-
maintained, such as most of the components of spray-dryer FGD ment.5 Both methods offer guidance for an excellent means of
systems, inlet ducts upstream of the wet/dry interface of all FGD providing protection using thin corrosion-resistant materials.
systems, lime/limestone storage silos, and fresh lime/limestone The most frequently reported failures for alloys in FGD
storage tanks and piping. Under acidic conditions, the carbon components are pitting and crevice corrosion (especially under
steel must be protected by a lining or by other corrosion-control scale-deposits), weld heat-affected-zone (HAZ), and weld attack.
techniques. Alternatively, corrosion-resistant alloys are used General corrosion, erosion-corrosion, or stress corrosion crack-
under these conditions. Stainless steels (e.g., type 316L, 317L, ing (SCC) can also occur. Many environmental factors are
317LMN, duplex 2205 and 2507, Ferralium 255, Zeron 100, responsible for the failures, but high levels of chloride combined
904L, 254 SMO, 25-6MO, 1925 hMo, and AL6XN) and nickel- with low pH and elevated temperatures play a major role.6 Fluo-
based alloys (e.g., G-3, G-30, 625, C-276, C-22, 622, 686, and 59) ride also can be a factor, but its role is complex. For example,
have been used in FGD system components, such as prescrub- acid fluorides are especially corrosive to certain metals, such as
bers, absorbers, spray nozzles, reheaters, and dampers. In critical titanium.7 Fluoride forms complex ions with species such as alu-
locations with more aggressive environments, such as reheaters, minum, magnesium, and silicon, which are typically present in
outlet dampers, outlet ducts, and gas mixing zones, nickel-based fly ash. Corrosion failure analysis studies have shown that the
alloys (e.g., alloys 625, G-3, C-276, C-22, 622, 686, and 59) and fluoride ion is interacting with the chloride ion in limestone-
titanium (grades 2 and 7) have been used. based FGD systems to cause severe crevice and pitting corro-
Because of the relatively high cost of nickel-based and tita- sion.8,9 Elevated temperatures, such as those encountered in pre-
nium alloys, a significant cost savings can be realized by using scrubbers and reheaters, increase SCC susceptibility, whereas
thin claddings of these alloys over carbon steel plates, rather erosive particulates play a role in influencing erosion-corrosion
than solid alloy plates, for absorbers, dampers, ductwork, and in prescrubbers.10
1
Alloy Consulting LLC, 20 Quail Dr., Ona, WV 25545, USA
2
ORGANICS LININGS
Nickel Institute, 77 Keeneland Dr., Huntington, WV 25705, USA
The authors acknowledge the previous authors of this chapter, Harvey
Organics linings have been used extensively in various FGD
S. Rosenberg, Guild Associates, Hilliard, OH and Eldon R. Dille, Specialists components, including prescrubbers, absorbers, tanks, outlet
in Solutions, Inc., Highland, IN. ducts, and stacks. These linings include polyesters, vinyl esters,
DOI: 10.1520/MNL202NDSUP20190021
epoxies, novolac epoxy, novolac phenolic epoxy, fluoroelasto- Fiberglass-reinforced plastic (FRP, also known as glass-
mers, and rubber. Organic linings are attractive because they can reinforced plastic [GRP or GFRP] in Europe) is used to fabricate
provide the low initial cost for many of these components, but mist eliminators, piping and spray headers, and stack liners. Vari-
they may have higher maintenance costs. The linings generally ous polymeric resins are used, including polyester, vinyl ester, and
are applied in liquid form by brushing, rolling, spraying, or novolac vinyl ester. The typical operating maximum temperature
troweling. To provide an effective barrier, the organic linings range of the FRP structures is 82 C (180 F) to 177 C (350 F). FRP
used in FGD systems are often applied in several layers. This also is a flammable material that must be protected against ignition
decreases the probability of through-thickness pinholes and from external sources. The types of FRP failures include mechani-
achieves a greater permeation thickness than typical coatings. cal damage, laminate degradation, physical damage, and fire. The
Moreover, the polyester, vinyl ester, epoxy, novolac epoxy, and causes of failure include inadequate engineering, poor fabrication
novolac phenolic epoxy linings often contain a mica flake or quality, abrasion, temperature excursions, and, depending on the
glass flake filler that further decreases the permeability and pro- resin, chemical attack (e.g., acid hydrolysis of polyester).
vides reinforcement. Mica flake-filled linings generally are not as
abrasion resistant as glass flake-filled linings. INORGANIC LININGS
In components for which high abrasion resistance is Nonmetallic inorganic materials are used in prescrubbers, spray
required, linings reinforced with glass cloth or inert matting nozzles, slurry pumps, outlet ducts, and stacks. The materials
along with abrasion-resistant pigments silicon dioxide, alumi- include prefired bricks and shapes, ceramic tiles, borosilicate
num oxide, and tungsten carbide have been used. Although rub- foamed-glass blocks, hydraulically bonded concretes and mor-
ber is an organic lining, it is often placed in a separate category tars, and chemically bonded concretes and mortars, all of which
because it is applied in sheet rather than liquid form. Three types are used as lining materials in cases in which temperature resis-
of sheet rubber have been used for lining absorbers: natural tance, chemical resistance, or abrasion resistance are required.
(gum), neoprene, and chlorobutyl. Of these, the rubber industry Acid-resistant bricks commonly are used as construction materi-
generally considers chlorobutyl to be the preferred material als for stack liners. A potential failure cause of these bricks is
for this application. Chlorobutyl rubber has low moisture mechanical stress from dimensional changes during service.
permeability. Also, several free-standing brick flues have been found to lean
Failure of organic linings can occur by blistering, dis- toward the outer concrete shell. This problem appears to be asso-
bonding, and wear from abrasive slurries.11 Blistering of organic ciated with mixing bypassed gas and scrubbed gas in the stack,
linings immersed in liquids is greatly increased when a thermal thus creating temperature and moisture gradients that cause one
gradient is present.12 Excursions to hot flue gas temperatures can side of the flue to expand more than the other side. A freestand-
damage or destroy organic linings. Fluoroelastomer linings can ing brick flue that is constantly wet with scrubbed FGD gas does
withstand excursions up to 260 C (500 F) and are resistant to not lean.14
chemical attack and abrasion. They are relatively permeable to Borosilicate foamed-glass blocks bonded with urethane-
moisture, however, and with the use of scrubbed flue gas in the modified asphaltic mastic have been used to line outlet ducts and
outlet duct, less-than-desirable coating life has been obtained. In stacks. The combination of these two materials results in a lining
addition, fluoroelastomer coatings generally are more expensive that is resistant to permeation by aggressive condensate and can
than other types of organic linings. Rubber sheet linings offer handle continuous temperatures to 205 C (400 F) and excur-
excellent resistance to abrasion, but rubber is a flammable mate- sions to 370 C (700 F). The urethane-modified asphaltic mastic
rial, so care must be taken to prevent ignition of these sheet lin- has a temperature limit of 82 C (180 F). As the mastic between
ings by external sources, such as welding on the steel side. It is the bricks is reduced to char by high temperatures, however, the
good practice to label the external surfaces of rubber sheet-lined char provides insulation for the remaining mastic. Moreover, the
absorbers to indicate the presence of a rubber lining. Close atten- thermal insulating properties of the glass block and the flexibility
tion to product specification and application is required to pre- of the membrane material contribute to the good performance of
vent short life and inconsistent performance of rubber linings.13 the lining. The foamed borosilicate glass can be mechanically
Fluoroelastomer, fluoropolymer, and fluorinated elasto- damaged easily, and failures can occur as a result of abrasion,
plastic materials, as well as rubber, are used in expansion joints, puncturing, and cracking. Also, scale that forms on the lining
typically with fabric reinforcement. The cost of the fluorine- cannot be removed easily. These problems can be minimized by
containing materials may be an order of magnitude higher than applying a topcoat of chemically bonded mortar over the borosil-
that of rubber materials, but longer life expectancy, higher tem- icate foamed-glass blocks.
perature tolerance, and better overall operating performance can Hydraulic-setting, cement-bonded concretes (hydraulic
easily offset the higher installed cost. Mixing reprocessed fluoroe- concretes) are used as linings for prescrubbers, outlet ducts, and
lastomer scrap with virgin fluoroelastomer can reduce the cost of stacks. These concretes contain aluminate to withstand tempera-
the material, but physical properties critical to the performance tures of 260 C (500 F) without strength degradation. In sulfuric
of expansion joints are impaired. The causes of failure of fluoroe- acid solutions (pH < 4), however, the cement is attacked because
lastomer expansion joints include thermal degradation induced of the dissolution of the calcium aluminate. This dissolution of
by temperature excursions or thermal cycling, acid attack, and the bond results in loosening of the aggregate and erosive wear
mechanical damage. of the lining.15
FLUE GAS DESULFURIZATION 411
Chemically bonded mortars are commonly used to bond

