Material 19

15 A MPTIAC

E A S E
Jeffrey Guthrie, Brigitte Battat and Chris Grethlein
AMPTIAC, Rome, NY

ACCELERATED CORROSION TESTING

“Corrosion is Corrosion” – we have heard that all too often at the
AMPTIAC inquiry desk. In our experience, corrosion is one of the most mis-
understood and mischaracterized forms of material degradation.
Consequently, corrosion analysis and mitigation methods tend to be some of
the most misapplied. This MaterialEASE is the third and final installment
excerpting a new AMPTIAC State-of-the-Art Review entitled “Accelerated
Testing: A Methodology for Determining Life and Degradation of Materials”.
It will be published in the near future. This article examines the fundamentals
of accelerated corrosion testing, the associated pitfalls therein, and what
tools today’s materials engineer will have to battle corrosion.
Background
The most accepted definition for corrosion is the destruction of material due
to a chemical reaction of the material with its environment. Generally, this
destruction takes place on its surface in the form of material dissolution or re-
deposition in some other form. Metallic systems are the predominant materi-
als of construction, and as a class, are generally susceptible to corrosion.
Consequently, the bulk of corrosion science focuses upon metals and alloys.
Corrosion does occur in polymers and ceramics but the mechanisms are
quite different from those of metals. As such, this article limits itself to a dis-
cussion of metallic corrosion.

The Problem: The Electrochemical Process

As recently as 1995, a major study concluded that the cost impact of corro- Corrosion consists of an oxidation reaction and a reduction reaction at the
sion to the U.S. economy totaled nearly $300 billion annually.[1] This repre- surface of the corroding material. The oxidation reaction generates metal
sents nearly 4% of the Gross Domestic Product, and is a conservative esti- ions and electrons; the electrons are then consumed in the reduction reaction.
mate at best – indirect costs, which are substantial and mostly unreported, For environments with water present including moisture in the air, the electrons
would greatly inflate the total estimated cost. Estimates suggest that about are consumed by converting oxygen and water to hydroxide ions. In iron and
two-thirds of present corrosion-related costs are unavoidable. In addition, cor- many iron alloys, these hydroxide ions in-turn combine with iron ions to form
rosion affects our Nation’s force effectiveness and readiness levels through a hydrated oxide (Fe(OH)2). Subsequent reactions form a mix of magnetite
the diminished safety and reliability of structures, mechanisms and electronics. (Fe3O4) and hematite (Fe2O3). This red-brown mixture of iron oxides is rust.
In many cases, corrosion is the life-limiting factor of a component. The figure below illustrates the basic oxidation/reduction reaction behind
Corrosive failures can occur unexpectedly at the worst possible moment. corrosion.
Corrosion testing can consume enormous blocks of time; particularly in the The higher the ionic conductivity, the quicker this reaction takes place.
case of outdoor atmospheric tests. Unfortunately, the timescales involved in This is why water containing electrolytes, such as salt, is far more damaging.
such tests preclude the opportunity for proper materials selection. In typical Another key point to note is that reducing the amount of dissolved oxygen in
circumstances, new systems may be halfway through their lifecycle before solution directly can inhibit corrosion. However, many other reduction reac-
real data on the fielded system would indicate any corrosion problems. tions can consume the electrons.
Under the right conditions, accelerated testing may yield data beneficial in
selecting the most corrosion resistant materials for an application. OH OH OH
Accelerated testing isn’t limited to the design stage of a system’s lifecycle, but
OH
can be used to provide in-field support, as the emergence of sudden corro-
sion problems on fielded systems requires quick answers.
Fe+2 H 2O O2 H2O
Managing corrosion in structural components and critical systems, to Fe+2
extend service life and ensure reliability, is paramount. Effective corrosion con-
trol requires meaningful test data in a reasonable time frame such that it may e e e e
be employed to influence materials selection and protection efforts. There are Ir on
presently hundreds of existing accelerated corrosion test methods and no
doubt there will be many more in the future. Figure 1. Electrochemical Process

The AMPTIAC Quarterly, Volume 6, Number 3 11

 Material
E A S E

Table 1. Traditional Corrosion Classifications[3].

Uniform (General) .. Occurs evenly over the entire surface. The rate of corrosion is often presented as a weight loss. Uniform corrosion is very
predictable, and is the basis of most corrosion prediction equations.
Galvanic .................. Corrosion caused by an electrochemical reaction between two dissimilar metals when placed in contact or electrically con-
nected with each other in an electrolyte.