acid-resistant brick stack liners. Chemically bonded concrete TABLE 1 ASTM Classification System for Environmental Factors
13
mixes also can be used as linings. These materials generally con- in FGD Systems
tain siliceous aggregates, a sodium silicate, potassium silicate, or
colloidal silica bond phase, and a silicofluoride, phosphate, or Level of
organic bond gelling agent. They also may contain potassium Severity Temperature Chemistry Abrasiveness
fluoride. Because chemically bonded concretes can withstand 1 Ambient to 60 C pH > 3 Low-velocity fluid
hot, acidic environments, they offer an abrasion-resistant alter- (140 F) with < 100 ppm F flow with no direct
native to organic linings. They do have a higher permeability and < 1,000 ppm Cl impingement of
than most organic linings and are subject to cracking, so that any particulates
(e.g., duct wall)
condensed acid will reach the substrates to which they are
2 60 C pH 0.1 to 6 with High-velocity fluid
applied. In many cases, an organic membrane is used under a
(140 F)–93 C 100 to 1,000 ppm F flow, spray
chemically bonded concrete lining to provide additional protec-
(200 F) and 1,000 to impingement, or
tion to the carbon steel substrate. Although this measure
10,000 ppm Cl, or strong agitation
increases the time for acidic condensate to reach the substrate, it saturated flue gas (e.g., absorber
can complicate repair procedures. When the membrane fails spray zone)
because of permeation by acidic species, the concrete must be 3 Above 93 C Greater than Very high-velocity
removed to repair or replace the membrane.16 (200 F) 15% acid with fluid flow with
> 1,000 ppm F and impingement
>10,000 ppm Cl, or of entrained
COST CONSIDERATIONS
intermittent wet/dry particulates
The prime objective in selecting construction materials for FGD
zones (e.g., venturi throat)
systems is to choose the most cost-effective or optimum material
for each component—that is, the one meeting the design require-
ments at the least cost over the life of the facility. Even though a condition is a mist eliminator (see fig. 1). By contrast, the most
more corrosion-resistant material may cost twice as much as a severe condition can be coded 3-3-3 and represents a tempera-
less corrosion-resistant material, the effect of the materials cost ture above 93 C (200 F), an acid concentration greater than 15%
may be a small percentage on the total construction cost. A with high concentrations of chloride and fluoride, and very high-
reduction in cost can result if the labor costs involved in the velocity fluid flow with impingement by entrained particulates.
installation are significant compared with the difference in the An example of this severe condition is the inlet of a venturi
cost of the materials. In addition to installed cost, it is necessary prescrubber. Several species in solution have been found to affect
to consider repair or replacement cost over the 20- to 30-year the corrosion of alloys in FGD systems. Most of these species,
design life of the plant when specifying the most economical however, are considered trace elements in scrubbing liquors.
materials available for the intended service conditions. Certain Notable exceptions are chlorine and fluorine, both of which are
materials, such as organic linings, cannot be expected to last the present in coal. Depending on the source, the makeup water can
plant lifetime without periodic maintenance touchup, repair, or also contribute chlorides, fluorides, and oxidizing species (e.g.,
replacement. ferric and/or manganate ions) to the FGD system. When the
water balance is tightly closed, dissolved ionic species, such as
chlorides, become highly concentrated. Chloride ions cause
localized corrosion in alloys. The corrosion rate for a given alloy
Description of Corrosion is a function of chloride concentration, pH, temperature, and, in
Environments Encountered many instances, the concentrations of trace elements present at
The environment in an FGD system depends on three factors: levels below 2,000 ppm (e.g., aluminum, copper, and iron).18,19
temperature, chemistry, and abrasiveness. ASTM has identified Uncomplexed fluoride ions can cause localized attack in the
three levels of severity, from 1 (mild) to 3 (severe), for classifying HAZ of welded austenitic and duplex stainless steels and can be
these three environmental factors (see table 1).17 Figure 1 is a sche- catastrophic to titanium. In addition to having its own effect on
matic diagram of environmental severity levels in the major corrosion rates, aluminum, dissolved from fly ash, can react with
components of a wet FGD system. In all three digit codes shown, fluorides to form the complex ions AlF2þ1 and AlFþ2. If there is
the first digit represents temperature, the second digit represents enough aluminum, free fluoride will not be available.
chemistry, and the third digit represents abrasiveness. (A code of
zero for a given environmental factor denotes that the factor
does not exist or is not applicable for a specific operating condi- Techniques Used for Controlling
tion.) For example, the mildest condition encountered can be Corrosion and Materials
coded 1-1-1 and represents a temperature below 60 C (140 F), a
pH greater than 3 with low concentrations of chloride and fluo-
Degradation
ride (as defined in table 1), and low-velocity fluid flow with no To avoid materials problems, it is important to ensure that the
direct impingement by particulates. An example of this mild selected material has adequate corrosion-resistance to give
13
FIG. 1 Schematic diagram of environmental severity levels in wet FGD systems.
satisfactory service in a well-defined environment. The applica- In certain cases, it may be possible to modify the environ-
bility of an alloy in the temperature range of a wet FGD environment, that is, temperature, chemistry, or abrasiveness, to extend
ment is mainly a function of pH, chloride concentration, and the useful life of a material. Temperature modifications in an
oxidizing ions (e.g., ferric). Because the condensate in an outlet FGD system can be accomplished only by a limited number of
duct or flue can have a pH of 2.5 or lower, a more corrosion- practical methods. These practical methods include (1) water
resistant alloy should be used for these components than for an sprays to protect against thermal excursions, and (2) insulation
absorber, where the pH of the scrubbing liquor is typically above to reduce thermal gradients. The scrubbed flue gas can be
5.0. (Under upset conditions, however, the pH may drop to 2.0 reheated by a variety of methods to prevent, for example, forma-
or lower). The chloride concentration in the scrubbing liquor tion of acidic condensate on the floor of the outlet duct or to
depends primarily on the type of coal burned in the boiler. In downstream fans in wet FGD systems. Most reheat methods,
addition, chlorides are provided by the water balance and the however, increase the capital and operating costs of an FGD sys-
type of makeup water. If there is carryover of scrubbing liquor tem, increase the energy consumption of the system, and create
from the mist eliminator, the chloride concentration in the outlet materials problems of their own. Bypass reheat can avoid an
duct can increase because of the evaporation of water during increase in energy consumption, but it also creates an extremely
periods of bypass of the absorber. Stainless steel Types 316L, aggressive environment in the mixing zone of the bypassed gas
317LMN, 904L, 254SMO, 25-6MO, and AL6XN have been used and the scrubbed gas. Therefore, bypass to the outlet duct or
successfully in the absorber vessels when the chloride concentra- stack for reheat or emergencies should be avoided, if possible.
tion is within the applicable range for these alloys. The process chemistry can be modified by using additives
In some FGD reaction tank vessels, for example, an electro- or by minimizing the chloride and fluoride concentrations in the
chemical potential adjustment protection (PAP) system has been scrubbing liquor. The use of additives that inhibit oxidation of
used successfully to control thiosulfate pitting, chloride/fluoride sulfite to sulfate reduces gypsum deposition, which, in turn, can
pitting, crevice corrosion, and general corrosion of all submerged reduce crevice corrosion that tends to occur under deposits. The
stainless steels Types 317L, 317LMN, and 904L. This combina- use of additives that buffer the pH of the scrubbing liquor may
tion of stainless steels with the PAP system allows for the use of prevent pH excursions that can cause failure of alloys.
an alternative cost-effective technique for corrosion control in Several methods are available for minimizing the chloride
FGD reaction tanks made of otherwise-susceptible materials.20 and fluoride concentrations in the scrubbing liquor. These
In outlet ducts exposed to both scrubbed flue gas and untreated include using a separate quench loop, operating the FGD system
flue gas, the use of a highly corrosion-resistant alloy, such as with an open water balance, or using sludge stabilization with fly
alloys C-276, C-22, 622, 686, or 59, generally is required to pre- ash and lime so that a considerable amount of water can be
vent corrosion.21 purged with the scrubber effluent. A minor reduction of chloride
and fluoride concentrations also can be achieved by using river specifications, qualified fabricators, and installation contractors,
water or well water, rather than cooling tower blowdown, for as well as thorough inspection and nondestructive testing of the
makeup. Because the chloride and fluoride ions are primarily welds.27 A great deal of care must be taken to avoid iron contam-
products of coal combustion, these non-coal-related methods for ination during fabrication (e.g., using stainless steel tools and
reducing chloride and fluoride result in only minor reductions. ceramic abrasives). To prevent rust blooms, any embedded iron
The abrasive effects of fly ash on downstream FGD compo- must be removed by an acid pickling treatment. Heat input
nents also can be minimized by using a separate quench loop, should be minimized using small-diameter welding electrodes
but in conjunction with a venturi prescrubber. Alternatively, a and stringer passes to avoid carbide precipitation and hot crack-
high-efficiency particulate collection device can be used ing. Welding defects (poor fit-ups, lack of penetration, weld spat-
upstream of a wet FGD system. ter, pencil markings, heat tint oxides) should be avoided or
Aside from the use of linings, other corrosion protection removed by grinding. If the proper alloy and welding electrodes
techniques include cathodic protection (CP) and corrosion inhibi- have been selected for the service environment, the quality of the
tors. Impressed current cathodic protection technology is attrac- welds is the next most critical item. Leaking welds can cause dis-
tive because it avoids the use of expensive alloys. The Electric charges of process fluids, which, in turn, can deteriorate external
Power Research Institute (EPRI) has developed a system that equipment. Corrosion of welds can cause a loss of structural
allows CP to be applied to duct walls having thin films of conden- integrity of the welded component (e.g., ductwork, absorbers,
sate, rather than immersed in a liquid.22 EPRI also has evaluated and internal supports).
the performance of several inhibitors on the corrosion behavior of Thin metallic linings require good welding procedures and
alloys in a pilot-scale scrubber. The data suggest that the use of inspections to achieve leak-tight welds. Improper welding results
corrosion inhibitors in FGD systems is possible, but the results in flaws and pinholes in the seal welds between the overlapped
from this study were not very encouraging.23 alloy sheets. Because of these flaws, liquid can get behind the
Another electrochemical technique, PAP, was patented by sheets and cause corrosion of the substrate. Also, during plug
the Pulp and Paper Research Institute of Canada.24 PAP is an elec- welding of the alloy sheets to the substrate, the proper welding
trochemical corrosion protection technique that is used to protect material and care must be used to ensure that iron dilution does
stainless steel in oxidizing chloride environments. The technique not adversely affect the corrosion resistance of the weld. One
uses a DC current source to move the electrochemical potential of approach is to cover the plug weld with a seal-welded patch of
the protected surface in the negative direction. This technique is the alloy lining.
not CP in the traditional sense. Although both CP and PAP move
the potential in the electronegative direction, CP requires the set
FIRE PROTECTION
potential to be in the immunity region as depicted by the Pourbaix
In cases in which combustible linings are used, fire protection
diagrams. In contrast, PAP takes advantage of the passive film
should be provided by an automatic water spray system.28 The
available in stainless steel/oxidizing environment and the set
system should be designed so that the spray patterns are not
potential is in the passive zone. Some of the economic advantages
obstructed, and the lining is completely covered by the spray.
of PAP versus CP are smaller current source requirements and
The spray nozzles should include corrosion-resistant blow-off
lower anode consumption. This method has now been used on 14
caps to prevent plugging. The scrubbing liquor spray nozzles are
FGD stainless steel reaction tanks.25
not suitable for fire protection in prescrubbers or absorbers.
Another technique for avoiding corrosion is the use of FRP
There have been a few costly and fatal fires in FGD systems
(GRP in Europe) for FGD components, such as absorbers and
where the ignition source has been linked to cutting and welding
tanks. FRP vessels as large as 30 m (100 ft) in diameter can be
operations during maintenance procedures. Absorbers can con-
fabricated on site by using a spinning process to produce multi-
tain a large quantity of combustible materials, including plastic
ple layers of material.26 After an initial 3-m-high (10 ft) cylindri-
mist eliminators and packing, as well as flammable linings. For
cal section is spun, it is hoisted to the top of the mandrel and
example, the plastic materials may be as much as 1.2 m (4 ft) in
another 3 m (10 ft) section is wound, overlapping the first. The
height and 15 m (50 ft) in diameter. The fire hazard is most prev-
overall height of the structure is limited by the mechanical prop-
alent when the unit is down for periodic maintenance. Typically,
erties of the composite unless external support is provided. A
the access hatches are open, allowing for a high volume of air
potential problem is abrasion from spray impingement and from
movement; the fire loading may be increased because of the pres-
highly agitated slurries. The interior surface of an FRP compo-
ence of combustible scaffolding; and ignition sources may be
nent can be lined with an abrasion-resistant lining, thus provid-
present because of cutting and welding activities.
ing additional vessel life.
The National Fire Protection Association (NFPA), in Report
No. NFPA 850, has recognized the fire hazard associated with
Specific Problem Areas FGD systems during outage and construction activities.29 The
NFPA committee responsible for this document is considering a
WELDING revision to enhance guidance. The proposed revision will include
The quality of the welding is critical in FGD components con- identification of hazards for combustible-lined equipment and
structed of stainless steels, nickel alloys, and titanium. Achieving will suggest closing the outlet damper during cutting and weld-
a high level of quality in alloy welding requires stringent ing operations to reduce airflow through the equipment.28
Use of Test Methods to Evaluate gas, it is difficult to match the composition of flue gas from a
large pulverized coal-fired boiler. Maintaining the proper ratio of
Corrosion and Degradation NO to NO2 is a special problem because NO oxidation to NO2 is
Continuous, online corrosion monitoring may be used to detect a function of the temperature, the initial NO concentration, the
active corrosion of FGD systems; however, this technique is not oxygen concentration, and the gas residence time in the exposure
widely utilized. Conventional corrosion monitors are designed chamber. The usual procedure is to use simulated flue gas with
for use in bulk liquids and do not function satisfactorily in the the same SO2 concentration as actual flue gas, but with different
thin condensate films that form on the surfaces of FGD ducts. concentrations of other species. This procedure can produce
EPRI has used an advanced electrochemical method of corrosion erroneous results.
surveillance developed by the Corrosion and Protection Centre Many species are typically present at various concentrations
Industrial Services (CAPCIS) in England.30 This method allows in FGD outlet duct condensate.15 Those typically present at con-
for online monitoring of corrosion activity in either thin conden- centrations greater than 100 mg/L include the following: alumi-
sate films or bulk liquids. EPRI sponsored demonstration tests of num, calcium, iron, potassium, magnesium, sodium, chlorine,
the CAPCIS system at several U.S. electric utility plants in 1985. fluorine, sulfate, borate, and phosphate. Species present in the
An electrochemical monitoring system that tracks the rate range of 10–100 mg/L include the following: manganese, sele-
and depth of permeation of aggressive chemicals in the walls of nium, silicon, tin, titanium, vanadium, zinc, and nitrate. Several
FRP or other nonmetallic vessels is also available.31 The system species, including barium, beryllium, cadmium, lead, and anti-
uses a set of conductivity probes mounted at various depths in mony, are present at concentrations less than 10 mg/L. The pH
the wall of an FRP component. The probes can be attached dur- ranges from less than 1.0 to about 2.5, depending on the FGD
ing fabrication, before final installation, or as a retrofit for equip- system operating parameters.
ment already installed. In preparing solutions for corrosion testing, solubility prob-
Methods to evaluate materials performance are used both lems need to be considered. If precipitation occurs in a solution,
for materials selection and for failure analysis. Materials selection the composition changes. If some species typically present in
can be based on prior service history, corrosion tests in operating FGD condensate are omitted from the test environment, the
commercial units, or in the laboratory.21 Field corrosion testing results can be erroneous. As previously mentioned, trace ele-
provides long-term performance results from actual FGD envi- ments can affect corrosion rates.
ronments, but the environmental conditions usually are not Many of the exposure tests in commercial units have
well-defined or constant. Laboratory tests with simulated flue gas involved the use of spools or racks of different materials placed
may not be representative of actual service conditions and may in various locations inside an FGD system.33 When using several
yield misleading results. corrosion racks, at many locations inside an FGD system, the
Failure analysis involves documentation of environmental probability is good that one or more of the corrosion racks will
conditions, inspection of the failed component, collection of sam- be exposed to the environment causing the failure. The environ-
ples of the failed material, any deposits on the material, and any ment in the bulk gas stream, in which the specimens are usually
liquids that condensed on or had contact with the material, and placed, is not the same as at a duct wall, where condensation can
appropriate laboratory analyses of the collected samples. The occur. In some field tests, the specimens were directly mounted
background information and laboratory results are analyzed to on the duct wall so that they experienced the same conditions as
identify the failure mechanism or the failure cause.32 The results the wall.34 Test coupons were mounted using bolts of the same
then lead to a plan to prevent a reoccurrence of the failure alloy as the duct wall, and in another method, sheets or plates
were welded onto the vessel wall. To avoid galvanic corrosion of
alloy coupons, the coupons were insulated from the bolts and the
TEST METHOD APPROACH
substrate with fluoropolymer film and washers.
Coal contains many of the elements in the periodic table, even in
trace amounts, which makes it difficult to simulate the environ-
ment of an FGD system. The scrubbed flue gas from coal-fired METHODS USED
power plants typically contains nitrogen, carbon dioxide (CO2), Some laboratory exposure tests are conducted in chambers like
oxygen, water vapor (H2O), sulfur dioxide (SO2), sulfur trioxide that described in ASTM B117, Standard Practice for Operating
(SO3), nitric oxide (NO), nitrogen dioxide (NO2), hydrogen Salt Spray (Fog) Apparatus. Because the environment is more
chloride (HCl), hydrogen fluoride (HF), trace organics, fly ash, corrosive than the salt fog described in ASTM B117, the variations
and solids carried over from the absorber slurry. The concentra- described in ASTM G85, Standard Practice for Modified Salt
tion of species such as HCl and HF are very low in the scrubbed Spray (Fog) Testing, are often used. Some investigators have used
gas, but can be significant if some flue gas is bypassed for reheat. a modified procedure in which the test coupons are mounted
In one of the early FGD units with bypass reheated flue gas in over holes on the outside wall of the exposure chamber so that
the outlet ducts, the scale that formed on the walls of the duct they can be subjected to a thermal gradient.35 Outside mounting
was 10% potassium fluoride (KF).8 of the coupons also affords the opportunity to conduct in situ
If gas cylinders are used to prepare simulated flue gas for electrochemical impedance measurements.
exposure testing, many cylinders may be required to run long Electrochemical impedance spectroscopy (EIS) is an AC
exposure periods. If a combustion source is used to supply flue technique used to determine the components of an analog
electric circuit that represents an electrochemical process.36 Elec- the scrubber slurry. Obviously, this environment, consisting of
trochemical impedance is the ratio of the change in potential to 19,000 ppm chlorides, will be aggressive for most materials of
the change in current (DE/DI) and is determined from the construction. Three types of scrubbers are used. Open-loop or
applied potential and the response current as a function of fre- once-through scrubbers use seawater with enough alkalinity to
quency (co) in an electrochemical cell, when potential and cur- remove the sulfur oxides from the engine exhaust. The resulting
rent are linearly related. The impedance, Z, is a complex number waste is discharged back into the ocean. Closed-loop systems use
incorporating both the magnitude of DE/DI and the phase shift seawater or fresh water mixed with chemicals, such as caustic
between E and I. EIS can give valuable mechanistic information soda, to provide the alkalinity of the scrubber liquor to neutralize
for analyzing the corrosion behavior of alloys37 and the perfor- the sulfur oxides. The scrubber liquor is recirculated through the
mance of coatings.38 system with no discharge. Hybrid systems operate in open- or
Two ASTM test methods are particularly useful for charac- closed-loop mode depending on the discharge regulations of the
terizing organic resin linings and bricks, respectively. These area. They can operate as a once-through (open-loop) system
methods include ASTM D1653, Standard Test Methods for Water using seawater, or in the closed-loop system using fresh water
Vapor Transmission of Organic Coating Films; and ASTM C20, mixed with caustic soda, which is less corrosive if there is little
Standard Test Methods for Apparent Porosity, Water Absorption, contamination by chlorides.39
Apparent Specific Gravity, and Bulk Density of Burned Refractory Marine scrubbers operate at up to 80 C (176 F), whereas
Brick and Shapes by Boiling Water. land-based FGD typically operate at 54 C (130 F). The higher
Two additional test methods regarding bricks are worthy of operating temperature makes the marine scrubbers more suscep-
mention. One is a laboratory test in which the moisture expansion tible to crevice corrosion and SCC. Unlike land-based scrubbers,
that occurred in service is recovered as a shrinkage during heating marine scrubber exhaust gas temperatures can reach 300–450 C
of a brick sample in a dilatometer. The dilatometer measures ther- (572–842 F) when operating in dry mode. Such high operating
mal expansion as a function of temperature. Shrinkage causes a temperatures will eliminate coatings and plastics and may
hysteresis in the thermal expansion curve so that the heating and increase the risk of embrittlement of duplex stainless steels. A
cooling curves do not coincide. The shrinkage is determined from typical marine scrubber system is similar to the design shown in
the difference in the curves at room temperature. figure 1. Like land-based FGD units, some shipboard scrubbers
The other method is a field test to document the amount of also may be designed without venturi sections.
lean in a free-standing brick flue. A laser beam is used to project The marine scrubber components are generally stainless
a target onto the interior surface of a flue in four compass direc- steels and nickel alloys, like the land-based FGD units. Slurry
tions spaced 90 apart. In each direction, the target is tracked at piping systems, which operate at lower temperatures and are not
predetermined incremental elevations for the entire height of the exposed to hot exhaust gas, are GFRP or FRP (also known as
stack. The precise position of the target is determined by a trian- GRP), and nickel alloys/stainless steels depending on scrubber
gulation method using two Kern electronic theodolites (precision slurry chemistry and the ship owners’ preference. The C-family
optical tooling instruments) and a computerized data acquisition of alloys (primarily alloys C-276, 686, and 59) with 55-59%
system. The data from each compass direction provide a profile nickel, 16–22% chromium, and 14–16% molybdenum (Mo) gen-
of the interior surface of the flue. Opposing wall profiles are used erally are required for optimum corrosion resistance if seawater
to calculate centerline profiles, which give the amount of lean as is used to scrub the exhaust gas. Some scrubbers are reportedly
a function of height.14 using 6–7% Mo super-austenitic and duplex stainless steel alloys,
Standard laboratory techniques are used to characterize but little information is available on their service performance.
samples for a failure analysis. These techniques include metallog- In fact, no detailed information is available in the open literature
raphy, scanning electron microscopy, electron probe microanaly- on corrosion performance of any marine scrubber system. In
sis, X-ray diffraction, Fourier transform-infrared analysis, and 2018, NACE International initiated Task Group 575 to deter-
analytical chemistry. mine corrosion performance of marine scrubbers and to prepare
an industry white paper report.40 In some cases, this industry
appears to be following the materials selection history of the
Marine Scrubbers land-based electric power plant’s experience.
In 1997, the International Convention for the Prevention of Pol- It is extremely important to identify shop or field fabrica-
lution from Ships Committee of the International Maritime tion and welding pitfalls (precautions) that may induce corro-
Organization (IMO) began setting limits of emissions of sulfur sion—for example, scratches (micro-crevices), weld heat tints,
oxides and particulates from exhaust from ships burning heavy and iron contamination on the metal surface. The 6–7% Mo
diesel fuel oil.39 The global shipping industry responded by using super-austenitic and duplex stainless steel alloys are especially
wet scrubber systems similar in design and operation to the susceptible to these surface defects and contamination.
land-based FGD units described earlier. As of 2022, more than Seventy very large, land-based FGD units made of alloy
5,000 ships are utilizing wet scrubber systems. By 2050, thou- 2205 duplex stainless steels failed between 2009 and 2011.41 The
sands of ships may be fitted with marine scrubber systems. reason for the failures was crevice corrosion (under-deposit
The primary difference between land-based versus ship- attack) under heavy deposits of scale, especially in cases in which
board FGD systems is that marine scrubbers may use seawater as high-heat-input welding lead to severe corrosion of welded
seams in the absorber sump walls. Although alloy 2205 failed in 14. H. S. Rosenberg, C. W. Kistler Jr., F. W. Brust, E. R. Dille, et al.,
land-based units, it may be appropriate for shipboard closed- Leaning Brick Stack Liners, Report GS-6520 (Palo Alto, CA: Elec-
loop scrubbers using caustic soda slurries containing less than tric Power Research Institute, 1989).
1,000 mg/L (ppm) chlorides. 15. H. S. Rosenberg, G. H. Koch, M. L. Meadows, and D. A. Stewart,
“Materials for Outlet Ducts in Wet FGD Systems,” Materials
Performance 25, no. 2 (February 1986): 41–55.
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Power Research Institute, 1987). 41. R. W. Ross, B. Phull, and E. R. Dille, “Recent Failures of 2205
Duplex Stainless Steel in FGD Scrubbers: Could They Have Been
35. H. S. Rosenberg and J. M. Spangler, Effect of Environmental Avoided?” (paper presentation, Corrosion/2017, paper no. 9747,
Parameters on the Performance of Coatings in FGD Ductwork, NACE International, New Orleans, LA, March 26–30, 2017).
419
Chapter 28 | Nuclear Power
Barry M. Gordon1 and George J. Licina1
Introduction localized corrosion. For example, steam generator tubes in pres-

surized water reactors (PWRs) have experienced general corro-
Minimizing corrosion is a primary objective of nuclear power sion, SCC, intergranular attack (IGA), pitting corrosion, and
plant design.1 Such plants use corrosion-resistant alloys and “denting” of support plates because of crevice corrosion. PWRs
high-purity (e.g., fleet average of 0.07 lS/cm water conductivity have suffered extensive primary water stress-corrosion cracking
in boiling water reactors [BWRs]) and well-controlled water (PWSCC) of alloy 600 and its weld metal, alloy 182. In BWRs,
chemistries in critical systems to achieve that objective. Despite recirculation system piping has been degraded by intergranular
such measures, nuclear plants have experienced various forms of stress-corrosion cracking (IGSCC), especially adjacent to weld-
corrosion in several plant components. These corrosion events ments because of weld sensitization. Irradiation-assisted stress
have had significant ramifications on plant operability because of corrosion cracking (IASCC) has degraded reactor internal struc-
the extremely stringent requirements on component reliability tural components in both BWRs and PWRs. The zirconium
and containment of radio-nuclides. Standards devoted to assess- alloys used for fuel cladding have been subject to hydriding,
ing susceptibility to localized corrosion, such as stress-corrosion SCC, under-deposit corrosion (e.g., under crud), and nodular
cracking (SCC), have been used to qualify materials and remedial corrosion. The occurrence of rapid general corrosion, pitting
countermeasures. In many cases, the evolution of nuclear plant corrosion, under-deposit corrosion, and microbiologically influ-
designs has required development of new standards. enced corrosion (MIC) have prompted increased attention to
Nuclear power plants convert heat energy from the fission nuclear service water systems.
of uranium (235U) into high-quality steam. The steam is used to
turn steam turbines and generate electricity. Large amounts of
electric power can be produced inexpensively with long refueling Materials of Construction
intervals (nominally 18 to 24 months) and small operating staffs.
These typically large plants (600–1400 MWe) are an excellent
and Specific Concerns
source for providing “base load” electricity; however, their large GENERAL
size and the long time from design to commercial operation rep-
Reliability is the major concern with components in nuclear
resent a significant investment of time and resources.
power plants. Component reliability must be ensured for plant
The total quantity of fuel material used, and the volume of safety and to protect the investment in the plant. The stringent
wastes generated by a nuclear plant per kW is very small; how-
regulations related to release of radioactivity to the environment
ever, the radioactive nature of much of the waste requires that
drive much of the materials selection, environmental controls,
they be contained and closely monitored well beyond the life of and inspection requirements of nuclear plants. Unlike fossil-
the plant. The potential dangers of radioactivity to operating per-
fueled plants, where repairs of leaking or flawed components are
sonnel, the public, and other living creatures dictate designs with
a routine fact of life, the availability of diverse and redundant
multiple barriers to the release of fission and activation products. systems for containment of radioactivity requires a far greater
The reliability of each barrier must meet exacting standards to
reliability of systems and components in nuclear systems.
ensure that releases to the environment, including leaks to the
air or water supply, do not occur.
MATERIALS OF CONSTRUCTION
Corrosion problems in nuclear plants have almost always
Primary Systems
been associated with both general corrosion and a few forms of
Both BWRs and PWRs presently use zirconium alloys for fuel
cladding. The “neutron economy” afforded by low cross-sectional
1
Structural Integrity Associates, Inc., San Jose, CA 95138, USA materials, such as zirconium, is critical for efficient operation of
The author acknowledges the previous author of this chapter, George J. Licina. the reactor’s core. Zirconium alloys also exhibit good resistance
DOI: 10.1520/MNL202NDSUP20180005
to corrosion in water–steam environments as well as to the high- REACTOR COOLANT SYSTEMS

temperature fission products (the fission of the uranium pro- Heat transport system piping in most PWRs (fig. 1) is fabricated
duces iodine, cesium, and cadmium). The fuel cladding thus from carbon steel and low-alloy steels, for strength and economy,
represents the first containment barrier to radioactive products. and often clad with roll-bonded or weld-deposited corrosion-
Fuel cladding is also subject to high heat fluxes. The effects of resistant cladding (either stainless steel or high-nickel alloys).4
heat flux and neutron and gamma irradiation can be synergistic Nickel-base alloys are used extensively as weld fillers for cladding
with the aggressiveness of the high-temperature water environ- and for joints between alloy steels and stainless steels for their
ment, producing corrosion effects that are more severe than superior corrosion resistance.
those encountered out-of-reactor or in non-heat-transfer appli- The primary coolant in PWRs is circulated through the
cations. Currently, several projects are under way to replace zir- core, through the reactor coolant piping, and to the steam gener-
conium alloy cladding with more accident-resistant alloys, such ators where it transfers its heat to a second, high-purity water
as high chromium ferritic steels2 or silicon carbide.3 loop. The water in the secondary loop is heated to steam. That
steam is expanded in the turbine where the thermal energy is
converted to mechanical energy to generate electricity.
Corrosion Tests and Standards The piping arrangement in a BWR is different from that of
a PWR. In the BWR, only a single coolant loop is used (fig. 2).4
Manual The same water that is heated in the core to produce steam is
Reactor internals include both fixed and movable components. expanded in the turbine. The water is further cooled in the con-
Examples of such components are control rods (movable), in- denser and is returned to the core as feed-water. Water is rap-
core instrumentation (fixed and movable), the core shroud, core idly recirculated through the core at about 7–10 times the mass
plate, jet pumps, top guide, and steam separators and steam dry- flow rate of steam, most often using jet pumps. Flow from the
ers (all fixed). Austenitic stainless steels are used for most of recirculation pumps “drives” the jet pumps, which have no
these components for their general corrosion resistance. In other moving parts. About a third of the flow from the vessel is
specific applications, such as in the control rod drives and jet returned to the recirculation loop. Water in the recirculation
pumps, precipitation-hardened nickel-base alloys (e.g., alloy loop is pumped through a header, through riser pipes, and dis-
X-750, UNS N07750) are used where greater corrosion resistance charged to the jet pumps, providing the jet pumps’ driving
and strength are required. flow. In the jet pumps, water in the down comer region is
FIG. 1 PWR components and alloys.4

NUCLEAR POWER 421
FIG. 2 BWR components and alloys.4
accelerated through the jet pump, and then discharged into the resistance is adequate) and a limited number of nickel-base
lower core plenum. alloys (e.g., for reactor vessel and piping safe ends).
Flow proceeds from the lower plenum through the core. The
steam and water are separated; the steam is then dried and passed Pressure Vessels and Heat Transfer Components
to the turbine. Other flow returns to the recirculation system. The key pressure vessels in the PWR system were discussed
Feedwater is introduced to the annulus between the core shroud in the section “Reactor Coolant Systems.” PWR vessels, includ-
and reactor vessel. The recirculation system piping is a primary ing the reactor vessel, steam generator shells, and pressurizer,
pressure boundary for the high-pressure, high-temperature reactor operate at pressures of approximately 2,000 psi (13.8 MPa) and
coolant. Type 304 stainless steel was selected for recirculation sys- temperatures of up to 625 F (330 C). These vessels are fabri-
tem piping and numerous other auxiliary systems (such as the cated from low-alloy steels (e.g., ASME SA-302, Grade B;
reactor water cleanup system, residual heat removal system, core SA-533, Grade B; SA-508, Classes 1, 2, and 3; UNS K12022,
spray, and other emergency core cooling systems) for its corrosion K12359, K12042, and K12766) and clad (usually weld clad) with
resistance and adequate mechanical properties. Failures of weld stainless steels or nickel-base alloys. The alloy steel provides ade-
heat-affected zones (HAZs) by IGSCC in the oxidizing environ- quate strength at a reasonable cost for the thick-walled vessels.
ment resulting from water radiolysis in the core have shown the The stainless steel cladding provides corrosion resistance.
selection of these stainless steels, at least grades with carbon con- BWR reactor pressure vessels operate at much lower inter-
tents of 0.04% and above, to have been a poor choice. Remedies, nal pressures than those of a PWR such as 1,000 psi (6.89 MPa)
implemented in the most recent designs and in some retrofits, at 550 F (288 C). As a result, BWR reactor vessels can be much
involved the use of special grades with very low carbon contents larger than those of PWRs, which permits much of the equip-
to avoid sensitization (and higher nitrogen to compensate for ment (such as jet pumps, steam driers, and steam separators) to
decreased mechanical strength), special welding procedures to be contained within the vessel. These pressure vessels are fabri-
minimize sensitization, and other remedial procedures to reduce cated from low-alloy steels (SA-533, Grade B; SA-508, Class 2;
residual stresses at welds. Decreasing the oxidizing power of the UNS K12539, K12766) for strength and economy and weld clad
high-temperature water environment also has been implemented. with stainless steel for corrosion resistance.
This is accomplished by injecting hydrogen into the feedwater to The steam generators in PWRs provide the boundary
recombine with the oxygen produced by radiolysis. between the primary (radioactive) and the secondary (nonradio-
The BWR also uses some carbon steel and low-alloy steel active) systems. Service experience has proven the steam genera-
for steam and other piping (to avoid IGSCC, when corrosion tor to be a key, if not the key, piece of equipment for PWRs.
Corrosion problems in the steam generators have been the prin- degrees. The requirements on the power conversion system are,
cipal cause of PWR downtime. therefore, much different. The great emphasis on reliability of
Nickel-base alloys (alloys 600, 690, and 800; UNS N06600, nuclear units often affects design and materials selection of power
N06690, and N08800) are most commonly selected for steam gen- conversion or balance of plant components. Finally, the "diverse
erator tubes for their good heat transfer properties and resistance and redundant" design philosophy inherent in the design of
to general corrosion. Because of its numerous corrosion problems, nuclear plants requires greater numbers of heat exchangers,
alloy 600 has been universally been replaced with higher chro- pumps, and valves, and far more piping in the balance of the
mium containing and more PWSCC-resistant alloy 690. plant than in a fossil-fired unit of comparable power output.
Like the steam generator shell, tubesheets are fabricated Many of these systems operate infrequently. The most common
from low-alloy steels for their strength and economy. In some operational conditions for many of these systems is a monthly or
designs, the tubesheets are clad with stainless steel or nickel-base quarterly demonstration of their operability to ensure that they
alloys for corrosion resistance during shutdowns. are functional in the event of an accident.
On the secondary side of the steam generator (i.e., where Nuclear units use all the commonly used condenser materi-
the steam is generated), carbon steel tube support plates initially als including brass (particularly Admiralty and aluminum brass),
were used (fig. 3). This selection was based on economics because copper-nickel (90-10 and 70-30), stainless steels, and titanium
the support plates have minimal structural function and repre- tubes, and Muntz metal and stainless steel tubesheets. Many re-
sent a relatively small area exposed to the coolant; the amount of tubed condensers have used specialty alloys, such as titanium or
iron released to the system from corrosion of the spacers can eas- the so-called super-ferritic (high chromium; very low carbon;
ily be accommodated by the cleanup system. Selection of carbon molybdenum contents to 4%), super-austenitic (basically 20%
steel support plates (e.g., SA-515, Grade 6; UNS K02401) proved Cr-25 %Ni and up to 6 %Mo) or duplex stainless steels, to elimi-
to be a poor choice. Corrosion of the support plates, especially nate pitting, SCC, and MIC. Tube replacements, with titanium
those with drilled holes, resulted in a thick, adherent magnetite or super stainless steels, have been performed most often in
corrosion product. The magnetite buildup caused a notable saline cooling waters; however, the critical nature of some heat
change in support plate dimensions (a decrease in the size of the exchangers and the insidious nature of under-deposit corrosion
holes), producing stresses that were sufficient to deform (i.e., and MIC have prompted the use of such alloys in freshwater-
dent) the steam generator tubes. Ferritic or martensitic stainless cooled systems.
steel tube support plates are used in newer designs. Carbon and low-alloy steels are most commonly used in the
condensate system for economy and their adequate resistance to
Power Conversion and Auxiliary Systems
corrosion. Austenitic stainless steels also have been used in some
The power conversion system and the balance of plant compo-
systems and in key components. Copper alloys also have been
nents for nuclear plants are like those for fossil plants with a few
used in some locations, although much less frequently.
significant differences. First, fossil plants are generally much
Copper alloys (Admiralty, copper-nickel) and austenitic
smaller than nuclear plants; hence, many of the key components
stainless steels are the most commonly used materials for feed-
in the power conversion system are smaller. Second, fossil plants
water heater tubing based on their resistance to general and
generally operate at significantly higher temperatures—that is,
localized corrosion, erosion-corrosion, and SCC, as well as their
steam may be superheated from a few degrees to hundreds of
adequate heat transfer performance.5,6 Carbon and low-alloy
steels are most often used for the shells of such heaters for econ-
FIG. 3 Steam generator tubing support plate designs.
omy and availability.
Much of the materials selection for service water systems
and closed cooling water systems is dictated by the water source
(e.g., carbon steel for fresh waters; coated or lined steel, copper
alloys, or stainless steels for saline waters). Coatings, linings,
copper alloys, stainless steels, super-austenitic stainless steels,
super-ferritic stainless steels, and titanium have been used for
replacements.
FAILURE MODES
Fine cracks or localized regions of attack, resulting from SCC,
corrosion fatigue, or localized corrosion, are the most common
corrosion failure modes in nuclear facilities. Small leaks can be a
major concern in nuclear power plants where the release of
radioactive products to the environment or leakage of extremely
expensive materials, such as heavy water from Canadian Deute-
rium Uranium (CANDU) plants must be avoided. CANDU
plants are a type of heavy water-moderated process using natural
uranium. The other major concern with small cracks or fine pits
NUCLEAR POWER 423
is their potential to act as initiation sites for cracks that could environments (e.g., oxygen concentration cells, both acidic and
lead to large leaks or unstable cracking and loss of coolant caustic pH excursions) that have led to pitting corrosion, IGA,
events. Almost without exception, the toughness of the alloys and SCC.5,6,8 Figure 4 summarizes the history of steam generator
used for piping and vessels is sufficiently high that nuclear piping failure from 1974 to 2004.9
and vessels are structurally stable, even with such flaws present. Single-cycle BWRs currently use very high-purity water
This assurance of "leak-before-break" is a critical criterion of (e.g., conductivity < 0.1 lS/cm) at a neutral pH. More recent expe-
nuclear plant reliability. rience has shown that control to levels far less than 0.1 lS/cm can
Radiation buildup, the result of general metal loss to the be achieved in large operating plants. The radiolytic decomposi-
heat transport system and the deposition of activated corrosion tion of water in the BWR core, however, produces dissolved
products on metal surfaces, can represent a serious corrosion oxidizing species (oxygen and hydrogen peroxide) that make the
concern unique to nuclear plants, as radiation levels can limit environment far more aggressive, particularly to the HAZs of
worker exposure and hinder maintenance. The dissolution of stainless steel welds. All of these factors produce an oxidizing
metal and subsequent loss of the metal to the system also has environment that, in concert with the sensitized microstructure
other potential ramifications as maintenance activities, such as and tensile stress, produce IGSCC of austenitic stainless steel,
refueling operations, depend on a high degree of water clarity. SCC of nickel-base alloys, and earlier onset of IASCC.
Nuclear plants are designed with minimal corrosion allowance In both PWRs and BWRs, the carbon steel feedwater train
on heat transfer surfaces, unlike the large fireside corrosion can be susceptible to flow-assisted corrosion and erosion-corrosion
allowance designed into fossil-fueled plants. The relatively low effects, especially at extremely low oxygen concentrations. Thin-
operating temperatures, high-purity water, and the extensive use ning of this piping, generally at areas of high turbulence, depends
of corrosion-resistant alloys permit the waterside corrosion on temperature, pH, and oxygen content. Oxygen additions are
allowances to be minimized. This reduction is driven by require- made to some feedwater lines in BWRs to support the formation
ments for water clarity and radiation buildup. Because much of of a protective magnetite film.
the in-vessel maintenance must be performed using water for The main heat removal system (e.g., the main condenser and
shielding, the clarity of the water is extremely important. associated equipment) and service water systems, which provide
cooling for auxiliary equipment, such as pumps, room coolers,
chillers, fire protection, and reactor heat removal systems used
under accident and other shutdown conditions, for both BWRs
Typical Environments, Metallurgical and PWRs are exposed to environments that are controlled by the
Conditions, and Corrosion Problems site’s water source—that is, the cooling water may be seawater,
brackish water, or a fresh water (lake, river, or pond). Fresh waters
The PWR primary system operates over a range of temperatures
may range from the acidic to the highly alkaline. The pH and con-
averaging approximately 617 F (325 C) and 2,000 psi (13.8
centration of dissolved minerals (particularly calcium and magne-
MPa), with a pH of 6.8 to 7.4 at operating temperatures and a
sium salts) or metals (manganese or iron) can have a strong
hydrogen overpressure (e.g., > 35 cc/kg) to suppress radiolysis
influence on the corrosivity of the water. Corrosion under deposits
and PWSCC. Boric acid is added for reactivity control—that is,
and MIC can result in a variety of such environments. Oxygen
higher concentrations early in a fuel cycle, and progressively
and flow rate are key factors in determining the aggressiveness of
lower concentrations as the enriched uranium is depleted. Lith-
ium hydroxide (LiOH) is added for pH control in U.S. PWRs.
Some components, particularly steam generators and control rod 9
FIG. 4 Steam generator failure history.
drive mechanism penetrations, have experienced PWSCC, a phe-
nomenon first discovered by Coriou et al. in 1959.7 Cracking
is intergranular and was not associated with any particular met-
allurgical anomaly. The major concerns with PWSCC are radio-
active contamination of the nonradioactive water or steam
environment (e.g., from steam generator leaks) or the potential
for a loss of coolant event from cracking in control rod drive
mechanism attachments to the reactor vessel head.
PWR steam generators are exposed to a hydrogen-rich pri-
mary water environment on the tube side (inner side) and deox-
ygenated water on the secondary side. The method for corrosion
control in the secondary circuit has evolved from a coordinated
phosphate treatment to the all-volatile treatment (AVT). Different
AVT treatments have included hydrazine and ammonia, hydra-
zine and morpholine, and the use of alternate amines. Crevices on
the secondary side, where impurities can concentrate, and other
locations where deposits develop thermal gradients that enhance
the concentration of impurities, have produced aggressive local
the environment. Very high flow rates produce flow-assisted cor- concentrated electrolyte, higher temperature, greater aeration or
rosion and, eventually, erosion-corrosion, especially on copper acidity, creviced conditions, applied electrochemical potentials,
alloys and carbon steels. Low flow rates encourage deposition and or stress. Mechanism test type 5 often incorporates environments
under-deposit corrosion and MIC. or loading conditions that have little correspondence to plant
The importance of corrosion in these balance-of-plant conditions; however, they have been formulated to provide a use-
(BOP) systems increased tremendously for nuclear plant owners ful indication of a particular characteristic that may be correlated
in the 1980s. Leakage and functional failures in safety-related with long-term service exposure. For example, the pitting corro-
and non-safety-related cooling systems as a result of general cor- sion resistance of stainless steels and nickel-base alloys may be
rosion, localized corrosion (especially under-deposit corrosion), compared by using a ferric chloride solution to determine the
and MIC became critical issues. Several plants in the United critical temperature above which pitting or crevice corrosion
States have completely replaced service water system piping, occurs (ASTM G48, Standard Test Methods for Pitting and Crev-
others have initiated planning for such a replacement, and the ice Corrosion Resistance of Stainless Steels and Related Alloys by
remainder have been faced with the need for local repairs, often Use of Ferric Chloride Solution), by determining the key corro-
on buried piping that is essentially inaccessible. Utilities are in sion potentials for pit initiation and pit growth (hysteresis loop)
the process of learning the importance of monitoring for corro- in chloride solutions (ASTM G61, Standard Test Method for Con-
sion and deposition and the necessity for early detection and ducting Cyclic Potentiodynamic Polarization Measurements for
actions to mitigate corrosion. The phenomenon of MIC is even Localized Corrosion Susceptibility of Iron-, Nickel-, or Cobalt-
more complex because the presence of living organisms makes it Based Alloys; and ASTM G192, Standard Test Method for Deter-
extremely dynamic. Many of the standard approaches to moni- mining the Crevice Repassivation Potential of Corrosion-Resistant
toring and control are not applicable. Similarly, the toxicity of Alloys Using a Potentiodynamic-Galvanostatic-Potentiostatic
many of the standard water treatments for biological control Technique) or using the electrochemical technique for determin-
have significant environmental and administrative ramifications ing the critical pitting temperature (ASTM G150, Standard Test
for storage and discharge. Most of the methods for testing MIC Method for Electrochemical Critical Pitting Temperature of Stain-
susceptibility in the laboratory or in service remain under less Steels and Related Alloys).11,12 These values are not directly
development. applicable to plant service but provide a useful basis for compar-
ing different alloys.
Similarly, ASTM A262, Standard Practices for Detecting Sus-
Testing for Corrosion ceptibility to Intergranular Attack in Austenitic Stainless Steels, is
a mechanism test used to screen alloys for their resistance to
PURPOSE OF TESTING AND TYPES OF TESTS
IGA associated with the precipitation of chromium carbides.
Corrosion tests are performed for the selection or qualification
This standard has been used to rank alloys and treatments for
of materials (including materials to be used for repairs or
their relative degree of sensitization and to infer their resistance
replacements), for monitoring (to assess corrosion or to track
to IGSCC. ASTM A262 provides a method for evaluating the
process controls such as water treatments), or to supplement and
sensitization of stainless steels. Both IGA and IGSCC have been
assist with failure analyses.
shown to strongly depend on sensitization.
Streicher10 identified the following five categories of corro-
sion test methods:
TEST METHODS
1. Plant service (i.e., how components behave in actual Most of the corrosion testing performed for the initial qualifica-
service) tion of materials in the environments encountered in nuclear
2. Tests in process streams or cooling waters power plants was based on the predominant materials in fossil-
3. Laboratory tests in plant solutions fueled power plants and nuclear-powered submarines in which
4. Laboratory tests with reagent chemicals in place of plant water is the heat transfer fluid. The extensive use of corrosion-
solutions resistant alloys, the lower temperatures used in nuclear plants,
5. Mechanism tests and the carefully controlled or high-purity environments of
nuclear plants suggested that corrosion problems should be at a
Test types 1 or 2 are most useful for monitoring perfor- minimum. Early work to qualify materials for the first generation
mance in existing facilities, in particular for evaluating the per- of reactors indicated that localized corrosion and SCC would not
formance of existing or candidate replacement materials or for be expected in BWR or PWR environments. Those tests showed
monitoring mitigation treatments. Type 2 tests may include that control of chlorides and other aggressive anions would avoid
immersion or electrochemical tests. Corrosion (or SCC) may be corrosion problems. Those tests did not include some of the sub-
accelerated by loading the specimen, forming a crevice (using a tle environmental effects produced in the nuclear plants, such as
washer or other means), or increasing the temperature. Test the radiolytic decomposition of water in the BWR core to pro-
types 3 and 4 have been used and continue to be used to qualify duce hydrogen peroxide and oxygen or the aggressive under-
materials for various service environments, including those in deposit environment in PWR steam generators. Many of the
which general corrosion, localized corrosion, or SCC are con- tests used to evaluate SCC resistance of material–environment
cerns. The corrosive conditions may be enhanced by using more pairs used deformation-controlled loading conditions (U-bends
NUCLEAR POWER 425
or C-rings) and test times on the order of thousands of hours. Evaluate the Susceptibility of Metallic Materials to Environmen-
Such methods include the following: tally Assisted Cracking, is useful for identifying materials that are
susceptible to SCC, but assessing the degree of susceptibility to
• ASTM G30, Standard Practice for Making and Using U-Bend be expected in service is far more difficult.
Stress-Corrosion Test Specimens This test, however, presents only those alloy-environment
• ASTM G38, Standard Practices for Making and Using C-Ring systems in which SCC can occur. CERT/SSRT is also known to
Stress-Corrosion Test Specimens be overly conservative in some instances and nonconservative/
insensitive in other cases in which the test standards provide no
• ASTM G39, Standard Practice for Preparation and Use of guidance or insight on this issue. CERT/SSRT inherently masks
Bent-Beam Stress-Corrosion Test Specimens most material effects that affect sustained dynamic deformation
• ASTM G49, Standard Practice for Preparation and Use of by inducing a forced strain rate.
Direct Tension Stress-Corrosion Test Specimens ASTM A262 was probably the most commonly used mecha-
• ASTM G58, Standard Practice for Preparation of Stress- nism (type 5) test for corrosion testing in support of nuclear
Corrosion Test Specimens for Weldments reactor materials. It provides a qualitative measure of the degree
of sensitization (DOS). The electrochemical potentiokinetic reac-
The constant deflection methods, in many cases, were inad- tivation (EPR) test13 provides a rapid method for generating a
equate to predict the corrosion effects that would be encountered more quantitative measure of DOS. This test (see ASTM G108,
in long-term service in the various reactor and coolant systems. Standard Test Method for Electrochemical Potentiokinetic Reacti-
For example, in constant deflection tests, load relaxation at tem- vation [EPR] for Detecting Sensitization of AISI Type 304 and
perature results in a much lower stress level in the specimen and 304L Stainless Steels1) involves polarizing a polished sample
a less aggressive test. (including pipe work in the field) at a controlled rate, and then
The constant extension rate testing (CERT) or the identical reversing the direction of polarization and returning to the open
slow strain rate test (SSRT) was developed to overcome the circuit potential. The area under the curve, normalized for the
deficiencies of deformation-controlled SCC initiation tests. Expe- grain boundary area exposed (fig. 5), provides a quantitative
rience with turbine rotor steels had revealed that U-bends, measure of the DOS as the width of the chromium-depleted
C-rings, and the like might not crack in environments that grain boundary. The “double-loop” method is similar but is less
would produce cracking in long-term service. Even constant load critical regarding specimen preparation and provides the quanti-
tests (actively loaded specimens exposed to aggressive environ- tative measure as a relative peak height by measuring the ratio of
ments) would under predict SCC susceptibility when tests were ir:ia (fig 6).
run for times on the order of (only) thousands of hours. In the Other methods that have been, and continue to be, used are
CERT/SSRT, a tension specimen is actively loaded at a slow, as follows:
nearly constant, strain rate in the environment of interest. That
environment may be the actual plant environment or may be • ASTM G1, Standard Practice for Preparing, Cleaning, and
accelerated by using a higher concentration of the species Evaluating Corrosion Test Specimens
responsible for the attack (e.g., oxygen, chloride, hydroxide) or
an applied potential. The slow and continuous strain rate produ-
ces deformation at the crack tip that maximizes the interaction FIG. 5 Plot of single-loop EPR test.
of the corrosion and the crack tip strain. That method initiates
cracks and causes film rupture events at the tips of existing
cracks. Under proper conditions, the bare metal surfaces (con-
tinue to) interact with the environment, resulting in crack
advance. Considerable development work has been devoted to
establishing optimum strain rates for the test. The CERT/SSRT
has been used extensively for investigating the cause of IGSCC in
BWRs and continues to be used for selection and qualification of
replacement materials and remediation processes.
The test produces results that look like those from a tensile
stress-strain curve. Like a tension test, the test always produces
a failure. Typical test times are of the order of weeks to a month
when extension rates from 10 8 to 10 6 /s are used. The inter-
pretation of the test results may be compared with the results for
the same material exposed to an environment where little or no
environmental degradation occurs based on one or more of the
tensile test parameters (e.g., maximum stress, elongation to fail-
ure, reduction of area). The standardized version of this test,
ASTM G129, Standard Practice for Slow Strain Rate Testing to 1
ASTM is working on incorporating the double-loop test into ASTM G108
potential measurement. The current reversal method, and the