Crevice .................... A localized form of corrosion which occurs within the stagnant zones created by the interfaces between two surfaces. Crevice
corrosion can occur under washers, gaskets, debonded coatings, surface deposits, sealing rings, rivets, sleeves, surface scale,
switch contacts, clamps, etc. The diverse environmental factors causing crevice corrosion make it almost impossible to simulate
field conditions in the laboratory. Predicted life from accelerated tests is also unlikely.
Pitting ...................... Pitting corrosion is a localized form of corrosion that proceeds with minimal overall metal loss, making it difficult to detect.
Consequently, it is difficult to predict, and its rate of attack is hard to quantify, as its reaction rate is not quantifiable.

Intergranular .......... This phenomenon occurs preferentially at grain boundaries, usually with slight or negligible attack on the adjacent grains.

Selective Leaching .. One element is preferentially removed from an alloy, leaving a residue (often porous) of the elements that are more resistant to
the particular environment. It is also called de-alloying or parting. Common forms of selective leaching are decarburization,
decobaltification, denickelification, dezincification, and graphitic corrosion.

Erosion .................... An action involving both corrosion and erosion in the presence of a moving corrosive fluid, leading to the accelerated loss of
material.

Stress ...................... Induced by the joint influence of mechanical stress and corrosion processes. Static-tensile stress causes stress corrosion crack-
ing (SCC). The stresses initiating SCC damage are in the form of applied mechanical stress or residual stress. Manufacturing
processes such as welding, bending, cold deformation (cold working), or electroplating of metallic components can bring
about residual stresses. Differences in the coefficients of thermal expansion (CTE) of the materials in contact increase the risk of
SCC. Corrosion fatigue is often considered to be a form of SCC. Cyclic loading brings about corrosion fatigue.

Table 2. Forms of Corrosion – ASM Classifications[4].

General Corrosion:
Corrosive attack
dominated by
uniform thinning
• Atmospheric Corrosion
• Galvanic Corrosion
• Stray-Current Corrosion
• General Biological
Corrosion
• Molten Salt Corrosion
• Corrosion in Liquid
Metals
• High-Temperature
Corrosion
Localized Corrosion:
High rates of metal
penetration at
specific sites
• Crevice Corrosion
• Filiform Corrosion
• Pitting Corrosion
• Localized Biological
Corrosion
Metallurgically
Influenced Corrosion:
Affected by alloy
chemistry & heat
treatment
• Intergranular Corrosion
• Dealloying Corrosion
Mechanically Assisted Environmentally
Degradation: Induced Cracking:
Corrosion with a Cracking produced
mechanical component by corrosion, in the
• Erosion Corrosion presence of stress.
• Fretting Corrosion • Stress-Corrosion
• Cavitation and Water Cracking (SCC)
Drop Impingement • Hydrogen Damage
• Corrosion Fatigue • Liquid Metal
Embrittlement
• Solid Metal Induced
Embrittlement