FIG. 6 Plot of double-loop EPR test. use of the potential amplitude compensates for long-term signal
drift, which thereby increases the stability and sensitivity of the
technique. Hundreds of potential measurements are collected
over the collection interval. At the end of the collection interval,
the active and reference potentials are averaged, ratioed, and
compared with the initial potentials collected at time zero (i.e.,
the start of the test). This results in a calculated change in crack
length that, when added to the initial crack length at time zero,
provides an average crack length for the collection interval. This
method provides precise crack-length measurements (5 lm/
0.0002 in.) on a real-time basis.
Future Outlook
Several unresolved issues remain in corrosion testing for nuclear
power plants. These include the following:
• ASTM G2, Standard Test Method for Corrosion Testing of • The SCC of austenitic stainless steels in PWR environments.
Zirconium, Hafnium, and Their Alloys at 680 F (360 C) or in
• IASCC in BWR environments has been observed in highly
Steam at 750 F (400 C)
irradiated components. Threshold levels of irradiation and
• ASTM G4, Standard Method for Conducting Corrosion Cou- methods to assess susceptibility and mitigate IASCC have
pon Tests in Field Applications been defined but require standardization.14
• ASTM G5, Standard Reference Test Method for Making Potentio- • Standard test methods are also required to qualify alternative
static and Potentiodynamic Anodic Polarization Measurements approaches to environmental controls, such as hydrogen
• ASTM G46, Standard Guide for Examination and Evaluation water chemistry (HWC) with and without noble metal injec-
of Pitting Corrosion tions. HWC has been shown to be effective for protection of
recirculation system piping against IGSCC (at the expense of
• ASTM G31, Standard Guide for Laboratory Immersion Corro-
higher radiation levels); however, the higher levels of hydro-
sion Testing of Metals
gen injection required to protect components in the reactor
• ASTM G61, Standard Test Method for Conducting Cyclic Poten- vessel may not be tolerable from a radiation dose (16N carry-
tiodynamic Polarization Measurements for Localized Corrosion over in steam) perspective. Therefore, noble metals are
Susceptibility of Iron-, Nickel-, or Cobalt-Based Alloys injected to catalyze the recombination of dissolved oxygen
• ASTM G96, Standard Guide for Online Monitoring of Corro- and dissolved hydrogen peroxide with hydrogen.
sion in Plant Equipment (Electrical and Electrochemical • PWSCC has been observed in PWR steam generator tubing,
Methods) control rod drive mechanism penetrations, and bolting
• ASTM G102, Standard Practice for Calculation of Corrosion materials. Methods to evaluate susceptibility of components
Rates and Related Information from Electrochemical Methods and mechanisms and methods to quantify alternate materi-
• ASTM G106, Standard Practice for Verification of Algorithm als for resistance to this specific form of IGSCC are required,
and Equipment for Electrochemical Impedance Measurements such as higher chromium-containing nickel alloys and weld
metals.
• ASTM G111, Standard Guide for Corrosion Tests in High Tem-
perature or High Pressure Environment, or Both • The nuclear industry has learned the value of online monitor-
ing to provide an early warning of corrosion problems. Stan-
The test technique most commonly used in the nuclear dard methods for automated and online methods (including
power industry is the reversing DC potential drop (DCPD) tech- measurements made at reactor system temperatures and pres-
nique for measuring real-time crack growth rates in compact sures) need to be developed.
tension fracture mechanics specimens, ASTM E647-00, Standard • The importance of corrosion effects in BOP components in
Test Method for Measurement of Fatigue Crack Growth Rates nuclear plants increased dramatically in the 1980s. BOP prob-
(Historical Version). Although this method is titled for fatigue lems, such as MIC, pitting, and under-deposit corrosion, had
testing, it is mainly used for SCC propagation measurements in a dramatic effect on plant performance. Methods for monitor-
cases in which after the potentials are measured, the DC current ing and for selecting materials for resistance to pitting and
is reversed, and the process is repeated. The ratio of the two crevice corrosion exist. Additional standard methods for MIC
active and reference probe sets are then considered to be a single testing are under development.15
NUCLEAR POWER 427
• Because of defense, depth design, and operating features, 2. P. L. Andresen, R. B. Rebak, and E. Dolley, “SCC Growth Rate of
Irradiated and Unirradiated High Cr Ferritic Steels” (paper
materials degradation issues, such as SCC of piping and core
presentation, 17th International Symposium on Environmental
internals, in current BWR and PWR designs do not increase
Degradation of Materials in Nuclear Power Systems—Water
significantly a plant’s baseline core-damage frequency (CDF) Reactors, Ottawa, Ontario, Canada, August 9–13, 2015).
or large energy release frequency (LERF).16,17 Without ques-
tion, however, such failures have a marked negative impact on 3. T. Koyanagi, Y. Katoh, G. Singh, and M. Snead, SiC/SiC Cladding
both the economy of plant operation and the public percep- Materials Properties Handbook, ORNL/TM-2017/385,
tion of nuclear reactor safety. Thus, the resolution of such (Washington, DC: U.S. Department of Energy, Nuclear
Technology Research and Development Advanced Fuel
problems is essential, especially with changes in the plants’
Campaign, August 2017).
licensing basis associated with, for example, life extension
and license renewal and power uprates that may affect 4. X. Ru and R. W. Staehle, “Historical Experience Providing Bases
environment-associated cracking susceptibility. for Predicting Corrosion and Stress Corrosion in Emerging
Supercritical Water Nuclear Technology: Part 1—Review,”
• The corrosion challenges for the future will be governed by
Corrosion 69, no. 3 (2013): 211–229.
changes in operating and regulatory conditions.16 For instance,
in the United States there is a steady movement toward regula- 5. P. Cohen, ed., The ASME Handbook on Water Technology for
tions that are not only performance-based but also risk- Thermal Power Systems (New York: American Society of
informed. This development emphasizes decision-making that Mechanical Engineers, 1989).
takes into account the relative importance of various mainte-
6. J. C. Danko, “Corrosion in the Nuclear Power Industry,” in Metals
nance, in-service inspection, and procurement activities in Handbook, 9th ed., vol. 13, Corrosion (Metals Park, OH: ASM
terms of their impact on plant safety (e.g., CDF, LERF; U.S. International, 1987), 927–937.
NRC Reg. Guides 1.174, 1.175, 1.176, 1.177, and 1.178). To
date, time-dependent materials degradation phenomena have 7. H. Coriou, L. Grail, M. LeGall, and S. Vettier, Third Colloque de
not been included in the probabilistic risk assessments and the Metallurgie, Corrosion (Amsterdam: North Holland, 1959),
161–169.
associated event- and fault-trees that address, for instance,
either the accident initiation frequency or the reliability of com- 8. C. S. Welty Jr. and J. C. Blomgren, “Steam Generator Issues,”
ponents that play a role in subsequent accident mitigation. in Proceedings of the Fourth International Symposium on
Thus, the near-term challenge in materials-degradation tech- Environmental Degradation of Materials in Nuclear Power
nology is to extend the current deterministic and mechanism- Systems—Water Reactors, ed. D. Cubicciotti (Houston, TX: NACE
informed understanding of the cracking phenomena to cover International, 1990), 1-27–1-36.
the uncertainties associated with the random crack initiation 9. X. Ru and R. W. Staehle, “Historical Experience Providing Bases
processes as well as the uncertainties associated with the propa- for Predicting Corrosion and Stress Corrosion in Emerging
gation rate data and models. Supercritical Water Nuclear Technology: Part 3—Review,”
• Another operational driver that presents challenges is the con- Corrosion 69, no. 5 (2013): 423–447.
stant desire for longer fuel cycles and the resultant increase in 10. M. A. Streicher, “Classification and Application of Corrosion
time between component inspections and more than 60 years Tests” (paper presentation, ASTM Symposium on Application of
of plant operation.16 This puts a premium on defining the Accelerated Corrosion Tests to Service Life Prediction of
kinetics of damage accumulation and the development of Materials, Miami, FL, November 16–17, 1992).
inspection techniques that have adequate resolution and prob-
11. A. Garner, “Materials Selection for Bleached Pulp Washers,”
ability of detection capabilities for the particular system at
Pulp and Paper Canada 82 (1981): T414.
risk.
• Note, finally, that this industry has experienced a long series 12. J. Kolts and N. Sridhar, “Temperature Effects in Localized
Corrosion,” in Corrosion of Nickel-Base Alloys (Metals Park, OH:
of surprises with essentially all being only partially (or
ASM International, 1985), 289–311.
mostly) addressed, coupled with a subsequent erroneous
perspective that there would be few future problems. Several 13. W. L. Clarke, The EPR Technique for the Detection of
disconnects exist between past and future performance in Sensitization in Stainless Steels, NUREG/CR-1095 (Washington,
plants, including lack of inspection, highly nonlinear devel- DC: U.S. Nuclear Regulatory Commission, 1981).
opment of cracks, increasing susceptibility with time (e.g.,
14. P. L. Andresen, F. P. Ford, S. M. Murphy, and J. M. Perks, “State of
IASCC), and sequential phenomena (e.g., alloy 182 attach- Knowledge of Radiation Effects on Environmental Cracking in
ment pads must crack before the underlying reactor pressure Light Water Reactor Core Materials,” in Proceedings of Fourth
vessel can). International Symposium on Environmental Degradation of
Materials in Nuclear Power Systems—Water Reactors, ed.
D. Cubicciotti (Houston, TX: NACE International, 1990), 1-83-1-121.
References 15. J. R. Kearns and B. J. Little, eds., Microbiologically Influenced
1. B. M. Gordon, “Corrosion and Corrosion Control in Light Water Corrosion Testing (West Conshohocken, PA: ASTM International,
Reactors,” Journal of Metals 65, no. 8 (August 2013): 1043–1056. 1994).
16. F. P. Ford, B. M. Gordon, and R. M. Horn, “Intergranular 17. D. G. Ware, D. K. Morton, M. E. Nitzel, and S. A. Eide, Evaluation
Stress Corrosion Cracking (IGSCC) in Boiling Water Reactor of Risk Associated with Intergranular Stress Corrosion Cracking
(BWRs),” in Nuclear Corrosion Science and Engineering, in Boiling Water Reactor Internals, NUREG/CR-6677, INEEL/EXT-
ed. Damien Féron (Cambridge, UK: Woodhead, 2000-00888 (Washington, DC: U.S. Regulatory Commission,
2012), 548–580. July 2000).
429
Chapter 29 | Food and Beverage
Dipak Negandhi1
Materials of Construction Used and solutions.4 The most common method is hot water with a low
concentration of hypochlorite. Most of the common stainless
Selection Criteria steels will handle this type of cleaning without significant prob-
In the food and beverage industry, the workhorse materials are lems, as long as the cleaning cycle is not too long and there are
the “300 series” austenitic stainless steels (i.e., S30400, S30403, no serious problems with residue buildup or leaving the cleaning
S31600, and S31603). S30100 and 30200 are used but less fre- solution in the equipment afterward. Steam cleaning is fre-
quently. The 300 series alloys are used because they resist corro- quently a part of the cleaning cycle. Quality of cleaning water
sion attack by most environments in the industry, are easily should properly be maintained to prevent chloride buildup and
fabricated, do not cause contamination of the products, and are other contaminants. Connolly3 describes cleaning solutions typi-
readily sanitized.1–3 As with any industry, many other unique cally used in wine, brewery, and sugar industries.
materials also are used. In neutral or slightly acid environments In some environments, the iron contamination of stainless
in which chlorides are significant, chloride-resistant stainless steel during fabrication must be removed before operation. This
steel or other high-alloy materials are used.4 Duplex stainless is done most often with nitric acid or nitric-hydrofluoric acid
steels are being used more and more frequently.5,6 In some serv- rinsing. The 300 series stainless steels and other high alloys can
ices like fats and edible oil, copper or copper-containing alloys be beneficial in avoiding loss of flavor, taste, color, or bouquet.
should be avoided. Complying materials with U.S. Food and Worldwide this industry cans large quantities of foods and
Drug Administration (FDA) and U.S. Department of Agriculture beverages for storage and distribution. Common canning materi-
(USDA) regulations for contact with foods and beverages during als used are steel, aluminum, and glass.9 In addition, any water
manufacture, processing, and handling is a significant issue. used for sanitation or for human consumption in the beverage
Users should be cautious about generic claims of materials being industry must comply with U.S. Safe Drinking Water Act of
“FDA approved.” 1974 and the 2018 Amendments. Additionally, particular atten-
Another unique factor in the food and beverage industry is tion is placed on brasses and copper-based alloys used in the
that the finish and polish of the equipment is often a consider- industry.10,11
ation. There are concerns about microbial sterility on the inside The food service industry encompasses hotels, restaurants,
of process equipment.2,7,8 Of concern are both the type of surface fast food kitchens, and institutional kitchens, such as cruise and
finish on the material and the assurance that fabrication and navy ships, schools and colleges, military bases, hospitals, and
welding practices prevent cracks or crevices. Surface finish is a prisons. The facilities utilize storage hot water heaters for their
valid consideration to cleanability. Eliminating crevices is an cooking, washing, and sanitation requirements. Potable water
important concern to maintaining cleanliness. Many plants want from public water source is stored; however, it has corrosive
the outside of the equipment to be “gleaming stainless steel” to components, such as chlorides, ammonia (chloramine), and sul-
give the appearance of purity and high quality to both visitors of fides. Many of these establishments pretreat incoming water to
the plant as well as to plant personnel. Although this is not remove corrosive and fouling chemicals. Storage water heaters
directly related to process needs, it is a frequent consideration. have steel tanks lined with porcelain enamel lining for corrosion
Much of the equipment is frequently sterilized and must protection. Because of the high fusion temperatures of the
resist modest cleaning with various kinds of antibacterial enamel coating to steel, the porcelain tends to pull away from
sharp corners and radii, leaving exposed metal. Additionally,
1
during the fusion process, reactions occur that involve the coat-
A O Smith Corp–Commercial Engineering, 25731 US Hwy 1, McBee, SC 29101, USA
ing components and gassing of the steel substrate. These form
The author acknowledges the previous authors of this chapter, W. E. Clayton and bubbles in the coating, exposing metal. These water heaters use
B. Tholke, The Proctor & Gamble Company, Cincinnati, OH. cathodic protection (CP) to minimize corrosion. CP provides a
DOI: 10.1520/MNL202NDSUP20190030
current to an area that otherwise would corrode in the presence wear and abrasion of moving parts and processing equipment
of an electrolyte (water, in this case). Current is supplied by elec- can be significant. The wear and abrasion resistance becomes the
trochemical reaction at the anode surface. The anode electro- dominant factor rather than corrosion. Materials often used to
chemical reaction is normally provided by an externally eliminate wear and abrasion include hard-faced cobalt or nickel-
impressed potential on an inert electrode, or by the galvanic based alloys for cutting, scraping, conveying, mincing, and atom-
potential of a sacrificial anode material. The sacrificial anode izing.26 Electroless nickel plating is sometimes used on carbon
material has a higher electrochemical driving force to oxidize steel parts.27 S44400 has been used for conveyor parts where cor-
than the metal to be protected. Thus, it corrodes (sacrifices itself rosion resistance similar to S30400 is needed.28 The author’s
by oxidizing) in favor of the tank.12 experience is that precipitation hardenable stainless steel alloys
like SI7400 are surprisingly successful for mechanical process
equipment when corrosion resistance similar to S30400 is needed
Typical Corrosive Environments but galling must be avoided.
As mentioned earlier, it is common to clean food processing
Encountered equipment with sanitizing solutions. For example, in fats and
No single or small group of appropriate environments adequately oils processing equipment, the equipment must be cleaned with
describes the “food and beverage industry.” The industry, how- caustic to remove organics. Steam cleaning is a common require-
ever, handles aqueous-based solutions that frequently contain ment. Almost all equipment is sanitized at some frequency and
acidic chlorides.4 When the chloride-containing aqueous solutions this often involves chloride environments.4,7 Clean-in-place sys-
are modest in temperature, they are typically handled with the tems are usually used. Steel used in canning industry is subjected
S30400/S31600 type stainless steels. At higher temperatures, how- to corrosive action with chlorides and sulfides being the most
ever, more chloride-resistant alloys are needed and must be used. aggressive.9 Austenitic stainless steels are subject to intergranular
The authors’ experience is that in most food and beverage services, or galvanic corrosions and oxidation. Appropriate preventive
pitting of S30400/S31600 stainless steel usually occurs only over measures include alloying and annealing (for intergranular
60 C and usually the temperature must be over 70 C for stress- corrosion), proper material selection to minimize electrolysis (gal-
corrosion cracking (SCC). The temperature to have pitting or SCC vanic corrosion), and appropriate preventive techniques following
can vary widely because of pH, inhibitor effect of other ingre- welding (oxidation corrosion).29
dients, or the many other factors well known about chloride cor- Because SCC is related to nickel content, 316 stainless steel
rosion of stainless steel.13 Pitting and stress corrosion can occur at offers no advantage over 304 SS with regard to this type of corro-
temperatures much lower than 60 C to 70 C.14 sion. Duplex (e.g., 2205) and superduplex stainless steel, however,
Typical examples of chloride corrosion of stainless steel in both offer excellent resistance to SCC. Resistance to SCC also can
the food and beverage industries have been described by Rich- be achieved by annealing processes and by using techniques that
ardson and Godwin4 and Page.15 Many food environments are apply compressive stress to the surface (e.g., shot peening).30
multiphase. Even if the overall chloride level is low, chlorides can Contact corrosion combines elements of galvanic and pit-
be very high in an aqueous phase and can be highly corrosive. ting corrosion, which occurs when small particles of foreign mat-
Other parts of the industry may be based on fats and edible ter (especially carbon) are left on a stainless steel surface as a
oils, which typically are not corrosive to even carbon steels as result of poor manufacturing techniques. Good manufacturing
long as the carbon steel equipment can stand the cleaning cycles. practices and specific standard operating procedures should be
The author’s experience is that carbon steels are widely used for followed during fabrication and installation to prevent cross-
fats and oils and typically resist corrosive attack well up to 90 C. contamination of stainless steel materials with mild steels,
When fatty acids are present in hot fats and edible oils, stainless embedded iron particles (caused by ferrous grinding), high-
steel must be used over 90 C. Also, copper or iron pickup can carbon “tramp” steel, and machine lubricants as well as other
cause rancidity. oils, crayon, paint, and other markings or shop dirt. If not ade-
S30400 and S31600 are widely used in the brewery and wine quately removed, these contaminants could lead to pitting, rust-
industry,16–19 although stress corrosion-resistant alloys are needed ing, and crevice or crack formation. Most important, the
at high chloride levels.20 Typical corrosion environments and grinding, sanding, or polishing tool used for stainless steel should
materials used in the brewery and wine industry are described by be segregated and should not be used for mild steels.30 A regu-
Dreyman21 and Connolly.3 The 300 stainless series alloys are larly scheduled preventive maintenance and sanitizing plan will
widely used in the dairy3,22,23 and citrus juice24 industries. S44400 reduce the occurrence of corrosion and will remove mild corro-
has been reported5,17 to be effective in brewery, meat processing, sion that may have been initiated.30
hot water tanks, and similar services in which chlorides are Passivation is done to maintain the passive (nonreactive)
present. The 300 series stainless steels are commonly used for oxide film to enhance the chrome content on the stainless steel
vegetable processing.25 surface and to protect the surface from corrosion. This is accom-
Some foods require heating to moderately high tempera- plished by exposing the surface to a solution of nitric acid at an
tures during processing to sterilize the product. The specific appropriate concentration and time. Passivation of stainless steel
composition of the solution and temperature governs whether or food contact surfaces is recommended after any surface repair,
not the environment is highly corrosive.3 In some food services, polishing, or rework. Detailed procedures for cleaning and
FOOD AND BEVERAGE 431
passivation using nitric acid and other acids are provided under zone. The NSF stipulates that in the food zone, “surface materials
ASTM A380, Standard Practice for Cleaning, Descaling, and Pas- shall be smooth, corrosion resistant, non-toxic, stable and non-
sivation of Stainless Steel Parts, Equipment, and Systems.30 absorbent under use conditions. They shall not impart odor,
color or taste, nor contribute to the adulteration of the food.
Exposed surfaces shall be easily cleaned.”31,32
Techniques Used to Control Equipment manufactured with a finely polished stainless
steel surface tends to have a better corrosion resistance relative
Corrosion and Materials to nonpolished stainless steel surface, and it is easier to clean and
Degradation maintain. Stainless steel sanitary tubing and pipelines intended
for use in the food industry should have special surface finishes,
In the food and beverage industry, the most common approach
as specified by ASTM A270, Standard Specification for Seamless
for controlling corrosion is to use resistant alloys. Because of
and Welded Austenitic and Ferritic/Austenitic Stainless Steel San-
concerns over product contamination, it is not as common to
itary Tubing. In addition to the mechanically rolled and polished
use other approaches for corrosion control. Linings and coatings,
finishes, other finishes achieved by chemical, electrochemical, or
however, are used for shipping by truck, barge, or rail.
thermal treatment aid sanitation. These techniques also are
Another significant criterion in selecting materials is that
applied for rehabilitation or rework of damaged stainless steel
they must comply with FDA/USDA regulations for contact with
surfaces.32
foods and beverages for the specific service.7,8 Many people do
Materials scientists at the University of Birmingham, United
not understand or recognize the process for obtaining such
Kingdom, made stainless steel surfaces resistant to bacteria in a
approval. The two possible methods or directions of approval to
project funded by the Engineering and Physical Sciences
consider are (1) external FDA/USDA approval and (2) internal
Research Council. By introducing silver or copper into the steel
FDA/USDA approval.
surface (rather than coating it on to the surface), researchers
In the case of external FDA/USDA approval, the approval is
developed a technique that not only kills bacteria but also has a
obtained from the manufacturer or supplier of the material and
surface that is very hard and resistant to wear and tear during
generally cannot be established or determined by the user com-
cleaning. This type of modified steel could be used in the food
pany. It is common practice to request that an officer of the com-
industry and kitchens.32
pany supplying the construction material sign a statement on
Under conditions of hot or boiling liquids, the environment
their company letterhead that the material complies with FDA
turns more aggressive because of the higher temperature and the
or USDA regulations for food and beverage contact and include
depletion of the oxygen content. This inconvenience is solved by
the basis for such approval. Caution should be used when using
the choice of a more strongly passivating stainless steel. For exam-
notes in product catalogues that refer to a material being FDA or
ple, S31600 is used for equipment, such as mash tuns, whirlpool
USDA approved. In the case of internal FDA/USDA approval,
separators, and heat exchanger plates in the wort cooler.32
the user needs to evaluate their own manufacturing, processing,
For hot water storage tanks, an impressed current (IC) sys-
or handling process to ensure that corrosion products or chemi-
tem is used. In an IC system, the output from the rectifier sup-
cals leached from organic materials do not contaminate the
plying the anode current is typically adjusted for the specific
product. With the extensive use of austenitic stainless steel,
water characteristics. The anodes used for IC cathode protection
FDA/USDA concerns exist mostly with nonmetals.
in water heaters are typically mixed metal-oxide anodes. These
In the canning industry, steel cans generally are coated with
are noble metal oxides on a titanium substrate. Power is obtained
tin or plastic. The layer of tin provides a discontinuous structure,
from an alternating current (AC) source and a direct current
because of their porosity and mechanical damage or defects
(DC) rectifier to deliver DC voltage to the anodes.12,33
resulting from handling the can. Plastic coatings have good resis-
tance to compression, and the resistance to corrosion is better
than the tin coating. Plastic coatings (e.g., oleoresins, phenolic,
epoxy, vinyl, acrylic, polyester) should be per FDA-approved for-
Specific Problem Areas
mulations.9 Lead-free brass is used for plumbing components to Chloride corrosion is a major corrosion problem. Another major
eliminate lead contamination.9 problem area requires ensuring that the materials used comply
Cooking, storage, and preparation equipment used by the with FDA/USDA regulations for contact with foods or beverages
food service industry (equipment used for cooking in hotels, res- during manufacture, processing, and handling.2,7
taurants, fast food kitchens, and institutional kitchens, such as Material selection and processing requirements to ensure
cruise and navy ships, schools and colleges, military bases, hospi- cleanliness and sterility are critical. For example, welding to
tals, and prisons) is manufactured to comply with and approved to ensure that crevices are not present at a level that would allow
the applicable National Sanitation Foundation (NSF)/ANSI Stan- microbial growth in service is a significant consideration. Some
dard. FDA or USDA approval for this equipment is not required.31 overly zealous people, however, often specify mirror finishes or
In the United States, the NSF is best known for its role in flush ground welds as a requirement. Usually this extreme is not
the development of standards for equipment, primarily in the necessary. Modest surface finishes as well as welds on the inside
food service area. The NSF’s materials and finishes guide refers of equipment that are ground smooth, but not flush, to a 150 sili-
to three zones: the food zone, the splash zone, and the non-food con carbide grit (30 to 35 rms) finish with fabrication consistent
with 3-A Sanitary Standard34 usually are adequate in most serv- electrochemical testing to evaluate pitting potential or crevice cor-
ices. Care should be taken that the grinding and polishing opera- rosion. In nonaqueous base solutions, this usually is evaluated by
tion does not cause contaminants, usually steel, to be imbedded in-service tests in pilot plants or in existing process equipment.
into the surface. Austenitic stainless steel has been shown to san- Wear-related or abrasion-related problems can be deter-
itize easily even when the surface has been abraded.2,35 As men- mined only by actually testing hardware in full-scale service.
tioned earlier, external appearance of a shiny polished stainless Accelerated tests have not proven to be successful in reflecting
steel is a frequent consideration. most service and performance.
Microbiological-induced corrosion (specifically bacteria,
fungi, and algae) is another problem area. These microorganisms IN-SERVICE MONITORING
are not corrosives by themselves, but because of the impossibility In-service monitoring is seldom used in the food and beverage
to produce their nutrients by photosynthesis, they must metabo- industry except in testing alternatives for known problem areas.
lize organic content present in the media, producing other sub-
stances that are returned to the solution. Bacteria are diverse and FAILURE ANALYSES
can live in extreme conditions, such as a high concentration of Normal “after-the-fact” failure analysis can be used,43 but there
chlorides (halophilic) or at higher temperatures (thermophilic), is no standard approach for simulating field failures, and lab
or to realize different chemical transformations. Bacteria can simulation is used infrequently.
participate in corrosion processes in different ways: changing the
environment by replacing a substance with another, covering TEST METHOD APPROACH
partially the metallic surface with their biofilms creating local Materials normally are evaluated by using field sample racks in
corrosion cells, or inducing the corrosion process by depolariza- pilot plant or full-scale equipment. Electrochemical tests are
tion of hydrogen at the metal.32 sometimes used in aqueous solutions to evaluate the likelihood
or propensity for localized corrosion caused by pitting or crevice
corrosion.
The Use of Test Methods to Evaluate
Corrosion METHODS USED
Industry standard field or laboratory immersion tests described
Several standard corrosion test methods are used, including
earlier are common and adequate for most food and beverage
immersion,36,37 intergranular,38 and electrochemical39 (for aqueous
service applications. Single-sided tests for linings and coatings44
solution) methods. Any of the specialized test methods described
also are used.
by Sprowls40 might be used for special testing conditions.
Food service equipment that complies with NSF/ANSI
Steel cans exposed to indoor conditions have been tested
requirements use materials specified in NSF/ANSI Standard 51.
according to ASTM G1, Standard Practice for Preparing, Clean-
Materials selected are corrosion resistant in the intended end-use
ing, and Evaluating Corrosion Test Specimens; ASTM G4, Stan-
environment. Conforming coatings may be applied to render a
dard Guide for Conducting Corrosion Tests in Field Applications;
material corrosion resistant. Materials that are worked (e.g.,
and ASTM G31, Standard Guide for Laboratory Immersion Cor-
bent, cut, sheared, extruded, drawn) during equipment manufac-
rosion Testing of Metals. The concentration levels of SOX (sulfur
ture may require additional treatment (i.e., passivation) following
monoxide, dioxide, trioxide, and disulfer monoxide) and chlo-
fabrication to render them corrosion resistant. Brass, bronze,
rine (for corrosion testing) were evaluated with the sulfation
copper, and copper alloys used in areas they may contact food
technique plate (SPT) and wet candle method (WCM); see
are rendered corrosion resistant.31
ASTM G91-97(2010), Standard Practice for Monitoring Atmo-
Special formulations of austenitic stainless steels such as
spheric SO2 Using the Sulfation Plate Technique (superseded);
17% chrome and 4% nickel are used to counteract SCC. This for-
and ASTM G140-02(2008), Standard Test Method for Determin-
mulation of stainless steel requires heat treatment and annealing
ing Atmospheric Chloride Deposition Rate by Wet Candle Method
at specific values to achieve optimum resistance to SCC. The
(Historical Version).9
author has personal experience with this approach to extend the
Corrosion resistance of materials is tested per ASTM B117,
life of stainless steel equipment used by food industry.45
Standard Practice for Operating Salt Spray (Fog) Apparatus,
Polished finish (No. 3) is a ground (80- to 100-grit abrasive)
Section 8.1.31
finish and is used extensively for food contact surfaces. The No. 4
ground finish (80- to 150-grit abrasive) is the most commonly
used general purpose stainless steel for food contact surfaces.
New Materials Selection Buffed finishes (Nos. 5, 6, 7, 8) are generally more expensive and
Several standard laboratory immersion tests described in the pre- thus are not used extensively in the food industry.30
vious section are used for new materials selection. U-bend stress The 3-A Sanitary Standard, as well as USDA guidelines,
corrosion tests13,41 and multiple crevice washer tests for crevice specify that all surfaces, including fabricated, welded, and sol-
corrosion42 are used to evaluate localized corrosion. dered joints, shall be at least as smooth as a No. 4 (150 grit) fin-
High-temperature chlorides can require unique chloride ish and shall be free of pits, folds, crevices, cracks, and
resistance testing.13 In aqueous solutions, it is common to use misalignments in the final fabricated form.30
FOOD AND BEVERAGE 433
Additional Comments and 9. G. L. Badilla, B. Valdez Salas, and M. Schorr Wiener, Scientific,
Health and Social Aspects of the Food Industry, ed. B. Valdez
Discussion (InTech, 2012).
Problems in the food and beverage industry are unique to specific 10. Safe Drinking Water Act (Title XIV of Public Health Service Act,
services within those industries. Many of the chloride-resistant chapter 373, 78th Congress, approved July, 1944, 58 Stat. 682;
stainless steels, duplex stainless steels,5 and high-alloy materials amended P.L. 115–270, enacted October 23, 2018).
have been used in specific applications with good success.3 11. A. A. Estelle, “Drinking Water Lead Regulations: Impact on the
One of the problem areas for food and beverage equipment Brass Value Chain,” Materials Science and Technology 32, no. 17
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12. NACE International, “A State-of-the-Art Report on the Internal
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4. J. A. Richardson and A. W. Godwin, “Localized Corrosion of
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435
Index
A MMCs of, 292–300, 292 (figure), 297 (figure), 299 (figure),
accelerated tests, for military aircraft, 396 300 (figure), 308
acceptance testing, 148 organic fluids and, 253, 253 (figure)
acid-producing bacteria (APB), 74 pitting electrochemical tests for, 10
acids/acidity pitting of, 4
automobiles and, 364 potentiodynamic polarization for, 123
in freshwater, 179 in seawater, 208, 209
hydrogen and, 60 sodium hydroxide and, 144
organic liquids and, 255–256 TSA, 172
adenosine phosphosulfate reductase (APS), 224 in water handling systems, 320 (table)
adenosine triphosphate photometry (ATP), 224 aluminum/copper MMCs, 305
aeration aluminum/magnesium MMCs, 301–302
organic fluids and, 253 aluminum/stainless steel MMCs, 303–304
of soils, 221 ammonia
aircraft. See commercial aircraft; military aircraft automobiles and, 364
alkalinity food and beverage and, 429
aluminum and, 129 immersion testing and, 143
crevice corrosion and, 15 SCC and, 192
in freshwater, 181 in seawater, 192
on RC, 345–346 AMPP SP0198, 169
alloys. See also specific types anions, 222–223
for galvanic corrosion computational models, 51–52 anode-cathode area ratio, 43, 44 (figure), 46, 47 (figure)
galvanic corrosion of, 52 anodes, 224
HE of, 127 anodic polarization curve, 46
industrial chemicals and, 407, 407 (table) anodic reactions
in petroleum chemistry, 249 electrochemical impedance and, 116
in seawater, 197 in galvanic corrosion, 41, 42, 52, 119
sensitization of, 128–129, 129 (figure) polarization resistance and, 114
SVET for, 120–121 in seawater, 192
tribocorrosion of, 81 API 510, 174, 174 (table)
alternating current (AC) API 570, 174 (table), 175
EFM and, 117–118 API 574, 175
electrochemical impedance and, 115–117, 115 (figure) API 653, 174 (table), 175
FGD and, 414–415 API RP571, 175
food and beverage and, 431 API RP572, 174
pipelines and, 327 (table), 330, 331 API RP575, 175
uniform corrosion and, 181 API RP580, 175
alternating current attenuation (ACA), 336–337, 337 (figure) API RP581, 175
alternating current voltage gradient survey (ACVG), 338 API RP583, 169
aluminum and aluminum alloys apparent specific gravity index, 219
atmospheric corrosion of, 153, 154, 154 (table), 155, asperity, 85–86, 85 (figure), 90
158 (table), 159 (table), 163 ASTM A123, 354
for automobiles, 360, 364 ASTM A153, 354
in commercial aircraft, 387, 390 ASTM A242, 154
critical potentials for, 124 ASTM A262, 129, 147 (table), 148, 185, 400 (table), 424, 425
EIS for, 130–131, 130 (figure), 131 (figure) ASTM A270, 431
FACT for, 129 ASTM A385, 354
FGD and, 411 ASTM A416, 356
in freshwater, 179, 181 (table) ASTM A480, 15
galvanostatic methods for, 123 ASTM A588, 154, 354
immersion testing for, 144 ASTM A615, 354
436 Index
ASTM A674, 222 ASTM D968, 286 (table)

ASTM A709, 347, 354 ASTM D1120, 377 (table)
ASTM A763, 147 (table) ASTM D1123, 377 (table)
ASTM A767, 354 ASTM D1141, 27, 198, 206
ASTM A923, 28 ASTM D1193, 143
ASTM A934, 356 ASTM D1384, 143, 147 (table), 377 (table)
ASTM A1010, 347, 354 ASTM D1653, 286 (table), 415
ASTM A1035, 356 ASTM D1654, 286 (table), 287, 371 (table), 389 (table)
ASTM B6, 354 ASTM D1735, 286 (table), 373 (table)
ASTM B68, 287 ASTM D1748, 373 (table)
ASTM B85, 414 ASTM D2010, 156
ASTM B117, 3, 199, 199 (figure), 207, 285, 285 (table), 286 (table), ASTM D2197, 286 (table)
287, 298, 331, 372, 373 (table), 375, 387, 388 (table), 390, 395, ASTM D2216, 218
414, 432 ASTM D2247, 285, 285 (table), 286 (table), 287, 373 (table), 394
ASTM B287, 285, 285 (table) ASTM D2248, 286 (table), 287
ASTM B368, 200, 285 (table), 286 (table), 373 (table) ASTM D2434, 219
ASTM B380, 373 (table) ASTM D2488, 217
ASTM B457, 130, 286 (table) ASTM D2570, 143, 147 (table), 377 (table)
ASTM B537, 371 (table) ASTM D2688, 182 (table)
ASTM B538, 129, 285 (table) ASTM D2758, 377 (table)
ASTM B627, 130 ASTM D2803, 371 (table), 388 (table)
ASTM B827, 372 ASTM D2809, 377 (table)
ASTM B895, 372 (table) ASTM D2847, 377 (table)
ASTM C20, 415 ASTM D2980, 219
ASTM C461, 172 ASTM D3258, 286 (table)
ASTM C533, 173 (table) ASTM D3273, 286 (table)
ASTM C536, 286 (table) ASTM D3306, 377, 377 (table)
ASTM C552, 173 (table) ASTM D3359, 285 (table), 286 (table), 287
ASTM C610, 173 (table) ASTM D3762, 391
ASTM C647, 172 ASTM D4145, 286 (table)
ASTM C692, 147 (table), 171, 172 ASTM D4340, 377 (table)
ASTM C743, 286 (table) ASTM D4585, 286 (table), 287, 373 (table)
ASTM C795, 171, 405 ASTM D4587, 287 (table)
ASTM C871, 171, 172 ASTM D4959, 330 (table)
ASTM C876, 354 ASTM D5894, 200, 206
ASTM C929, 171, 172 ASTM D7028, 356
ASTM C1029, 173 (table) ASTM D7091, 286 (table), 287 (table)
ASTM C1617, 172 ASTM D7337, 356
ASTM D130, 377 ASTM D7913, 356
ASTM D512, 223 ASTM E3, 103, 185, 185 (table)
ASTM D522, 286 (table) ASTM E45, 101
ASTM D609, 371 (table) ASTM E112, 101, 129
ASTM D662, 286 (table) ASTM E399, 68, 69, 274
ASTM D665, 377 ASTM E407, 185, 185 (table)
ASTM D714, 286 (table), 287 ASTM E466, 205
ASTM D823, 286 (table) ASTM E606, 205, 206
ASTM D870, 286 (table), 287 ASTM E647, 205, 206, 426
INDEX 437
ASTM E1049, 206 ASTM G49, 147 (table), 164 (table), 185, 185 (table), 204, 207, 274,
ASTM E1064, 260 401 (table), 425
ASTM E1122, 101 ASTM G50, 47, 49, 147 (table), 163 (figure), 164, 164 (table), 208, 354
ASTM E1351, 101 ASTM G51, 222, 330 (table), 354
ASTM E1356, 356 ASTM G52, 206, 354
ASTM E1382, 101 ASTM G53, 287 (table)
ASTM E1447, 277 ASTM G54, 280
ASTM E1524, 206 ASTM G57, 219, 220, 237, 330 (table), 354
ASTM E1681, 67, 205, 206, 274 ASTM G58, 164 (table), 185, 185 (table), 401 (table), 425
ASTM E1820, 68, 69, 274, 275 ASTM G59, 111, 113, 113 (figure), 182 (table), 207, 229, 236, 260,
ASTM F326, 65 372 (table)
ASTM F483, 389 (table) ASTM G60, 147 (table), 148, 287 (table), 373 (table)
ASTM F519, 66, 69, 388 (table), 390 ASTM G61, 6, 22 (table), 31–33, 35, 122, 147 (table), 183,
ASTM F519-18, 66 183 (table), 184 (table), 185, 186 (table), 201, 202, 207, 229, 246,
ASTM F746, 21 (figure), 30–31, 31 (figure), 123, 183, 183 (table), 260, 354, 372 (table), 400 (table), 424
184 (table) ASTM G64, 185, 185 (table), 387
ASTM F897, 185, 186 (table) ASTM G66, 372 (table)
ASTM F1113, 65 ASTM G67, 372 (table)
ASTM F1459, 66, 67 ASTM G69, 4, 207, 372 (table), 388 (table)
ASTM F1624, 69, 79, 205, 274, 277 ASTM G71, 28, 52, 55, 142 (table), 143 (table), 147 (table), 184,
ASTM F1864, 396 184 (table), 207, 229, 371 (table), 400 (table)
ASTM F1940, 66, 69 ASTM G73, 184, 184 (table), 203, 207, 395
ASTM F2129, 147 (table) ASTM G75, 142 (table), 147 (table)
ASTM F3044, 47, 147 (table) ASTM G78, 20 (table), 21 (table), 24, 28, 31, 142 (table),
ASTM G1, 1, 52, 147 (table), 182 (table), 207, 260, 270, 307, 147 (table), 183, 184 (table), 207, 354, 400 (table)
371 (table), 432 ASTM G80, 287 (table)
ASTM G3, 143 (table), 147 (table), 182 (table), 207, 229, ASTM G82, 43 (figure), 48, 52, 55, 119, 183, 184, 184 (table), 207,
371 (table) 307, 371 (table), 400 (table)
ASTM G4, 1, 147 (table), 182 (table), 207, 246, 261, 334, 402, ASTM G84, 49, 155, 164 (table), 208, 287 (table)
403 (figure), 432 ASTM G85, 3, 199, 199 (figure), 200, 285, 285 (table), 287,
ASTM G5, 35, 111, 142 (table), 147 (table), 207, 229, 246, 260, 306, 287 (table), 373 (table), 388 (table), 390, 391, 395
308, 372 (table) ASTM G87, 287 (table), 354, 372
ASTM G8, 287 (table) ASTM G90, 287 (table)
ASTM G12, 287 (table) ASTM G91, 156, 156 (figure), 164 (table), 208, 354, 432
ASTM G15, 180 ASTM G92, 47, 163, 164 (table), 287 (table)
ASTM G16, 2, 183 (table), 207, 339 ASTM G96, 113, 182 (table), 246, 403, 404, 404 (figure)
ASTM G28, 147 (table), 400 (table) ASTM G97, 48
ASTM G30, 55, 164 (table), 184, 185 (table), 207, 234, 260, 274, ASTM G100, 8, 123, 207, 260, 372 (table)
401 (table), 407, 425 ASTM G101, 153, 154, 164 (table), 354
ASTM G31, 142 (table), 143 (table), 146, 147 (table), 182 (table), ASTM G102, 53, 111, 182 (table), 207, 229, 237, 246, 260, 307,
198, 207, 237, 246, 260, 371 (table), 400, 400 (table), 402, 432 371 (table)
ASTM G32, 184, 185 (table), 203, 207 ASTM G106, 115, 142 (table), 147 (table), 229, 246, 372 (table),
ASTM G33, 47, 163, 164, 164 (table), 208, 354, 371 (table) 388 (table)
ASTM G34, 147 (table), 372 (table), 388 (table), 390 ASTM G107, 207
ASTM G35, 142 (table), 147 (table), 401 (table) ASTM G108, 142 (table), 147 (table), 185, 186 (table), 372 (table),
ASTM G36, 142 (table), 147 (table), 204, 401 (table), 407 400 (table), 425, 425 (figure)
ASTM G37, 401 (table) ASTM G109, 354
ASTM G38, 164 (table), 184, 185 (table), 207, 234, 260, 274, ASTM G110, 372 (table)
401 (table), 425 ASTM G111, 246, 400 (table)
ASTM G39, 164 (table), 184, 185 (table), 260, 274, 401 (table), 425 ASTM G112, 334, 371 (table), 390
ASTM G40, 184 (table) ASTM G116, 49–50, 51 (figure), 160, 161, 164 (table), 354
ASTM G41, 275, 401 (table) ASTM G123, 401 (table), 407
ASTM G42, 287 (table) ASTM G129, 66, 67, 204, 207, 260, 275, 401 (table), 425
ASTM G43, 285 (table) ASTM G134, 203
ASTM G44, 147 (table), 198–199, 204, 206, 372 (table), 388 (table), ASTM G139, 204, 207, 390
390, 391, 401 (table) ASTM G140, 156, 208, 432
ASTM G46, 2, 25, 26, 52, 103, 183 (table), 207, 229, 234, 246, 334, ASTM G142, 66, 67, 400 (table)
339, 354, 371 (table), 400 (table) ASTM G148, 126, 229
ASTM G47, 184, 185 (table), 207, 388 (table), 390 ASTM G149, 50, 160, 164 (table)
ASTM G48, 2, 19, 20 (table), 24–26, 25 (figure), 28, 31, 142 (table), ASTM G150, 10, 22 (table), 31, 31 (figure), 124, 142 (table), 202,
147 (table), 149, 183, 184 (table), 372 (table), 400 (table), 407, 424 207, 372 (table), 400 (table), 424
438 Index
ASTM G154, 287, 287 (table) B