12 The AMPTIAC Quarterly, Volume 6, Number 3

 A D VA N C E D M AT E R I A L S
Table 3. ASTM Standard Test Methods for Various Environments
Environment causing corrosion Types of Tests
Fresh Water 39 ASTM Standards
Seawater Environments ASTM B117, Salt Spray, Fog Test (Oldest and Most Widely used Cabinet Test)
General Environments ASTM G31 (Immersion Corrosion Testing), ASTM G50 (Atmospheric Corrosion Testing)
(e.g., atmospheric, galvanic)
The corrosion of iron illustrates that many reactions can occur. Similar to
iron, aluminum forms an oxide scale; however, the oxide scale formed (alumi-
na) is cohesive, adherent and inhibits further corrosion. The oxide film formed
ennobles the metal and reduces electrical current density by as much as six
orders of magnitude. Materials like aluminum exhibit three corrosion regions:
a. Active Region -Increases in the oxidation potential lead to increasing corro-
sion rates. This region corresponds to the beginning of corrosion.
b. Passive Region - Increasing the oxidation potential past the active region
reduces the corrosion rate.
c. Transpassive Region - Increasing the oxidation potential past the passive
region, increases corrosion rate.
If the oxidizing potential is raised to high enough levels the oxide film
breaks down and the material begins to actively corrode again. Given the
many reactions that can occur and the corrosion regions possible, accelerat-
ing the corrosion process is difficult without altering the corrosion mechanism.
Categorizing corrosion forms into specific groups is not straightforward,
because such groups have overlapping characteristics, which influence the ini-
tiation and propagation of corrosion. However, corrosion is often categorized
by how it manifests itself, as described in Table 1, Traditional Corrosion
Classifications.
Classes of Corrosion
ASM offers a complementary classification of corrosion that can be useful for
designers. This classification, shown in Table 2, categorizes various corrosion
processes by mechanism of attack. Inspection of this table indicates that some
forms of corrosion affect (relatively) large areas as indicated in the section
addressing “General Corrosion” while other mechanisms are very local in
nature. Other corrosion mechanisms are facilitated by metallurgical factors
while still others rely upon the movement of two structures relative to each other
or a structure or component subjected to moving fluids or slurries. The final cat-
egory identifies corrosion mechanisms that result from the inspection of a
“stressed” material in the presence of a corrosive agent. Some of these mech-
anisms can be easily dealt with or mitigated through proper design and mate-
rials selection decisions. Accelerated testing can be a useful tool in this process
as long as the investigator realizes the intent of the test. Accelerated tests can
seldom be used to accurately predict the life of a structure. Rather, they more
appropriately give insight in a qualitative fashion to how materials will behave
when subjected to an environment.
In either classification system, the corrosion categories overlap and often
influence each other. Consequently, the classification of corrosion into groups
may be gradually losing its significance as understanding of basic corrosion
mechanisms continues to grow. Because of its intricacy, accelerated testing for
corrosion is difficult to implement, and most types of corrosion do not lend
themselves to prediction of performance through accelerated tests.
AND PROCESSES TECHNOLOGY
A MPTIAC
Corrosion Testing
Typically, all conventional corrosion testing requires long testing times and is
expensive. There are three major types of corrosion tests: Laboratory, Field,
and Service Testing.
Naturally, service testing provides the highest fidelity results followed by
field testing. However, the service and field tests have limited prospects for
accelerated testing. Accelerated corrosion testing, like any other form of accel-
erated testing, becomes increasingly more realistic as the laboratory environ-
ment approaches that of the service environment. To account for the variation
of corrosion properties with configuration, several other standardized tests are
performed for particular corrosion types, such as uniform attack, pitting, stress
corrosion, and crevice corrosion. There are many ASTM and ISO publications
describing standard test methods for different types of corrosion testing in var-
ious atmospheres. Table 3 shows several common tests addressing a variety of
environments.
Before testing
Before implementing any corrosion test, care must be taken when selecting the
corrosive media and preparing the test specimen. Accelerating tests often rep-