ASTM G155, 395 bacteria. See microbiologically influenced corrosion
ASTM G157, 147 (table), 407 barnacle electrode, 127
ASTM G158, 230 beverage. See food and beverage
ASTM G162, 147 (table), 229 bicarbonates
ASTM G168, 204, 260, 274, 388 (table), 390, 401 (table) in freshwater, 179
ASTM G168-17, 67 military aircraft and, 393
ASTM G170, 147 (table) in soils, 222
ASTM G180, 354 biofilms
ASTM G185, 400 (table) from MIC, 74
ASTM G186, 406, 407 (figure) in seawater, 192, 197
ASTM G187, 220, 221 (figure), 330 (table) biopotentiostat, 121
ASTM G188, 406 Boltzmann superposition, 85–86, 86 (figure)
ASTM G189, 147 (table) boron/aluminum MMCs, 292
ASTM G189, 172 boron carbide/aluminum MMCs, 295, 295 (figure), 296 (figure)
ASTM G189, 172, 406 (figure) boron/magnesium MMCs, 300
ASTM G192, 22 (table), 23 (table), 33, 202, 261, 424 bottom-of-the-line corrosion (BLC), 326
ASTM G193, 15, 29, 207, 224, 371 (table) boundary element analysis, for galvanic corrosion, 51
ASTM G199, 11, 30, 202, 207 brass, 103–104, 104 (figure)
ASTM G200, 246, 330 (table) atmospheric corrosion of, 155
ASTM G202, 400 (table) in freshwater, 181 (table)
ASTM G205, 147 (table) LDF and, 405
ASTM G208, 400 (table) for nuclear power, 422
ASTM G210, 147 (table) bridges
ASTM G215, 47, 404 coatings for, 346–347, 349–350
ASTM G217, 55 concrete for, 349–350
atmospheric corrosion corrosion resistance for, 354
classification of, 157–158, 158 (table), 159 (table) corrosion standards for, 354–356
exposure standards for, 164–165, 164 (table), 165 (table) CP for, 350
exposure types for, 155 electrochemical tests for, 350
indoor, 158–159, 159 (table), 163 LACR for, 354
kinetics of, 153–155, 154 (table) RC for, 345–346, 349
monitoring variables for, 155–157, 156 (figure), salt exposure of, 346
157 (figure) sea-level change and, 354
outdoor exposure to, 162–163, 162 (figure) steel for, 346–349
seawater and, 188, 188 (table) vulnerable areas of, 352–354, 353 (figure)
site monitoring and evaluation of, 163–164 water exposure of, 346
atmospheric tests, 159–164 bright-field illumination (BF), 100
exposure program for, 159–160 bronze, 181 (table)
for galvanic corrosion, 49–50, 50 (figure), 51 (figure), 55 butane, 242, 242 (table)
program development for, 159, 159 (table)
specimen preparation for, 160–162, 160 (figure), 161 (figure), C
162 (table) cadmium, 390
automatic transmission fluid (ATF), 365, 377 calcium
automobiles, 359–379 in freshwater, 179
coatings for, 360, 360 (table) in seawater, 187 (table)
corrosion control for, 368–371, 370 (figure), 371 (figure) in water handling systems, 320 (table)
corrosion tests for, 371–379, 371 (table), 372 (table), capillary water, 219
373 (table), 374 (figure), 376 (figure), 377 (table), carbonates
378 (table) in freshwater, 179
corrosive mechanisms of, 366–368, 366 (table), in seawater, 192
366–368 (figure) in soils, 222
design, 361 carbon dioxide
electrochemical tests for, 272 (table), 372 automobiles and, 364
external exposure of, 361–365, 362 (figure), 363 (figure), in freshwater, 179, 181
363 (table) immersion testing and, 143
immersion testing for, 272 (table), 372 MIC and, 75
internal combustion exposure in, 365 in petroleum chemistry, 241–243, 242 (table)
internal functional liquids of, 365–366 carbon steel
materials, 359–360, 360 (table) CUI of, 170, 172
processes for, 360–361 for food and beverage, 430
INDEX 439
for nuclear power, 422 for highways, bridges, and tunnels, 346–347, 349–350
for pipelines, 325 noncorrosive effects of, 284
in seawater, 208 for nuclear power, 422
seawater temperature and, 190, 191 (figure) for pipelines, 332
in soils, 228 SECM for, 121–122, 122 (figure)
in water handling systems, 317, 317 (figure) service life testing for, 288
cast iron SKPFM for, 132–133, 132 (figure)
dealloying of, 103–104 SKP for, 132–133, 132 (figure)
in freshwater, 181 (table) in soils, 228
cathodes, 224 standards for, 172–173
cathodic protection (CP), 236–237 testing of, 283–288, 286 (table), 287 (table), 288 (table)
for FGD, 413 cobalt, in soils, 228
for food and beverage, 429–430 cobalt-chromium alloys, 81, 84, 87 (figure), 90
for highways, bridges, and tunnels, 350 coefficient of friction (COF), 85, 89, 90
for pipelines, 325, 340 commercial aircraft, 385–391, 385 (table)
cathodic reactions aluminum in, 387, 390
electrochemical impedance and, 116 corrosion control for, 386–387
in galvanic corrosion, 41, 42, 43, 44, 46, 47 (figure), 52, 119 corrosion tests for, 387–391, 388 (table), 389 (table)
polarization resistance and, 114 in-service testing for, 387
in seawater, 192 inspection of, 387
cations, 222–223 paints for, 390
cavitation service environments of, 385–386, 386 (table)
in freshwater, 184, 185 (table) surface finish of, 390–391
in seawater, 196 concentration cell corrosion, 180, 183
ceiling panels, of tunnels, 351 concrete. See also reinforced concrete
chemical microbially influenced corrosion (CMIC), 74 for highways, bridges, and tunnels, 349–350
chloride pressure pipe, in soils, 228
atmospheric corrosion from, 156–157, 158 (table) constant extension rate testing (CERT), 425
automobiles and, 361, 363–364 constant phase elements (CPE), 116–117
crevice corrosion and, 16, 19, 24, 29 copper and copper alloys
CUI from, 172 atmospheric corrosion of, 153, 154, 154 (table), 155,
ECE for, 350 158 (table), 159 (table), 163
FGD and, 411, 415 for commercial aircraft, 390
food and beverage and, 429, 431, 432 for food and beverage, 430
in freshwater, 179, 180, 181 in freshwater, 179, 180, 181 (table)
MIC and, 75 MIC of, 78
in nuclear power, 425 MMCs, 304–305
in seawater, 187 (table) for nuclear power, 422
in soils, 222–223 SCC of, 192
titanium and, 267 in seawater, 196, 208–209
chromium in soils, 228, 229, 235, 235 (table)
electrolytic corrosion test and, 129–130 titanium and, 267
in freshwater, 180 in water handling systems, 320 (table)
MIC and, 75 copper-nickel alloys
in nuclear power, 424 atmospheric corrosion of, 155
SCC of, 102–103, 103 (figure) in freshwater, 180
tribocorrosion and, 84 MIC and, 77
chromium-nickel-iron alloys, 104–105 for nuclear power, 422
closed-system boundary condition, 62–63 in seawater, 209
close-interval potential survey (CIPS), 336, 336 (figure) copper-zinc brass, 103–104, 104 (figure)
coatings corrosion fatigue
atmospheric tests for, 161 of Al MMCs, 299–300, 308
for automobiles, 360, 360 (table) of industrial chemicals, 400 (table)
in commercial aircraft, 387 in nuclear power, 422
CUI and, 172–173, 173 (figure) in seawater, 196
descriptions of, 285 (table), 286 (table) corrosion potential
effects of corrosion on, 284 in crevice corrosion, 21 (table)
EIS for, 130–131, 130 (figure), 131 (figure) in electrochemical tests, 110
electrochemical tests for, 129–130 in galvanic corrosion, 45–46, 46 (figure)
EN for, 131 corrosion rates
environmental corrosive exposure of, 284 for commercial aircraft, 385
440 Index
electrochemical tests for, 110–111, 110 (figure) geometry of, 15, 16 (figure)
for FGD, 411 immersion testing for, 141, 142 (table), 146
for galvanic corrosion, 120 of industrial chemicals, 400 (table)
immersion testing and, 143, 144–145 mechanisms of, 16–18, 17 (figure), 18 (figure)
penetration rate and, 111 of nickel alloys, 17, 24
in petroleum chemistry, 249 nonelectrochemical tests for, 23–27, 25 (figure), 27 (table)
polarization resistance and, 114 in nuclear power, 423
in seawater, 195–196 ohmic potential drop in, 18–19
in soils, 236 pitting and, 4–6, 17, 24, 30–31, 31 (figure)
Tafel extrapolation for, 112 potentiodynamic polarization and, 123
for titanium, 271–272 in seawater, 195
in water handling systems, 317, 317 (figure), 319 stages of, 19
corrosion resistance of stainless steel, 2–3, 16, 17, 24, 27
to atmospheric corrosion, 154 test methods for, 19–20, 20 (table), 23 (table)
in automobiles, 361 of titanium, 272–273, 272 (figure), 273 (figure)
for bridges, 354 uniform corrosion and, 181
of crevice corrosion, 19–20, 20 (table), 23 (table) critical acidification model, 17–18, 17 (figure), 18 (figure)
in food and beverage, 432 critical crevice solution (CCS), 16–17, 19, 35
to pitting, 24 critical crevice temperature (CCT), 25–26, 27 (table)
of titanium, 265–266 critical pitting temperatures (CPT)
corrosion-resistant alloys (CRAs) CCT and, 26, 27 (table)
crevice corrosion of, 26, 28 in crevice corrosion, 19
FGD and, 409 in pitting electrochemical tests, 10
for pipelines, 325–326 seawater and, 202
of steel, 347–348 crude oil, 243–245, 243 (figure), 245 (figure), 243 (table),
of titanium, 265 244 (table)
corrosion under insulation (CUI), 169–175, 404–405, 405 (figure), corrosion tests for, 247, 248 (figure)
406 (figure) CSA CHMC1, 67
coatings and, 172–173, 173 (figure) culverts, 350
incidents of, 170 current
inspection planning for, 174–175, 174 (table) CMEAs and, 125
insulation materials in, 172, 173 (table) in galvanic corrosion, 44–46, 45 (figure), 46 (figure)
laboratory tests for, 171–172 polarization resistance and, 114
mechanisms of, 170 in soils, 226–227, 226 (figure), 227 (figure)
moisture entry sources for, 170–171, 171 (figure) SVET and, 120
susceptible temperatures for, 170 tribocorrosion and, 81, 83, 86, 88
coupled multi-electrode arrays (CMEAs), 125–126, 126 (figure) uniform corrosion and, 182
coupon testing cyclic potentiodynamic polarization
for organic liquids, 259 complications of, 123
for pipelines, 334 for crevice corrosion electrochemical tests, 29
for pitting, 1–4, 3 (figure) for localized corrosion, 122–123, 122 (figure)
for water handling systems, 315–318, 316 (figure), 316 (table), in pitting electrochemical tests, 6–8, 7 (figure), 8 (figure)
317 (figure), 317 (table) for saltwater, 201, 201 (figure)
crack growth resistance curve, 65, 65 (figure) cyclic tests, 148
crevice corrosion, 15–35. See also fretting corrosion
atmospheric corrosion and, 154 D
CCS for, 16–17, 19, 35 dark-field illumination (DF), 99, 100
CCT for, 25–26, 27 (table) dealloying
CMEAs and, 125 in freshwater, 185
in commercial aircraft, 387 immersion testing for, 142 (table)
corrosion potential in, 21 (table) metallographic analysis of, 103–104, 104 (figure)
corrosion resistance of, 19–20, 20 (table), 23 (table) in seawater, 195
CPT in, 19 decks, of bridges, 352, 352 (figure)
of CRAs, 26, 28 deep ocean, seawater in, 189, 189 (figure)
critical acidification model for, 17–18, 17 (figure), 18 (figure) depth of attack, on MMCs, 306
critical potentials for, 124 differential interference contrast microscopy, 100
electrochemical tests for, 27–35, 28 (figure), 32 (figure), differential variable reluctance transducers (DVRTs), 88 (figure),
34 (figure), 35 (figure) 89
EN for, 21 (table) dilatometer, 415
in food and beverage, 429, 432 Dimension and Conductivity Scaling (DACS), 48
in freshwater, 183, 184 (table) direct assessment (DA), of pipelines, 338–339
INDEX 441
direct current (DC) electrochemical impedance and, 115–117

for EIS, 130 electrode reaction thermodynamics and kinetics and,
food and beverage and, 431 109–111, 110 (figure)
pipelines and, 327 (table), 330 frequency modulation and, 117–119, 117 (table)
polarization resistance and, 114 for galvanic corrosion, 48–49, 53, 119–120, 119 (figure)
for seawater, 202–203 for highways, bridges, and tunnels, 350
uniform corrosion and, 182 immersion testing and, 146
direct current voltage gradient survey, 337–338, 338 (figure), for industrial chemicals, 403–404, 404 (figure)
338 (table) for localized corrosion, 122–124, 122 (figure), 124 (figure)
disc spring multiple crevice assembly (DSMCA), 23, 24 (table) for MIC, 78
disk pressure tests, 67 for organic liquids, 252–255, 252 (figure), 255 (figure), 259–261
dissolved oxygen for pitting, 4–11, 5 (figure), 10 (figure)
in seawater, 190–191, 191 (table) polarization methods in, 111–117, 113 (figure), 115 (figure)
in water handling systems, 320–321 potential probe methods in, 120–133
DNA analysis, for MIC, 76 for SCC, 126–129, 128 (figure), 129 (figure)
double cantilever beam (DCB), 67–68, 68 (figure) for seawater, 200–203
ductile iron for soils, 229–230, 230 (figure)
in freshwater, 181 (table) for tribocorrosion, 87–89, 88 (figure), 90
in soils, 228 electrode potential, 81–82, 84
electrolytes, 224
E in commercial aircraft, 387
EFC-55, 170 in freshwater, 181
elastic modulus, 64 organic liquids and, 255–256
electrical microbially influenced corrosion (EMIC), 74 electrolytic corrosion test, 129–130
electrical resistance (ER) probes electron microprobe analyzer (EMPA), 100
for industrial chemicals, 403, 403 (figure) energy dispersive spectrometer (EDS)
for pipelines, 335 for dealloying, 185
for seawater, 206 for metallographic analysis, 100
for water handling systems, 316 (table), 319–320, 319 (figure), for soils, 237
320 (figure) epifluorescent microscopy, 224
electric resistance welded (ERW), 180 erosion corrosion (EC)
electrochemical cells, 224 in freshwater, 184, 185 (table)
electrochemical chloride extraction (ECE), 350 immersion testing for, 142 (table)
electrochemical frequency modulation (EFM), 117–119, 117 (table) of pipelines, 329 (table)
electrochemical impedance, 115–117, 115 (figure), 115 (table) in seawater, 196
electrochemical impedance spectroscopy (EIS) ER probes, 236, 237 (figure)
for aluminum, 130–131, 130 (figure), 131 (figure) ethane, 242, 242 (table)
for coatings, 130–131, 130 (figure), 131 (figure) external chloride stress corrosion cracking (ECSCC), 169, 170,
for FGD, 414–415 171–172
for organic fluids, 253 external corrosion direct assessment (ECDA), 237–238
for seawater, 202 extracellular DNA (e-DNA), 76
for soils, 229, 237 extracellular electron transfer MIC (EET-MIC), 74
for uniform corrosion, 182 extracellular polymeric substances (EPS), 74
electrochemical noise (EN)
for coatings, 131 F
for crevice corrosion, 21 (table) Faraday’s constant, 83, 109
EFM and, 117–118 Faraday’s law, 90, 111
in pitting electrochemical tests, 10–11 ferric chloride (FeCL3)
for SCC, 125 crevice corrosion and, 24
seawater and, 202 pitting and, 2–3
in ZRA for crevice corrosion, 21 (table), 28–29 titanium and, 267
electrochemical polarization, for soils, 235–236, 235 (figure), Fick’s first law, 60, 112
236 (figure) film creep, 159
electrochemical realkalisation (ER), 350 finite difference analysis, 51
electrochemical tests, 109–133 finite element analysis, 51, 52
for alloy sensitization, 128–129, 129 (figure) flood gates, of tunnels, 351
for automobiles, 272 (table), 372 flow-induced localized corrosion (FILC), 329 (table), 330 (table)
for coatings, 129–130 flow rate, in galvanic corrosion, 43–44, 44 (figure), 45 (figure)
for corrosion rates, 110–111, 110 (figure) flue gas desulfurization (FGD)
for crevice corrosion, 22 (table), 23 (table), 27–35, 28 (figure), corrosion control for, 411–413, 412 (figure)
32 (figure), 34 (figure), 35 (figure) corrosion environments of, 411, 411 (table)
442 Index
corrosion testing for, 413–415 polarization curve for, 53

fire protection for, 413 in seawater, 195
inorganic linings for, 410–411 in soils, 237
marine scrubbers and, 415–416 SVET for, 52, 53–55, 53 (figure), 55 (figure), 120
organic linings for, 409–410 test results evaluation for, 52–55
welding and, 413 tests for, 46–52, 50 (figure), 51 (figure)
fluorescence in situ hybridization (FISH), 76 galvanic couples, 46–48, 52, 119–120, 119 (figure)
fly ash/aluminum, 298, 411 galvanic series, 41–42, 42 (figure), 43 (figure), 48
fly ash/magnesium MMCs, 302 galvanostaircase technique, 29
food and beverage, 429–433 galvanostatic methods
corrosion control for, 431 for crevice corrosion electrochemical tests, 29
corrosion testing for, 432 for localized corrosion, 122 (figure), 123
corrosive environments of, 430–431 for pitting electrochemical tests, 8
in-service testing for, 432 galvanostep technique, 29
materials of construction for, 429–430 global positioning satellite (GPS), 231
new materials selection for, 432 glucose oxidase (GOD), 27
specific problem areas in, 431–432 grain-boundary area (GBA), 129, 195
Ford anodized aluminum corrosion test (FACT), 129 graphite/aluminum (Gr/Al) MMCs, 292–294, 292 (figure),
freshwater, 179–185 294 (figure)
biological factors of, 180 graphite/copper MMCs, 305
cavitation in, 184, 185 (table) graphite/magnesium MMCs, 300–301, 300 (figure)
chemistry of, 179–180 gravimetric evaluation, of MMCs, 306
concentration cell corrosion in, 180, 183 gravitational water, 218
crevice corrosion in, 183, 184 (table) guardrails, for highways, 350
dealloying in, 185 guided wave testing (GWT), 334
electrolytes in, 181
erosion corrosion in, 184, 185 (table) H
fretting corrosion in, 185, 186 half-cell reactions, 109–110, 116
intergranular corrosion in, 185, 186 (table) harmonic frequency modulation, 117–119, 117 (table)
metallurgy of, 180 heat-affected zone (HAZ)
pitting in, 183, 184 (table) FGD and, 409
process conditions of, 180 nuclear power and, 421
SCC in, 184–185, 185 (figure) heat transfer
test methods for, 180–185, 181 (table), 186 (table) for nuclear power, 422
uniform corrosion in, 181–182, 182 (table) in water handling systems, 316 (table), 321–322, 321 (figure)
fretting corrosion heavy metals
in freshwater, 185, 186 in freshwater, 181
tribocorrosion and, 89, 89 (figure) in seawater, 194
high-strength low-alloys (HSLA)
G for commercial aircraft, 390
galvanic anode cathodic protection (GACP), 350 for pipelines, 325
galvanic corrosion high velocity flow tests, for seawater, 203
anode-cathode area ratio in, 43, 44 (figure), 46 highways, 345–356
atmospheric tests for, 49–50, 50 (figure), 51 (figure), 55 ancillary structures of, 351
in automobiles, 367 coatings for, 346–347, 349–350
computational modeling for, 50–52 concrete for, 349–350
corrosion potential in, 45–46, 46 (figure) corrosion standards for, 354–356
corrosion rates for, 120 CP for, 350
current in, 44–46, 45 (figure), 46 (figure) culverts for, 350
electrochemical reactions in, 41, 42 (figure) electrochemical tests for, 350
electrochemical tests for, 48–49, 53, 119–120, 119 (figure) guardrails for, 350
factors in, 46, 47 (figure) LACR for, 354
flow rate in, 43–44, 44 (figure), 45 (figure) luminaires of, 351
in freshwater, 184 (table), 183–184 RC for, 345–346, 349
galvanic couples and, 46–48, 52, 119–120, 119 (figure) salt exposure of, 346
immersion testing for, 141, 143 (table), 146 sea-level change and, 354
of industrial chemicals, 400 (table) steel for, 346–349
mixed potential theory for, 42–43, 43 (figure), 119–120 vulnerable areas of, 350
of MMCs, 307 water exposure of, 346
from oxidation, 41 hot-dip galvanizing (HDG), 347
INDEX 443
humidity tests electrochemical tests for, 403–404, 404 (figure)

for automobiles, 372 pilot plant tests for, 402–403, 402 (figure), 403 (figure)
for coatings, 285 specialized testing for, 404–407, 405 (figure), 407 (figure)
for military aircraft, 394 in-line inspection (ILI), for pipelines, 333
hybrid organic acid technology (HOAT), 365 inorganic linings, for FGD, 410–411
hydraulic brake fluid, 365–366, 377 in seawater, 196
hydrogen, 59–70 in-service testing
barnacle electrode for, 127 for commercial aircraft, 387
crack growth resistance curve and, 65, 65 (figure) for food and beverage, 432
disk pressure tests for, 67 of seawater, 205–206
in galvanic corrosion, 41 intergranular attack/corrosion (IGA)
MIC and, 75 in food and beverage, 430
in nuclear power, 423 in freshwater, 185, 186 (table)
permeation method for, 127–128, 128 (figure) immersion testing for, 142 (table)
quantitative measurements for, 66–70, 68 (figure), of industrial chemicals, 400 (table)
69 (figure) in nuclear power, 419, 423, 424
rising displacement test for, 69–70 intergranular stress corrosion cracking (IGSCC), 102–103
in soils, 224 iron and iron alloys. See also cast iron; ductile iron
strain localization and, 63–65, 64 (figure) coatings and, 284
stress and, 60–65, 64 (figure) in freshwater, 179
sustained load test for, 67–68, 68 (figure) galvanic corrosion of, 41, 42 (figure)
tensile testing for, 66–67 MIC of, 74, 75, 77
testing for failures with, 65–66 in nuclear power, 423
threshold stress intensity factor and, 67–70, 68 (figure), titanium and, 267, 268
69 (figure) iron-chromium alloys, 104–105, 104 (figure)
trapping of, 61, 61 (figure) iron-chromium-zinc alloys, 124
uptake of, 59–60 ISO 45-40, 165 (table)
hydrogen embrittlement (HE), 62–65, 64 (figure), 65 (figure) ISO 45-42, 165 (table)
of alloys, 127 ISO 1462, 207
of industrial chemicals, 400 (table) ISO 4540, 207
of pipelines, 328 (table) ISO 4623, 206
SCC and, 126 ISO 7384, 206, 371 (table)
in seawater, 196–197 ISO7441, 49
of titanium, 268–269, 276–277, 276 (figure), 277 (figure) ISO 7441, 165 (table)
hydrogen sulfide ISO 7539, 207
atmospheric corrosion from, 159 ISO 8565, 165 (table)
automobiles and, 364 ISO 8993, 207
immersion testing and, 143 ISO 8994, 165 (table), 207
MIC and, 77 ISO 9223, 153, 165 (table)
in petroleum chemistry, 241 ISO 9224, 165 (table)
in soils, 223 ISO 9225, 165 (table)
ISO 9226, 165 (table)
I ISO 9227, 199–200, 373 (table)
ignition testing, for titanium, 277–279, 278 (figure), ISO 9591, 207
279 (figure) ISO 10062, 373 (table)
immersion testing, 141–150, 142 (table), 143 (table) ISO 10289, 371 (table)
for automobiles, 272 (table), 372 ISO 11303, 165 (table)
physical parameters for, 144–145, 145 (table) ISO 11306, 207
precautions and validity of results of, 150–151 ISO 11463, 207, 339
for seawater, 198–199 ISO 11782-2, 207
test conditions for, 143 ISO 11845, 207
types of, 146–148, 147 (table), 148 ISO 11997, 373 (table)
impressed current cathodic protection (ICCP), 350 ISO 15156, 241
for food and beverage, 431 ISO 16539, 206
incremental step loading (ISL), hydrogen and, 66 ISO 23226, 206
industrial chemicals, 399–407, 399 (table) ISO DTR 10783, 66
alloys and, 407, 407 (table) ISO TCI56/WG4, 153
corrosion testing for, 399–404, 400 (table), 401 (table),
401 (figure), 404 (figure) K
CUI with, 404–405, 405 (figure), 406 (figure) Kohler principle, 99, 99 (figure)
444 Index
L of stainless steel, 104–105, 104 (figure)

laser ablation coating removal (LACR), 354 of sulfidation, 105
lead and lead alloys of TBC, 106–107, 106 (figure)
in freshwater, 179 metal-matrix composites (MMCs), 291 (figure)
MMCs, 302–303 of aluminum, 292–300, 292 (figure), 297 (figure), 299 (figure),
in soils, 228–229 300 (figure)
leak detection fluid (LDF), 405, 407 (figure) aluminum/copper, 305
light optical microscope (LOM), 100 aluminum/magnesium, 301–302
linear polarization-resistance (LPR) probes aluminum/stainless steel, 303–304
for pipelines, 335 boron/aluminum, 292
for water handling systems, 316 (table), 317 (figure), boron carbide/aluminum, 295, 295 (figure), 296 (figure)
318–319, 318 (figure) boron/magnesium, 300
liquid metal embrittlement (LME), 105, 105 (figure), copper, 304–305
105 (table) corrosion evaluation for, 305–306
liquid penetrant (LP), for pipelines, 332–333 corrosion susceptibility of, 291–305
lithium perchlorate, 255 depth of attack on, 306
localized corrosion fly ash/aluminum, 298
electrochemical tests for, 122–124, 122 (figure), 124 (figure) fly ash/magnesium, 302
in nuclear power, 422–423 galvanic corrosion of, 307
low-pressure degradation, of military aircraft, 395 graphite/aluminum, 292–294, 292 (figure), 294 (figure)
LPR probes, 236 graphite/copper, 305
luminaires, of highways, 351 graphite/magnesium, 300–301, 300 (figure)
gravimetric evaluation of, 306
M lead, 302–303
macrofouling organisms, in seawater, 193 magnesium, 300–302
magnesium and magnesium alloys mica/aluminum, 298
for automobiles, 360, 364 pitting of, 307–308
in freshwater, 179 silicon/aluminum, 297
MMCs, 300–302 silicon carbide/aluminum, 294–296, 294 (figure),
in seawater, 187 (table), 209 295 (figure)
in water handling systems, 320 (table) silicon carbide/copper, 305
magnesium rich primer (MgRP), 52 silicon carbide/magnesium, 301, 301 (figure)
magnetic particle (MP), 332–333 silicon carbide/titanium, 305
manganese stainless steel, 303–304
atmospheric corrosion of, 154 stress on, 308
in freshwater, 179, 180, 181 testing for, 306–308, 306 (figure), 307 (figure)
MIC and, 75 titanium, 304, 304 (figure)
in nuclear power, 423 uniform corrosion in, 307
marine scrubbers, 415–416 uranium, 303
mass balance, 82–84, 83 (figure) yttria/stainless steel, 304
mass loss electrochemical tests, 111 zinc, 305
mass transport-controlled corrosion, 196 ZRA for, 307
metabolite MIC (M-MIC), 74 methane, 242, 242 (table)
metabolomics, 76–77 mica/aluminum MMCs, 298
metallographic analysis, 93–107 microbiologically influenced corrosion (MIC), 73–78
of chromium-nickel-iron alloys, 104–105 corrosion mechanisms of, 73–75
of dealloying, 103–104, 104 (figure) diagnosis of, 76–77
etching for, 97–99, 97 (figure), 98 (table) electrochemical tests for, 78
grinding for, 95–96, 95 (figure) in food and beverage, 432
interpretation of, 99–101 on military aircraft, 394
of iron-chromium alloys, 104–105, 104 (figure) monitoring of, 77–78
of LME, 105, 105 (figure), 105 (table) in nuclear power, 419, 422, 423–424
NDT for, 101–102, 101 (figure) of pipelines, 328 (table)
of pitting, 103, 103 (figure), 104 (figure) scope of problem with, 73
polishing for, 96–97, 96 (table), 97 (figure) in soils, 223–224, 237
quantitative, 100–101 soils oxidation-reduction potential and, 222
sample selection for, 93 standards for, 75–76
for SCC, 102–103, 102 (figure), 103 (figure) micro-electrode (ME), 121–122
sectioning for, 93 microfouling organisms, 193
specimen preparation for, 93–95, 95 (figure) MIL-C-81309, 378 (table)
INDEX 445
military aircraft, 393–397 NACE SP0116, 338

accelerated tests for, 396 NACE SP0169, 234
environmental testing for, 394–396 NACE SP0206, 338
humidity tests for, 394 NACE SP0207, 234
low-pressure degradation of, 395 NACE SP0288, 338
MIC on, 394 NACE SP0502, 338, 339
mission of, 393–394 NACE SP21427, 356
rain exposure testing for, 395 NACE TM0106, 76
salt spray testing for, 394–395 NACE TM0109, 338
sand and dust testing for, 395–396 NACE TM0169, 147 (table), 182 (table)
solar radiation on, 395 NACE TM0170-70, 165 (table)
standards and specifications for, 396 NACE TM0171, 182 (table)
storage, transportation, and deployment of equipment for, NACE TM0174, 147 (table)
393 NACE TM0175-75, 165 (table)
thermal shock on, 394 NACE TM0177, 147 (table), 148
MIL-STD-810, 394, 395 NACE TM0196, 147 (table)
MIL-STD-1530, 396 NACE TM0212, 76
MIL-STD-1568, 394 NACE TM0274, 182 (table)
MIL-STD-3033, 396 NACE TM0284, 147 (table), 148
MIL-T-5422, 378 (table) NACE TM0286, 147 (table)
mixed potential theory, 110–111, 110 (figure), 113 (figure) NACE TM0416, 49, 147 (table)
for galvanic corrosion, 42–43, 43 (figure), 119–120 NACE TM0497, 234
for seawater, 200–201 Nernst equation, 109–110
molecular microbiological methods (MMMs), for MIC, 76, 77, 224 neutral salt spray (NSS), 372–373
molybdenum nickel and nickel alloys
atmospheric corrosion of, 154 atmospheric corrosion of, 154
crevice corrosion of, 15 crevice corrosion of, 17, 24
MIC, 73 electrolytic corrosion test and, 129–130
for nuclear power, 422 FGD and, 409
in soils, 228 for nuclear power, 422
MTI1, 148 (table) potentiodynamic polarization for, 123
MTI2, 148 (table) in seawater, 208
MTI3, 148 (table) in soils, 228
MTI4, 148 (table) titanium and, 267
MTI5, 148 (table) nickel-chromium-molybdenum, 208
mud, seawater in, 188 (figure), 190 nickel silvers, atmospheric corrosion of, 155
multiple-crevice assembly (MCA), 19, 23, 24 (table), 33 niobium, atmospheric corrosion of, 154
nitrate
N in freshwater, 179, 181
NACE RP0172-72, 165 (table) MIC and, 75
NACE RP0173-73, 207 in soils, 222
NACE RP0174, 234 titanium and, 267
NACE RP0176-83, 165 (table) nitric oxide
NACE RP0177, 234 automobiles and, 364
NACE RP0187-2005, 356 FGD and, 414
NACE RP0194, 234 nitrogen
NACE RP0274, 234 atmospheric corrosion and, 154
NACE RP0281-86, 165 (table) immersion testing and, 143
NACE RP0281-2004, 356 nondestructive examination (NDE), of CUI, 174
NACE RP0285, 234 nondestructive testing (NDT)
NACE RP0286, 234 for CUI, 169
NACE RP0287, 356 for metallographic analysis, 101–102, 101 (figure)
NACE RP0290, 356 for pipelines, 331–334, 331 (table)
NACE RP0375, 234 nuclear power, 419–427
NACE RP0502, 234, 238 corrosion tests for, 420–426, 420 (figure), 423 (figure),
NACE RP0692-92, 165 (table) 425 (figure)
NACE RP0775-87, 182 (table) environments, metallurgical conditions, and corrosion
NACE RPO272, 371 (table) problems of, 423–424
NACE SP024, 339 failure modes of, 422–423, 423 (figure)
NACE SP104, 234 materials of construction for, 419–420
446 Index
O pH
ohmic potential drop, 18–19 in nuclear power, 423
oil and gas industry. See pipelines of seawater, 192
oils of soils, 222
for automobiles, 365 titanium and, 268
specimen preparation for, 231–233, 232 (figure) pickling, 24
open-circuit corrosion rate, 42 pilot plant tests, for industrial chemicals, 402–403, 402 (figure),
open-circuit potential (OCP), 111 403 (figure)
galvanic corrosion and, 120 pipelines
polarization resistance and, 114 ACA for, 336–337, 337 (figure)
Tafel extrapolation and, 112 ACVG for, 338
open-system boundary condition, for hydrogen, 62 carbon steel for, 325
organic acid technology (OAT), 365 CIPS for, 336, 336 (figure)
organic liquids coatings for, 332
ASTM standards for, 260–261 corrosion threats to, 326–330, 327 (table), 330 (figure)
classification of, 251 coupon testing for, 334
corrosion types with, 252 CRAs for, 325–326
coupon testing for, 259 DA of, 338–339
electrochemical tests for, 252–255, 252 (figure), 255 (figure), DCVG for, 337–338, 338 (figure), 338 (table)
259–261 ER for, 335
environmental factors with, 255–259, 256 (figure), GWT for, 334
258 (figure), 256 (table) ILI for, 333
field tests for, 261–262 LP for, 332–333
laboratory tests for, 259–261, 260 (figure), 261 (figure) LPR for, 335
SCC with, 253, 256, 256 (figure), 260, 260 (figure) materials for, 325–326
oxidation modeling and predictions for, 339
galvanic corrosion from, 41 MP for, 332–333
metallographic analysis of, 105–106 NDT for, 331–334, 331 (table)
from MIC, 73, 74 potential measurement for, 335–336, 335 (figure)
Nernst equation for, 109–110 present condition testing of, 334–335
of titanium, 265, 279–280, 280 (figure) proactive testing for, 335–340, 335 (figure), 338 (figure),
tribocorrosion and, 81–82, 84 338 (table)
oxidation-reduction potential (ORP) in soils, 326–330, 327 (table), 330 (figure)
in soils, 221–222, 222 (table) statistical evaluation of, 339–340
in water handling systems, 321 thermoplastic liners for, 326
oxygen. See also dissolved oxygen visual inspection of, 331–332, 332 (table)
in nuclear power, 423–424 piping
organic fluids and, 253, 253 (figure) CUI from, 170–171
in soils, 221, 225, 225 (figure) freshwater in, 180
titanium and, 267 for nuclear power, 429–430
in soils, 225, 225 (figure), 227–229, 227 (figure), 237–238
P in water handling systems, 315–318, 316 (figure), 316 (table),
paint adhesion on scribed surface test, 130 317 (figure), 317 (table)
paints pitting, 1–12
for commercial aircraft, 390 of aluminum alloys, 4
for steel, atmospheric corrosion of, 155 CMEAs and, 125
passivation corrosion resistance to, 24
in food and beverage, 430–431 coupon testing for, 1–4, 3 (figure)
of titanium, 266–267 crevice corrosion and, 4–6, 17, 24, 30–31, 31 (figure)
penetration rate, corrosion rates and, 111 critical potentials for, 124
pentane, in petroleum chemistry, 242, 242 (table) cyclic potentiodynamic polarization and, 123
permeation method, for hydrogen, 127–128, 128 (figure) electrochemical tests for, 4–11, 5 (figure), 10 (figure)
petroleum chemistry, 241–249 in freshwater, 183, 184 (table)
in crude oil phase, 243–245, 243 (figure), 245 (figure), immersion testing for, 141, 142 (table)
243 (table), 244 (table) of industrial chemicals, 400 (table)
in gas and gas condensate phases, 241, 241 (table) metallographic analysis of, 103, 103 (figure), 104 (figure)
laboratory corrosion tests for, 245–248 of MMCs, 307–308
in liquid water phase, 242–243, 243 (table) in nuclear power, 422–423
new production corrosion tests for, 248–249, 248 (figure), of pipelines, 329 (table), 330
249 (table) potentiodynamic polarization and, 123
temperatures and pressures with, 242, 242 (figure) predictive capabilities with, 11–12
INDEX 447
in seawater, 195 risk-based inspection (RBI), for CUI, 175