resent the worst-case scenario, requiring a very aggressive corroding factor.
The onset of corrosion may seriously accelerate damage in an entirely unpre-
dictable manner. Caution must be exercised to make certain the corrosion
mechanism is not altered. Consequently, most accelerated tests should not be
used to predict life or corrosion rates. These tests are typically qualitative, and
the information obtained from them is best used to down-select the most
appropriate materials for use in specific applications.
Selection of Corrosive Media: The corrosion process largely depends
on the corrosive environment. A thorough study of this environment is sug-
gested before planning any corrosion test. In addition to analyzing the char-
acteristics of that environment, make sure that the test does not introduce addi-
tional corrosion mechanisms. For instance, inadvertently using a bolt and test
specimen which create a galvanic couple will lead to spurious results. If the
corrosion experiment has an extremely stagnant electrolyte for a crevice cor-
rosion test, the results may not show as aggressive an attack as desired since
the amount of dissolved oxygen in a liquid environment greatly impacts the
corrosion rate.
Test Specimen Preparation: In addition to carefully selecting the corrosive
environment, the corrosion specimen must be prepared in a fashion indicative
of the service material. Corrosion behavior is influenced by the slightest varia-
tion in metallurgical structure and surface preparation - thus care must be taken
while preparing the surface of the testing specimens. Avoid excessive heating
of the surface from grinding operations to remove scale and remove excessive
cold worked surfaces from sample machining, like those found near sheared
surfaces or stamped edges.
The AMPTIAC Quarterly, Volume 6, Number 3 13
 Material Acceleration
E A S E Testing does not have to correlate exactly to the service environment as
long as the corrosion mechanism remains the same. However, the results
of accelerated testing should correlate to results from more reliable
sources, e.g., service experience and field testing. The method of accel-
Table 4. Summary of Specific Laboratory Corrosion
erating corrosion testing will depend upon the material being examined,
Tests and Their Corresponding Standards
the environment and the type of corrosion mechanism. Several common
Electrochemical Methods ASTM Standard
methods for acceleration include increasing:
Electrochemical polarization resistance G-59, D-2776
• Aeration for immersion tests
Electrochemical impedance G-106
• Temperature (The most common and greatest accelerating factor for
Cyclic potentiodynamic polarization G-61
many corrosion mechanisms.)
Galvanostatic polarization D-6208
• Pressure for stress corrosion cracking tests
Scratch-repassivation D-6208
• Acidity in immersion tests
Immersion Tests
• The amount of NO2 and SO2 for atmospheric tests
Total Immersion G-31
• Relative humidity for atmospheric tests
Partial immersion G-31
• Impingement velocity in erosion corrosion tests
Intermittent immersion G-44
• Current in electronic parts prone to corrosion
Salt Spray (Fog) Testing
Additionally for aqueous corrosion, the corroding electrolyte and the
Neutral B-117
ionic conductivity help determine the rate of corrosion attack. Even when
Acetic Acid G-85 Annex A1
accelerated, corrosion tests can be inherently slow; hence, testers must
Cyclic Acidified G-85 Annex A2
exercise control of these variables. Besides altering the main corrosion
Cyclic Seawater Acidified G-85 Annex A3
mechanisms, gross variations of all these factors can alter the kinetics of
Cyclic SO2 G-85 Annex A4
several intermediate corrosion reactions leading to spurious results.
Dilute Electrolyte Cyclic Fog Dry G-85 Annex A5
Since most laboratory corrosion tests are accelerated tests, careful
Copper-Accelerated Acetic Acid B-368
attention to, and meticulous execution of, their procedure is necessary to
obtain useful results. Standard testing procedures have been set up for the
various laboratory tests. These are described in some detail in Reference
0.8
5, and an outline of some of the specific tests and their corresponding
Extrapolation of ASTM standards is given in Table 4.
Initical Corrosion
0.7 Rate There are many other factors affecting corrosion rates, which lead to
countless test methods. There are fifteen ASTM standards on controlled
humidity tests alone. Moreover, each test includes a range of test condi-
0.6
tions. ASTM B 117 allows the concentration of NaCl solution to range
from 3.5% to 20%. The goal is to accelerate the test as much as possible
Average Penetration, mm