in soils, 227–228, 227 (figure) RNA analysis, 76
of titanium, 273–274
uniform corrosion and, 181 S
pitting resistance equivalence number (PREN), 183, 208 SAE J400, 373 (table)
polarization curve, for galvanic corrosion, 53 SAE J1703, 377
polarization methods SAE J2020, 373 (table)
concentration effects with, 112–113, 113 (figure) SAE J2334, 373 (table)
in electrochemical tests, 111–117, 113 (figure), 115 (figure) salinity, of seawater, 191–192, 191 (table)
polarization resistance, 113–114, 113 (figure) salts
uniform corrosion and, 182 automobiles and, 361–363, 362 (figure), 363 (table)
polarized light (PL), 100 immersion testing and, 146
polychlorotrifluoroethylene (PCTFE), 19 in soils, 218
polymerase chain reaction (PCR), 76 salt spray (fog) testing
polytetrafluoroethylene (PTFE), 2, 5, 5 (figure), 19, 30, 33, 95 for commercial aircraft, 390
polyvinylidene difluoride (PVDF), 19, 23 for military aircraft, 394–395
potential measurement for pitting, 3–4, 3 (figure)
in electrochemical tests, 120–133 for seawater, 199–200, 199 (figure)
for pipelines, 335–336, 335 (figure) saltwater. See seawater
for soils, 234–235 sand and dust testing, for military aircraft, 395–396
potentiodynamic galvanostatic-potentiodynamic technique saturated calomel electrode (SCE), 129
(PD-GS-PD), 33–35, 34 (figure), 35 (figure) seawater and, 201
potentiodynamic polarization scanning electrochemical microscopy (SECM), 121–122, 122 (figure)
for crevice corrosion electrochemical tests, 29, 31–35, for pitting electrochemical tests, 11
32 (figure), 35 (figure), 43 (figure) scanning electron microscope (SEM)
for galvanic corrosion electrochemical tests, 48 for metallographic analysis, 100
immersion testing and, 146 for soils, 237
for localized corrosion, 123 scanning Kelvin probe (SKP)
for SCC, 126–127 for coatings, 132–133, 132 (figure)
potentiokinetic polarization, 29 for pitting electrochemical tests, 11
potentiostaircase technique, 29 scanning Kelvin probe force microscopy (SKPFM)
potentiostatic methods for coatings, 132–133, 132 (figure)
for crevice corrosion electrochemical tests, 30–31, 30 (figure), for pitting electrochemical tests, 11
31 (figure) scanning vibrating electrochemical technique (SVET), 120–121,
for galvanic corrosion electrochemical tests, 48 121 (figure)
for localized corrosion, 122 (figure), 123 for galvanic corrosion, 52, 53–55, 53 (figure), 55 (figure), 120
for pitting electrochemical tests, 8–10, 9 (figure) for pitting electrochemical tests, 11
for tribocorrosion, 87–89, 88 (figure) scratch tests
potentiostatic polarization, 29 for localized corrosion, 124, 124 (figure)
potentiostep technique, 29 for pitting electrochemical tests, 8–9, 9 (figure)
preferential weld corrosion (PWC), 330 (table) for SCC, 126
probes. See also electrical resistance; linear polarization-resistance sea-level change, highways, bridges, and tunnels and, 354
for galvanic corrosion tests, 49 seawater, 187–209
for soils, 236, 237, 237 (figure) atmospheric corrosion and, 188, 188 (table)
propane, 242, 242 (table) automobiles and, 361
pyrite, 77 biological organisms in, 192–193
carbonates in, 192
Q composition of, 187–188, 187 (table)
quantitative PCR (qPCR), 76 corrosion mechanisms of, 194–197, 197 (figure)
corrosion testing of, 197–205
R crevice corrosion in, 26–27
rain exposure testing, for military aircraft, 395 cyclic potentiodynamic polarization for, 201, 201 (figure)
reinforced concrete (RC), for highways, bridges, and tunnels, DC for, 202–203
345–346, 349 in deep ocean, 189, 189 (figure)
remote crevice assembly, 28 dissolved oxygen in, 190–191, 191 (table)
repassivation potential EIS for, 202
in crevice corrosion electrochemical tests, 32 electrochemical tests for, 200–203
in pitting electrochemical tests, 9–10, 10 (figure) EN and, 202
potentiodynamic polarization and, 123 environmental zones of, 188–190, 188 (figure), 188 (table),
tribocorrosion and, 82–83, 84 189 (figure)
rising displacement test, for hydrogen, 69–70 flow velocity of, 193–194, 193 (figure)
448 Index
heavy metals in, 194 pipelines in, 326–330, 327 (table), 330 (figure)
high velocity flow tests for, 203 piping in, 225, 225 (figure), 227–229, 227 (figure), 237–238
immersion testing for, 198–199 pitting in, 227–228, 227 (figure)
in-service testing of, 205–206 probes for, 236, 237, 237 (figure)
laboratory evaluation of, 195–196 resistivity of, 219–220, 219 (figure), 221 (figure), 220 (table)
MIC and, 78 SRB in, 223–224, 223 (figure)
mixed potential theory for, 200–201 stainless steel in, 228
in mud, 188 (figure), 190 stray current corrosion in, 226–227, 226 (figure), 227 (figure)
pH of, 192 solar radiation, on military aircraft, 395
salinity of, 191–192, 191 (table) solution resistance
salt spray testing for, 199–200, 199 (figure) polarization methods and, 112
SCC in, 196, 203–205 polarization resistance and, 114
small-specimen testing for, 205–206 specimen preparation
splash-spray zone of, 188 (figure), 189 for atmospheric tests, 160–162, 160 (figure), 161 (figure),
standards for, 206–207 162 (table)
in submerged/shallow ocean, 189, 189 (figure) for immersion testing, 144, 148–150, 149 (figure)
sulfides in, 192, 194, 194 (table) for metallographic analysis, 93–95, 95 (figure)
temperature of, 190, 190 (table) for pitting electrochemical tests, 4–5
tidal zone of, 189, 189 (figure) for soils, 231–233
uniqueness of, 190 splash-spray zone
service life testing, for coatings, 288 automobiles and, 361
r-phase metallographic analysis, 104–105, 104 (figure) of seawater, 188 (figure), 189
silicon/aluminum MMCs, 297 stainless steel
silicon carbide/aluminum (SiC/Al) MMCs, 294–296, 294 (figure), atmospheric corrosion of, 153–155, 154 (table), 159 (table)
295 (figure) crevice corrosion of, 2–3, 16, 17, 24, 27
silicon carbide/copper MMCs, 305 critical potentials for, 124
silicon carbide/magnesium MMCs, 301, 301 (figure) cyclic potentiodynamic polarization for, 122
silicon carbide/titanium MMCs, 305 ECSCC of, 170, 171–172
simulated service testing, 148 electrolytic corrosion test and, 129–130
for seawater, 206 FGD and, 409, 411
slow strain rate test (SSRT), for nuclear power, 425 for food and beverage, 430
small-specimen testing, for seawater, 205–206 in freshwater, 181 (table)
soil box corrosion testing, 229 galvanic corrosion of, 52
soils, 217–238 immersion testing for, 146
aeration of, 221 metallographic analysis of, 104–105, 104 (figure)
anions in, 222–223 MMCs, 303–304
carbon steel in, 228 for nuclear power, 422
cations in, 222–223 for pipelines, 325
coatings in, 228 pitting electrochemical tests for, 5–6, 5 (figure), 7 (figure)
concrete pressure pipe in, 228 polarization resistance and, 113
copper and copper alloys in, 229, 235, 235 (table) potentiodynamic polarization for, 123
corrosion in, 224–229 SCC of, 102
corrosion monitoring in, 234–238, 235 (figure), 237 (figure), soil pH and, 222
235 (table) in soils, 228
definition and classification of, 217–218, 217 (figure), tribocorrosion of, 81
218 (table) steel. See also high-strength low-alloys; stainless steel
disturbance of, 224 in freshwater, 181 (table)
ductile iron in, 228 for highways, bridges, and tunnels, 346–349
electrochemical polarization for, 235–236, 235 (figure), for nuclear power, 419–420
236 (figure) strain
electrochemical tests for, 229–230, 230 (figure) hydrogen and, 63–65, 64 (figure)
field corrosion tests for, 229–234, 232 (figure), 233 (figure) tribocorrosion and, 81
galvanic corrosion in, 237 stray current corrosion, in soils, 226–227, 226 (figure), 227 (figure)
laboratory corrosion tests for, 229–230, 229 (figure), stress
230 (figure) hydrogen and, 60–65, 64 (figure)
lead in, 228–229 on MMCs, 308
MIC in, 223–224, 237 in soils, 234
moisture in, 218–219 tribocorrosion and, 81
oxidation-reduction potential in, 221–222, 222 (table) stress corrosion cracking (SCC)
oxygen in, 221, 225, 225 (figure) ammonia and, 192
pH of, 222 of commercial aircraft, 390
INDEX 449
of copper and copper alloys, 192 threshold stress intensity factor, hydrogen and, 67–70, 68 (figure),
electrochemical tests for, 126–129, 128 (figure), 129 (figure) 69 (figure)
EN for, 125 tidal zone, of seawater, 189, 189 (figure)
FGD and, 409 tin, atmospheric corrosion of, 154
in food and beverage, 430 titanium, 266 (table)
in freshwater, 184–185, 185 (figure) atmospheric corrosion of, 154
immersion testing for, 142 (table), 146 corrosion forms of, 269–270, 269 (table)
industrial chemicals and, 400 (table), 406 corrosion resistance of, 265–266
metallographic analysis for, 102–103, 102 (figure), corrosion testing for, 270–280, 270 (figure), 271 (table),
103 (figure) 272 (figure), 273 (figure), 275 (figure), 280 (figure)
in nuclear power, 419, 422–423 crevice corrosion of, 272–273, 272 (figure), 273 (figure)
with organic liquids, 253, 256, 256 (figure), 260, 260 (figure) HE of, 268–269, 276–277, 276 (figure), 277 (figure)
in petroleum chemistry, 249 ignition testing for, 277–279, 278 (figure), 279 (figure)
of pipelines, 328 (table), 330 MMCs, 304, 304 (figure)
in seawater, 196, 203–205 for nuclear power, 422
in soils, 227–228, 234 oxidation of, 265, 279–280, 280 (figure)
of titanium, 268, 270, 274–275, 275 (figure) passivation of, 266–267
uniform corrosion and, 181 pitting of, 273–274
submerged/shallow ocean, seawater in, 189, 189 (figure) SCC of, 268, 270, 274–275, 275 (figure)
substructure, of bridges, 353–354 SCL of, 269, 277
sugars, automobiles and, 364 in seawater, 208, 209
sulfate in soils, 228
atmospheric corrosion from, 156–157, 158 (table) tribocorrosion of, 81, 83, 84
in freshwater, 179, 180 titanium and titanium alloys, 265–280
MIC and, 75 toluene diamine (TDA), 401–402
in soils, 222 top-of-the-line corrosion (TLC), of pipelines, 326, 327 (table)
sulfate-reducing bacteria (SRB) transgranular stress corrosion cracking (TGSCC), 102–103
MIC from, 74, 77 transmission electron microscope (TEM), 100
soil pH and, 222 tribocorrosion
in soils, 223–224, 223 (figure) asperity and, 85–86, 85 (figure), 90
soils oxidation-reduction potential and, 222 Boltzmann superposition for, 85–86, 86 (figure)
sulfide-producing prokaryotes (SPP), 74, 75 contact mechanics and, 84–87, 85 (figure)
sulfides electrochemical tests for, 87–89, 88 (figure), 90
food and beverage and, 429 electrode potential in, 81–82, 84
in seawater, 192, 194, 194 (table) fretting corrosion and, 89, 89 (figure)
sulphate-reducing bacteria (SRB), 197 maps of, 90
super-duplex stainless steels (SDSS), crevice corrosion of, 27 mass balance in, 82–84, 83 (figure)
superstructure, of bridges, 352–353, 353 (figure) material characterization in post-testing of, 89–90
sustained-load cracking (SCL), 269, 277 mechanisms of, 81–82
sustained load test, for hydrogen, 67–68, 68 (figure) potentiostatic methods for, 87–89, 88 (figure)
repassivation potential and, 84
testing of, 87–89, 88 (figure)
T tunnels
Tafel extrapolation coatings for, 346–347, 349–350
for corrosion rates, 112 concrete for, 349–350
for seawater, 201, 202–203 corrosion standards for, 354–356
uniform corrosion and, 181, 182 CP for, 350
Tafel parameters, for EFM, 117 electrochemical tests for, 350
Tafel slope LACR for, 354
in galvanic corrosion, 43 RC for, 345–346, 349
in polarization methods, 111 salt exposure of, 346
in tribocorrosion, 83 sea-level change and, 354
uniform corrosion and, 182 steel for, 346–349
tensile testing, for hydrogen, 66–67 vulnerable areas of, 351
test heat exchanger, for water handling systems, 322, 322 (figure) water exposure of, 346
thermal barrier coatings (TBC), 106–107, 106 (figure)
thermally grown oxide (TGO), 107 U
thermal shock, on military aircraft, 394 ultrasound (UT)
thermal spray aluminum (TSA), 172 for pipelines, 333–334
thermal spray coating (TSC), 347 for seawater, 206
thermoplastic liners, for pipelines, 326 underdeposit corrosion (UDC)
450 Index
of nuclear power, 422 X

of pipelines, 329 (table) X-ray diffraction, for MIC, 77
uniform corrosion
in freshwater, 181–182, 182 (table)
in MMCs, 307 Y
in seawater, 195 yield strength, hydrogen and, 63
uranium. See also nuclear power yield stress
MMCs, 303 hydrogen and, 64, 68 (figure)
SCC and, 196
V yttria/stainless steel MMCs, 304
vanadium, atmospheric corrosion of, 154
W Z
wallpapering, 409 zero resistance amperometry (ZRA), 109
water handling systems, 315–323 for crevice corrosion, 21 (table), 28–29, 29 (figure)
chemical analysis of, 320, 320 (table) EFM and, 117–118
corrosion rates in, 317, 317 (figure) EN and, 131
coupon testing for, 315–318, 316 (figure), 316 (table), galvanic corrosion and, 120
317 (figure), 317 (table) for MMCs, 307
dissolved oxygen in, 320–321 for pitting electrochemical tests, 10
ER for, 316 (table), 319–320, 319 (figure), 320 (figure) zinc and zinc alloys
heat transfer in, 316 (table), 321–322, 321 (figure) atmospheric corrosion of, 153, 154 (table), 155, 158 (table),
LPR for, 316 (table), 317 (figure), 318–319, 318 (figure) 159 (table), 163
ORP in, 321 for automobiles, 360
test heat exchanger for, 322, 322 (figure) electrolytic corrosion test and, 129–130
wavelength-dispersive spectrometer (WDS) in freshwater, 179, 180
for dealloying, 185 MMCs, 305
for metallographic analysis, 100 in water handling systems, 320 (table)
welding, FGD and, 413 zirconium, for nuclear power, 419–420
Hibner | Hack | Scully
EDWARD L. HIBNER is a Metallurgical and Corrosion consultant. He was
most recently with Haynes International as a Senior Metallurgical Consultant
and prior to that a Code Manager at Special Metals Corporation, formerly
Inco Alloys International, in Huntington, West Virginia. He received his BS
in Chemistry from Marshall University and in Metallurgy from the University
of Cincinnati. He is the recipient of the ASTM Award of Merit, the ASTM
Committee G01 Francis L. LaQue Memorial Award, the ASTM Committee
G01 Certificate of Appreciation, and the NACE Fellow Award, and is currently
Vice-Chairman and the Editorial Review Chairman of ASTM Committee G01
on Corrosion of Metals. He has served as Chairman and as Trustee of the
West Virginia Section of NACE International and is currently serving on the
NACE MR0175/ ISO 15156 Maintenance Panel. He has extensive experience ASTM INTERNATIONAL
in alloy development for chemical process, flue gas desulfurization, marine, Helping our world work better
and oil field applications. He has written widely on materials applications and
corrosion topics in these fields and has four patents and 60 publications. In
Supplement to
Application and Interpretation: Second Edition

Supplement to Corrosion Tests and Standards:
addition to ASTM International, he is a member of the International Desalination
Association, the Society for Petroleum Engineers, ASME International, SAE
International, NACE International, and the Naval Submarine League.
Corrosion Tests and
HARVEY P. HACK Dr. Hack is a Northrop Grumman Fellow for Northrop
Grumman Corporation, where he does materials selection and corrosion Standards: Application
and Interpretation:
control for underwater vehicles and systems for the Department of Defense.
He received his B.S. and M.S. from Carnegie-Mellon University, and his Ph.D.
in Metallurgy from The Pennsylvania State University. He is the recipient of
Second Edition
the ASTM International Award of Merit and is past Chairman of the Board of
Directors of ASTM International. Dr. Hack has received the Distinguished
Service Award from NACE International (now AMPP), the Francis L. LaQue
Memorial Award from ASTM Committee G-1 on Corrosion of Metals, and the
Francis L. LaQue Award from the Sea Horse Institute. He is a Past President
of NACE International, a NACE Corrosion Specialist, Cathodic Protection
Specialist, and Coatings Inspector, a Fellow of NACE International, ASTM
International, the Washington Academy of Sciences, and the Institute of
Corrosion in the United Kingdom. Dr. Hack was the Associate Editor for the
Edward L. Hibner,
Materials Performance and Characterization section of the Journal of ASTM
International (JAI) and is a past President of the Council of Engineering and
Harvey P. Hack, and
Scientific Specialty Boards. Dr. Hack has approximately 100 publications and John R. Scully, Editors
is the author, editor, or major contributor to five books.
JOHN R. SCULLY received his B.S, M.S., and Ph.D. in Materials Science
and Engineering from Johns Hopkins University. While pursuing his Ph.D.,
he worked at David Taylor Naval Ship R&D Center in Annapolis, Maryland
in the Marine Corrosion Branch. He then joined Sandia National Laboratory
after a term as a Visiting Scientist at AT&T Bell Laboratories. In 1990, he
joined the faculty of the Department of Materials Science and Engineering
at the University of Virginia and is now the Charles Henderson Chaired
Professor of Materials Science and Engineering, Department Chair of MSE
and co-directs the Center for Electrochemical Science and Engineering.
He is the technical editor of CORROSION. Professor Scully has received
numerous awards for corrosion research and education of the next
generation of corrosion professionals. Professor Scully has published over
300 technical papers, given invited talks around the world, and edited
several books on corrosion.
www.astm.org
ISBN: 978-0-8031-7134-3
Stock #: MNL20-2ND-SUP
ISBN-EB: 978-0-8031-7135-0
Stock #: MNL20-2ND-SUP-EB
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Hibner | Hack | Scully

EDWARD L. HIBNER is a Metallurgical and Corrosion consultant. He was

Application and Interpretation: Second Edition

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Supplement to Corrosion Tests

ASTM Stock Number: MNL20-2ND-SUP

Analysis, Testing, and Environments

8 Electrochemical Tests 109

9 Immersion Testing 141

11 Standards and Practices on Corrosion under Insulation 169

15 Petroleum Chemistry 241

16 Organic Liquids 251

Materials and Applications

18 Corrosion Testing of Nonmetallic Coatings 283

19 Metal-Matrix Composites 291

20 Water Handling Systems 315

22 Highways, Tunnels, and Bridges 345

24 Commercial Aircraft 385

25 Military Aircraft and Associated Equipment 393

26 Industrial Chemicals: Manufacture and Usage 399

27 Flue Gas Desulfurization 409

28 Nuclear Power 419

29 Food and Beverage 429

Robert G. Kelly,1 Ryan M. Katona,1,2 and Eric J. Schindelholz3

Droplet Exposures stabilization as a parameter to quantify pitting resistance. That

FIG. 2 Stern-Makrides electrode assembly: (A) glass tub that

specimens tested. An example of the differences that one can

ACOUSTIC EMISSION MONITORING OF CORROSION

Chapter 2 | Crevice Corrosion

Mariano Iannuzzi,1 Edgar Hornus,1 and Mobin Salasi1

Introduction become susceptible in alkaline environments free of aggressive spe-

study speciﬁc crevice corrosion parameters and prevention strat-

solution” (CCS).22 The formation of the CCS represents the transi-

The Critical Acidification Model

STAGES OF CREVICE CORROSION

TABLE 1 Comparison of Nonelectrochemical Test Methods to Evaluate Crevice Corrosion Resistance

Assessment • ECrit (pitting or crevice)

Test specimen • Modiﬁed to include creviced coupons.

Exposure conditions • Electrolyte:

TABLE 5 Results of the Second Interlaboratory Test Program

other values can be used. A test at þ600 or þ800 mVSCE can be

POTENTIOKINETIC ELECTROCHEMICAL TEST

Modified ASTM G150: Potential-Independent Critical

Terms and Definitions

As proposed by Oldﬁeld and Sutton, the depassivation pH ER Repassivation potential

critically acidic environment that develops inside a crevice, as g Crevice gap

References 18. J. R. Galvele, “Transport Processes and the Mechanism of Pitting

Harvey P. Hack,1 Carol Glover,2 and Jason Lee3

Basic Principles oxygen reduction occurring primarily in acids

ELECTROCHEMICAL REACTIONS O2 þ 4Hþ þ 4e ! 2H2 O, and (4)

Log Reaction Rate, i

by the cathodic reaction. This can occur as shown in ﬁgure 1 only

coupled potential, Ecouple. The mixed potential of the couple is

EFFECTS OF ANODE–CATHODE AREA RATIO

ICoupled, Anode, Large Cathode

ﬁgure 6. When the diffusion-limited cathodic curve is present in Passivity Caused by

externally applied current will follow a shape called a polariza-

CURRENT AND POTENTIAL DISTRIBUTIONS

FIG. 9 Creating polarization curves from Evans diagrams.

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