0.5 while keeping the test corrosion mechanism the same as the service cor-
rosion mechanism.
0.4 2-Point Estimate of
Linear Rate Interpreting the results
In order to correctly interpret the results of any corrosion test, a com-
0.3
plete pedigree of material information and testing parameters should
accompany the test results. Variations in the material’s chemical composi-
Actual Corrosion
0.2 Curve tion, fabrication history, shape and size of the specimen all affect the cor-
rosion rate. For example, the corrosion rate of wrought versus cast alloy
will likely be different. Classifying materials in broad categories such as
0.1
“Stainless Steel” or “Aluminum” is a mistake.
The changes in specimen weight versus time are most often used to
0 calculate corrosion rates. They are the easiest measurement to make.
1 2 4 8 16
Additionally, electrochemical polarization methods for measuring corro-
Exposure Time, years
sion rate are amenable to aqueous corrosion.[4] Other methods, such as
directly measuring a “depth-of-penetration,” can be difficult.
Figure 2. Example of How Short-Term Corrosion Test Results
Can Be Misleading.[7] Unfortunately, measuring weight loss is unsuitable for localized corrosion
effects such as pitting, crevice and intergranular attack since total weight
loss can be minimal while local damage can be severe.

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A D VA N C E D M AT E R I A L S
For general corrosion, (uniform thinning) the corrosion rate is proportional
to the weight loss and inversely proportional to the area, exposure time and
density of the specimen. (Use the original area, not the reduced area, to cal-
culate rates.) Even with general corrosion, care must be taken while testing to
correlate a weight loss to a corrosion rate. For example, many materials pro-
duce a scale. If this scale is adherent but does not protect the base metal, it
must be removed before weighing. Adherent scales may exhibit a weight
growth even though the material is severely damaged. Note, the sample
should be carefully examined before cleaning to gain insight into the corrosion
mechanism. For example, adherent deposits or encrustations may cause pitting
or crevice corrosion.
To compound the damage assessment, the corrosion rate often changes
with time due to film formation on the material’s surface. This change in corro-
sion rate can even undergo cyclical acceleration and deceleration if a scale
thickens and sloughs off. For example, copper immersed in tropical seawater
corrodes at a rate that is proportional to the square root of exposure time and
not linear to it (Figure 2). Curves α and β were calculated from short-term test
data (6-months and 2-year rate respectively). Curve γ is the actual corrosion
rate, which resembles a long-term corrosion rate at short exposure times. On
the other hand, low-carbon steel immersed in a similar environment initially
forms a protective film after which the corrosion rate becomes almost linear
with time. The ASM Handbook on Corrosion[5,6] recommends that at least
three replicate sets of specimens should be tested through exposure at
increased duration, to validate the data.
Pitfalls of Accelerated Testing
With any accelerated testing, caution must be exercised to gain meaningful
results. This is particularly true with accelerated corrosion testing, where the
“pitfalls” are numerous. The following describes some of the more prominent
ones.
Multiple Failure Modes complicate the design of accelerated testing.
New failure modes may appear that can cause the component or the materi-
al to degrade or fail. The example mentioned earlier describing scale
creating sites for pitting or crevice corrosion is a common case of multiple
mechanisms at work. Test specimens which fail by an alternate mechanism not
experienced in the field must be considered invalid.
Misapplied Models are responsible for many of the errors of corrosion
rate and life prediction. Many of the corrosion rate formulas are frequently
misused. Most common among these is the application of predictive equa-
tions (often derived from uniform corrosion phenomena) to characterize and
predict the behavior of localized phenomena, such as pitting or crevice
corrosion. While some debate in this area still exists, one thing is clear:
uniform corrosion models cannot and should not be applied to localized
phenomena.
Model Uncertainty is tremendously amplified via extrapolation of results
from the accelerated test. For example, small sample size, sample shape, small
numbers of failures, and large degrees of extrapolation from available data all
combine to create great uncertainty.
Unquantifiable Corrosion factors are major contributors to the uncertain-
ty of models and their frequent misapplication. Certain factors render com-
ponents much more susceptible to corrosion, such as geometry (crevice
corrosion, pitting) or welds (selective leaching, SCC). Such effects, while sub-
stantial, are not readily quantifiable. Consequently, data from accelerated
A MPTIAC
AND PROCESSES TECHNOLOGY
testing cannot provide reliable life predictions in such cases, and is instead
limited to qualitative assessments.
Multiple Factors Change Degradation when Multiple Time Scale is
Involved. Most failures are the result of several factors. If only one of these fac-
tors is accelerated, it may invalidate the contributors of non-accelerated fac-
tors. A classic “snake in the grass” is the case of immersing a steel specimen in
water near the boiling point. As the temperature approaches the boiling point
the corrosion rate decreases since the free oxygen in the solution is driven off.
While accelerating one failure mode, a different failure mode (that is usually
the first to appear in the field) is masked.
Acceleration of Specific Variables May Actually Decelerate Failure. For
example, in the case of accelerated testing of a circuit-pack, the test increased
temperature, thus lowering humidity and inhibiting corrosion. The result was
fewer test failures as compared to field conditions.
Prototype Articles for Laboratory Testing May Vary from Production
Units. Materials and parts used to build prototypes may vary from the ones
used in production, partly due to different levels of cleanliness, as well as the
extra attention paid when building them. Test units should be taken from the
field, and should use raw materials from actual production. Manufacturing
conditions should be closely simulated in the accelerated test.
These pitfalls illustrate that, among other difficulties, the field environment is
not as carefully controlled as the laboratory. Because of this, it is difficult to
design an accelerated test that can predict field reliability. Climate, which is
supremely stochastic and essentially random, greatly affects the environmental
conditions, thus rendering test variables highly unpredictable. Some have
attempted to “average” out environmental conditions for accelerated life tests
in the hope of reproducing the variable effects of climate. However, experi-
ence has shown that “smearing” environmental effects in accelerated tests
does not provide good prediction of field reliability.
Conclusion
Corrosion is a complex electrochemical process dependent upon a myriad of
factors. Be extremely cautious when devising any accelerated test technique
or using a corrosion rate as gospel for predicting lifetimes. Accelerated corro-
sion testing is a necessary and powerful tool when used to: (a) help with mate-
rials selection as a relative indicator of corrosion resistance, (b) help examine
potential environments for new materials, and (c) help determine corrosion
control strategies of fielded items.
References
[1] Kuruvilla, A.K., Life Prediction and Performance Assurance of Structural
Materials in Corrosive Environments - A State of the Art Report (AMPT-15),
AMPTIAC, 1999.
[2] Fontana, M.G., Corrosion Engineering, 3rd Edition, McGraw-Hill Book
Company, 1986, pp 39-152.
[3] Metals Handbook Ninth Edition, Vol. 13, ASM International, 1987, pp.
79-189
[4] Scully, J.R., Taylor, D.W., “Electrochemical Methods of Corrosion Testing,”
Metals Handbook, Vol. 13, ASM, 1987, pp. 212-228
[5] Metals Handbook Ninth Edition, Vol. 13, ASM International, 1987, pp.
191-317
[6] Baboian, Robert, Editor, “Corrosion Tests and Standards: Application and
Interpretation,” ASTM, 1995.
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